energies

Article
The Effect of a Reduction in the Catalyst Loading on a Mini
Passive Direct Methanol Fuel Cell
C. S. Moreira 1,2 , A. M. F. R. Pinto 1,2, * and V. B. Oliveira 1,2, *

1 CEFT—Transport Phenomena Research Centre, Faculty of Engineering, University of Porto, Rua Dr. Roberto
Frias, 4200-465 Porto, Portugal; [email protected]
2 ALiCE—Associate Laboratory in Chemical Engineering, Faculty of Engineering, University of Porto, Rua Dr.
Roberto Frias, 4200-465 Porto, Portugal
* Correspondence: [email protected] (A.M.F.R.P.); [email protected] (V.B.O.)

Abstract: Mini passive direct methanol fuel cells (mpDMFCs) appear to be a promising alternative
for powering portable devices, since they use a liquid fuel, have a fast refuelling time, have a high
efficiency and have a low environmental impact. However, some issues need to be solved before
their commercialization, such as methanol crossover, short lifetime and high costs. The present
work studies the effect of reducing the anode and cathode catalyst loading on the performance of
a mpDMFC towards a reduction in the system costs and the characterization of the system losses.
The undesirable losses that affect the fuel cell performance were identified and quantified using the
electrochemical impedance spectroscopy (EIS) technique. Accordingly, a novel equivalent electric
circuit (EEC) was proposed, accurately reproducing the mini pDMFC. In this work, a maximum power
density of 7.07 mW cm−2 was obtained, with a methanol concentration of 5 M, using 2 mg cm−2 Pt-
RuB and 4 mg cm−2 PtB. The mpDMFC allowed the cell to work with high methanol concentrations
and reduced anode catalyst loadings.

Keywords: mini passive direct methanol fuel cell; catalyst loading; power density; electrochemical
impedance spectroscopy; equivalent electric circuit

1. Introduction
Citation: Moreira, C.S.; Pinto,
A.M.F.R.; Oliveira, V.B. The Effect of a Alternative power sources with low environmental impacts are of vital importance
Reduction in the Catalyst Loading on to the planet’s health. Additionally, the growing interest in portable electronic devices
a Mini Passive Direct Methanol Fuel motivates research on finding alternative technologies to overcome the limitations of
Cell. Energies 2024, 17, 5174. https:// conventional batteries. Mini passive direct methanol fuel cells (mpDMFCs) appear to be a
doi.org/10.3390/en17205174 promising solution due to their low environmental impact, high efficiency, quick refuelling
Academic Editor: Massimo Guarnieri
and simplicity, since methanol is a liquid. In contrast to rechargeable batteries, mpDMFCs
do not require recharging, only refuelling, which is a fast process, and they are able to
Received: 29 July 2024 operate while the fuel is being supplied. Furthermore, the fact that the fuel cell operates on
Revised: 20 September 2024 passive mode allows the transport of the reactants to the system by a natural mechanism,
Accepted: 7 October 2024 such as capillarity, convection and diffusion, not requiring external energy to operate [1,2].
Published: 17 October 2024
Additionally, in isolated areas and developing countries, where there is limited access to the
grid, mpDMFCs allow easier and local electricity production. Nevertheless, these systems
present some barriers that need to be overcome before their commercialization, such as
Copyright: © 2024 by the authors.
slow electrochemical reactions, methanol crossover through the membrane, high costs and
Licensee MDPI, Basel, Switzerland. short lifetime [3,4].
This article is an open access article The mpDMFC catalysts, where the electrochemical reactions occur, are responsible
distributed under the terms and for a major fraction of these system costs, since the most used catalysts are noble metals,
conditions of the Creative Commons like platinum (Pt) and ruthenium (Ru). Based on that, many efforts have been made to
Attribution (CC BY) license (https:// improve the activity of the anode catalyst of a DMFC, but Pt-hybrid nanocatalysts are still
creativecommons.org/licenses/by/ the most effective for the methanol oxidation reaction (MOR) [5–8]. As this reaction occurs
4.0/). in an incomplete way on the Pt surface, with the formation of intermediate compounds that

Energies 2024, 17, 5174. https://doi.org/10.3390/en17205174 https://www.mdpi.com/journal/energies

Energies 2024, 17, 5174 2 of 15

poison the catalyst, a second metal is needed to provide the removal of these compounds.
Among the different metals studied, Ru is still the most effective. On the cathode catalyst
of a DMFC, the oxygen reduction reaction (ORR) and the parasitic methanol oxidation
reaction occur due methanol crossover. The competition between these two species for the
cathode catalyst active sites is negatively potentialized, decreasing the catalyst availability
for the ORR, limiting this reaction rate, increasing the cathode losses and decreasing its
performance and consequently the mpDMFC performance. Therefore, noble metals, such
as Pt, are used to overcome the sluggish ORR kinetics and circumvent the presence of
methanol [8–14]. Moreover, to overcome the slow kinetics, high catalyst loadings are
commonly used at the anode and cathode, namely 4 mg cm−2 Pt-Ru on the anode and
4 mg cm−2 Pt on the cathode, increasing the system costs [15].
The mpDMFC performance is commonly analysed through the polarization and power
curves, which allow the key losses that affect the fuel cell efficiency to be recognized, such
as activation, ohmic and concentration losses [16]. Nevertheless, since different phenomena
occur in these fuel cells and all of them are affected by the operating and configuration
conditions employed, the identification and quantification of their impact on the different
losses is a difficult task by these techniques. Thus, electrochemical impedance spectroscopy
(EIS) emerges as a powerful complementary tool to be used on the pDMFC diagnosis,
since it provides useful information to identify and quantify the different phenomena
that occur in the system and affect its performance. More specifically, this technique
allows the identification and quantification of the main losses that negatively affect the
fuel cell [15,17,18]. The EIS measurements can be performed in situ using a two-electrode
configuration, allowing the cell to be studied as a whole, or ex situ through a classic
three-electrode configuration, allowing the analysis of each fuel cell component [17]. Since
ex situ measurements are conducted without the fuel cell normal operation, the in situ
tests are the ideal approach to study the pDMFC in a real environment [1,19–22]. In situ
measurements can be conducted with an independent reference electrode, which is very
challenging when solid electrolytes are used and requires a modification of the fuel cell
system [23]. As an alternative, a dynamic hydrogen electrode (DHE) can be used through
replacing one of the reactants (methanol or oxygen) with hydrogen, which acts as the
reference electrode. Using this methodology, it is considered that the losses of the DHE
are irrelevant, with all the losses being associated with the other electrode, the one under
analysis [17]. Different works demonstrate the use of the DHE technique to study the losses
that negatively affect the passive DMFCs, through the comparison between the overall fuel
cell spectrum (obtained when the system operates in real conditions with methanol and
air) with the single-cell spectrum (given by the DHE measurements) [15,24–30]. Despite
being a much-used solution, this method also leads to a change in the fuel cell system
and in its behaviour, since one of the reactants is replaced with hydrogen. Siracusano
et al. [31] showed how the EIS technique can be applied as a non-invasive diagnostic tool
in electrolysis, using lower catalyst loadings on one electrode to suppress one electrode
behaviour and obtain useful information from the other. Based on this study and in order
to avoid the disadvantages of using a DHE, in this work, it was studied the effect of a
reduction in the anode and cathode catalyst loading on the performance of an mpDMFC.
This also allowed us to evaluate the possibility of using lower loadings to decrease the fuel
cell costs without a significant decrease in the system efficiency.
As the methanol concentration has a clear impact on the pDMFC performance, the
effect of the methanol concentration was also evaluated, studying different methanol/water
solutions. The methanol concentration that leads to a higher performance results in a
balance between the negative effect of an increase in the alcohol concentration on its
crossover rate and the positive effect of an increase in its concentration on the anode
oxidation reaction rate [32].
Another target of this work was to estimate the major losses that affect the system (ac-
tivation, ohmic and concentration losses) at the anode and cathode using the EIS technique.
Energies 2024, 17, x FOR PEER REVIEW 3 of 16
Energies 2024, 17, 5174 3 of 15

