Catalysis for Low Temperature Fuel Cells

PART II: THE ANODE CHALLENGES

By T. R. Ralph and M. P. Hogarth
Johnson Matthey Technology Centre, Blounts Court, Sonning Common, Reading RG4 9NH. U.K

In thefirst part of this three partpaper; published in January 2002, we dealt with enhancing
the performance of low temperature proton exchange membrane fuel cells by improvements
to the platinum-based cathode materials and to the cathode design. In this second part of
the paper we shall discuss the improvements in the reformate (CO and COJ tolerance at the
anode and in extending the MEA durability. Improvements have been achieved by advances
in platinum/ntthenium electrode design, in the application of bilayer anodes for durable air
bleed operation, and in the addition oja water electrolysis electrocatalyst to the anode for
cell reversal tolerance. In the third part of the paper the particular challenges presented by
the direct methanolfuel cell will be discussed.
The proton exchange membrane fuel cell
(PEMFC) operating on air (or oxygen for space
applications) and on selected fuels, is being developed as an electrochemical power source for a
variety of applications (1). While at the cathode,
the choice of oxidant is either air or oxygen, the
selection of the fuel is not so stmghtforwardand a
number of options are being pursued.

Fuel Selection
The simplest and highest performing PEMFC
systems employ pure hydrogen as the fuel. For
example, DaimlerChrysler and Ballard Power
Systems are manufactwing transit buses with a 250
kW PEMFC engine that can provide a range of
250 miles using compressed hydrogen stored in the
roof space, with overnight refuelling at the depot.
This hydrogen system is envisaged as an early market entry for fuel cells. For the automotive market,
using the currently available storage technology,
there is not sufficient space in a car to store hydrogen as a gas, while for stationary power generation
the hydrogen supply infrastructure does not exist.
In an automobile requiring 75 kW of fuel cell
power, a liquid methanol feed is normally
employed, although gasoline is now being examined. For stationary power generation in the home
3 to 5 kW fuel cell systems are required, while 250
kW power plants are being built for larger industrial or residential sites. In this case natural gas is

Pkdnnrn Met& Ray., 2002,46, (3), 117-135

used as the fuel since it is readily available and

there are significant worldwide reserves.
The methanol, gasoline or natural gas is
reformed using steam, partial oxidation or
autothermal reforming to produce the reformate a hydrogen-rich gas stream ( H z , @70/.) containing carbon dioxide (COz, 15-25%), carbon
monoxide (CO, 1-2Y0) and small quantities of
inert gases, such as nitrogen and water vapour.
However, at current PEhfFC stack operating temperatures of around 80C the membrane electrode
assemblies (MEAs) within the stack cannot tolerate such hgh CO levels. Therefore, the reformate
must be passed from the reformer to a shift reactor and then to a catalytic preferential oxidation
(CPOq reactor to reduce the CO content to less
than 100 ppm, and in some cases down to a few
ppm. The reformate can then enter the stack and
react in the anode electrocatalyst layer of the M F A
The additional reformer, shift and CPOX reactors
significantly complicate and add extra cost to the
PEMFC system (see (1) and (19)).

Hydrogen Electrooxidation
The electrochemical oxidation of hydrogen is
extremely facile on a wide range of metals (20).
The platinum group metals (pgms) such as platinum (Pt) and palladium (Pd) show a key
advantage: they have the required stability to operate in the acidic environment inside the MEA. The

117

Fig. 9 Progressive poisoning

jrom IO, 40 and I00 ppm CO
on pure Pt and Pto.jRuoJ alloy
anodes. Increased CO
tolerance is shown by the
Pto sRuo J alloy anodes.
The anodes are preparedjbm
20 wt.% Pt/Vulcan XC72R or
20 wt.% PI. 10 wt.% RdVulcan
XC72R at a loading of0.25
mg Pt cm-..
The cathode uses 40 wt.%
Pt/Vulcan XC72R at a loading
of0.6 mg Pt cm. The MEAs
are based on catalysed
substrates bonded to Nafion
NE-115 membrane. The
Ballard Mark 5E single cell is
operated at S O T , 308/308
kPu, 1.3/2 stoichiometry with
full internal membrane
humidif cation

hgh activity of Pt for hydrogen electrooxidationis

shown by an exchange current density of
A
cm- Pt at ambient temperature. This is some lo7
to lo9times more facile than oxygen reduction at
the cathode. As a consequence, when operating
with pure hydrogen, at practical current densities,
the anode potential is typically less than + 0.1 V
(vs. RHE (reversible hydrogen electrode)), which
is only some 0.1 V from the standard reversible
potential for hydrogen electrooxidation (Reaction
6)):
Hz = 2H

+ 2e-

E0z50c= 0.00V (vs. NHE)

6)

where NHE is the normal hydrogen electrode.

Under such operating conditions the cell potential
is only shghtly lower than the cathode potential
and the MEA performance essentially reflects the
cathode operation.

CO Poisoning on Pt
The mechanism of hydrogen electrooxidation
on Pt in acid electrolytes is thought to proceed by
rate-determining dissociative electrosorption of
molecular hydrogen (Reaction (ii)followed
)
by
facile electron transfer (Reaction CI)) (21):
Hz + 2Pt = 2Pt-HA
2Pt-Hd. = 2Pt + 2H i
2e-

P)

At the typical MEA operating temperature of

80C, the CO in the reformate stream binds very

strongly to the Pt electrocatalystsites in the anode

layer. Even at ppm levels of CO, the CO coverage
is above 0.98 (22). The adsorbed CO prevents the
dissociative electrosorption of hydrogen (Reaction
(ii)) and dramatically lowers the cell potential produced by the MEA since a much hgher anode
potential is required to sustain the rate of hydrogen electrooxidation (23). This is demonstrated in
Figure 9 by the effect of pprn levels of CO on an
MEA with a Pt anode. The anode contains 0.25
mg Pt cm-, and is based on a 20 wt.% Pt/Vulcan
XC72R carbon-supported electrocatalyst.
As the CO content is increased from 10 to 100
ppm there is a progressive lowering in the cell
potential from that achieved with pure hydrogen.
At such low Pt loadmgs on the anode, the cell
potential losses are s@cant even at low current
densities below 200 mA cm. But at %her current densities the cell potential losses are more
dramatic. Eventually the cell potential is reduced
to 0.3 V, at which the electrooxidationof CO to
C 0 2can occur (Reaction (iv)).

CO + HzO = COZ+ 2H+ + 2eE0z5C = 4.10V (VS.NHE) (iv)

Under these circumstancesthe anode potential

reaches +0.45 V (vs. RHE),some 0.55 V anodic of the standard reversible potential for Reaction
(iv). This is sufficientto drive CO electrooxidation
and some of the poisoned Pt sites are now free to

