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A highly stable catalyst for PEM fuel cell based on durable titanium diboride
support and polymer stabilization
Shibin Yin a, Shichun Mu a,b,*, Haifeng Lv a, Niancai Cheng a, Mu Pan a, Zhengyi Fu a
a
b
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China
Department of Chemistry, Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, OX1 3QR, UK
A R T I C L E I N F O
A B S T R A C T
Article history:
Received 24 June 2009
Received in revised form 3 September 2009
Accepted 26 September 2009
Available online 11 November 2009
Titanium diboride (TiB2) is an electrically conducting ceramic with good conductivity, excellent thermal
stability and corrosion resistance in acid medium. Here we report for the rst time its application as a
new catalyst support in proton exchange membrane (PEM) fuel cells. This novel catalyst (Pt/TiB2) was
formed by a colloid route, in which the highly dispersed Pt nanoparticles were stabilized by Naon
functional polymers. This signicantly facilitates the dispersion of Pt nanoparticles on TiB2. The
electrochemical stability of TiB2 was investigated and showed almost no changes in redox region after
oxidation during 48 h at 1.20 V. Further, it was found that the electrochemical stability of Pt/TiB2 catalyst
is about four times higher than that of the commercial Pt/C under electrochemical oxidation cycles in the
potential range of 0.61.2 V. The excellent stability of Pt/TiB2 could be attributed to the stability of TiB2
support as well as the introduction of Naon as stabilizer, which enhance both the metalsupport
interaction and the steric hindrance effect of the surface of Pt nanoparticles.
2009 Elsevier B.V. All rights reserved.
Keywords:
Catalyst
Conducting ceramic
Titanium diboride
Stability
Proton exchange membrane fuel cells
1. Introduction
Proton exchange membrane (PEM) fuel cells have drawn a great
deal of attention from the aspects of both fundamental studies and
applications as powerful energy converting devices. However, the
commercialization of PEM fuel cells has been seriously obstructed by
their poor durability [1]. The catalyst degradation is one of the most
important reasons for fuel cell performance deterioration. Commonly, the catalysts used in PEM fuel cells are carbon supported Pt or
Pt-based catalysts. The catalyst degradation is mainly caused by
carbon corrosion, which leads to the agglomeration of Pt nanoparticles under extremely harsh working environments [25].
Carbon can be oxidized in the event of fuel starvation [4] or partial
hydrogen coverage [6], and this process will be even promoted by
the catalysis of Pt [7]. Therefore, highly stable catalyst supports are
urgently desired to enhance catalyst lifetime.
Carbon nanotubes (CNTs) have been employed to improve
catalyst durability. It has been reported that Pt/CNTs catalysts have
a lower electrochemical surface area loss, and a higher oxygen
reduction reaction activity and corrosion resistance in comparison
with Pt/C [810]. Usually, a pre-oxidation of the CNTs surface is
necessary to facilitate the Pt precursor distribution throughout the
Fig. 1. Schematic of the Pt colloid particles and the Pt/TiB2 catalysts with peruorosulfonic acid Naon as a stabilizer of Pt particles (A); TEM image of the Pt colloid particles (B)
and SEM micrograph of TiB2 powders (C).
235
EAS
QH
Pt 0:21
(1)
Fig. 2. XRD pattern of (a) as prepared TiB2 powders and (b) the prepared Pt/TiB2 (A); FTIR spectra of the prepared Pt/TiB2 with the peruorosulfonic acid Naon as the
5O asymmetric stretching (SO2OH
protecting agent of Pt nano-particles and the reference peruorosulfonic acid Naon (B), the bands at b1, b2, b3, b4 and b5 are assigned to S5
group), CF2 asymmetric stretching, CF2 symmetric stretching, SO symmetric stretching (SO3 ion) and COC symmetric stretching of Naon respectively; TGA data of Pt/
TiB2 and commercial 20 wt.% Pt/C (C): (a) TG of Pt/C, (b) DSC of Pt/C, (c) TG of Pt/TiB2 and (d) DSC of Pt/TiB2.
Fig. 3. CV curves of TiB2 (A) and carbon supports (Vulcan XC-72) (B) by held at1.20 V (versus RHE) for different durations (0.5 M H2SO4, scan rate: 20 mV s1, temperature:
25 8C).
Fig. 4. CV curves of Pt/TiB2 (A) and the commercial 20 wt.% Pt/C (B) by accelerated durability tests (0.5 M H2SO4, scan rate: 20 mV s1, temperature: 25 8C); oxygen reduction
reaction on the as-prepared Pt/TiB2 and the commercial 20 wt.% Pt/C (C). Changes of electrochemical surface area (ESA) of catalysts related to Pt catalytic surface area with the
increased potential cycles (D).