2. Materials and Methods

2. Materials and Methods
The mpDMFC has an active area of 2.25 cm2, and it is composed of two acrylic end
plates The
(withmpDMFC has an of
a fuel reservoir active area
1.8 cm 3 atofthe
2.25 cm2 , and
anode and an
it isopening
composed of two
at the acrylictwo
cathode), end
plates (with a fuel reservoir of 1.8 cm 3 at the anode and an opening at the cathode), two
rubber plates, two stainless-steel current collectors (with an open ratio of 28% at the anode
rubber
and 17% plates, two stainless-steel
at the cathode) current electrode
and a membrane collectors assembly
(with an open ratio
(MEA) of 28%
(Figure 1).at the anode
and 17% at the cathode) and a membrane electrode assembly (MEA) (Figure 1).

Figure 1. Schematic representation of the mini passive DMFC.

Figure 1. Schematic representation of the mini passive DMFC.
The MEA was acquired from FuelCellEtc, Bryan, TX, USA, and is composed of carbon
The
cloth MEA
with was acquiredlayer
a microporous from (MPL)
FuelCellEtc,
as theBryan,
anodeTX, andUSA,
cathodeand is composed
diffusion of carbon
layers (with a
cloth
thickness of 0.410 mm and a porosity of 0.8), Pt-RuB as the anode catalyst, PtB as the(with
with a microporous layer (MPL) as the anode and cathode diffusion layers cathodea
thickness of 0.410
catalyst and mm and
a Nafion ® 117 amembrane
porosity of 0.8), Pt-RuB
(Chemours as the Wilmington,
company, anode catalyst, DE,PtBUSA).as the
cathode catalyst and a Nafion ® 117 membrane (Chemours company, Wilmington, DE,
The experimental tests were performed at room temperature and pressure, with differ-
USA).
ent methanol solution concentrations and different anode and cathode catalyst loadings (4,
The0.5experimental
2 and tests were
mg cm−2 ), setting performed
a loading on one at room
side of thetemperature
cell and using anddifferent
pressure, with
loadings
different methanol
on the other side. solution concentrations and different anode and cathode catalyst
loadingsThe(4,mpDMFC
2 and 0.5 behaviour
mg cm−2), setting a loading
was analysed on one
through side of theand
polarization cell power
and using different
density curves
loadings
and EISon theusing
data other aside.
commercial fuel cell test station, Zahner Elektrik GmbH & Co. KG
The mpDMFC
(Zahner from Kronach, behaviour
Germany). was The
analysed through
polarization polarization
tests were conducted and power density
in galvanostatic
curves
mode,and EIS the
while dataEISusing
ones a commercial
were conducted fuel cell test station, Zahner
in potentiostatic mode. Elektrik GmbH & Co.
The impedance tests
KG (Zahner, Kronach, Germany). The polarization tests were conducted
were performed in situ at three voltages (0.4, 0.3 and 0.2 V), with an amplitude of 10 mV in galvanostatic
mode,
and awhile the EIS
frequency rangeones were conducted
between 0.01 Hz andin100potentiostatic mode. The
kHz. The impedance impedance
data were fittedtests
to an
were
EECperformed
to quantifyinthe situ at threeresistances
different voltages (0.4, 0.3 and
(losses) that0.2 V), withaffect
negatively an amplitude
the mpDMFC of 10 using
mV
and
theaThales
frequency
Z2.02range between
software from0.01 Hz and 100 kHz. The impedance data were fitted to
Zahner.
an EEC to quantify the different resistances (losses) that negatively affect the mpDMFC
3. Results
using and Discussion
the Thales Z2.02 software from Zahner.
In this section, the experimental results are presented and discussed in light of the
3.polarization
Results andand Discussion
power density curves and the EIS data, presenting a selected set of values
thatInshow
this section, thepatterns
the same experimentaland trends
resultsasare
thepresented
other results. The EIS in
and discussed results
light are first
of the
interpreted, an EEC is proposed and the quality of the EEC fitting
polarization and power density curves and the EIS data, presenting a selected set of valuesis presented. The effect
of ashow
that reduction in thepatterns
the same catalystand loading onas
trends both
thesides
otherofresults.
the mini ThepDMFC performance
EIS results are firstis
analysed and discussed, identifying and quantifying the different
interpreted, an EEC is proposed and the quality of the EEC fitting is presented. The effect losses/resistances that
negatively affect the anode and the cathode of the cell under
of a reduction in the catalyst loading on both sides of the mini pDMFC performance is study. Since the methanol
concentration
analysed (Cmethanolidentifying
and discussed, ) has an important impact onthe
and quantifying thedifferent
passive DMFC performance,
losses/resistances the
that
effect of its concentration on the mini pDMFC behaviour is also
negatively affect the anode and the cathode of the cell under study. Since the methanol presented in this section.
concentration (Cmethanol
3.1. Electrochemical ) has an important
Characterization impact
of a Mini on the passive DMFC performance, the
pDMFC
effect of its concentration on the mini pDMFC behaviour is also presented in this section.
As mentioned, the EIS measurements are realized as a complementary diagnostic
technique, allowing the identification and quantification of the undesirable losses that
affect the mpDMFC. The EIS data are, usually, represented using a Nyquist plot, where
the imaginary impedance (Zim ) is represented as a function of the real impedance (Zre )
(Figure 2). The different losses are identified based on the characteristics and shape of
each plot and quantified by fitting an EEC to the plots (Table 1). Consequently, different
 As mentioned, the EIS measurements are realized as a complementary diagnostic
technique, allowing the identification and quantification of the undesirable losses that
affect the mpDMFC. The EIS data are, usually, represented using a Nyquist plot, where
Energies 2024, 17, 5174 the imaginary impedance (Zim) is represented as a function of the real impedance 4(Zofre15 )
(Figure 2). The different losses are identified based on the characteristics and shape of each
plot and quantified by fitting an EEC to the plots (Table 1). Consequently, different
combinations
combinations andand different electrical elements
different electrical elementsshould
shouldbebeused
usedto to develop
develop thethe
EECEEC
thatthat
will
will be used to describe the impedance spectrum (Figure
be used to describe the impedance spectrum (Figure 3). 3).

