Phosphoric Acid Doped Poly(2,5-benzimidazole)

(ABPBI) and Sulfonated ABPBI Membranes for NH2 N

membrane
PPA / N2 / 200ºC casting
Polymer Electrolyte Fuel Cells HO NH2 N n
O H
ab b
Juan Antonio Asensio, Salvador Borrós, Roberto
3,4-diaminobenzoic acid
Ruiz,b and Pedro Gómez-Romero.a* ABPBI

-
SO3
a, Institut de Ciència de Materials de Barcelona (CSIC), N H2SO4
H
N
Thermal H
treatment N
Campus UAB, E-08193 Bellaterra (Barcelona), Spain. + +
b, Institut Químic de Sarrià, Universitat Ramon Llull, Vía N n N n N n
H -
HSO4 H H
Augusta 390, E-08017 Barcelona, Spain.
ABPBI membrane ABPBI· x H2SO4 SABPBI
* E-mail pedro@icmab.es

Figure 1.- Synthesis and sulfonation of ABPBI by heat

The current technology in polymer electrolyte treatment of H2SO4 doped membranes.
membrane fuel cells (PEMFC) is based on proton
conducting membranes made of perfluorosulfonated 0.04
polymers, ie. Nafion®. These membranes have two
limitations. First, Nafion® and the other perfluorinated
membranes are very expensive. This high cost makes 0.03

-1
difficult the commercialization of PEMFC. On the other

σ / S·cm
hand, perfluorosulfonated membranes need a high 0.02
humidification to keep their good proton conductivity,
therefore this conductivity decay sharply above 100 ºC,
and water management is very important in PEMFC. 0.01
Furthermore, working over 150 - 200 ºC would benefit
PEMFC because over these temperatures CO present as
impurities in H2, is not absorbed on Pt poisoning the Pt/C 0
catalyst. These reasons have focused research to high 70 90 110 130 150 170 190
temperature proton conductors.
T / ºC
When doping a membrane of commercially available
PBI, it becomes a proton conducing electrolyte with good Figure 2.- Conductivity of sulfonated S-ABPBI (41 % -
thermal and chemical stability and high proton SO3H)·
4.6 H3PO4 ( ), S-ABPBI (28 % -SO3H)· 3.4
conductivity at 80 - 200 ºC. These properties make H3PO4 ( ), and non sulfonated ABPBI · 2.7 H3PO4 (  ).
phosphoric acid doped PBI useful for PEMFC at The three membrane were doped in the same H3PO4 85 %
temperatures up to 200 ºC.(1, 2) In addition, conduction / H2O bath for 3 days. Measures were made on the dry
mechanism do not implies water, so water management in membranes.
PBI· x H3PO4 PEMFC is much easier.(3)
As PBI is the only commercially available, it is the 100
most widely studied polybenzimidazole membrane. Only -0.8
phosphoric acid doped poly(2,5-benzimidazole) (ABPBI) 80
have been studied by Savinell and Litt.(4) This second Derivative / %·ºC-1
-0.6
benzimidazole polymer is also a very promising proton 60
SABPBI 41 % -SO H
Weight / %

3
SABPBI 41 % -SO H · 4.6 H PO
conductor showing good thermal stability and proton 3 3 4

conductivity at the desired temperatures of 150-200 ºC. humidity

-0.4
40
In this work, we report the synthesis (figure 1), H PO
3 4
-SO H
3

membrane preparation, physico-chemical characterization 20

dehydration
-0.2
(figures 2 and 3) and H2/O2 PEMFC test of phosphoric
acid doped ABPBI and PBI (figure 4), as well as 0.0
0
sulfonation,(5) phosphoric acid doping and 0 200 400 600
characterization of previously cast ABPBI membranes. Temperature /ºC

Both benzimidazole type polymers, ABPBI and Figure 3.- TGA of SABPBI (41 % -SO3H) and SABPBI
sulfonated ABPBI, when doped with phosphoric acid, are (41 % -SO3H) · 4.6 H3PO4 in air at 10 ºC·min-1.
as good or even better proton conductors as commercially
available PBI. For this reason, ABPBI and sulfonated
0.90 160
ABPBI are very good candidates for use in PEMFC at
0.80 140
high temperatures, up to 200 ºC.
0.70 120
Power / mW

Aknowledgements : 0.60
Voltage / V

100
Spanish Ministry of Science and Technology, Projects 0.50
80
MAT 2001-1709-C04-01 y MAT 2002-04529-C03. 0.40
60
0.30
References: 40
0.20
1. J. S. Wainright, J. T. Wang, D. Weng, R. F. Savinell,
0.10 20
and M. Litt, J. Electrochem. Soc., 142, L121 (1995).
2. J. T. Wang, R. F. Savinell, J. S. Wainright, M. Litt, 0.00 0
and H. Yu, Electrochimica Acta, 41, 193 (1996). 0.00 0.20 0.40 0.60 0.80 1.00
3. L. Qingfeng, H. A. Hjuler, and N. J. Bjerrum, J. Intensity / A·cm-2
Appl. Electrochem., 31, 773 (2001).
Figure 4.- ABPBI · 2.8 H3PO4 120 µm at 180 ºC, H2 / O2
4. M. Litt, R. Ameri, Y. Wang, R. Savinell, and J.
humidified at room temperature. E-TEK electrodes 0.35
Wainwright, Mater. Res. Soc. Symp. Proc., 548, 313
mg Pt·cm-2.
(1999).
5. J. E. Kuder and J. C. Chen, US Patent 4,634,530
(1987).