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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.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
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
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)
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
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
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
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
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
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.
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
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
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%
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
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
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
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