Energies 2024, 17, x FOR PEER REVIEW 5 of 16

Impedancespectrum
Figure2.2.Impedance
Figure spectrumofofthe
thempDMFC
mpDMFCfor fordifferent
differentcell
cellvoltages.
voltages.Lines:
Lines:EEC
EECfitting;
fitting;dots:
dots:
experimental data. Methanol concentration: − 2
experimental
Based on data.
theMethanol
plots concentration:
depicted 33M;
in Figure M; anodecatalyst:
anode catalyst:
2 representing the44mg
mg cmpDMFC
cm
mini
−2 Pt-RuB;
Pt-RuB; cathodecatalyst:
cathode
behaviour, catalyst:
and
44mg
mgcm
cm −2−PtB.
2 PtB.
on the values of the resistances that affect the system under study presented in Table 1, it
can be 1.concluded thatvalues
Resistances the mini pDMFC
obtained is not greatly
fittingaffected by massvoltages.
transportMethanol
losses.
Table
The impedance spectrum can through EEC
be divided in for different
three different cell
regions based on its
This is evidenced by the decrease in the− two
2 resistances representing
concentration: 3 M; anode catalyst: 4 mg cm Pt-RuB; cathode catalyst: 4 mg cm PtB.the −arcs
2 shown in
frequency range: the high-frequency region (lower real impedance values), the medium-
Figure 2 with a decrease in cell voltage (Table 1). Thus, the two arcs that appear in the
frequency region (intermediate values)
Rohm (Ω) and the lower-frequency
Ract1 region (higher
Ract2 values),
NyquistVoltage (V)due
plot are to activation losses, characterized in (Ω)
the EEC (Figure 3) by a(Ω)resistor
each region being associated with one type of loss [17,33]. In the high-frequency region,
(Ract) in parallel
0.4 with a constant-phase
0.411 element (CPE). The CPE is associated with10.6
0.789 the double-
the spectrum is described by a point where the plot intercepts the real impedance axis,
layer interfaces
0.3 in the system, describing
0.409 the capacitance 0.691 properties. As can be seen 2.28in Figure
known as the 0.2 high-frequency resistance (HFR), representing
0.405reproduces the experimental
0.534 the ohmic losses/resistance
2, the EEC proposed (lines) accurately data (dots). 1.15
(Figure 2). This time-independent loss is characterized using Ohm’s law and is expressed
by a resistor in the EEC, namely ohmic resistance (Rohm)(Figure 3). The medium-frequency
region usually resembles an arc, which represents the activation losses/resistances,
described by a decrease in its value with a decrease in the cell voltage. The low-frequency
region can also resemble an arc, associated with mass transport or concentration losses,
where the resistance increases with a decrease in the fuel cell voltage [17].

Table 1. Resistances values obtained through EEC fitting for different cell voltages. Methanol
concentration: 3 M; anode catalyst: 4 mg cm−2 Pt-RuB; cathode catalyst: 4 mg cm−2 PtB.
Equivalentelectric
Figure3.3.Equivalent
Figure electriccircuit
circuitapplied
appliedtotocharacterize
characterizethe
thempDMFC.
mpDMFC.
Voltage (V) Rohm (Ω) Ract1 (Ω) Ract2 (Ω)
The impedance spectrum can be divided in three different regions based on its fre-
Besides identifying and quantifying the different losses that adversely affect the
quency range: the high-frequency
0.4 analysis, 0.411 region (lower real
0.789 impedance values),10.6 the medium-
system under it is important to link each loss with the different phenomena that
frequency0.3region (intermediate0.409 values) and the lower-frequency
0.691 region (higher
2.28 values),
occur in the system, to avoid and/or minimize them. In a working fuel cell, the activation
each region0.2being associated with one type of loss [17,33].
0.405 In the high-frequency region, the
losses are due to the electrochemical reactions taking0.534
place on both sides of 1.15
the cell: the
spectrum is described by a point where the plot intercepts the real impedance axis, known
fuel oxidation at the anode side and the oxygen reduction at the cathode side.
as the high-frequency resistance (HFR), representing the ohmic losses/resistance (Figure 2).
Nevertheless, as in a direct methanol fuel cell, both electrochemical reactions have a
This time-independent loss is characterized using Ohm’s law and is expressed by a resistor
marked impact on the cell performance, and it is very difficult to link each activation
in the EEC, namely ohmic resistance (Rohm )(Figure 3). The medium-frequency region
loss/resistance (Ract1 and Ract2) to each electrochemical reaction. Therefore, to address this
usually resembles an arc, which represents the activation losses/resistances, described by
issue, a study was conducted where the catalyst loading of one side of the cell was reduced
a decrease in its value with a decrease in the cell voltage. The low-frequency region can
toalso
a very low value,
resemble an arc,0.5associated
mg cm−2, with
to trymass
to distinguish
transport or theconcentration
losses of each electrode.
losses, whereThethe
following section examines the impact of reducing catalyst
resistance increases with a decrease in the fuel cell voltage [17]. loading on both the anode and
cathode sides on the cell performance and impedance spectrum, in order to identify the
activation resistances, Ract1 and Ract2, as anode and cathode resistances.

3.2. Analysis of the Mini pDMFC with Reduced Anode and Cathode Catalyst Loadings
It is known that the methanol concentration has a significant influence on the passive
DMFC behaviour, since the optimal concentration is a balance between the positive effect
Energies 2024, 17, 5174 5 of 15

Based on the plots depicted in Figure 2 representing the mini pDMFC behaviour, and
on the values of the resistances that affect the system under study presented in Table 1, it
can be concluded that the mini pDMFC is not greatly affected by mass transport losses. This
is evidenced by the decrease in the two resistances representing the arcs shown in Figure 2
with a decrease in cell voltage (Table 1). Thus, the two arcs that appear in the Nyquist
plot are due to activation losses, characterized in the EEC (Figure 3) by a resistor (Ract ) in
parallel with a constant-phase element (CPE). The CPE is associated with the double-layer
interfaces in the system, describing the capacitance properties. As can be seen in Figure 2,
the EEC proposed (lines) accurately reproduces the experimental data (dots).
Besides identifying and quantifying the different losses that adversely affect the system
under analysis, it is important to link each loss with the different phenomena that occur in
the system, to avoid and/or minimize them. In a working fuel cell, the activation losses
are due to the electrochemical reactions taking place on both sides of the cell: the fuel
oxidation at the anode side and the oxygen reduction at the cathode side. Nevertheless,
as in a direct methanol fuel cell, both electrochemical reactions have a marked impact on
the cell performance, and it is very difficult to link each activation loss/resistance (Ract1
and Ract2 ) to each electrochemical reaction. Therefore, to address this issue, a study was
conducted where the catalyst loading of one side of the cell was reduced to a very low
value, 0.5 mg cm−2 , to try to distinguish the losses of each electrode. The following section
examines the impact of reducing catalyst loading on both the anode and cathode sides on
the cell performance and impedance spectrum, in order to identify the activation resistances,
Ract1 and Ract2 , as anode and cathode resistances.