118

Table 111

Physical Characterisation of PtRu Alloy Electrocatalysts

~~~

XRD crystallite
size,
nm

Calculated
metal area,
m2g-' PtRu

CO chemisorption
metal area,
m2 g-' PtRu

XRD lattice
parameter,
nm

67 wt.% Pt, 33 wt.% R U

(unsupported)

2.9

114

77

0.388

40 wt.% Pt, 20 wt.% RU

supported on XC72R

2.5

131

104

0.388

20 wt.% Pt, 10 wt.% RU

supported on XC72R

1.9

150

139

0.388

Electrocatalyst

take part in hydrogen electrosorption and electrooxidation (Reactions (ii) and (iii)).The cell potendal
then levels out.

PtRu Alloy Electrocatalysts

It is well documented (24-27) that in the
PEMFC at 80C platinum-ruthenium (PtRu)
alloys are much more tolerant to CO poisoning
than pure Pt electrocatalysts. This has made them
the electrocatalysts of choice for reformate operation.
For example, Figuie 9 shows the large improvement in CO tolerance for an MEA with an anode
based on a PbdtQ5 alloy electrocatalyst prepared
as 20 wt.% Pt, 10 w t % Ru/Vulcan XC72R The
cell potentials are sgdicantly hgher at all current
densities compared with the MEA based on pure
Pt, for operation with hydrogen containing 10,40
and 100 ppm CO. This improved CO tolerance
has resulted in much effort to optimise the PtRu
electrocatalystfor reformate operation.
For industrial-scale manufacture of PtRu alloy
electrocatalystsJohnson Matthey use an aqueous
slurry route with chemical reduction to form the
metal alloy particles (3). Table III shows physical
characterisation data of an unsupported Pb 5Rw
alloy black electrocatalyst and two hgh metalloaded Pto5R~5alloys supported on Vulcan
XC72R carbon black at 40 wt% Pt, 20 wt.% Ru
and at 20 wt.% Pt, 10 wt% Ru.
Particularly interesting is the hlgh metal dispersion of all of the electrocatalysts, especially at

Pkatinnm Metah Rm, 2002,46, (3)

high metal lo-.

The X-raydifftacton (XRD)

crystallite sizes are 2.9 nm (PtRu black), 2.5 nm (40
wt.% Pt, 20 wt.% Ru) and 1.9 n m (20 w t % Pt, 10
w t % Ru). These are much lower than the correspondmg values of 5.8 nm (Pt black), 4.5 nm (60
wt.% Pt) and 2.8 nm (30 w t % Pt) for the correspondmg pure Pt electrocatalysts. The hlgh degree
of PtRu dispersion is most probably a reflection of
the surface characteristics of the materials.
Although the Pb.5Ru0.5electfocatalysts were wd
alloyed the contraction in the lattice parameter
shown in Table III suggests all were shghtly Pt rich
(that is Pb.5pRuo.41).
The lack of any crystalhe Rurich phases in the XRDs suggests that the
unalloyed Ru is present as an amorphous phase.
Cyclic voltammetty and X-ray photoelectron spectroscopy (XPS) studies performed at Johnson
Matthey indicate that the surface of the electrocatalysts were rich in amorphous Ru oxide. This
amorphous Ru oxide may play an important role in
the codeposition of the PtRu particles and in
reducing the degree of sintering during the electrocatalyst manufacturingprocess.
It is also interesting to compare the measured
CO chemisorption metal areas with the calculated
metal areas from the XRD crystallite sizes (assuming spherical particles of density 18.2 g
Table llI shows the measured CO chemisorption
metal areas of 77 m2g-' PtRu (PtRublack), 104 mz
g-' PtRu (40 wt.% Pt, 20 wt% Ru) and 139 m2g-'
PtRu (20 wt.% Pt, 10 w t % Ru) are 48,26 and 8%
lower, respectively, than the calculated values. The

119

Fig. 10 TEMs o f 2 0 wl.% Pt,IO wt.% Ru/Vulcan XC72R

and unsupported PtRu alloy black electrocatalysts.
L e j : Highly dispersed PtRu alloy crystallites on the
surface ofthe primary carbon black particles.
Right: The PtRu black particles clump together to form
small aggregates and larger agglomerate structures

measured values become progressively lower than

the calculated metal areas as the metal loadmg on
the electrocatalystincreases. This probably reflects
the increased clustering and fusing of the PtRu
alloy crystallites as the metal 10increases.
Figure 10 shows the transmission electron
micrographs QTMs) of the 20 wt.% Pt, 10 wt.%
Ru/Vulcan XC72R and of the unsupported PtRu
black electrocatalysts. For the carbon-supported
electrocatalyst, the hghly dispersed PtRu alloy
crystallites are clearly evident on the primary carbon black particles that are fused together to form
the aggregate and the larger agglomerate structure
typical of fuel cell supports. This is in contrast to
the unsupported electrocatalyst where a large
number of small PtRu alloy particles form an
extended array of PtRu aggregates and agglomerates. The morphology of the unsupported
electrocatalystis very different from the supported
materials.

Effect of PtRu Composition

For the volume manufacture of PtRu electrocatalysts it is important to understand the effect of
the composition on the MEA performance. Using
a 20 wt.% Pt, 10 wt.% Ru/Vulcan XC72R electro-

Phtnum Metah Rev., 2002,46, (3)

catalyst, the effect of alloy formulation on CO tolerance was examined. Electrocatalysts were
prepared, both as fully alloyed and as completely
unalloyed materials, with a nominal composition
of pb 5Ru05.
The unalloyed Pb5Ruo5 was prepared by
depositing Ru onto a pre-reduced Pt electrocatalyst XRD confirmed that there was no alloying
from the Pt lattice spacing of 0.392 nm, that is
equivalent to pure Pt. In addition there was no significant crystalline Ru, suggesting the Ru was
present as amorphous Ru oxide. Half-cell studies
at 80C
were performed in sulfuric acid & S o d )
using typical PEMFC anode structures containing
Nafion perfluorinated sulfonic acid. Cyclic
voltammetry provided insight into the nature of
the electrocatalyst surface. Figure 11 shows typical
cyclic voltammograms for a PbsRu05 alloy and a
pure Pt electrocatalyst recorded at a lower temperature of 25C.
The alloyed P b 5Ru05 had features that are predominantly Ru in character with no resolvable Pt
hydtide peaks. The unalloyed P~&.Iosshowed
predominately Pt character with resolvable Pt
hydride peaks, although there was strong evidence
of surface interaction between the Pt and the Ru

120

oxide. The peak potential for CO electrooxidation

(Reaction (iv)) occurred at +0.44 V (vs. RHE),
dose to the +0.37 (vs. RHE)for the P ~ & I alloy
OS
and much lower than the +0.58 V (vs. RHE) for
the pure Pt electrocatalyst. The peak potentials are
much lower than in Figure 11, due to the much
hgher electrolyte temperature employed, although
the relative peak positions are comparable.
With hydrogen containing 100 pprn CO as reactant the specific activity for hydrogen
electrooxidation was measured. At +0.010 V (vs.
RHE) the specific activity increased from 8 mA
an-Pt for pure Pt to 25 mA an-PtRu for the
unalloyed Pb&u05 and to 60 mA an-PtRu for
the Pb&u05 alloy. This suggests that the alloying
process which incorporates the Ru into the Pt lattice (and reduces the Pt lattice spacing) is
important for improving the CO tolerance.
Besides enhancing the intimate contact between
the Pt and the Ru, extended X-ray absorption fine
structure (EXAFS) analysis has shown that alloying removes electron density from the Pt (28).
Both these effects are capable of promoting a
lower CO coverage on Pt and increasing the
hydrogen electrooxidationactivity of the anode.
A possible consequence of these finis that
low Ru contents mght not show such htgh CO
tolerance in the PEMFC. As an interesting exercise
the Ru content in the PtRu alloy was reduced to
match the output ratio of the pgms fiom the refinery. Thus the Ru content in a fully alloyed 20 wt.%
Pt, Ru/Vulcan XC72R electrocatalyst was lowered
from Pb 5Ruo5 to the mined ratio of Pb 7Ruo 3, and
then examined in the PEMPC. The XRD lattice
spacing of 0.390 n m confirmed a Pb7Ru03 d o y
was formed. For hydrogen containing 10, 40 and
100 pprn CO MEAs prepared with Pb7Ru03
matched the performances in Figure 9 for the
Pbau05 electrocadyst at an identical anode loading of 0.25 mg Pt cm?. This coniirmed that using
the Johnson Matthey manufacturing route at an
atomic ratio of Pt,&u03 there is sufficient Ru
incorporatedinto the Pt lattice to adequately modlfy the CO tolerance of Pt.
were in agreement with the funThese findamental kinetic work of Gasteiger et al. (29) who
used 1000 pprn CO in hydrogen and bulk, planar