237
quinone (HQ-Q) redox couple on the carbon black surface [28]. The
current peak at about 0.60 V in XC-72 electrode indicates a higher
oxidation degree of carbon with potential-holding time. These
results suggest that TiB2 is more resistant to electrochemical
oxidation than carbon black. Meanwhile, the concentration of Ti
ion in solution was ca. 0.07 mg ml1 at 1.20 V for 48 h identied by
inductively coupled plasma atomic emission spectrometry (ICPAES, PE). And the corrosion rate of Ti in TiB2 is only ca. 0.2 mg h1.
The initial and nal CVs of Pt/TiB2 during the ADT are shown in
Fig. 4. The initial ESA of Pt/TiB2 is 34.7 m2 g1, which is lower than
that of Pt/C (61.4 m2 g1) as shown in Fig. 4A and B. This ESA
decrease can be attributed to the large particle size and density of
Fig. 5. TEM images of the as-prepared Pt/TiB2 before accelerated durability tests (ADT) (A) and EDX patterns of the Pt/TiB2 for the selected spot as shown in (A) before ADT (B);
after 6000 potential cycles (C); EDX patterns of the Pt/TiB2 for a selected spot as shown in (C) after ADT (D); particle size distribution of Pt before and after ADT (E).
TiB2 compared with that of carbon support and also the possibility
of the surface of Pt is partially occupied by Naon. However, an
improvement of ORR activity of Pt/TiB2 is observed in terms of
onset potential. The Pt/TiB2 shows a higher reduced current of
0.29 mA cm2 at 0.9 V as compared to Pt/C (0.11 mA cm2 at
0.9 V) with the same Pt loading (see in Fig. 4C). Similar to TiB2
supports, Avasarala et al. [23] have demonstrated that TiNsupported Pt catalysts have an excellent activity of oxygen
reduction in comparison with carbon-supported catalyst. This
further validates that the improved activity of Pt can be attributed
to the inuence of support materials [30,31]. That is, the
conductive ceramics, as the supports of Pt catalysts, are helpful
to enhance the electrocatalytic activity of Pt catalysts. In addition,
our experimental results indicate a negligible effect of Naon
layers of the outer Pt surfaces on the catalytic activity of the
supported particles. In fact, Tian [32] and our previous studies [33]
have shown that SO3 end groups in the polyelectrolyte chain
structure of Naon can facilitate the reaction species transfer
process for ORR.
Fig. 4D shows the ESA loss of Pt versus the electrochemical
oxidation cycle number. The ESA of Pt/C decreases rapidly with the
cycle numbers increment. However, there is no obvious ESA loss in
the rst 600 cycles for Pt/TiB2, and only a slow decrease in the further
cycles. The ESA loss rate of the Pt/C reaches 1.56 102 m2 g1
cycle1, whereas the Pt/TiB2 has only 4.08 103 m2 g1 cycle1,
which is 3.8 times lower than the Pt/C. This indicates Pt/TiB2 has
Fig. 6. TEM images of the commercial 20 wt.% Pt/C catalyst before ADT (A) and after 5100 potential cycles (B); particle size distribution of Pt before and after ADT (C).
239
Fig. 7. Schematic of the migration model of Pt particles movement on support surfaces. Pt colloid particles migration driven by an electric eld force (A) and Pt particles
migration companying with Naon polymer oxidization (B).
TiB2 with both electron rich SO3 groups in Naon and highly
electron decient surface of TiB2 can offer a strong adhesion to
Naon modied Pt and support surface, which may increases the
interaction between Pt particles and conductive supports. Therefore, the Pt particles can be anchored tightly on the TiB2 surface. At
the same time, the electrostatic repulsion between self-assembled
Naon layer on different Pt surfaces may supply more strong steric
hindrance than that of pure Pt particles that probably enhances the
resistance to Pt particle migration.
Fig. 7 shows two simple migration models of Pt particles
stabilized with Nation on support surfaces. We propose that Pt
particles are mainly driven by a changeable electric eld force (f1)
during electrochemical acceleration tests, and Pt particles only
moves when the electric eld force (f1) applied to the particles is
greater than the friction resistance (f2) of Pt particles. Pt colloid
particles should have a high resistance to migration because of the
strong Ptsupports interaction. Therefore, the gathering of
particles is relatively difcult. When f1 is sufcient magnitude
as compared to f2, as shown in Fig. 7A, the migration and gathering
of Pt colloid particles take place, but the aggregation is possibly
hindered by Naon polymer layer distributed on Pt surfaces, and
can occur when Naon is decomposed by a long-term electrochemical oxidation. When the electric eld force (f1) is not
sufcient magnitude, as shown in Fig. 7B, the migration of Pt
colloid particles will not take place. However, Naon can be
decomposed with the time, leading to the decrease of resistance to
particle migration. Once the critical force to drive particles is
achieved, the Pt particles may move onto the support surface and
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