3.2. Analysis of the Mini pDMFC with Reduced Anode and Cathode Catalyst Loadings
It is known that the methanol concentration has a significant influence on the passive
DMFC behaviour, since the optimal concentration is a balance between the positive effect on
the MOR rate and the negative effect on the alcohol crossover rate [34]. Therefore, this sub-
section presents the results regarding the study of a mini pDMFC using reduced loadings
on both the anode and cathode sides for different methanol concentrations (Tables 2 and 3).

Table 2. Values of the maximum power density achieved for the different cathode catalyst loadings
and different methanol concentrations tested.

Maximum Power Density (mW cm−2 )

Cmethanol (M) Cathode Catalyst
4 mg cm−2 PtB 2 mg cm−2 PtB 0.5 mg cm−2 PtB
1 5.34 2.92 0.778
2 7.04 3.34 1.32
3 6.54 3.40 1.71
4 - 3.79 1.89
5 - 4.00 2.03
6 - 3.95 2.05
7 - 3.21 2.74
8 - - 2.54

As can be seen in Tables 2 and 3, the best concentration, the one that leads to a higher
performance, was 2 M for the highest loading used, 4 mg cm−2 . For concentrations above
this value, the negative impact of increased methanol concentrations on methanol crossover
outweighs any potential gains in the MOR rate, resulting in decreased cell performances.
To study the impact of changing the cathode catalyst loading on the mini pDMFC
behaviour, three different catalyst loadings, 4, 2 and 0.5 mg cm−2 PtB, were tested, keeping
the anode catalyst loading at 4 mg cm−2 Pt-RuB. Figure 4a,b show the polarization and
power density curves, respectively, for the different catalyst loadings tested at the cathode
side and the two methanol concentrations selected, 1 M and 3 M. These concentrations were
chosen as they are common to all the loadings studied and exhibit the same patterns and
 Maximum Power Density (mW cm−2)
Cmethanol (M) Anode Catalyst
4 mg cm−2 Pt‐RuB 2 mg cm−2 Pt‐RuB 0.5 mg cm−2 Pt‐RuB
1 5.34 2.57 0.23
Energies 2024, 17, 5174 2 7.04 2.98 0.60 6 of 15
3 6.54 4.06 0.98
4 - 5.42 1.12
5 - 7.07 1.39resistances affecting
trends as the other concentrations tested. The values of the different
6 - 6.64 1.98
the system for the different voltages tested (0.4, 0.3 and 0.2 V) obtained by fitting the
7 - - 2.50
experimental data to the EEC proposed (Figure 3), as well as the maximum power density
8
obtained -
for each condition, - 4.
are given in Table 2.92
9 - - 2.55
Table 3. Values of the maximum power density achieved for the different anode catalyst loadings
As can be seen in Tables 2 and 3, the best concentration, the one that leads to a higher
and different methanol concentrations tested.
performance, was 2 M for the highest loading used, 4 mg cm−2. For concentrations above
this value, the negative impact of increased methanol
Maximum Powerconcentrations
Density (mW on cm−methanol
2)
crossover outweighs any potential gains in the MOR rate, resulting in decreased cell
Cmethanol (M) Anode Catalyst
performances.
4 mg cm −2 Pt-RuB 2 mg cm −2 Pt-RuB 0.5 mg cm−2 Pt-RuB
To study the impact of changing the cathode catalyst loading on the mini pDMFC
behaviour, three
1 different catalyst loadings,
5.34 4, 2 and 0.5 mg cm −2 PtB, were tested, keeping
2.57 0.23
the anode catalyst
2 loading at 4 mg 7.04
cm−2 Pt-RuB. Figure 4a,b2.98 show the polarization and 0.60
power density3 curves, respectively, for
6.54the different catalyst loadings
4.06 0.98
tested at the cathode
side and the4two methanol concentrations- selected, 1 M and5.42
3 M. These concentrations 1.12
were chosen 5as they are common to all- the loadings studied and 7.07exhibit the same patterns
1.39
and trends as6 the other concentrations - tested. The values 6.64 of the different resistances1.98
7 - -
affecting the system for the different voltages tested (0.4, 0.3 and 0.2 V) obtained by fitting2.50
8
the experimental -
data to the EEC proposed - as the maximum power
(Figure 3), as well 2.92
9 -
density obtained for each condition, are given in Table 4. - 2.55

Energies 2024, 17, x FOR PEER REVIEW 7 of 16

Figure
Figure 4. 4. Effect
Effect of aof a loading
loading reduction
reduction in thein the cathode
cathode catalystcatalyst on the mpDMFC
on the mpDMFC performance
performance for two for two
methanol
methanolconcentrations,
concentrations, 1 M
1M and 3 3M.M.(a)
and (a)Polarization
Polarizationand
and(b)(b)power
powerdensity
densitycurves.
curves.Anode
Anode catalyst:
catalyst:
4 mg cm 4 mg cm−2 Pt-RuB.
−2 Pt-RuB.

Analysing Figure 4, despite some overlapping points at the open-circuit voltage

(OCV), it is possible to verify that the OCV decreases with increasing methanol
concentration. This trend occurs because higher concentrations lead to a larger
concentration gradient between the anode and cathode sides, resulting in greater
methanol crossover rates through the membrane towards the cathode. This leads to a loss
of fuel at the anode side, where it is needed for the fuel oxidation reaction, and to the
Energies 2024, 17, 5174 7 of 15

Table 4. Resistances values obtained by the EEC fitting for the different cathode catalyst loadings
tested and two methanol concentrations, 1 M and 3 M, and its maximum power density. Anode
catalyst: 4 mg cm−2 Pt-RuB.