PLdinnnz Mefa.lr Rcv., 2002,46, (3)

Fig. I 1 Cyclic voltammograms recorded in I mol dm-

H ~ S O at
Q 25Cfor Pto.75Moo.zs, Pto JRUO
5 and pure Pt
electrodes. For the Pto.7~Moo.z~
alloy#CO
electrooxidation activity starts at +O.15 V (vs. RHE).
For the PIOJRUO5 alloy, the peak potential for CO
electrooxidation is at the lowest electrode potential.
The electrodes are prepared.from 35 wt. % Pt, 5 wt. %
Mo/Vulcan XC72R. 40 wt.% Pt, 20 wt.% Ru/Vulcan
XC72R or 40 wt.% Pt/Vulcan XC72R at a loading of
0.25 mg PI em-. The electrodes were placed in a
3-compartment cell with a palladium/carbon electrode
purged with hydrogen to act as the RHE and a Pt
counter electrode. The electrolyte was first purged with
pure CO to poison the electrode at +0.I5 V (vs. RHE)
and then with nitrogen to remove any solution hase CO.
The electrode potential was swept at 10 m V s- from
i0.15 to i 1 . 0 V (vs. RHE) then back to 0 V (vs. RHE).
The second (dashed lines) and subsequent potential
sweeps are between 0 V and +I.0 V (vs. RHE)

P.

pb&u05 and Pb&uOl alloys. The h d q s also

agree with the more applied results in the PEMFC
of Iwase and Kawatsu (26) for alloys of composition Pbs5Rua15to Pbl&uOs5all based on 20 wt.%
Pt, 10 wt.% Ru/Vulcan XC72R electrocatalysts.
They found that the CO tolerance was sqpticantly
lower only at Ru contents below P b BRuo 2 or above
P b 2 R ~ aHowever,
.
there have also been a few
reports of lower CO tolerance at lower Ru levels

121

including P t d h 3 (27). This highhghts the importance of the manufacturingroute on the degree of
PtRu alloying and on the nature of the electrocatalyst surface. This variability probably accounts for
the significant spread in CO tolerances reported
for PtRu anode electrocatalysts(24).
Mechanism of CO Tolerance on PtRu
While it is dear that PtRu provides considerably
enhanced CO tolerance, an understandmg of the
mechanism operating at the anode is needed for
the development of improved electrocatalysts.
Based on early work by Watanabe and Motoo (30)
(methanol electrooxidation)a bifunctional mechanism involving water activation by Ru (Reaction
(v)) and subsequent CO electrooxidation on a
neghbouring Pt atom (Reaction (vi)) has been postulated by a number of groups (26,27,29,31-33).
Pt-CO

Ru + H20 = Ru-OH + H++ e(v)

+ Ru-H = COz + Hf + e- + Pt + Ru (vi)

To investigate the mechanism of CO tolerance

of PtRu, half-cell studies in H2S04at 80C with
PEMFC anode structures containing Nafion were
performed using pure CO as the reactant. The
half-cell outlet gas was analysed using in-line mass
spectrometry for evidence of COZ - to examine
PtRu for CO electrooxidation activity (Reaction
(vi)). The results indicated that CO electrooxidation was occurring on PtRu at above +0.25 V (vs.
ME). This is some 0.2 V less anodic than
required for pure Pt electrocatalysts and reflects
the greater ability of the Ru to adsorb water
(Reaction (v)) compared with Pt. Figure 11 shows
that, in the cyclic voltammograms measured in
&So4 at 25"C, the promotiod effect from PtRu
is also reflected in a lower peak potential for CO
electrooxidation at the electrodes: PtRu (+0.5 V
(vs. RHE)) compared with Pt (+0.8V (vs. RHE)).
Both the half-cell and the cyclic voltammetry studies confirmed that at anode potentials above +0.25
V (vs. RHE) the improved CO tolerance of PtRu
is due to the enhanced electrocatalysis of CO electrooxidation to COz @actions (v) and (vi)).
At lower anode potentials, where the more efficient anode electrocatalysts function during
PEMFC operation 6.e. < +0.2 V (vs. ME)), the

Pbdnwm Meta.lr Rev., 2002,46, (3)

situation is open to debate. In half-cell/mass spectrometry studies at low anode potentials of 0.0 to
+0.2 V (vs.RHE), there was no measurable CO
electrooxidationcurrent or detection of COzproduct in the half-cell outlet gas. While it has been
calculated that currents as low as
A cm-' Pt
can remove sufficient CO from the electrocatalyst
to give effective CO tolerance (34), it is reasonable
to argue that CO removal is more likely due to a
weakening of the P t X O bond strength. As discussed, EXAFS has shown (28) that alloying does
reduce the Pt electron density which should weaken the Pt-CO bond strength and decrease the CO
coverage on PtRu. This will increase the number
of electrocatalystsites available for hydrogen electrosorption and electrooxidation. The rate of
Reactions (iiii and (ii) would then increase. This
mechanism would also be consistent with the
observed importance of PtRu alloying on the CO
tolerance discussed earlier. Particularly relevant is
the observation that the unalloyed PtRu material
shows comparable CO electrooxidation activity in
the cyclic voltammograms, although it is not as
CO tolerant. Thus, it seems more probable that
the mechanism of CO tolerance at practical anode
potentials is due to a weakening in the Pt-CO
bond strength rather than to the promotion of CO
elemooxidation to C02.

CO, Poisoning in the PEMFC

While it has been known for many years that
CO poisons Pt-based electrocatalysts, it has only
recently been discovered that COZ also acts as a
poison in the PEMFC (25, 35). As shown in
Figure 12, the effect on a Pt anode of a hgh COz
concentration of 25%, typical of many reformate
streams, is modest. Only at the hghest current
densities do cell potential losses become significant In fact, comparing the performance of an
h4EA with an identical Pt anode in the presence of
10 ppm CO (Figure 9) and 25% COz (Figure 12)
shows that the cell potentials are much lower with
10 ppm CO under the particular smgle-cell operating conditions examined.
COZ poisoning can come from two sources
both of which generate CO which then poisons
the Pt electrocadyst sites for hydrogen electroox-

122

Fig. 12 Poisoning effect of 25%

C02 on Pt and Ptn 5 R U O alloy
anodes. The plots show the
increased C02 tolerance of the
Pto sRun 5 alloy anodes.
The anodes and Pt loading are as
described in Fig. 9.
The cathode and MEA are as
described in Fig. 9. The Ballard
Mark 5E single cell operating
conditions are as described in Fig.
9. except that here it is using
hydrogen or (hydrogen with 25%
CO2)/air

idation. The CO sources are: the reverse water gas

shift reaction (RWGSR, Reaction (vii)) and the
electrochemical equivalent of the RWGSR
(Reaction (viii)).

able to promote COZ electroreduction. Indeed, the

'Pt-CO' coverage correlates well with the Pt-Hd,
coverage.
The 'Pt-CO' poison was removed by sweeping
the electrode to &her potentials. The characterisCOz + Hz = H20 + CO
(4 tic CO electrooxidation peak was evident in the
2Pt + 2H' + 2e- = 2Pt-HA
cyclic voltammogramsat peak potentials of +0.4
2Pt-Hds + COz = Pt-CO + H20 + Pt
V (vs. RHE) for the Pb ~RUO
5 d o y electrode, and
EO25-c = 4.10V (a.
NHE) (a)
+0.6 V (vs. RHE) for the pure Pt electrode. It
From thermodynamics it has been calculated was therefore concluded that at operating anode
that at 80C for refonnate containing 25% COZin potentials in the PEMFC, COz poisoning occurs
hydrogen, 100 to 200 ppm CO could be generated predominantly by the electrochemical reduction
by the RWGSR (36). The exact amount of CO reaction (Reaction (viii)), with the 'Pt-CO' poison
produced is however hlghly dependent on the removed at much hgher anode potentials.
Most significantly, as shown in Figure 13, the
water concentration. In practice, as shown by compacing Figures 9 and 12, with the JohnsonMatthey potential-dependent coverage by the 'Pt-CO' poianodes much less than 10 ppm CO is produced. son, calculated from the CO electrmxidation
This suggested that with these anode designs, the current in the cyclic voltammograms, is much
RWGSR may not be the major mode of poisoning. %her for the Pt than for the P b a m 5 d o y electrocatalyst For example, the maximum coverage
C 0 2Electroreduction
recorded at +0.05 V (vs. RHE) is 0.9 on the pure
Consequently, at a Pt and a PbdtuoS alloy elec- Pt electrode and 0.5 on the Pb &Q 5 doy. The
trode in HzS04 at 70C, an examination of the lower 'Pt-CO' coverages on the Pbauos d o y
electrochemicalpoisoning by CO2 was performed. electrocatalyst suggested that it should provide an
