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Plasma sputtering deposition of PEMFC active catalytic layer

Article · July 2007

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 28th ICPIG, July 15-20, 2007, Prague, Czech Republic Topic number: 13

Plasma sputtering deposition of PEMFC active catalytic layer

H. Rabat1, P. Brault1, A. Caillard1, A.-L. Thomann1

1
Groupe de Recherches sur l’Energétique des Milieux, CNRS-Université d’Orléans, 45067 Orléans cedex 2,
France
A novel method is proposed to synthesize the active catalytic layers of Proton Exchange
Membrane Fuel Cell (PEMFC). A plasma sputtering technique is used to deposit a porous
columnar carbon film (column diameter of 20 nm) and the catalyst (platinum) directly on the
protonic membrane. The study of Pt diffusion shows that the optimized catalyzed layers
correspond to low plasma pressure operation (0.5 Pa) below a platinum loading limit of about 0.1
mg.cm-2. The initial carbon porosity is then maintained and Pt nanoparticles are present in all parts
of the carbon layer. A MEA (Membrane Electrode Assembly) is then achieved by alternate
depositions of carbon and platinum onto both sides of the membrane. The results show the
importance of the porous carbon structure and an increase of 12 % of the catalyst activity
compared to a commercial fuel cell (0.1 mg.cm-2).

1. Introduction leads to the formation of nano-aggregates (diameter

In regard to the development of clean energies, range between 2 and 10 nm) [11].
fuel cells are suitable candidates. For example, the
In this work, we investigate a new process to
proton exchange membrane fuel cell (PEMFC) is an
achieve the active catalyzed layers directly onto the
interesting power source, delivering high power
protonic exchange membrane i.e. the synthesis of a
densities with a high efficiency of energy conversion
one-piece MEA by alternate steps of plasma
[1]. Moreover, it operates at low temperatures (less
sputtering of carbon and platinum. Beyond the
than 90°C), can be miniaturized and can cover a
improvement of the platinum use efficiency, due to
large power range. It is one of the most promising
the well controlled dispersion by plasma, the aim is
candidates for both portable, transport or stationary
to simplify the MEA fabrication process.
applications [2].
2. Experimental details
Since few years, research has been carried out to a) Water b)
transform this credible candidate into mass market Matching network cooling
Target bias

product. Nevertheless, it is necessary to still RF generator

TCP antenna
improve the fuel cell performances, to reduce its cost
50 mm
Pt

and to simplify its production processes. These +

Dielectric window
+
80 mm

parameters mainly depend on the heart of the fuel

+ +
+ Target Substrate Rotation
+ 45°
cell called the MEA (Membrane Electrode C
Substrate

Assembly): a protonic membrane enclosed between +

+

two electrodes. Generally, a PEMFC electrode + Gas flow

consists of a carbon cloth which behaves like a
diffusion layer for the gases (GDL), and of an active
layer of a few tens of micrometers made up of an ink
of a carbon powder supporting a catalyst, a protonic
exchange polymer and some polytetrafluoroethylene
(PTFE) [3-4]. Unfortunately, the expensive platinum
still remains the best catalyst. Thus, research on
electrodes deals with the optimization of the active
catalyzed layer structure.
The aim is to increase the three-fold contacts
between carbon, catalyst and protonic exchange
polymer into the active layer by an increase of Pt
surface area. Most studies show that a porous thin
active layer with small Pt particles must be used [5-
7]. As a matter of fact, high power densities were
obtained by using a sputtering process [8-10]. This
technique enables to control the Pt deposition and
+
Target bias
Pump
FIG. 1. Transformer coupled plasma device for alternate
plasma sputtering: a) cross-section view, b) top view.
Figure 1 presents the plasma sputtering
experimental device. The carbon and platinum
depositions are performed in a cylindrical stainless
steel low pressure transformed coupled plasma
device (AprimVide; height=260 mm, diameter=210
mm). An argon plasma is coupled in the chamber
using a planar external RF antenna (13.56 MHz, 300
W). The base pressure is about 5.10-5 Pa. Two planar
targets of pure graphite C (99.9999%) and of pure Pt
(99.999%) are placed at the middle height in the
chamber. They are both DC biased at -300 V.
The films are analyzed by the SEM (Scanning
Electron Microscopy) technique and by the RBS