Cmethanol : 1 M Cmethanol : 3 M
4 mg cm−2 2 mg cm−2 0.5 mg cm−2 4 mg cm−2 2 mg cm−2 0.5 mg cm−2
Voltage (V)
PtB PtB PtB PtB PtB PtB
0.4 0.452 0.413 0.441 0.411 0.395 0.497
Rohm (Ω) 0.3 0.449 0.409 0.444 0.409 0.390 0.495
0.2 0.446 0.407 0.439 0.405 0.384 0.490
0.4 2.38 5.33 19.0 0.789 3.79 8.60
Ract1 (Ω) 0.3 1.51 3.70 14.9 0.691 2.94 7.09
0.2 1.11 2.31 8.94 0.534 1.58 4.74
0.4 6.50 19.1 13.6 10.6 20.3 13.2
Ract2 (Ω) 0.3 2.54 4.81 11.6 2.28 6.97 10.0
0.2 2.50 1.89 7.32 1.15 1.82 2.76
Maximum power density
5.34 2.92 0.778 6.54 3.40 1.71
(mW cm−2 )

Analysing Figure 4, despite some overlapping points at the open-circuit voltage (OCV),
it is possible to verify that the OCV decreases with increasing methanol concentration.
This trend occurs because higher concentrations lead to a larger concentration gradient
between the anode and cathode sides, resulting in greater methanol crossover rates through
the membrane towards the cathode. This leads to a loss of fuel at the anode side, where
it is needed for the fuel oxidation reaction, and to the poisoning of the cathode catalyst
through the methanol oxidation reaction that occurs at this side. Based on the plots from
Figure 4 and the values of the maximum power density summarized in Table 4, it can also
be concluded that lower cathode loadings result in lower performances. Reduced loadings
result in fewer active sites available for the oxygen reduction reaction, decreasing the rate
of this reaction. Moreover, due to methanol crossover, higher cathode loadings are needed
to overcome the competition between the oxygen and the methanol for the catalyst active
sites. Therefore, the optimal power outputs were achieved with a cathode catalyst loading
of 4 mg cm−2 (Tables 2 and 4).
As shown in Table 4, the values of Rohm do not significantly change with the methanol
concentration and cathode catalyst loading, as these parameters do not significantly affect
the contact and electronic transport in the fuel cell.
Examining the two activation resistances values, it is evident that these resistances
increase with a decrease in cathode catalyst loading. Lower loadings result in lower reac-
tion rates, thus contributing to the observed trend. Analysis of the values for the different
voltages tested reveals that at 0.4 V, where the methanol crossover rate is higher, both acti-
vation resistances have the highest values, but Ract1 decreases with an increase in methanol
concentration, while Ract2 increases. Furthermore, these values demonstrate a tendency
to increase with a decrease in cathode catalyst loading, indicating higher activation losses
due to reduced electrochemical reaction rates within the cell. As already mentioned, the
methanol that crosses the Nafion® membrane reacts on the cathode electrode, decreasing
the catalyst available sites for the oxygen reduction reaction. Therefore, it is expected that
lower loadings and higher methanol concentrations result in less available catalyst for the
ORR, leading to increased cathode losses and decreased cathode performance, which is
in accordance with the obtained Ract2 values. At 0.2 V, where crossover effects are less
relevant, a decrease in cathode loading results in an increase in Ract2 . However, this increase
is lower compared to the one observed at 0.4 V, as the parasitic reaction occurs to a lesser
extent, and more catalyst active sites are available for the ORR. As the anode catalyst is the
same for all experiments in this study, it is expected that the anode will not suffer to a great
extent from the different cathode loadings, being more influenced by voltage and methanol
 cathode performance, which is in accordance with the obtained Ract2 values. At 0.2 V,
where crossover effects are less relevant, a decrease in cathode loading results in an
increase in Ract2. However, this increase is lower compared to the one observed at 0.4 V, as
the parasitic reaction occurs to a lesser extent, and more catalyst active sites are available
Energies 2024, 17, 5174 for the ORR. As the anode catalyst is the same for all experiments in this study, 8itofis15
expected that the anode will not suffer to a great extent from the different cathode
loadings, being more influenced by voltage and methanol concentration. Therefore, it is
expected to have
concentration. higher losses
Therefore, for higher
it is expected voltages
to have duelosses
higher to methanol
for highercrossover,
voltagesbutduean to
increase in the methanol concentration and a decrease in
methanol crossover, but an increase in the methanol concentration and a decreaselower
the cell voltage can lead to in the
losses, as more
cell voltage can methanol
lead to loweris available
losses, as for
more themethanol
MOR, increasing
is availablethe
foranode performance,
the MOR, increasing
which is consistent with the values of R act1. These findings suggest that Ract2 corresponds
the anode performance, which is consistent with the values of Ract1 . These findings suggest
to cathode
that resistance, while
Ract2 corresponds Ract1 corresponds
to cathode to anode
resistance, while Ract1resistance.
corresponds to anode resistance.
To
Toconfirm
confirmthis thisconclusion,
conclusion,aasimilar
similarstudy
studywaswasconducted
conductedon onthe
theanode
anodeside,
side,using
using
three different catalyst loadings (4, 2 and 0.5 mg− 2cm −2) of Pt-RuB, while keeping the
three different catalyst loadings (4, 2 and 0.5 mg cm ) of Pt-RuB, while keeping the cathode
cathode catalyst atloading
catalyst loading 4 mg cmat −2 4 mgthecm
PtB, −2 PtB, the loading that leads to the higher
loading that leads to the higher performances. This
performances. This study was performed
study was performed for different methanol concentrations for different methanol
to evaluate concentrations
the impact of theto
evaluate
solution the impact of the
concentration solution
on the concentration
cell performance andonmethanol
the cell performance
crossover rateand methanol
(Table 3). The
crossover
polarization rateand
(Table
power3).density
The polarization
curves for two and methanol
power density curves for1 M
concentrations, twoandmethanol
3 M, are
concentrations,
shown, respectively,1 M and 3 M, are
in Figure shown,
5a,b, while respectively,
the values of in the
Figure 5a,b, while
different the values
resistances and theof
the differentpower
maximum resistances
outputsandarethe maximum
displayed in power
Table 5.outputs are displayed in Table 5.

Energies 2024, 17, x FOR PEER REVIEW 9 of 16

Effectofofaaloading
Figure5.5.Effect
Figure loadingreduction
reductionin
inthe
theanode
anodecatalyst
catalyston
onthe
thempDMFC
mpDMFCperformance
performancefor
fortwo
two
methanol concentrations, 1 M and 3 M. (a) Polarization and (b) power density curves.
methanol concentrations, 1 M and 3 M. (a) Polarization and (b) power density curves. Cathode Cathode
catalyst:44mg
catalyst: mgcmcm−2−PtB.
2 PtB.

Figure 5 shows that reducing the anode catalyst loading and increasing the methanol
concentration results in a decrease in OCV, since less catalyst is available for the methanol
oxidation reaction, and consequently, more alcohol crosses the membrane to the cathode
side. However, for 0.5 mg cm−2, the OCV is lower for the lower concentration tested,
showing that using a lower concentration with a lower loading at the anode side has a
more relevant impact on the reaction rate of the methanol oxidation reaction, owing to a
lack of available catalyst sites for this reaction, than on the methanol crossover rate.
Energies 2024, 17, 5174 9 of 15

Table 5. Resistances values obtained through the EEC fitting for the different anode catalyst loadings
tested and two methanol concentrations, 1 M and 3 M, and its maximum power density. Cathode
catalyst: 4 mg cm−2 PtB.