By holding the electrode potential constant and improved CO2 tolerance in the PEMFC.
saturahg the &so4 with pure COZit was shown
that both the pure Pt and the Pb&uo5 alloy elec- COz Performance at PtRu Anodes
Figure 12 shows that for single-cell operation
trocatalysts form a 'Pt-CO'-like poison at
electrode potentials below + 0.4 V (vs. RHE). In on 25% COZin hydrogen, the Pb &uo 5 alloy has
this potential range there is sufficient Pt-Hdd, avd- improved the COZtolerance compared to the pure

Pbtinum Metah h.
2002,46,
,
(3)

123

W E ) . While the precise nature of the adsorbed

CO intermediate(s) from COz electroreduction are
not clear (37-39) the cyclic voltammograms for
the electrooxidation of the Pt-CO poison in&cate that they are very similar to those produced by
pure CO in this potential range.

1 ,

Anode Design for Reformate Tolerance

0.1
0.2
0:3
ELECTRODE POTENTIAL FOR COz
POISONING, V vs. RHE

04

Fig. 13 Lower Pt-CO coverage due to CO2

electroreduction at a Pt0.sRu0.5alloy electrode compared
to pure Pt. as a function of the electrode potential. The
electrodes and Pt loading are as described in Fig. 9 for
the anodes.
The electrode was placed in a 3-compartment cell
containing I mol dm- H2S04 at 70C with a palladium/
carbon electrode purged with hydrogen. to act as the
RHE and a Pt counter electrode.
The electrolyte was purged with pure C02 to poison the
electrode at the selected rest potential. then with nitrogen
to remove any solution phase C02. The electrode
potential was swept at 10 m V s-from the rest potential
to t1.0 V (vs. RHE) then back to 0 V (vs. M E ) . The
Pt-CO electrooxidation current was used to determine
the Pt-CO coverage

Pt anode. The clear benefit from the Pb.5Ruo.5alloy

becomes progressively greater as the current density increases - because the COZ losses on pure Pt
increase. Indeed, at a current density of 1 A cm-
the cell potential of the Pb.5Ru0.5alloy-based MEA
is some 0.2 V higher. This is a significant benefit.
The better CO2 tolerance of the PtRu anode is
probably due to a weakening in the Pt-CO bond
strength that is believed to be the source of the
improved CO tolerance of PtRu below +0.2V (vs.

As with the development of improved cathodes

for the PEMFC discussed in Part I of this paper
(40),the optimum anode for reformate operation
requires not only a PtRu electrocatalyst but also an
optimised anode electrocatalyst layer.
The importance of the anode design in promoting the CO tolerance of some Pb 5Ruo5 anodes
is hhlighted in Figure 14.This shows for singlecell operation at 538 m A cm, the cell potential
loss (relative to pure hydrogen) with fuel contairing from 10 to 100 ppm CO. While anode loadmgs
of 1.0 mg Pt
are not economicd for the
majority of PEMFC applications, the performance
of unsupported PtRu black layers at this h g h loading shows the importance of the anode layer
thickness and the in sitrr anode electrode Pt surface
area (EPSA), measured using cyclic voltammetry
(4).The cell potential losses in Figure 14 are only
5 mV (at 10 ppm CO), 30 mV (at 40 pprn CO) and
40 mV (at 100 pprn CO). This is because the
anode layer thickness is less than 10 pm and the
measured in ritrr anode EPSA is high at close to
770 cmz PtRu ad.
It is important to maximise the anode EPSA as
this measures the maximum PtRu surface area
available for hydrogen electrooxidation in the

At 538 rnAcrr-

In-

0.25
PtRu I X C 7 2 R
PtRu/ XC72R
Medium EPSA

High EPSA
20

60
100
CO CONCENTRATION, ppm

Phtiinum Metah Rev., 2002, 46, (3)

140

Fig. 14 Reduction in the cell potential loss at

538 mA c K 2 (relative to pure hydrogen
operation) due to 10. 40 and I00 ppm CO as the
anode EPSA is increased.for Pto.sRuo.salloy
anodes. The anodes are prepared from 40 wt. %
Pt, 20 wt. % Ru/Vulcan XC72R or PtRu black at
and 1.0 mg Pt
a loading of 0.35mg Pt
cm-2 , respectively. The cathode and MEA are as
described in Fig. 9. The Ballard Mark 5E single
cell operating conditions are as described in
Fig. 9 except that here it is operating at 1.512
stoichiometry

124

Fig. 15 The reduction in cell potential loss at

754 mA cm-2 (relative to pure hydrogen operation) due to 25% CO2 as the anode EPSA is
increased for Pto 5Run J alloy anodes. The
anodes and Pt loadings are as described in Fig.
14. The cathode is as described in Fig. 9. The
MEAs are based on catalysed substrates bonded
to Dow XUS13204.10 membrane. The Ballard
Mark SE single cell operating conditions are as
described in Fig. 9, except that here it is
operating at 1.5/2 stoichiometry

0.07 At 7 5 4 m A cm-2

0.060.05 0.04.

0.03-

0.02-

0.01

100

200

so0

400

500

600

760

EPSA, cm2 P ~ R Ucm?

absence of CO and COZ poisoning. As the anode

layer is thin, the whole anode layer thickness is
active and all of the EPSA can therefore be utilised
during PEMFC operation. Proton conductivity
and hydrogen permeability do not limit the active
layer thickness of the anode. This is particularly
important at hlgh current densities (41).
In contrast, even using a hlgh loaded 40 wt.%
Pt, 20 wt.% Ru/Vulcan XC72R-supportedelectrocatalyst at 1.0 mg Pt cm-, the anode layers are
much too thick. As a consequence, much of the
depth of the anode layer is redundant and the cell
potential losses are much higher than shown in
Figure 14 for the unsupported PtRu black anode
layer at 1.0 mg Pt m-.
Significantly, however, at more economical
electrode Pt loadmgs of 0.35 mg Pt cm- the anode
layer is sufficiently thin for the carbon-supported
electrocatalyststo ensure all of the anode thickness
is used during PEMFC operation. In this case, the
PtRu black anode cannot achieve the same degree
of CO tolerance as a well designed anode layer
using 40 wt.% Pt,20 wt% Ru/Vulcan XC72R
This is because the CO metal area is lower for the
PtRu black (see Table m) and the anode EPSA is
reduced.
For carbon-supported electrocatalysts to
achieve a lugh anode EPSA it is necessary to pay
attention to the interaction between the PtRu sites
on the carbon support (shown in the TEM in
Figure 10) and the protons in the perfluorinated
sulfonic acid solution used to provide proton conduction within the anode layer. With the traditional
aqueous-based electrocatalyst inks employed at
Johnson Matthey to deposit the anode layer, the

Phtinnm Metab Rnt., 2002,46, (3)

initial in situ anode EPSAs for the 40 wt.% Pt, 20

wt.% Ru/Vulcan XC72R layers were low. Initial
measurements at an anode loachg of 0.35 mg Pt
cm-2indicated that the anode EPSA was below 200
cm PtRu m-.This was much lower than the 364
cmPtRu cm potentially available.
Therefore, improved aqueous-based PtRu inks
were manufactured which enhanced the interaction between the electrocadyst and the Nafion
proton conducting polymer solution. With the
improved inks, the in situ anode EPSA of the
resulting anode layers was raised much closer to
the maximum 364 cm PtRu cm-. This produced
the significantly lower cell potential losses in
Figure 14 for the 40 wt.% Pt, 20 wt.% Ru/Vulcan
XC72R anodes. The increasing anode EPSA produces cell potential losses at 538 mA m- that are
reduced by 40 mV (at 10 ppm CO), 70 mV (at 40
pprn CO) and 60 mV (at 100 ppm CO), respectively.
Comparable improvements in the COZ tolerance of the h4EA are also observed for the better
PtRu anode designs. Figure 15 shows, for smgle
cell operation at 754 mA cm-, the relationship
between the cell potential loss (relative to pure
hydrogen) with 25% CO, in hydrogen and the in
situ anode EPSA. As the EPSA is increased from
160 to 600 m PtRu cm? for the 40 wt.% Pt, 20
wt.% Ru/Vulcan XC72R and the unsupported
PtRu black-Nafion ink layers, the CO2 tolerance is
improved. In Figure 15, the cell potential loss is
reduced from 65 mV to as little as 10 mV.
Further work has shown the importance of
ensuring that the in sih anode EPSA does not fall
below the values in F w e 15. For an anode layer

125

containing 0.25 mg Pt cm-', and based on 20 wt.%

Pt, 10 wt.% Ru/Vulcan XC72R, removing the
Nafion from the catalyst ink (by using an altemative binder) dramatically lowers the COz tolerance.
For single-cell operation at 538 mA cm-' with 25%
C02 in hydrogen at the operating conditions
detailed in Figure 12, the cell potential was nearly