653
28th ICPIG, July 15-20, 2007, Prague, Czech Republic
(Rutherford Backscattering Spectroscopy)
technique. Coupled with SimNRA [12] software, the
latter is a powerful method for composition and in-
depth concentration profile measurements. From the
RBS analysis the total number of atoms per cm² (Ns)
of the deposited film is measured, and the SEM
analysis of the film cross-sections gives an estimate
of the film thickness h. The film density ρ in g.cm-3
units is calculated using ρ = (Ns/h)×(M/NA) where
M is the molar mass and NA the Avogadro number.
Comparing with the theoretical bulk density value,
the layer porosity can be deduced. This parameter is
not a true porosity, since the deposited carbon may
not be graphite. However it gives a good indication
of the void fraction in the carbon film and can be
used as reliable parameter when comparing the
various catalyzed samples.
The MEAs are realized by the direct electrodes
deposit on the protonic membrane Nafion® 112 (a
soft material currently used as fuel cell membrane)
which is not chemically treated as usually made
[13]. They are tested in a simple fuel cell station
(Heliocentris® kit) powered with H2 and O2 gases at
atmospheric pressure. Before testing, a protonic
exchange solution (5 wt.% Nafion® solution from
Dupont de Nemours) is squished on the two active
layers and the MEA is heated for one hour at 60°C
for solvent evaporation. There is not PTFE addition
into the active layers.
3. Results and discussion
3.1. The columnar meso-porous carbon layer
FIG. 2. Carbon film on Nafion® 112 (P=2 Pa; t=60min).
For SEM analysis, the sample has been metallized by Au
atoms evaporation.
The SEM image in Figure 2 shows a typical
carbon film deposited by plasma sputtering on
Nafion® 112. As this substrate is non-conductive,
Au atoms evaporation is carried out prior to the
SEM analysis. Despite the broadening effect due to
this Au coating, Figure 2 shows that the carbon layer
is rather uniform and consists of columns. This open
structure exhibits adequate porosity and can be used
as a support for the catalyst.
3.2. The Pt diffusion into the carbon layer
654
Depositions of platinum onto the porous carbon
layer are subsequently carried as a function of the Pt
depositions parameters to get some insight into the
resulting morphology changes. To simplify the
analyses, the films are deposited on pieces (10×10
mm²) of Si (100). The Pt/C layers are deposited in
two consecutive steps. Initially, identical carbon
layers are simultaneously grown at room
temperature onto ten samples fixed onto the holder
for one hour at a pressure of 2 Pa. Subsequently,
each carbon layer is used as a support for the
catalyst sputter-deposition step using various
experimental conditions.
200nm 200nm
a b
200nm 200nm
c d
FIG. 3. SEM pictures of the carbon layers (t=60 min, P=2
Pa) after deposit of platinum: (a) without Pt deposit; (b)
t=5 min, P=1 Pa; (c) t=15 min, P=1 Pa; (d) t=10 min,
P=0.5 Pa.
The SEM image in Figure 3a shows a typical
cross-section of the carbon layer, which compares
well with the carbon deposition on Nafion shown in
Figure 2. The carbon layer is uniform and has a
columnar, pillared shape (mean column diameter
about 20 nm) due to shadowing effects [14]. The
layer porosity is about 65 % in this case.
Onto these carbon layers, platinum was deposited
by plasma sputtering for different sputtering times
(from 1 min to 15 min at 1 Pa) and for different
pressures (from 0.5 Pa to 5 Pa during 10 min). The
SEM images in the Figures 3b to 3d display the
cross-sections of carbon layers coated by platinum.
Pt atoms appears brighter than carbon ones. It is
clearly seen on the images that the columns are
modified by the platinum deposits. Table 1 shows
the corresponding deposited quantities of platinum
and the physical characteristics of the different thin
films. For a fixed pressure, the increase of deposited
platinum quantity leads to a growth and a
broadening of the columns, and thus to a porosity
decrease. Broadening mainly occurs at the top of
columns but is also present at the base. Hence the
28th ICPIG, July 15-20, 2007, Prague, Czech Republic