Cmethanol : 1 M Cmethanol : 3 M
4 mg cm−2 2 mg cm−2 0.5 mg cm−2 4 mg cm−2 2 mg cm−2 0.5 mg cm−2
Voltage (V)
Pt-RuB Pt-RuB Pt-RuB Pt-RuB Pt-RuB Pt-RuB
0.4 0.452 0.405 * 0.411 0.383 *
Rohm (Ω) 0.3 0.449 0.402 0.378 0.409 0.377 0.494
0.2 0.446 0.397 0.377 0.405 0.370 0.492
0.4 2.38 3.58 * 0.789 1.78 *
Ract1 (Ω) 0.3 1.51 2.84 2.89 0.691 1.33 1.30
0.2 1.11 2.26 2.55 0.534 0.980 1.04
0.4 6.50 17.9 * 10.6 26.3 *
Ract2 (Ω) 0.3 2.54 5.10 58.4 2.28 4.65 27.3
0.2 2.50 2.91 38.9 1.15 1.50 9.47
Maximum power density
5.34 2.57 0.233 6.54 4.06 0.980
(mW cm−2 )
* The OCV for an anode catalyst loading of 0.5 mg cm−2 was lower than 0.4 V, so it was not possible to estimate
the resistances for this voltage.

Figure 5 shows that reducing the anode catalyst loading and increasing the methanol
concentration results in a decrease in OCV, since less catalyst is available for the methanol
oxidation reaction, and consequently, more alcohol crosses the membrane to the cathode
side. However, for 0.5 mg cm−2 , the OCV is lower for the lower concentration tested,
showing that using a lower concentration with a lower loading at the anode side has a
more relevant impact on the reaction rate of the methanol oxidation reaction, owing to a
lack of available catalyst sites for this reaction, than on the methanol crossover rate.
As observed in Table 5, for the lower loading used at the anode side, 0.5 mg cm−2 , the
losses are so high that the OCV is lower than 0.4 V, not allowing us to estimate the resistance
values for this condition. The results in Table 5 demonstrate that reducing the anode catalyst
loading leads to increased activation resistances (Ract1 and Ract2 ). However, the impact on
Ract2 is more pronounced, as it exhibits higher values. A reduction in the anode catalyst
loading results in a reduction in the active sites for the MOR, decreasing the reaction rate.
Additionally, it leads to an increase in the methanol crossover rate, as less methanol reacts
at the anode side, allowing more methanol to cross the membrane towards the cathode side.
As the alcohol that crosses the membrane has a more relevant impact on the cathode side,
due to the competition of the MOR and ORR for the cathode catalyst sites, it is expected
that this resistance/loss will be higher for lower loadings (Ract2 ). Additionally, for 0.4 V,
where the methanol crossover is more relevant, an increase in the concentration leads to an
increase in the Ract2 , indicating that this resistance is associated with the methanol crossover
losses. For the other two voltages tested, 0.3 V and 0.2 V, as the methanol crossover effect
decreases, an increase in the concentration leads to lower Ract2 , as more methanol reacts
at the anode and consequently less methanol is available to cross to the cathode side.
Therefore, it can be concluded that Ract2 is associated with the cathode losses, being the
cathode activation resistance. This conclusion is consistent with the observed Ract1 values,
which correspond to anode losses or anode activation resistance. These values decrease
with an increase in methanol concentration and a decrease in voltage. An increase in the
methanol concentration leads to an increase in the MOR rate and consequently a decrease
in the anode activation resistances/losses. For the lower loadings tested, 2 mg cm−2 and
0.5 mg cm−2 , this resistance decreases with an increase in methanol concentration. This
trend occurs because the deficiency of catalyst available for the MOR is offset by a higher
methanol concentration at the anode. Consistently, for both concentrations tested, Ract1
Energies 2024, 17, 5174 10 of 15

increases with a decrease in the anode catalyst loading due to a decrease in the available
catalyst for the MOR.
For the two concentrations displayed in Figure 5, the best performance was achieved
for the higher loading used at the anode side, 4 mg cm−2 Pt-RuB. However, after analysing
all the concentrations and loadings tested at the anode side, presented in Table 3, it can be
concluded that a slightly higher power output was obtained using an anode loading of
2 mg cm−2 Pt-RuB. This is a very important result, since a reduction of 50% in the anode
loading allowed the cell to work with higher methanol concentrations without sacrificing
performance, thereby reducing costs.
Figure 6 presents the catalyst cost associated with each electrode tested, as well as the
maximum power density obtained by the mpDMFC. It is evident that a reduction in metal
loading results in a notable decrease in catalyst cost, as a smaller quantity of noble metal is
necessary. Furthermore, the mpDMFC performance is also compromised by the reduction
in the quantity of metal available for the desired electrochemical reactions. However, this
study identified an electrode for the anode side (2 mg cm−2 Pt-RuB) that enabled a reduction
in metal loading and costs without a significant decline in the mpDMFC performance.
Nevertheless, this analysis was conducted on a limited basis, and further investigation is
Energies 2024, 17, x FOR PEER REVIEW
required to assess additional factors, such as the cost of all cell components, stability and 11
durability, with the objective of advancing the system towards commercialization.

Figure
Figure 6. Catalyst cost6.and
Catalyst
mpDMFCcost and mpDMFCachieved
performance performance achieved
for each for each
electrode electrode studied.
studied.

3.3.Methanol
3.3. Effect of the Effect of the Methanol Concentration
Concentration
Based on theBased
resultson the results
presented in presented
the previousin the previous Section
sub-section, sub-section,
3.2, itSection 3.2, it was ver
was verified
that better performances were achieved for 2 mg cm − 2 Pt-RuB of −2
anode catalyst
that better performances were achieved for 2 mg cm Pt-RuB of anode catalyst load loading
and 4 mg cm− 2 PtB of cathode
and 4 mg cm−2 PtB catalyst loading.
of cathode Therefore,
catalyst these
loading. two loadings
Therefore, thesewere
two used to were u
loadings
study the methanol
to studyconcentration
the methanol effect on the mini effect
concentration pDMFC onperformance
the mini pDMFC towards a further towar
performance
increase in itsfurther
powerincrease
output. inTheitscorresponding
power output. polarization and power
The corresponding density curves
polarization and power den
are presentedcurves
in Figure
are 7, while theindifferent
presented Figure 7,values
whileofthe
thedifferent
resistances and the
values maximum
of the resistances and
power densities obtainedpower
maximum for each concentration
densities tested
obtained for(1each
M toconcentration
6 M) are depicted in Table
tested (1 M6.to 6 M)
Figure 7depicted
shows that for the
in Table 6.different solution concentrations tested, the OCV is consid-
erably lower than the ideal value (1.21 V) and decreases with an increase in the methanol
concentration, due to methanol crossover through the membrane. As already mentioned,
higher methanol concentrations lead to higher concentration gradients between the two
electrodes, which is the force of diffusion, increasing the rate of methanol crossing the
membrane towards the cathode side and its concentration at the cathode. At this side, the
methanol reacts incompletely at the cathode catalyst (PtB) that is not the most suitable one
for this reaction, poisoning the catalyst active sites and lowering its activity and availability
 Figure 6. Catalyst cost and mpDMFC performance achieved for each electrode studied.

