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Department of Chemical Engineering Indian Institute of Technology-Delhi, New Delhi 110 016, India Poly(AAc-co-DMAPMA): A cost effective ion exchange membrane for fuel cell application A.Das 1 , A. Verma 2 , K. Scot 3 , S. Suddhasatwa Basu 1* 1 Indian Institute of Technology Delhi 2 Indian Institute of Technology Guwahati 3 University of Newcastle Upon Tyne December 10-12, 2013, ICAER, IIT Bombay, India

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Page 1: 320 s basu

Department of Chemical Engineering

Indian Institute of Technology-Delhi, New Delhi 110 016, India

Poly(AAc-co-DMAPMA): A cost effective ion

exchange membrane for fuel cell application

A.Das1, A. Verma2, K. Scot3, S. Suddhasatwa Basu1*

1Indian Institute of Technology Delhi

2Indian Institute of Technology Guwahati

3University of Newcastle Upon Tyne

December 10-12, 2013, ICAER, IIT Bombay, India

Page 2: 320 s basu

Department of Chemical Engineering

Indian Institute of Technology-Delhi, New Delhi 110 016, India

Fuel Cell Program at IIT Delhi

• Direct alcohol PEM fuel cell – Anode electrocatalyst, DEFC • Direct Glucose AEM fuel cell – electrocatalyst, micro DGFC • PEMFC – cathode electrode degradation, Non PGM catalyst • PEMWE/SOEC – electrocatalyst for Hydrogen generation • SOFC - LT/IT-SOFC – electrolyte, electrocatalyst – cathode - HT SOFC – Ni-YSZ anode instability and mitigation - HT SOFC – Electrolyte supported cell - Direct Hydrocarbon - anode development • CO2 electro-reduction – artificial leaf • Mathematical modeling of PEMFC/SOFC - overpotentials

SOFC Material and

Cell Testing

Electrolyte

• YSZ, SDC, GDC

Cathode

• MIEC

• Sr doped LaMnO3

(LSM)

• La1-xSrxCo1-yFeyO 3-!,

(LSCF)

•PCGO, TCGO

Anode

• Ni-YSZ, Ni-SDC

• Cu-Co/Ceria; Fe-

Co/Ceria

• Titanates - LST, LYST

PEMFC Material and Cell Testing

Catalyst support – CNx, f-Gr (chemically), f-MWCNT

Catalyst – PGM/Non-PGM – Pt-Re,Pt-Sn,Pt-Ir; MnO2, PA-Mn-Cu

Electrolyte – high temperature PEM

Dissemination (Fuel Cell)

• Publication – IJHE, JPS, Electrochim Acta, etc; h-index – 20; Conferences –ISE, GRC, MRS, ECS,Grove

• Patent – two granted • Ph.D. thesis 9 completed, 9 in progress ; Post-doctoral fellow 5; M.Tech. thesis 21 • Exchanges – 10 with NCL, LTU, ICL

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Department of Chemical Engineering

Indian Institute of Technology-Delhi, New Delhi 110 016, India

H2 2 H+ + 2e- (Anode, Pt)

2 H+ + 1/2 O2 + 2e- H2O (Cathode, Pt)

H2 + 1/2 O2 H2O (Overall)

e-

2

5

1

Oxidant O2/Air

Fuel (H2)

4

1. Fuel chamber 2. Oxidant chamber 3. Anode (Pt) 4. Electrolyte (PEM) 5. Cathode (Pt/C)

Water

3

Load

Efficient Power Generation Environmental Friendly

Automobile Distributed Power Gen. Portable Electronics Eqpt.

Advantages

Proton Exchange Membrane Fuel Cell (PEMFC)

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Department of Chemical Engineering

Indian Institute of Technology-Delhi, New Delhi 110 016, India

Hydrophobic part

Hydrophilic part

Perfluro-sulphonic Acid Membrane PEM Anode

Cathode

MEA

70 oC, 1 Bar

Polymer Electrolyte Membrane (PEM)

PEM

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Department of Chemical Engineering

Indian Institute of Technology-Delhi, New Delhi 110 016, India

Kinetics of both the electrode reactions enhanced

Tolerance of the Platinum electrodes to CO increased

Non-noble metal catalysts may be used

Integration of reformer technology simpler

Cooling system for facilitating heat dissipation simplified.

Present commercial PEM not suitable for the temperature higher

than 1000C due to dehydration of the membrane

PBI and other organic membranes have serious problem – such

as leaching of phosphoric acid

Advantages of High Temperature PEM

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Department of Chemical Engineering

Indian Institute of Technology-Delhi, New Delhi 110 016, India

Previous Works

Strategy to work on high temperature electrolyte

(i) Modified perfluorosulphonated membranes

(ii) Alternative sulphonated polymers and their composites

(iii) Acid-base polymer membranes and their composites.

Objective

Synthesis of the poly(AAc-co-DMAPMA) (PADMA) hydrogel membrane

Preliminary characterization of the membrane for PEMFC use

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Department of Chemical Engineering

Indian Institute of Technology-Delhi, New Delhi 110 016, India

N2 gas purged for 15 min.