150 mV lower. The reduction in COz tolerance is
due to a very low in J&-+ anode EPSA below 100
cmzPtRu ~ n - It~ seems
.
that the Pt not in contact
with Nafion can catalyse the RWGSR (Reaction
(vii)) to generate levels of CO approachmg 100
PPm.
It is therefore clear that to achieve a hgh
degree of reformate tolerance it is important to
maximise the in siru anode EPSA by increasing the
Pt dispersion of the electrocatalyst and by maximising the proton contact to the PtRu sites from
the proton conducting polymer in the anode.
Equally important to the in situ anode EPSA is the
production of thin electrocatalyst layers. This
reduces the possibility of the proton conductivity
and the hydrogen permeability in the anode layer
from limiting the performance of the MEA, particularly at htgher current densities (41).

Alternative Reformate Tolerant

Electrocatalysts
There has been a significant effort over several
decades to mitigate the effects of CO poisoning at
the anode by developing electrocatalysts that are
superior to PtRu (36,42,43). The electrocatalysts
generally fall into two categories.
(i) Intrinsic Mechanism
The fist category is the wide range of Pt alloys
that have been examined in an attempt to modify
the CO and hydrogen electrosorption properties
of Pt - to reduce the CO coverage and increase
the rate of hydrogen electrooxidation.Much study
has focused on PtRu, PtRh and PtIr alloys. These
were ori@y
examined in the 1960s by General
Electric (e.g. see 44-46) as unsupported metal
blacks at high anode loadmgs of 30 mg Pt ern-'.
More recently (47) they have been prepared on
carbon supports and examined at lower anode
loacllngs of 0.5 mg Pt cm-'. It was shown that at

Phtinum Metals Rev., 2002, 46, (3)

below 100C none of the Pt alloys was superior to

PtRu but that the CO tolerance of PtRh
approached that of PtRu. Iwase and Kawatsu (26)
also found that at 80C a large number of Pt alloys
supported on Vulcan XC72R (PtRh, PtIr, PtPd,
PtV, PtCr, PtCo, PtNi, PtFe, PtMn) a l l gave inferior CO tolerance compared to PtRu.
However, there is a considerable drive to raise
the operating temperatures of the PEMFC to
above 100C. This would raise the system efficiency and dramatically improve the CO tolerance of
Pt-based electrocatalysts. For example, the CO
coverage on Pt drops from in excess of 0.98 at
80C to 0.5 at 160C (43). At this temperature a
Pt-based anode can function in the presence of 1
to 2% CO rather than with ppm levels of CO,
eliminating the need for the CPOX reactor. If the
temperature can be raised to 160"C, studies in the
phosphoric acid fuel cell (PAFC) with 1 to 2% CO
indicate that PtRh and PtNi may offer superior
CO tolerance (48, 49).
Indeed, at 200C pure Pt is the favoured electrocatalyst in the PAFC. At hlgher temperatures
PtRu may not be the electrocatalyst of choice in
the PEMFC. There is currently much research (50)
aimed at developingmembranes capable of proton
conduction at 120 to 200C.

(ii) Promoted Mechanism

The second category of electrocatalysts
involves modlfymg Pt with metal oxides to catalyse the electrooxidation of CO to COZ (Reaction
(iv)) at operating anode potentials. This would
reduce the CO coverage and increase the number
of Pt electrocatalyst sites available for hydrogen
electrooxidation.Agam the most promising group
of materials date from the early General Elecmc
work (44,51). Based on these studies, carbon-supported platinum-molybdenum (PtMo), PtCoMo,
PtWOt and PtCoWO3 have recently been investigated. The electrocatalysts were shown to have
enhanced CO tolerance properties compared to
carbon-supportedPtRu electrocatalysts (47,52).
In particular, it was recently reported (53) that
a carbon-supported Pb M
oo alloy electrocatalyst
produced, in a small PEMFC smgle cell operating
at 85"C, only a 50 mV loss in cell potential for

126

Fig. 16 Speci/ic activity as

m./unction of anode potential
,for hvdrogen
electroo.ridation in the
presence of 100ppm CO and
.for pure CO electroosidation
at pure Pt, Pto jRirn 5 alloy
arid Pto.7 . 4 f o g . 2 . ~alloy
electrodes. At low anode
potentials the Pto.7jMO0.25
allov shows a higher specijic
activiy,for hj'drogen and
CO electrooxidation.
The electrodes and Pt
loading are as described in
Fig. 11.
The electrodes were
located in a hulf'cell with a
hvdrogen-putged platinised
Pt electrode as the RHE and
a PI counter electrode.
The halfcell was placed in
I ntol dnii3 H ~ S O at
J
80C and the electrolyte
deo.iygenated with nitrogen.
The stea(i).-state current was measured at selected electrode potentials from 0 V (vs. RHE) using hydrogen with 100
ppm CO und then pure CO. The electrode potential was returned to 0 V (vs. W E ) . Cyclic voltammograms were
recorded at 10 ni V s-' between 0 and t1.0 V Ivs. RHE) to obtain the CO electroosidation currents used to calculate
the EPSAs and the speci/ic activities

operation with hydrogen containing 100 pprn CO.

In contrast, the carbon-supported Pb.sRu0.~alloy
electrocatalyst showed a cell potential loss of 160
mV. The promising PtMo system has been examined at Johnson Matthey.

PtMo Alloy Electrocatalysts

A Pto 7&00 25 alloy was prepared as 20 wt.% Pt,
3 wt.% Mo by sequentiallydepositing Pt oxide and
Mo oxide followed by thermal reduction at high
temperature. Half-cell measurements in HZS04 at
80C using Nation-containing electrodes were performed to determine the specific activity for
hydrogen electrooxidation in the presence of 100
pprn CO. Figure 16 shows the resulting plots of
anode potential versus the specific activity for the
Pb 7 5 M 0 0 . 2 5 alloy electrode compared to the corresponding PtosRuo.5 alloy electrode and a pure Pt
electrode. As expected, due to the greater level of
CO poisoning it is only at the pure Pt electrode
that anode potentials in excess of +0.05 V (vs.
W E ) are required to sustain hydrogen electrooxidation. Most significantly, at anode potentials
below +0.025 V (vs. W E ) a higher specific activ-

Plarinum Met& Rm, 2002,46,(3)

ity for hydrogen electrooxidation is measured for

the Pb.75Mo0.25 alloy electrode compared to the
Pto.sRu0.5 alloy electrode.
The source of the improved hydrogen electrooxidation activity was confirmed by using pure
CO as the reactant and monitoring the half-cell
exhaust for product COZ using mass spectrometry
(Reaction (iv)). Figure 16 shows that, for the
Pb.7&fo0.25alloy electrode with pure CO, there is
considerable specific activity for CO electrooxidation starting fi-om anode potentials of +0.05 V (vs.
WE). Mass spectrometry of the exhaust gas confirmed that the electrooxidationcurrent was due to
product COZ formation.
This indicated that at anode potentials below
+0.2 V (vs. RHE) (needed for efficient PEMFK
operation), the CO tolerance of the PtMo
electrocatalyst comes from promoting C O
electrooxidation (Reaction (iv)). The low electrode
potentials required for CO electrooxidation were
also evident in the cyclic v o l t a m m o p s . Figure 11
shows for the Pb,&fo0.~alloy electrode a broad
oxidation current starting at +0.15 V (vs. RHE) that
is complicated by Mo surface redox reactions (54).

127

Fig. I 7 The ability of

Pto 7 M o o 25 and Pto 5& 5
alloy anodes to tolerate 46
ppm CO in hydrogen and
25% C02 in hydrogen. The
Ptn 75MOo 25 alloy is more
CO tolerant but much less
C02 tolerant. The PtMo
and PtRu anodes and their
Pt loading are as described
in Fig. 11. The cathode and
MEAs are as described in
Fig. 9. The Ballard Mark
5E single cell operating
conditions are as described
in Fig. 9, except that here it
is operating at 1.512
stoichiometry

These results are in direct contrast to those

from both the pure Pt and the Pb.&w.5 alloy electrodes. There is no detectable specific activity for
CO electrooxidation below +0.2 V (vs. RHE) in
Figure 16 and no product COZ was detected in the
haf-cell exhaust gas. Figure 11 confirmed that
there was no electrooxidation activity measured at
these low electrode potentials for either the
Pb.&u~.~
alloy or the pure Pt electrodes in the
cyclic voltammograms.
C O Tolerance of PtMo MEAs
Based on the promise offered by the half-cell
results, the P b 7 ~ o 0 2 5alloy electrocatalyst was