3.3. Effect of the Methanol Concentration

Energies 2024, 17, 5174 11 of 15
Based on the results presented in the previous sub-section, Section 3.2, it was verified
that better performances were achieved for 2 mg cm−2 Pt-RuB of anode catalyst loading
and 4 mg cm−2 PtB of cathode catalyst loading. Therefore, these two loadings were used
for the ORR. This leads to a decrease in the cathode performance and an increase in the
to study the
cathode methanol
losses. However, concentration effect
as can be seen in on the mini
Figure 7 andpDMFC performance
on the maximum towards
power a
density
further increase in its power output. The corresponding polarization and power
values presented in Table 6, the best performance was achieved with a methanol concentra-density
curves
tion of are
5 M,presented
this beinginthe Figure 7, while
optimal the different
concentration. Thisvalues of the resistances
concentration allowed anand the
optimal
maximum
balance between the positive effect of the methanol concentration on the MOR rate andare
power densities obtained for each concentration tested (1 M to 6 M) the
depicted
negativein Table
effect of6.the methanol crossover rate.

Energies 2024, 17, x FOR PEER REVIEW 12 of 16

Figure 7. Effect of the methanol concentration on the mpDMFC performance. (a) Polarization and
Figure 7. Effect of the methanol concentration on the mpDMFC performance. (a) Polarization and
(b) powerdensity
(b) power densitycurves.
curves.Anode
Anodecatalyst:
catalyst:22mg cm−2−Pt-RuB;
mgcm 2 Pt-RuB; cathode catalyst: 4 mg cm−2 PtB.
cathode catalyst: 4 mg cm−2 PtB.

Analysing the values of the two activation resistances presented in Table 6 for 0.4 V,
Figure 7 shows that for the different solution concentrations tested, the OCV is
where the methanol crossover is dominant, it can be observed that Ract2 increases with
considerably lower than the ideal value (1.21 V) and decreases with an increase in the
the methanol concentration, while Ract1 decreases. Additionally, as the voltage decreases,
methanol concentration, due to methanol crossover through the membrane. As already
the impact of the methanol concentration on R becomes less relevant as the amount of
mentioned, higher methanol concentrations act2 lead to higher concentration gradients
methanol available at the anode side is lower, due to its oxidation at the anode side, and
between the two electrodes, which is the force of diffusion, increasing the rate of methanol
less methanol crosses to the cathode side. This behaviour is in line with the cathode losses.
crossing the membrane towards the cathode side and its concentration at the cathode. At
Therefore, as concluded in the previous sub-section, Ract2 represents the cathode activation
this side, the methanol reacts incompletely at the cathode catalyst (PtB) that is not the most
losses. It can also be seen that Ract1 decreases with a decrease in the cell voltage and
suitable one in
an increase forthe
thismethanol
reaction,concentration,
poisoning the which
catalystisactive sites with
consistent and lowering
the anodeitsactivation
activity
and availability
losses. for the
An increase ORR.
in the Thisconcentration
alcohol leads to a decrease
leads toinathe cathode
higher performance
methanol diffusionand
rateanat
increase in the cathode losses. However, as can be seen in Figure 7 and on the maximum
this side, increasing the amount of methanol that reaches the anode catalyst active sites,
power density values presented in Table 6, the best performance was achieved with a
methanol concentration of 5 M, this being the optimal concentration. This concentration
allowed an optimal balance between the positive effect of the methanol concentration on
the MOR rate and the negative effect of the methanol crossover rate.

Table 6. Resistances values obtained through the EEC fitting for the different methanol
−2
Energies 2024, 17, 5174 12 of 15

increasing the methanol oxidation rate and decreasing the activation losses associated with
this reaction.

Table 6. Resistances values obtained through the EEC fitting for the different methanol concentrations
tested and its maximum power density. Anode catalyst: 2 mg cm−2 Pt-RuB; cathode catalyst:
4 mg cm−2 PtB.

Cmethanol (M)
Voltage (V)
1 2 3 4 5 6
0.4 0.405 0.351 0.383 0.330 0.367 0.285
Rohm (Ω) 0.3 0.402 0.346 0.377 0.324 0.363 0.284
0.2 0.397 0.339 0.370 0.324 0.357 0.282
0.4 3.58 2.57 1.78 1.27 0.768 0.675
Ract1 (Ω) 0.3 2.84 1.94 1.33 0.966 0.647 0.610
0.2 2.26 1.43 0.980 0.696 0.482 0.432
0.4 17.9 26.2 26.3 27.4 30.4 31.8
Ract2 (Ω) 0.3 5.10 5.50 4.65 4.46 4.36 6.46
0.2 2.91 2.09 1.50 1.23 1.05 1.49
Maximum power density
2.57 2.98 4.06 5.42 7.07 6.64
(mW cm−2 )

The maximum power density obtained (7.07 mW cm−2 ) is compared with other similar
works [35,36], as shown in Table 7. Nevertheless, it should be noted that Zuo et al. [36]
demonstrated a higher power density, although this was achieved through the utilization
of higher catalyst loadings. In contrast, Abdullah et al. [35] employed lower catalyst
loadings, resulting in considerably inferior performance. Therefore, the results obtained in
the present work demonstrate a notable accomplishment, with a reduction in the anode
catalyst loading, operation at elevated methanol concentrations and a decreased active area.

Table 7. Comparison of the performance of the presented mpDMFC with similar research works.