Acrylic Acid (25.8 % mole) + [dimethylamino) propyl]-methacrylamide

(DMAPMA) (4.2 % mole) mixed in cold condition over magnetic stirrer

Distill water (70 % mole) added & mixed thoroughly

Added: conc. aq. solution of ammonium persulphate (APS – 0.50 mol % of

total monomer) as initiator and N,N,N’,N’-tetramethyl ethylene diamine

(TEMED -1 mol %) as accelerator.

Reaction mixture transferred into a mold of PTFE, placed in water bath at 41 ± 10C

Membrane removed from mold and cut into pieces

Washed in regularly changed distilled water for 3 days and dried in vacuum

Experimental

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Department of Chemical Engineering

Indian Institute of Technology-Delhi, New Delhi 110 016, India

C

C

O

H

C

OC

N

N H

H

C

N

N H

O

O

H2C H2C

(CH2)3

CH3 CH3

CH3

( H2C CH

CO2H

)m( H2C C )n

+CH3

(AAc)

(DMAPMA)

(CH2)3

CH3 CH3

Poly(AAc-co-DMAPMA)

APS-TEMED

41±1°C, 24 h

Reaction Schemen: Synthesis of Poly(AAc-co-DMAPMA) Hydrogel Membrane

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Department of Chemical Engineering

Indian Institute of Technology-Delhi, New Delhi 110 016, India

SEM of PADMA Membrane

made up of closely packed nanogels of ~300 nm

diameter

Macroporous: enough space to accommodate water

or suitable electrolyte

Densely packed - may not allow the fuel to pass

through and at the same time the inner structure may help

to improve the conductivity.

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Department of Chemical Engineering

Indian Institute of Technology-Delhi, New Delhi 110 016, India

TG for PADMA Membrane

Membrane is thermally stable up to 190oC, thereafter the

polymer chain degradation starts

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Department of Chemical Engineering

Indian Institute of Technology-Delhi, New Delhi 110 016, India

Stress-strain Curve for Swollen PADMA Membrane

Elastic modulus of the membrane found to be around 16.0-24.0 kPa

(cf. Nafion ~ 0.5 - 1.28 MPa)

Shear-stress curve of the membrane indicates good tenacity up to 5

kPa stress

No fracture of

membrane was

observed

Page 12: 320 s basu

Department of Chemical Engineering

Indian Institute of Technology-Delhi, New Delhi 110 016, India

Ionic Conductivity of PADMA Membranes

1.E-06

1.E-05

1.E-04

1.E-03

1.E-02

1.E-01

1.E+00

1 3 5 7 9 11

Co

nd

ucti

vit

y (

S/c

m)

pH

PADMA; Temp = 25 °C PADMA; Temp = 40 °C

PADMA; Temp = 60 °C PADMA; Temp = 80 °C

Nafion; Temp = 25 °C Nafion; Temp = 60 °C

Nafion; Temp = 80 °C Heat treated PADMA; Temp = 80 °C

Increase in ionic conductivity of PADMA membrane at low (2.2) and high

(10.6) pH indicates that the membrane may work both as proton and

hydroxyl ion conductor.

EIS: 100 Hz and 30 kHz

PADMA : 625 mm thick

Nafion®512: 133 mm thick

Water starved condition:

RH = 39%

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Department of Chemical Engineering

Indian Institute of Technology-Delhi, New Delhi 110 016, India

C

OC

N

NH

C

OC

NH

C

OC

N

NH

H

O O O O

N

H

( )m

CH3

CO2H

CH3

CH2 CH2CH

CH3

( )n

Poly(AAc-co-DMAPMA)

( )m

C

CH2 CH2CH

CH3

( )n ( )m

CH3 CH3

CH2 CH2CH

CH3

( )n

+

-C

-

CH3

+

CH3pH<3.5 pH=3.5 pH>3.5

a b c

Predominant molecular composition of PADMA membrane in buffers of

various pH values: a) pH < 3.5; b) pH=3.5; c) pH > 3.5.

pH Effect

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Department of Chemical Engineering

Indian Institute of Technology-Delhi, New Delhi 110 016, India

Summary

PADMA hydrogel membrane successfully synthesized

PAMMA Membrane characterized using SEM,

compression testing, TGA and Ionic conductivity

Investigation points out that PADMA membrane would

work as a good matrix for membrane electrolyte

Membrane may work as both proton and hydroxyl ion

exchange membrane

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Department of Chemical Engineering

Indian Institute of Technology-Delhi, New Delhi 110 016, India

Acknowledgement MNRE, DST, UKIERI, Shell Hydrogen, CSIR, ISRO, DIT, EPSRC (UK)

9 Ph.D. Students

5 Post-doc

4 M.Tech students

Page 16: 320 s basu

Department of Chemical Engineering

Indian Institute of Technology-Delhi, New Delhi 110 016, India

Fuel cell group at IIT Delhi

Varagunapandiyan N

Rajelakshmi pillai

Pankaj Kumar Tiwari

Gurpreet Kaur

Jyoti Goel

Shaneeth (part time)

Amandeep Jindal

Harikrishnan N

Neetu Kumari

Debika Basu

Rahul Pal

Merajul Islam

Dyuti Pandey

Mridul Kumar

Ph.D Students Post-Doctoral Fellows