2.

0
Figure 6. Impedance Spectroscopy of a URFC in
1.8 mode electrolyzer at room temperature and 1.5 V.
Hydrogen energy storage systems coupled to renewable power 1.6
sources are being proposed as a means to increase energy
1.4
independence, improve domestic economies, and reduce
E = 1.5 V
greenhouse gas emissions from stationary and mobile fossil-fueled 1.2

2
sources. New technologies for production and utilization of

- Zi / cm
hydrogen as energy carrier are electrolysers 1-3 and fuel cells 4,5, 1.0
respectively. Both processes may alternatively occur in the same 0.8
device based on a proton exchange membrane (PEM). This device is
called unitized regenerative fuel cell (URFC). Compared with conventional secondary batteries, 0.6
URFCs advantages rely on high energy density, long-term energy storage, durability and 0.4
Rs + Rp
environmental protection. Whereas in comparison to the separate fuel cell and electrolyzer
0.2 Rs
based systems, URFCs are significantly more compact and they allow considerable system
simplification. Moreover, URFC devices are characterized by rapid start up, they can operate 10 mHz
0.0 10kHz
efficiently at low temperature without the need of cumbersome power consuming auxiliaries and
can provide stable operation even in the presence of a large number of start up/ shut down 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
cycles. 2
Zr / cm

boiling water
Heat filtered NaOH H2IrCl6
treatment
400C 2.0

1.8
t = 10 min t = 10 min
1.6
Becker (100 mL) 1 mL
50 mg 25 mL Ultrasounds Figure 8. Time-stability test under electrolysis mode at 1.8 V
T= 70 C 0.5 M 1.4
IrO2 ethylene glycol and room temperature for the MEA based on Pt/ IrO2 (50:50
H2PtCl6
wt % ) electrocatalyst. The inset shows the fuel cell 1.2 Electrolysis
polarization and power density curves before and after the
t = 10 min E/ V 1.0 Fuel Cell
stability test at room temperature.
0.6 0.8
Washed with
NaOH 0.6
water T=80C t 0.55
and filtered pH
1.2 0.4
-2
Current density / A cm

0.5 Before time test @ 1.8 V

1 0.2
After time test @ 1.8 V
0.8
Potential / V

0.45 0.0
0.6 -100 0 100 200 300 400 500 600
-2
11
Figure 2. Variation of Pt crystallite size
0.4 0.4 j / mA cm
10 as a function of pH for a reaction time of
IrO2 0.2
10 min.
Pt 9
Pt Crystallite Size / nm

0.35 0
8
0 0.1 0.2 0.3 0.4
Intensity / a.u.

7 Current density / mA cm -2

f
0.3
Figure 7. URFC polarization curves at room
6

0 20 40 60 80 100 120 temperature of the MEA based on Pt/ IrO2 ( 50:50
e 5
Time / h
wt % ) electrocatalyst.
d 4

c 3

b 2
a
10 20 30 40 50 60 70 80 90 100 110 1
2 4 6 8 10 12
E FC
RT
2 / degree EFC : cell voltage fuel cell
pH
EWE: cell voltage water
EWE
IrO2 Pt

8.0
IrO2

electrolyzer
IrO2
Intensity / a.u.

50 7.5
Pt

7.0
IrO2

40 6.5
Table 1. Results of round-trip energy efficiency .
Pt
Pt

Crystallite size / nm

f 6.0
5.5
50 mA/cm2 100 mA/cm2 200 mA/cm2
% Pt wt.

30
20 40 60 80 100
5.0
2 / degree
4.5
20
Figure 1. Powder XRD patterns of Pt-IrO2 at different pH 4.0
Figure 3. XRF variation of percent by weight of Pt with
values: a) 3, b) 5, d) 9, e) 10 and f) 11.7.
respect to time at T = 70 C and variation of crystallite
size at pH 11.7. 10
3.5 47 % 37 % 30 %
3.0
2.5
0
10 20 30 40 50 60
Time / min
A)
70
60

IrO2 50 C)
number

Pt
40

30
The development of high energy density, efficient, non polluting energy storage systems is fundamental for
20
renewable power sources. A new process for synthesizing a nanosized Pt/IrO2 electrocatalyst for URFCs was
Intensity / a. u.

10

0
3 3.5 4 4.5 5 5.5 6 6.5 developed. An advance with respect to the state of the art was achieved since a chemical deposition of Pt

Pt Diameter / nm
nanoparticles onto an IrO2 support was obtained without modifying the oxidation state of Ir. Whereas, a common
80
b 70
60 D)
approach to avoid modification of IrO2 status consists in the mechanical mixing of Pt and IrO2 nanopowders. TEM
50
observation showed an intimate contact between Pt and IrO2 phases as required for a dual function catalyst
number

40
30
20
10
operating in both electrolysis (oxygen evolution) and fuel cell (oxygen reduction) modes. Electrochemical data
a 0
5 5.6 6 7 7.5 8 8.5 9 showed good performance at room temperature and atmospheric pressure, as required for operation in conjunction
20 40 60 80 100 IrO2 Diameter / nm

2 / degree
with renewable power sources, especially in the electrolyzer mode. To reduce the asymmetry of the overpotential for
Figure 4. Powder XRD patterns of IrO2 via colloidal process
Figure 5. HR-TEM images of sample Pt-IrO2 50:50 wt. at different magnifications: A) 330 kx, B)
570 kx, C) Particle size distribution for Pt and D) Particle size distribution for IrO2.
operation under electrolysis and fuel cell mode, it appears appropriate to tailor the catalyst composition as well as
(a) and Pt-IrO2 (~ 50:50 wt. %) via polyol ultrasonic the hydrophilic/hydrophobic properties of the Ti-grid backing layer. However, to reduce the occurrence of corrosion
process (b).
phenomena, it is also necessary to avoid any increase of the maximum operating potential of the unitized
regenerative fuel cell.

[1] E. Rasten, G. Hagen, R. Tunold, Electrochim. Acta, 2003, 48, 3945.

References

[2] A. de Oliveira-Sousa, M.A.S. da Silva, S.S. Machado, L.A. Avaca, P. de Lima-Neto, Electrochim. Acta, 2000, 45,
The authors acknowledge the support of bilateral CNR (Italy) -CONACYT (Mexico) joint agreement 4467.
2009-2011 (project Aric/Arriaga Hurtado). J.C. Cruz and L.G. Arriaga thank the Mexican Council for [3] J. C. Cruz, V. Baglio, S. Siracusano, R. Ornelas, L. Ortiz-Frade, L. G. Arriaga, V. Antonucci, A. S. Aric, J.
Science and Technology (Conacyt, Fomix-Zacatecas 81728) for financial support. The efforts addressed Nanopart. Res., 2011, 13, 1639.
[4]A. Morozan, B. Jousselme, S. Palacin, Energy & Environmental Science, 2011, 4, 1238.
by Tozzi Renewable Energy to this research topic are also acknowledged. CNR-ITAE authors
[5]W. Zhang, P. Sherrell, A.I. Minett, J.M. Razal, Energy & Environmental Science, 2010, 3 1286.
acknowledge financial support from the FIRB MIUR Project Rinnova.s