PHOSPHORIC ACID DOPED TETRAZOLE SUBSTITUTED

POLY(ARYL ETHER) FOR PROTON EXCHANGE

MEMBRANE

2014 / 06 / 13
Duong Ngoc My Hanh
Fuel cell research center
KIST

CONTENT
1. Introduction
2. Experimental
3. Result and Conclusion
4. Future plan

1. INTRODUCTION
World energy
demand

Proton Exchange Membrane Fuel Cell

1. INTRODUCTION
PEM Material of Choice for H2/Air Fuel Cell at 80oC is
Nafion
What is Needed:
A membrane with a high proton conductivity at T120oC and
25% RH
A membrane that operates without water at elevated T
The Problems with Nafion
Nafion dehydrates at T>80oC and RH < 100%.
Expensive
Introduce the tetrazole group to the aromatic polymer backbone for
high proton conductivity and thermal stability

2.EXPERIMENTAL
Synthesize -CN containing Poly(aryl ether )

K2CO3, DMAc
170oC

Tetrazole substituted Poly(aryl ether) by

Click Chemistry
NaN3,ZnCl2
NMP

NaN3,ZnCl2
NMP

Characterize the attained polymer by NMR, IR,

TGA

2.EXPERIMENT
Phosphoric acid doping process
-Cast the membrane in DMAc solvent
-Wash up and dry in vacuum oven for 24 hours to completely remove salt
-Prepare the samples ( size 1x4 cm)
-Dip samples in Phosphoric acid solution 85% wt
-Measure the weight uptake every 2 hours

-Dry in vacuum oven at 1100C to the pristine weight of membrane

-Measure in-plane conductivity in anhydrous condition at various temperature from 40 oC 160oC
-Fuel cell test, Long term test
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3. RESULTS AND CONCLUSIONS

NMR study
2.96
2.80
2.54
2.53
2.53
2.52
2.52
2.51
2.51

.e s p

0.030

2.23

0.020

2.31

3.34

0.015

0.010

0.005

8.0

7.5

7.0

6.5

6.0

5.5

5.0
4.5
Chemical Shift (ppm)

4.0

3.5

3.0

2.5

2.0

1.5

.e s p
0.13

0.12

0.11

0.10

0.09

N orm alized In ten s ity

Normalized Intensity

0.025

0.08

0.07

0.06

0.05

0.04

0.03

0.02

0.01

0
8.0

7.5

7.0

6.5

6.0

5.5

5.0

4.5
4.0
Chemical Shift (ppm)

3.5

3.0

2.5

2.0

1.5

1.0

3. RESULTS AND CONCLUSIONS

NMR study
.e s p
0.55
0.50
0.45
0.40

Normalized Intensity

0.35
0.30
0.25
0.20
0.15
0.10
0.05
0
1.00
0.95
0.90

21.94

.e s p

0.42 1.29 2.211.88

5.12 0.03 0.70 0.72

8.0

7.5

7.0

6.5

6.0

5.5

5.0

8.0

7.5

7.0

6.5

6.0

5.5

5.0

4.5
4.0
Chemical Shift (ppm)

4.33

0.70 10.63

0.04

3.5

3.0

2.5

2.0

1.5

1.0

3.5

3.0

2.5

2.0

1.5

1.0

0.85
0.80
0.75
0.70

N orm alized Intens ity

0.65
0.60
0.55
0.50
0.45
0.40
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0
4.5
Chemical Shift (ppm)

4.0

10

3. RESULTS AND CONCLUSIONS

FT-IR study

TZPEEN before and after acid doped

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3. RESULTS AND CONCLUSION

Phosphoric acid doping

The maximum acid uptake of TZPEEN is 115 wt% at 120oC

The maximum acid uptake of TZSPEEN is 52 wt% at 120oC

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3. RESULTS AND CONCLUSIONS

Thermogravimetric analysis

I prepared another TZPEEN membrane,dried in

vacuum until the weight is unchanged the
Old chart with tzpeen membrane still have
solvent

5% wt. Loss temperature of TZPEEN is higher

than the old one.
For the acid doped membrane, I used the
highest acid doping level membrane for the
TGA test
TZPEEN acid doped: doped at 120 oC, ~24
h, ~115% wt. Acid uptake
TZSPEEN acid doped: doped at 120 oC,
~24 h, ~52% wt. Acid uptake

Thermogravimetric analysis (TGA) curves of membrane before and after acid

doped under nitrogen

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3. RESULTS AND CONCLUSIONS

Mechanical test

Mechanical test for TZPEEN and TZSPEEN membrane before PA doped and after PA doped at different temperatures
I use 3-4 samples for each polymer, cut from one membrane
Measurement temperature: 27 oC
Humidity: 31 %

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3. RESULTS AND CONCLUSIONS

n-plane conductivity

Activation energy
TZPEEN: 25.54 KJ/mol
TZSPEEN: 29.65 KJ/mol

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3. RESULTS AND CONCLUSION

Fuel cell test
- 1.03 mg/cm2 Pt loading
- Activation time: 24 hrs
- Cell temperature: 160oC

-Doping level : 50%

- Active area: 7.84 cm2

-Thickness: 70 um

IV curve after 24 hours activation

IV curve after 96 hours activation

Equilibrium time for acid doped membrane is 24 hours

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3. RESULTS AND CONCLUSION

Fuel cell test
- 1.03 mg/cm2 Pt loading

-Doping temperature: 120 oC

- Activation time: 24 hrs

-Time: 24 h

- Cell temperature: 160oC

-Doping level : 85.67 %

- Cell area: 7.84 cm2

-After took the membrane out of PA solution, did

not dry in vacuum, measure wet membrane
-Thickness after doping: 50 um

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Fuel cell test

Conditions:
- 1.03 mg/cm2 Pt loading
- Activation time: 24 hrs
- Cell temperature: 160oC
- Active area: 7.84 cm2

-Doping level : 61.94%

-Thickness: 50 um

4. FUTURE PLAN

Use higher acid doping level membrane for fuel cell test

Measure the hydrogen crossover to check the stability of the membrane

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