examined in the PEMFC. The ME4 performances
confirmed the much improved CO tolerance for
hydrogen containing from 40 to 100ppm CO. For
example, Figure 17 shows that for operation with
hydrogen containing 46 pprn CO, at an electrode
loadmg of 0.25 mg Pt cm?, the P b 7 & h 0 2 5 d o y
provides much higher performance than the
P b &Q5 anode. The performance benefit increases progressively from 400 mA cm- and at 1.0 A
cm- the Pb7@0025 alloy is operating at some 0.2
V above the Pb 5Rw 5 alloy.
However, as the CO concentration is reduced
the benefit due to the Pb 7@00 25 d o y electrocatalyst is reduced, until at 10 pprn CO, the Pb5RuO5
alloy electrocatalyst is the more CO tolerant. The
difference in reaction order for the Pb 7 5 M o o 25 and

Pkatinum Metah REV., 2002,46, (3)

the P b . 5 R ~alloys
. 5 is perhaps indicative of the distinct mechanisms of CO-tolerance operating at the
electrocatalysts.

COz Tolerance of PtMo MEAs

However, a much larger issue than the MEA
performance at low ppm levels of CO was found
for the Pb&i0025 alloy. When operating on
hydrogen with 25% C02, the p b 7 & k 1 0 2 5 alloy
shows poor CO2 tolerance. As shown in Figure 17
the Pb7&f0025alloy shows a similar performance
to hydrogen containing 46 pprn CO. This contrasts with the Pb5Rw5alloy where the single-cell
performance in Figure 17 with hydrogen c o n k ing 25% CO2 is much &her than with hydrogen
containing 46 ppm CO. Indeed, comparison with
Figure 9 shows the cell potential loss with 25%
COz is less than with 10 pprn CO. As a consequence, for full reformate operation with
hydrogen conboth 25% COZand 40 pprn
CO, the Pb &a, alloy is much more tolerant than
the Pb7&f0025alloy. Figure 18 indicates that at 538
mA cm , compared with the hydrogen performance, the Pk&w5 alloy shows a cell potential
loss of 100 mV but the Pb7@0025 alloy shows a
much higher cell potential loss of 215 mV. As
expected, the pure Pt-based anode provides the
lowest performance and is operating at 390 mV
below its performance with pure hydrogen. Thus,
today, with typical reformate feeds that contain

128

C02, PtRu remains the electrocatalyst of

choice for PEMFC operation below 100C.
It is worth considering the reason for the
poor COZ tolerance of the PtMo electrocatalyst and the impact on the anode design for
the PEMFC. The poor C02 tolerance of the
PtMo system reflects an increased ability of
the electrocatalyst to promote the electroreduction of COa (Reaction (viii)). This
produces much higher coverages of the
'PtXO' poison. The source of the CO tolerance shown by the PtMo electrocatalyst, Fig. 18 The reformate tolerance ofpure Pt, Pto 7sMoo.z~alloy
namely its ability to electrooxidise CO and Pto 5RUO 5 alloy anodes. The change in cell potential with
(Reaction (iv)) also results in an ability to time at 538 mA cm-2 on switching the anode fuel from
hydrogen to hydrogen with 40ppm CO and 25% C02 shows
catalyse the reverse electroreduction reaction the much higher tolerance of the Pto 5Ruo s alloy anode. The
(Reaction (viiii). The relative magnitude of anodes and Pt loading are as described in Fig. 11. The cathode
and MEAs are as described in Fig. 9. The Ballard Mark 5E
the electrooxidation of CO and the elec- single cell operating conditions are as described in Fig. 9,
troreduction of COzwill depend strongly on except that here it is operating at 1.5/2 stoichiometry
the concentrations of each reactant and on
the PEMFC operating conditions. At present, for by injecting a small air bleed (I2%) just ahead of
operation below lOO"C, the reformate streams usu- the PEMFC stack (23) or within the stack itself
ally contain much more COz than CO. Figure 18 (56). This air removes the CO from the PtRu elecindicates in t h i s situation the rate of C02 electrore- trocatalyst sites by gas phase dissociative
duction is dominant. This implies that the search chemisorption of oxygen on the CO-free Pt catafor alternativeelectrocatalyststo provide improved lyst sites, followed by bimolecular surface reaction
CO tolerance by electrooxidisingCO at low anode between Pt-CO and Pt-0 to form C02 (Reaction
potentials may be fundamentally flawed for current C
W (57, 58):
PEMFC stack operating conditions.
CO + %OZ= COZ
AH = -283 kJ mol-' (is)
The work to develop new membranes to allow
operation of the stack at lugher temperatures,
The gas-phase catalytic oxidation reduces the
above 100C could change the situation.For exam- CO coverage on the PtRu electrocatalyst and
ple at 160C much greater CO concentrations of 1 increases the hydrogen electrooxidation activity.
to 2% can be fed to the MEA. Alternatively, mem- Normally temperatures in excess of 100C are
brane purification (55) could be adopted to reduce required for catalytic oxidation of CO, but since
C02 to ppm levels. Using membrane purification the CO levels are low (10-100 ppm) there are sufwould allow PtMo to show a clear benefit over ficient free Pt sites to promote Reaction (ix) at
PtRu electrocatalystsat CO concentrations greater 80C. It seems that the presence of hydrogen and
than 10 ppm.
water in the PEMFC has little impact on the catalytic oxidation. In fact, complete tolerance to CO
The Air Bleed Technique
levels of up to 100 ppm can be achieved in w d At present, for PEMFC operation below lOO"C, designed PtRu anode structures.
PtRu is s t i l l the favoured electrocatalyst for full
Typically, however, with PtRu anodes the small
reformate operation. However, even with PtRu in loss in cell potential due to COZpoisoning, shown
a thin anode layer designed to have a hlgh EPSA in Figure 12, is not completely recovered. This is
there are still losses in cell potential with full probably because there are some PtRu electrocatareformate operation that lower the MEA's lyst sites not in contact with the proton conducting
performance. The losses can be largely mitigated polymer that are free to promote the RWGSR

PMnnm Mexklr Rm, 2002,46, (3)

129

Fig. 19 Durabilit>j of a standard arid a bilaver anode (se1o.v layer) structuse f o s lydrogen/ais and refosmaie (70%
Iiydrogen. 5% nitrogen, 25% CO., 40 ppni CO)/uis operution at 754 mA em-- with an air. bleed. The standard anode
,fails after 1000 h0ur.s hut the hilayer anode is siiN,functioning ufter 2000 1iour.s of continuous operation with a 3% air
bleed.
The anodes use based on 20 wi.% Pi. 10 wt.% Ru/Vulcan XC72R at a loading of 0.25 mg Pt cni . The bilayes anode
cont$ns a catal\.iic o.riduiiori IaJjes (selox laver) psepared,froni 20 wt.% Pi/Shawinigan at a loading of0. I mg Pt
cnii. The cathode is as descrihed in Fig. 9. The MEAs use as de.scrihed in Fig. 15. The Ballasd Mark 5E single cell
operating condiiions use as described in Fig. 9, except that here it is operating ai 70C at stoichiometsies o f l . 5 / 2

(Reaction (vii)). There have been a few recent

reports (24) that the COZ losses can be completely
mitigated in very thin anode layers at electrode
loadings below 0.2 mg Pt crn-. In this case, all of
the PtRu electrocatalystis probably in contact with
the proton conducting electrolyte.
Durability Issues
While the air bleed technique is capable of
recovering the cell potential losses due to CO poisoning and most of the losses due to CO,
poisoning there are s t i l l issues to be addressed. For
instance, in addition to the catalytic oxidation of
C O to CO2 (Reaction (ix)) the air can recombine
with the hydrogen fuel in the presence of Pt-based
catalysts (Reaction (x)):
H2 + %02
= H20

AH = -251 kJ mol

(x)

Recombination removes a little of the hydrogen

fuel but the major concern is that both the CO
oxidation and the recombination reactions are
highly exothermic. This increases the local temperature within the MEA, and indeed, temperatures

Platinum Metah Rev., 2002,46, (3)

exceeding 100C have been recorded in MEAs

that are functioning in PEMFC stacks operating at
80C.
The increased temperature can result in sintering of the PtRu electrocatalyst and eventually to
pin-holing of the membrane and failure of the
MEL4 and the stack. Figure 19 shows, for example,
the performance with time of a standard Johnson
Matthey anode based on a Pb&h5 alloy electrocatalyst. The MEA is operating at 754 mA cm?
