Anion conducting membranes for Energy Applications

Duong Ngoc My Hanh

Fuel cell research center

KIST

CONTENT
1. Introduction 2. Experimental overview 3. Experimental 4. Result 5. Further work

1. INTRODUCTION
Alkaline anion exchange membrane fuel cells (AAEMFC) - Operate between ambient temperature and 90 C - Electrical efficiency > proton exchange membrane fuel cells (PEMFC), solid oxide fuel cell and phosphoric acid fuel cell - Employ a solid polymer electrolyte membrane Advantages - Using inexpensive, non-noble metal catalysts nickel for the fuel electrode silver, iron phthalocyanines etc. for the oxygen electrode - Accelerates oxidation of methanol Fig 1. Alkaline anion exchange membrane fuel Easy to transport cell

http://en.wikipedia.org/wiki/Alkaline_anion_exchange_membrane_f _cells

1. INTRODUCTION
Challenges: Conductivity and stability

Ion
H+ OHCO32IHCO3-

0 [Scm2/mol]
349.6 176% 199.1 100% 138.6 70% 76.8 39% 44.5 22% OH-

Limiting Molar Ionic Conductivities in aqueous L. Coury (1999) Current separations 18(3): 91 - 96.

solutions at 25C

Stability:

Degradation: Mainly SN2 and Hofmann Elimination

Changing the backbone will not improve the stability 2 ether groups blocking and stabilizing the 2position of the imidazolium ion of the ammonium groups Charged groups in the side chain Anion exchange membrane (AEM) must Increase conductivity have - High OH- ion conductivity A very stable, highly hydroxide - Mechanical stability under chemical conducting anion exchange membrane for 4 deterioration conditions alkaline anion exchange membrane fuel cells

2. EXPERIMENT
Reaction procedure 1. Step 1

Water outlet

2. Step 2

Water inlet

3. Step 3

5
International journal of hydrogen energy 36 (2011) 7152-7161

3. RESULT
Experime nt No. Reagent 2,6-dihydroxybenzoic acid DFDPS N,N-difluorobenzonitrile Potassium carbonate 2,6 dihydroxybenzoic acid Bisphenol A 2,6- difluorobenzonitrile Potassium carbonate 2,6-dihydroxybenzoic acid DFDPS Bisphenol A Potassium carbonate 2,6-dihydroxybenzoic acid DFDPS Bisphenol A Potassium carbonate 2,6-dihydroxybenzoic acid DFDPS Bisphenol A Difluorobenzonitrile Potassium carbonate 1 Mol (mmol ) 20 10 10 40 10 10 20 40 5 10 5 25 5 10 5 25 5 6.5 5 3.5 25 Solvent Membrane Brittle

DMAc

Brittle

Brittle

Brittle

DMSO Brittle

Difficult to start from 2,6-dihydroxybenzoic acid

6

3. RESULT
+ + Tetrazole substituted polymer
Experiment No. 1 Reagent N,N-difluorobenzonitrile Bisphenol A Hydroquinone sulfonic acid, K s alt Potassium carbonate Mol (mmol) 20 12 8 40 Solvent DMAc

TP
Membrane Tough Modified membrane Tough (easily dissol ed in solvent)

remove CN groups

IR spectrum before modification

IR spectrum after modification

3.37

.esp

2.12

3. RESULT

.esp

0.45
0.30

0.40 0.35

Normalized Intensity

Normalized Intensity

0.25

0.30 0.25 0.20 0.15 0.10

0.20

2.55 2.54 2.54

0.15

1.73 1.73

1.74 1.74

7.59 7.58 7.42 7.41 7.40 7.22 7.38 7.39

0.10

2.58 2.55 2.53

3.36 3.34 3.33

2.74 2.73 2.55 2.54 2.53 2.54

3

7.39 7.20 7.18 7.17

2.13 2.12 2.00

7.63

2.98

0.05

6.78 6.76 6.66 6.65 6.64 6.63 6.47 6.45

0.05 0 6.76 1.09 0.03 0.02 0.36

1.74 0.03 2.63 0.05 10.73 0.04 0.09 1.79 19.28 1.81 3.55 5 4 Chemical Shif t (ppm) 2 1 0

9.0

8.5

8.0

7.5

7.0

6.5

6.0

5.5 5.0 4.5 Chemical Shif t (ppm)

4.0

3.5

3.0

2.5

2.0

1.5

1H

NMR (400 MHz, DMSO-d6)

.esp 0.020

1H

NMR (400 MHz, DMSO-d6)

0.015

Normalized Intensity

0.010

0.005

6.76 9.0 8.5 8.0

1.090.03 0.02 0.36 6.5 6.0 5.5

7.5 7.0 Chemical Shif t (ppm)

2.22 2.12 1.96 1.94

2.13

4. FUTURE WORK
Doping polymer by H3PO4

Modify 2,6-dihydroxybenzoic acid