Active Area Cmethanol Maximum Power

Anode Catalyst Cathode Catalyst
(cm2 ) (M) Density (mW cm−2 )
2 mg cm−2 4 mg cm−2
Present work 2.25 5 7.07
Pt-RuB PtB
Zuo et al. [36] 4 mg cm−2 4 mg cm−2
4 2 12.05
(2018) Pt-Ru Pt
Abdullah et al. [35] 2 mg cm−2 2 mg cm−2
4 3 2.2
(2018) Pt-Ru/C Pt/C

4. Conclusions
Costs, efficiency and lifetime are key challenges to overcome in order to introduce
the mini pDMFC into the market, aiming towards the replacement of lithium batteries in
portable electronic applications. Based on that, this work presents the effect of a reduction
in the anode and cathode catalyst loading on the performance of a mini pDMFC with an
active area of 2.25 cm2 . This study was performed to identify and quantify in detail the
different losses that negatively affect the system using the EIS technique. Additionally,
we explored the possibility of reducing the system costs by reducing the catalyst loading,
without a significant loss in the cell efficiency. Despite the initial anticipation that the results
might fall below the desired values, a low loading of 0.5 mg cm−2 was tested at both the
anode and cathode sides, since the losses of the electrode using this loading overlap with
the losses of the other electrode, allowing its characterization.
The cell behaviour was analysed through polarization curves, power density curves
and EIS data by fitting it with an electric equivalent circuit proposed in this work, which
showed good agreement with the experimental data. The electrochemical characterization
Energies 2024, 17, 5174 13 of 15

of the mini pDMFC allowed us to verify that, besides the ohmic losses, the cell major losses
are activation ones, which decrease with a decrease in the cell voltage.
Energies 2024, 17, x FOR PEER REVIEW 14 of 16
The study regarding the analysis of the mini pDMFC with reduced anode and cathode
catalyst loadings allowed the identification of Ract2 as the cathode activation resistance and
Ract1 as the anode activation resistance and the quantification and contribution of these
two the different
losses for theconditions
overall cell tested, the cathode
performance. It wasactivation
observed that resistance
for thetends to be
different higher than
conditions
thatthe
tested, of cathode
the anode, showingresistance
activation that the cathode
tends tolosses contribute
be higher than thatto aofgreat extent to
the anode, the overall
showing
that the cathode losses contribute to a great extent to the overall cell losses. The results in
cell losses. The results demonstrated that the cathode losses decrease with a decrease
the cell voltage,
demonstrated that the as cathode
under theselosses conditions,
decrease withthe cell suffers toinathe
a decrease lesser
cellextent
voltage, from methanol
as under
crossover, and more active sites are available for the
these conditions, the cell suffers to a lesser extent from methanol crossover, and moreORR. Furthermore, as the voltage
active sites are available for the ORR. Furthermore, as the voltage decreases, the impact losses
decreases, the impact of the higher methanol concentrations on the cathode of
becomes
the higher less relevant,
methanol as more methanol
concentrations reacts at
on the cathode the anode
losses becomes side,
lessdecreasing
relevant, as themore
amount
of methanol
methanol reacts that
at the reaches
anodeand side,crosses the membrane.
decreasing the amount Despite this, duethat
of methanol to the methanol
reaches andthat
reaches the cathode side, it is necessary to work the
crosses the membrane. Despite this, due to the methanol that reaches the cathode side, cell with higher cathode catalyst
loadings to ensure a proper amount of
it is necessary to work the cell with higher cathode catalyst loadings to ensure a properthat
catalyst for the ORR. Therefore, it was verified
the best
amount powerfor
of catalyst outputs
the ORR. were achievedit for
Therefore, wasaverified
cathodethat catalyst
the bestloading
powerofoutputs
4 mg cm −2. The
were
lower for
achieved loadings
a cathode tested at the cathode
catalyst loading side leadcm
of 4 mg − 2
to similar
. The power
lower outputs.
loadings tested at the
cathode sideThe lead
anode to losses
similardecrease with a decrease in the fuel cell voltage due to a decrease
power outputs.
inThe
theanode
loss of fueldecrease
losses due to crossover.
with a decrease For the lower
in the fuel loadings
cell voltage tested,
due to ana increase
decrease in in the
methanol
the loss of fuelconcentration
due to crossover. leads Fortothea decrease in the anode
lower loadings tested, losses since in
an increase thethelack of catalyst
methanol
for the MOR
concentration leadsis offset by the higher
to a decrease concentrations.
in the anode losses since The results
the lack of showed
catalystthatfor better
the MOR overall
is offset by the higher
performances were concentrations.
achieved usingThe an results
anode showed that better
catalyst loading of 2overall
mg cmperformances
−2 Pt-RuB.
were achieved −2 Pt-RuB.
For theusing an anode
conditions catalyst
tested loading
and this of 2 cell
specific mg cm design, the maximum power density,
For mW
7.07 the conditions tested and
cm−2, was obtained this 2specific
using mg cmcell design,
−2 Pt-RuB ofthe
anodemaximum
catalystpowerloading density,
and 4 mg
7.07cm mW − 2
cmof ,cathode
was obtained − 2 Pt-RuB of anode catalyst loading and
−2 PtB catalystusing
loading 2 mg
withcm a methanol concentration of 5 M. Although this
cm−2 output
4 mgpower PtB of cathode
is not very catalyst
high, loading
it can with a methanol
be enough for someconcentration of 5 M. Although
specific applications and was
this obtained
power output is not very high, it can be enough for some
with an anode catalyst loading 50% lower than the most common one specific applications and used
was on
obtained with an anode catalyst loading 50% lower than the most
this type of fuel cell, which is 4 mg cm Pt-Ru, allowing a decrease in the system costs.
−2 common one used on
− 2
this type of fuel cell, which is 4 mg cm Pt-Ru, allowing a decrease in the system costs.
Author Contributions: Investigation, C.S.M.; Writing—original draft, C.S.M.; Writing—review &
Author Contributions:
editing, Investigation,
A.M.F.R.P. and C.S.M.; Writing—original
V.B.O.; Supervision, draft, C.S.M.;
A.M.F.R.P. and V.B.O.; FundingWriting—review & All
acquisition, V.B.O.
editing, A.M.F.R.P.
authors andand
have read V.B.O.; Supervision,
agreed A.M.F.R.P.
to the published and of
version V.B.O.; Funding acquisition, V.B.O. All
the manuscript.
authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by FEDER funds through COMPETE2020—Programa
Funding: This research
Operacional was fundedeby
Competitividade FEDER funds through
Internacionalização COMPETE2020—Programa
(POCI) and by national funds Opera-
(PIDDAC)
cional Competitividade
through FCT/MCTES, e Project
Internacionalização (POCI) and by national funds (PIDDAC) through
PTDC/NewPortCell-POCI-01-0145-FEDER-032116.
FCT/MCTES, Project PTDC/NewPortCell-POCI-01-0145-FEDER-032116.
Data Availability Statement: The original contributions presented in the study are included in the
Dataarticle, furtherStatement:
Availability inquiries can beoriginal
The directedcontributions
to the corresponding
presentedauthors.
in the study are included in the
article, further inquiries can be directed to the corresponding authors.
Acknowledgments: This work was supported by LA/P/0045/2020 (ALiCE), UIDB/00532/2020 and
UIDP/00532/2020
Acknowledgments: (CEFT),
This work funded by national
was supported funds through FCT/MCTES
by LA/P/0045/2020 (PIDDAC).
(ALiCE), UIDB/00532/2020 and
UIDP/00532/2020 (CEFT), funded by national funds through FCT/MCTES (PIDDAC).

Conflicts of Interest: The authors declare no conflict of interest

Conflicts of Interest: The authors declare no conflict of interest.
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