and 70C on reformate containing 25% COZand
40 ppm CO. Initially a 3% air bleed is sufficient to
sustain the cell potential but this has to be
increased progressively with time to 4, 5 and then
7% to maintain the MEAs performance. Cyclic
voltammetry in situ in the PEMFC indicated that
the anode EPSA was decreasing with time. XRD
confirmed that this was due to sintering of the
P~.sRuo.s
d o y electrocadyst.
The resulting reduction in the number of active
electrocatalyst sites was balanced by increasing the
air bleed, to sustain the number of CO-free PtRu
electrocatalyst sites. However, Figure 19 shows

130

that the pure hydrogen performance was not

affected as only a few electrocatalyst sites are
required in this case. Half-cell studies have shown
that in the absence of reformate poisoning, as little
as 0.025 mg Pt cm- of a 20 wt.% Pt/Vulcan
XC72R electrocatalyst is sufficient to sustain
hydrogen electrooxidation below +0.05 V (vs.
M E ) . Eventually at a very hlgh air bleed level of
74 applied after 1000 hours of continuous operation, the MFA based on the standard anode failed
due to pin-holing of the membrane.

produce the required MEA lifetimes for PEMFC

applications which need an air bleed to sustain
reformate operation.
Cell Reversal Tolerant Anodes
The use of an air bleed is not the only durabilty issue evident at the anode. During operation it is
possible that one or more MEAs in a stack, or even
a complete stack in a multi-stack system, will show
a reverse in polarity. Such cell reversal incidents
reduce the power output from the system and can
irreversibly damage the stack. There can be sevetal
sources of cell reversal but most damaging is
reactant starvation of the MEA, especially at the
anode. Fuel and oxidant starvation can arise from
a lack of system control during a sudden change in
reactant demand. Alternatively, a flow field channel may be blocked due to stack material debris or
by water flooding and inert gas blanketing of the
MEA.

Bilayer Anodes
Johnson Matthey and Ballard Power Systems
have significantly extended anode lifetimes by
introducing a bilayer anode structure. In this structure, a carbon-supported Pt-based catalyst layer is
inserted between the PtRu electrocatalyst layer and
the anode subsixate (59). As the function of the
additional layer is to promote gas-phase CO oxidation, it does not contain a proton conducting
ionomer - in contrast to the electrocatalyst layer. Air Starvation
If the MEA is starved of oxidant, then rather
The ionomer can hinder the distribution of the air
than oxygen reduction sustainingthe current flowbleed.
Figure 19 shows that the bilayer anode structure ing through the cathode, hydrogen evolution takes
(that is the selox layer) achieved a comparable place (Reaction (xi)):
M E A performance to the standard anode when
2Hf + 2e- = Hz
E 2 y c = 0.00 V (vs. NHE) (xi)
operating both on reformate and on pure hydroThe anode reaction and the anode potential
gen. More importantly, the bilayer anode did not
require an increase in the level of the air bleed remain unchanged and the PEMFC acts as a
beyond 3% to sustain the MEA performance, even hydrogen pump. The cell potential at 500 m A cm-
after 2000 hours of continuous operation. The is typically close to -0.1 V since both hydrogen
heat generated by Reactions (ix) and (x) has been electrooxidation and hydrogen evolution are facile
largely removed from the electrocatalyst layer and on Pt-based electrocatalysts.Such a condition does
the electrocatalyst layer-membrane interface. This raise reliability concerns since hydrogen is prominimises the degree of electrocatalyst sintering duced in the cathode chamber and significant heat
and significantly reduces the possibility of mem- is generated in the MEA. With a lack of water probrane pin-holing. The anode gases and the stack duced at the cathode, this can damage the membrane.
cooling can more effectively remove the heat genFuel Starvation
erated in the gas-phase selox layer.
However, more dramatic effects arise if the
Using the bilayer anode has resulted in stable
MEA performances over many thousands ofhours MEA is starved of fuel. Studies at Ballard Power
of continuous operation. For example, for an Systems (60) have shown that the electrochemical
MEA with a bilayer anode containing 0.35 mg Pt processes in this case can be monitored by followcm- the reformate performance with a 2% air ing the cell potential with time and by gas
bleed was stable after in excess of 8000 hours of chromatographic analysis of the anode outlet gas
continuous operation. This bilayer approach may for oxygen and CO2 production. Figure 20 shows

Pkztinnn Me& Rcu., 2002,46, (3)

131

Fip. 20 The chanpe i n the

ceil potential 111 41) niA cm
arid the rate ofoxygen arid
CO2 produced at un MEA
during cell reversal due to
,file1 starvation. The anode
is prepared,frvm2 0 $!'I.%
Pt. 10 wt.!% Ric/Shuwiriiguri
at u,loading 01'0.25 mg Pt
cm--. The cathode uses Pt
black at ( I loading of'4.0 nig
Pi c K 2 . The MEAs are
based on cuta!vsed substrates bonded to Nufiori
NE- I 13.5 membrane. The
Ballard Murk S E single cell
operating conditions are us
described iri Fig. 9. except
that here it i s operuting
with nitrogen at the anode (replirating,fiiel starvation)/aic 200/200 kPa, 1 3 2 stoicliionietn. The o.:vgen and C'O?
were detected in the anode outlet gas using gus chromatogruphv

'

cell potential reaches -1.4 V, corresponding to an

anode potential of +2.1 V (vs. WE). At this stage
the current is sustained increasinglyby carbon corrosion rather than by water electrolysis, as shown
in Figure 20 by the increase in the rate of COZproduction and the decrease in the rate of oxygen
production in the anode chamber. Significant irreversible damage to the MEA occurs since the
H20 = % 0 2 + 2H' + 2 4
anode electrocatalyst carbon support, the anode
Ezyc = +1.23 V (VS. NHE) (s)
gas diffusion substrate and the anode flow field
Figure 20 shows that at 40 mA cm-' this corre- plate (if carbon-based) all corrode. After a few
sponds to a cell potential of 4 . 6 V. After falling minutes in this condition the h4EA is normally
quickly to 4 . 6 V, the cell potential gradually electrically shorted due to the significant amount
of heat generated in the membrane.
decays to -0.9 V correspondtng to an anode
potential of +1.4 to +1.7 V (vs. WE). That the
Water Electrolysis Electrocatalysts
resulting water electrolysis plateau in Figure 20 is
The effects of cell reversal can be mitigated by
due to Reaction (xii) was confirmed by the hlgh
using diodes to carry the stack cutrent past each
current efficiency for oxygen evolution. At such a
high anode potential, a small degree of carbon corMEA or by monitoring the cell potential of each
rosion (Reaction (xiii)) accompanies water
MEA and shutting the stack down if a cell potenelectrolysis as shown in Figure 20 by the small tial is low. However, such measures are complex
and expensive to implement. A more practical
quantity of COZ detected in the anode outlet gas:
approach to protect the carbon-based compoC + 2Hz0 = COz + 4H' + 4e
nents at the anode is to incorporate an additional
E"2yc = -0.21 V (VS.NHE)
(xiii)
electrocatalystin the anode catalyst layer to sustain
If the supply of water to the anode electrocata- the rate of water electrolysis. This approach has
lyst runs out or if the Pt-based anode electro- been jointly investigated by Johnson Matthey and
catalyst is deactivated for water electrolysis, the
Ballard Power Systems (60).
F w e 21 shows the performance in Ballard stack
cell potential moves to more negative potentials.
Figure 20 shows a carbon corrosion plateau as the
hardware of three different cell-reversal-tolerant

the typical response from an MEA with a carbonsupported PtRu anode. In this case the cathode
reaction and the cathode potential remain
unchanged and the change in cell potential reflects
the anode potential. As the anode is starved of fuel
the anode potential increases until water electrolysis occurs (Reaction (xii)):

Phtinrm Met& Rm, 2002,46, (3)

132

(i.e. water electrolysis) electrocatalysts prepared by

