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Synthesis and characterization of modified S-PEEK

Proton Exchange Membranes with ZrO2-PWA and their


application in Fuel Cells
P. Hernndez-Muoz, S. Rivas and J.L. Pineda, J. Ledesma-Garca, L.G.
Arriaga, A. U. Chvez-Ramrez

PEM Fuel Cells


A fuel cell is a system that converts the chemical energy, stored in a fuel such
as hydrogen, ethanol or methanol, directly in electrical energy.

2H2 4H+ + 4e-

(Barbir, n.d.; Carrette, Friedrich, & Stimming, 2001)

O2 + 4e- + 4H+ 2H2O

Proton Exchange Membranes (PEM)

Nafion

H+

S-PEEK

(Iojoiu et al., 2006; Miyatake, Chikashige, Higuchi, &

Non-fluorinated
structure.

with

an

aromatic

Proton conductivity comparable


fluorinated membranes.

Less fuel permeability

Thermal and mechanical stability.

Higher wter uptake

to

Addition of ZrO2 and PWA

ZrO2

12-phosphotungstic acid structure.


H3PW12O40 (PWA)

Proton conductors super acids.


Inorganic fillers with termal stability.

(Bardin et al., 1998; Keggin, 1934; Liu et al., 2014)

Hydrophilic nature
Thermal stability.

(Daiko, Klein, Kasuga, & Nogami, 2006)

Membrane characteristics (PEM)


High proton conductivity
Low electronic conductivity
High water retention
High thermal and mechanical stability
Low fuel permeability
Low production costs with respect to the desired
application.

mitha, Sridhar, & Khan, 2005)

Experimental
Synthesis of the modified S-PEEK
membranes

Sulfonation reaction of PEEK


(Victrex)

Casting method
S-PEEK

DMF

Stirring at 80 oC
(Huang, Shao, Burns, & Feng, 2001; Li, 2003; Roelofs, 2010)

T = 35 oC
Time: 3 24 h
ZrO2 (prepared by sol-gel
method)
PWA
ZrO2/PWA-imp
ZrO2/PWA-in-situ (in situ
impregnation)

Characterization of S-PEEK
membranes
Sulfonation degree (SG) and ionic exchange
capacity
(IEC)titration
Acid-base
Water uptake and swelling

Drying at 80 oC

Dry weight
Area
Thickness

S-PEEK in H2O

T=30 oC y T=70 oC
(Yang, 2008)

Wet weight
Area
Thickness

Proton conductivity

Potenciostate
PGSTAT
302
AUTOLAB
Fuel Cell Station PSCompuCell
by Electrochem

PEM
Fuel
Cell
by
Electrochem

Conductivity cell BT-115 by


Scribner Associates

PEM Fuel Cell evaluation


Potenciostate PGSTAT 302
AUTOLAB
Fuel
Cell
Station
PSCompuCell
by
Electrochem
PEM
Fuel
Cell
by
Electrochem
Linear voltammetries from
OCP to 0.2 V, 50 mV/s.
Temperatures from 30 80
o
C.
INNOVATION MATCH MX Guadalajara, Jal. 6-8 Abril del 2016
www.innovationmatchmx.com

Results and Discussion


Synthesized composite S-PEEK membranes

Name

Polymer
content (%
peso)

Filler

Specifications

Filler content (%
peso)

S-PEEK

100

S-PEEK+ZrO2

90

ZrO2

Sol-gel

10

S-PEEK+PWA

70

PWA

30

S-PEEK+ZrO2-PWA-imp

90

Conjunto
ZrO2/PWA

Estndar
impregnation

10

S-PEEK+ZrO2-PWA-in-situ

90

Conjunto
ZrO2/PWA

In situ impregnation

10

Sulfonation degree and IEC


Relation of IEC and SG with respect to time. T=35 oC.
IEC (meq/g)
1.681
1.888
1.908
1.971
2.310
2.327
2.474
2.740

S.D. (%)
56.12
64.28
65.08
67.62
82.31
83.86
89.21
101.55

2.4

Datos: GS(tsulfonacion)

2.2

Ajuste lineal

2.0

- ln (1 - G S ) (-)

Time (h)
3
4
5
6
17
18
22
24

1.8
1.6
1.4
1.2
1.0

-ln (1- GS) = 0.0688(tsulfonacin) + 0.626

0.8
0

10

15

t sulfonacion (h)

(Huang et al., 2001)

20

25

Water uptake and swelling

Feature

S-PEEK

S-PEEK+ZrO2

S-PEEK+PWA

S-PEEK+ZrO2PWA-imp

Wup (%) a 30 oC
Wup (%) a 70 oC
Swelling a 30 oC
Swelling a 70 oC
(mol H2O/mol
SO3H)

18.45
28.13
1.041
1.088

53.22
97.56
0.978
1.069

12.33
21.94
0.985
1.065

36.08
29.85
1.012
1.025

5.43

15.66

3.63

Membranes with ZrO2 content presented higher


Wup (%).