porosity depends on the amount of deposited The considered MEA design is shown in Table 2.
platinum. The results show that platinum diffuses The total Pt load is about 0.1 mg.cm-2. The first step
inside the porous carbon layer. For long deposition is a platinum deposition followed by a carbon
times, some contiguous columns join to form deposition. This step is then repeated five times. The
columns with larger diameters. Moreover, for carbon deposit thickness increases from the protonic
deposition times of more than 12 min (Figure 3c), membrane to the GDL in order to ensure an open
the columnar structure is drastically modified. The porosity through the active layer. In Table 2, the
total height is strongly reduced, and the carbon parameters of each layer of carbon and of platinum
column structure has collapsed. are deduced from the SimNRA simulations of
TAB. 1. Amount of deposited Pt and thin film physical
previous experiments, with Pt diffusion into the
parameters (Column height, Top column diameter, carbon layers not being taken into account.
Bottom column diameter, and mean porosity). TAB. 2. Parameters used and estimated quantities for the
Pt .1015 Height Bottom Top Porosity alternate depositions of C and Pt to achieve the active
deposit at.cm-2 (nm) (nm) (nm) catalyzed layer with a 0.1 mg.cm-2 platinum total load.
t=0 0 176 10 24 65 % Layer Q (×1015 at.cm-2) P (Pa) Time
t=1min 7 C (GDL) 400 1.5 30min
131 178 16 31 58 %
P=1Pa
6-b Pt 15 0.5 30sec
t=5min 6-a C 300 1.5 25min
245 187 18 35 42 %
P=1Pa
5-b Pt 20 0.5 45sec
t=10min 5-a C 250 1.5 20min
408 243 24 46 31 %
P=1Pa 4-b Pt 40 0.5 1min30sec
t=15min 52<w 4-a C 200 1.5 16min
458 177 ⎯ 19 %
P=1Pa <84 3-b Pt 50 0.5 1min50sec
t=10min 3-a C 150 1.5 12min
441 231 27 54 23 %
P=0.5Pa 2-b Pt 60 0.5 2min15sec
t=10min 2-a C 100 1.5 10min
408 243 24 46 31 %
P=1Pa 1 Pt (Nafion) 90 0.5 3min20sec
t=10min
395 241 22 47 39 %
P=2Pa For simplicity, we chose to give the same structure
t=10min
P=5Pa
326 245 19 43 45 % to both active catalyzed layers i.e. to the cathode and
to the anode. As shown by Antoine et al [5], for a
The platinum deposition rate and the top and porous active layer, the better catalyst utilization is
bottom diameters of the carbon column decreases obtained when the platinum nanoparticles are
with increasing operating pressure as shown in Table preferentially located close to the proton exchange
1, resulting in a linear increase of the porosity from membrane. That is why the platinum is successively
23 to 45 percent. At 0.5 Pa, the large bottom deposited at different amounts which vary from one
diameter of carbon column suggests that the deposition step to another. Then a gradient of
platinum diffusion into the carbon thin film is platinum concentration is synthetized into the active
favored at this low pressure. layer.
Interestingly, the platinum quantity deposited at 0.5 4500

Pa for 10 min is similar to that of film deposited 4000

Platinum
quantity at 1 Pa during 15 min (about 450×1015 3500

at.cm-²). The corresponding film morphologies 3000

(Figure 3c and 3d) are however very different. The
Intensity (a.u.)

film deposited at 0.5 Pa maintains a columnar 2500 Carbon layer

structure despite a large platinum content. The fact 2000

Nafion membrane

that the platinum diffuses deeper at low pressure 1500 Carbon Fluorine Sulfur

comes from higher kinetic energy of sputtered 1000

platinum atoms and to simultaneous ion 500

bombardment occurring during deposition which
enhance in diffusion [15]. 0
0 200 400 600 800 Channel 1000

Thus, for several alternated deposition steps, the
carbon layers must be thick enough for the columnar
structure to be formed and the platinum should be
deposited at low pressure and in sufficiently little
quantities to maintain the open porosity.
3.3. The sputtered active catalyzed layer
FIG. 6. Experimental RBS spectrum of the MEA made by
alternating plasma sputtering of carbon and platinum onto
the both sides of the membrane.
Figure 6 presents the experimental RBS spectrum of
our “alternate” MEA, called MEA 1. The total
platinum quantity is about 0.1 mg.cm-2 as expected.

655
 28th ICPIG, July 15-20, 2007, Prague, Czech Republic

A Pt concentration gradient is well observed on the We have shown that an active catalyzed layer can
Pt peak and the Pt diffusion into the porous carbon be achieved by plasma sputtering directly on the
layers leads to continuous catalyst distribution into protonic membrane by alternating several porous
the active layer. This induces an increase of the carbon and catalyst deposition steps. For a given
catalyst surface area and, additionally, promotes the catalyst load, first test results show that the catalyst
electronic conductivity of this layer. utilization increases about 12%. This method is
0.9
MEA Commercial 0.1mg.cm
-2 shown to be a pertinent new way to simplify the
0.8
Catalyst
activation
MEA 1
MEA 2
0,84
process of fuel cell synthesis.
0.7 MEA 3 0,78
0.6
Acknowledgement
0,75
0.5 This work is supported by CadD, MID, FSE,
U (V)

Ohmic
0.4 losses
0,70
XbyBus, ACI Plasmapac and GDR-I CNRS
0.3
Mass “Plasmas”. Authors would like to thank Y. Tessier
0.2

0.1
transport
(GREMI, France), A. Richard (CME, France) and T.
0
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1 0.11
Sauvage (CERI, France).
I (A)

FIG. 7. Polarization curves for various MEAs tested with References

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4. Conclusion

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