Johnson Matthey. In this case the MEAS have
received significant prior cell-reversal periods to
drive the anodes to the limit of their tolerance. The
impact that inclusion of a water electrolysis electrocatalyst has on the ability of the anode to sustain
water electrolysis is evident. At the standard 40
wt.% Pt, 20 wt.% Ru/Shawinigan carbon blackbased anode the water electrolysis plateau is so
short it is difficult to detect. Only by using a cellreversal-tolerant electrocatalyst in the anode are
water electrolysis plateaux evident in Figure 21.
As a result, the degree of carbon corrosion is
significantly reduced by the cell-reversal-tolerant
electrocatalysts.The typical PtRu anode electrocatalyst layer shows carbon corrosion after only 15
seconds of operation under the final cell-reversal
conditions of Figure 21. This is extended to 4.5
minutes by adding RuOZ to the electrocatalyst
layer, to 24 minutes using Ru02/Ti02and to 48
minutes with RuOz/Ir0~in the anode layer. While
the carbon corrosion plateaux are not clear in
Figure 21, the relative rate of production of COz
and oxygen conhrmed the time-scale required for
significant levels of carbon corrosion.

After this extended cell-reversal tesang, returning the more cell-reversal-tolerant anodes
(optimised for PEMPC operation) to normal fuel
cell operation indicated that there was negligible
loss in the MEA power output This contrasts with
MEA failure in the absence of the cell-reversaltolerant electrocatalyst. In addition, incorporation
of the water electrolysis electrocatalyst in the
favoured anode structures adds very little extra
pgm to the MEA (< 0.1 mg cm-3. Thus, this safeguard to the stack durability comes at little
additional MEA cost.

Conclusions
At the current MEA operating temperature of
80C there are sgmficant reformate poisoning
issues at the anode. The most tolerant electrocatalyst is still PtRu alloy. While unalloyed PtRu does
promote CO electrooxidation above +0.25 V (vs.
WE) the alloying process is important for maximising the CO tolerance below +0.20 V (vs.
RHE). This is probably because it weakens the
Pt-CO bond srrength. With the Johnson Matthey
manufacturing process the Ru content can be
to Pb ,Rue without any loss
reduced from Pt0.5Ruo.~

Fig. 21 The
change in cell
potential at 200
mA em- during
cell reversal due to
fuel starvation at a
PIO5RUQ J alloy
anode containing
different water
electrolysis
electrocatalysts.
The MEAs were
first subjected to
cell reversal at
200 mA cm for 5
minutes then for 3
sets of 30pulses
(10 seconds on, 10
seconds om with
I5 minute recovery
Deriods on
hydrogedair and ajinal overnight recovery period. The anodes are as described in Fig. 20 but at a loading of 0.I mg
Pt
The water electrolysis electrocatalysts were prepared from 20 wt. % Ru02 /Shawinigan. 20 wt. % Ru02, no2
(Run PEO
t)/Shawinigan or 20 wl.% RuO2, Ir02 (Run.9lro.t)/Shawiniganand added at an anode loading of 0.1 mg Ru
em . The cathode is as described in Fig. 9. The MEAs are as described in Fig. 20. The Ballard Mark 5E single cell
operating conditions are as described in Fig. 9, except that here it is operating at 75C using nitrogen at the anode
(replicatingfuel starvation)/ai,: 160/160 kPa. with stoichiometries of 1.311.5

P h f j n mMefuhRey., 2002,46, (3)

133

in anode performance, presumably because there is

sufficient Ru incorporated into the Pt lattice.
To realise the highest reformate tolerance from
PtRu it is important to maximise the in situ anode
EPSA and to produce thin anode layers. The high
in sitI4 EPSA increases the number of poison-free
PtRu sites and minimises CO production from the
RWGSR Thin layers are produced by using high
loadings of 40 wt.% Pt, 20 wt.% Ru with carbonsupported materials, and high in situ anode EPSAs
from good PtRu ink preparations. Unsupported
PtRu black functions well in PEMFC applications
that employ high anode Pt loadings.
Efficient anodes operate at electrode potentials
below +0.2 V (vs. RHE). At such anode potentials
the PtRu alloy provides CO and C 0 2 tolerance by
weakening the Tt-CO bond strength. Only at
much higher anode potentials does water adsorption on Ru promote significant levels of CO
electrooxidation to CO,. The search for electrocatalysts capable of electrooxidising CO at much
lower anode potentials has led to PMo alloys that
are capable of promotion below +0.1 V (vs.
RHE). Consequently, in PEMFC testing above 10
ppm CO, carbon-supported Pf0.,&i0,,.2~ alloy
shows an increased level of CO tolerance compared to PtRu.
However, the CO2 tolerance of the Pb.&f00.2~
alloy is very poor. The electrocatalyst also promotes the electroreduction of COz to a Tt-CO
poison. The result is much poorer reformate tolerance compared to PtRu using typical anode feeds
containing CO and CO2. Application of a membrane purifier to significantly reduce the C 0 2
content and raising the MEA operating temperature to 160C might allow the improved CO
tolerance of the PfO.7&f0~.~~
alloy to be realised.
Even with PtRu in a well-designed anode layer
there are losses in cell potential, with reformate
operation, that are not recovered. The air bleed
technique must be employed to introduce S 2% air
into the fuel stream to catalyse the oxidation of
CO to COZ. This recovers the cell potential losses
at 100 ppm CO and most of the small loss due to
25% CO2. However, in standard anode designs the
air bleed introduces durability issues, due to s@icant local heat generation within the anode from

Platinrrm MetaLr Rev., 2002, 46, (3)

the catalytic oxidation of CO and the recombination of hydrogen and oxygen. The PtRu
electrocatalyst sinters and the membrane eventually pin-holes. To extend the anode lifetime it is
necessary to adopt a bilayer anode structure using
a pgm-based gas-phase cataly& oxidation layer
between the gas diffusion substrate and the PtRu
electrocatalyst layer. This moves the heat generation away from the the PtRu electrocatalyst layer
and the membrane.
An additional major durability issue arises at the
anode if the MEA is starved of fuel. The MEL4
changes polarity due to cell reversal. Initially water
electrolysis sustains the power output but after
some 20 minutes at 200 mA cm-2 the PtRu electrocatalyst is deactivated for water electrolysis and
significant rates of carbon corrosion are detected.
This quickly destroys the carbon-supported PtRu
electrocatalyst, the gas-diffusion substrate and the
flow field plate in contact with the anode.
However, adding a RuO2/1102 water electrolysis
electrocatalyst into the anode layer can provide a
h g h degree of cell reversal tolerance. This sustains
the rate of water electrolysis for an additional 40
minutes. Rather than MEA failure after 20 minutes
the MEA can be returned to normal PEMFC
operation after experiencing 60 minutes under the
conditions of cell reversal due to fuel starvation.
The approach of using a bilayer anode for air
bleed operation and of including a water electrolysis electrocatalyst for cell-reversal tolerance can be
provided at little additional cost. With continued
development of the concepts, the pgm levels used
can probably be thtifted to below 0.05 mg cm .

Acknowledgement
Part of this paper is based on a keynote lecture by T. R.
Ralph at the 17th North American Chemical Society Meeting
held at the Westin Coast Harbour Castle Hotel, Toronto,
Ontario, Canada, from the 3rd June to 8th June 2001.

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The Authors
Tom Ralph is Product Development Manager at the Johnson
Matthey Technology Centre, responsible for MEA design. He has
been working with PEMFCs since 1991 and with developing all
aspects of the MEA: electrocatalyst, electrocatalyst layer, gas
diffusion substrate and solid polymer membrane, and in
integrating MEAs into customer hardware.
Martin Hogarth is a Senior Scientist at the Johnson Matthey
Technology Centre and has worked in the area of DMFCs since
1992. His main interests are the development of new catalyst
materials and high-performance MEAs for DMFCs. More recently
his interests have expanded into novel high-temperature and
methanol-impermeable membranes for the PEMFC and DMFC,
respectively.

135