10.62

SPEEK+ZrO2PWA-in-situ
106
32.05
1.0002
1.333
31.19

Hydrophilic nature of ZrO2 (Du et al., 2012; Zhai,


Zhang, Hu, & Yi, 2006)

Proton conductivity
0.45
S-P EEK
S-P EEK+ZrO2
S-P EEK+PWA
S-P EEK+ZrO2/PWA-imp
S-P EEK+ZrO2/PWA-in-situ

0.40

-1

Conductivity (S cm )

0.35

H.R. = 100 %

0.30
0.25
0.20
0.15
0.10
0.05
30

40

50

60

70

80

Temperature ( C)

Proton conductivity of S-PEEK composite membranes.

PEM Fuel Cell Performance


Polarization curves and power density of S-PEEK composite membranes.

0.12
0.10

Voltaje (V)

1.0

S-PEEK
S-PEEK+PWA
S-PEEK+ZrO2-PWA-in-situ

Power density (W/ cm )

1.2

0.08

0.8

0.06
0.6

0.04
0.02

0.4

0.00
0.2
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40
2

Current density (A/cm )

100 % H.R. Pin = 0 psi, T = 30 oC.

S-PEEK+PWA
and
SPEEK+ZrO2-PWA-in-situ
presented a higher current
density
than
S-PEEK.
However, S-PEEK+ZrO2PWA-in-situ performance
was reduced at higher
temperatures
and
at
higher pressures due to
flooding problems in the
fuel cell

PEM Fuel Cell Performance


Polarization curves and power density of S-PEEK composite membranes.

S-PEEK+PWA presented a best

1.2

Voltage (V)

conductivity,

fuel

cell

0.090

0.060

0.8

0.045
0.6

0.030
0.015

0.4

0.000
0.2
0.00

0.05

0.10

0.15

0.20

0.25
2

Current density (A/cm )

0.30

0.05

0.10

0.15

0.20

0.25
2

Current density (A/cm )

100 % H.R. Pin = 0 psi. a) T = 50 oC. b) T = 80 oC

0.30

0.075

performance,

mechanical and termal stability at


higher temperaturas.

b)

Power density (W/ cm )

1.0

tested.

Addition of PWA enhanced proton

S-PEEK
S-PEEK+PWA

a)

performance under all the conditions

PEM Fuel Cell Performance


Polarization curves and power density of S-PEEK composite membranes.
1.2

0.08

1.0

S-PEEK+PWA membrane delivered a


current density of 0.25 A/cm2, under low
relative humidity conditions and high
temperatures.

Voltage (V)

0.06

Power density (W/cm )

S-P EEK+P WA

0.8

0.04

0.6
0.02
0.4
0.00
0.2
0.00

0.05

0.10

0.15

0.20
2

Current density (A/cm )

50 % H.R. Pin = 15 psi, T = 80 oC.

0.25

Conclusions
S-PEEK+PWA
and
SPEEK+ZrO2-PWA-imp showed
a stable proton conductivity,
despite the high temperatures,
which suggests the addition of
these compounds improves
thermal
and
mechanical
stability.

Fuel Cell performance of


membranes with zirconium
oxide content was remarkably
low despite the improvement
in the thermic stability and
higher water uptake.

Conclusions
Finally, among all the inorganic fillers that were tested, PWA
and its addition to the S-PEEK polymeric matrix presented the
best results:
Proper water uptake
Stable proton conductivity (0.114 S cm -1 0.12 S cm-1)
Better performance in PEM fuel cells (0.2 0.3 A cm -2), in
all the conditions tested (temperature, pressure, and
relative humidity).
This makes the PWA a promising material for its application a
membrane modifier, especially in the S-PEEK, and the
application in PEM fuel cells.

References

Barbir, F. (n.d.). PEM Fuel Cells.

Carrette, B. L., Friedrich, K. A., & Stimming, U. (2001). Fuel Cells Fundamentals and Applications, (1), 539.

Huang, R. Y. M., Shao, P., Burns, C. M., & Feng, X. (2001). Sulfonation of poly(ether ether ketone)(PEEK):
Kinetic study and characterization. Journal of Applied Polymer Science, 82(11), 26512660.
http://doi.org/10.1002/app.2118

Li, L. (2003a). Sulfonated poly(ether ether ketone) membranes for direct methanol fuel cell. Journal of Membrane
Science, 226(1-2), 159167. http://doi.org/10.1016/j.memsci.2003.08.018

Li, L. (2003b). Sulfonated poly(ether ether ketone) membranes for direct methanol fuel cell. Journal of
Membrane Science, 226(1-2), 159167. http://doi.org/10.1016/j.memsci.2003.08.018

Roelofs, K. S. (2010). Sulfonated Poly ( Ether Ether Ketone ) Based Membranes For Direct Ethanol Fuel Cells
(Vol. 5).

References

Wang, Y., Chen, K. S., Mishler, J., Chan, S., & Cordobes, X. (2011). A review of polymer electrolyte
membrane fuel cells: Technology , applications , and needs on fundamental research. Applied
Energy, 88(4), 9811007. http://doi.org/10.1016/j.apenergy.2010.09.030

Yang, T. (2008). Preliminary study of SPEEK/PVA blend membranes for DMFC applications.
International
Journal
of
Hydrogen
Energy,
33(22),
67726779.
http://doi.org/10.1016/j.ijhydene.2008.08.022