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320 s basu 320 s basu Presentation Transcript

  • 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 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 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; FeCo/Ceria • Titanates - LST, LYST 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
  • Proton Exchange Membrane Fuel Cell (PEMFC) eLoa d Wate r 4 1 Fuel (H2) 3 2 5 Oxidant O2/Air H2 2 H+ + 2e2 H+ + 1/2 O2 + 2eH2O H2 + 1/2 O2 H2O 1. Fuel chamber 2. Oxidant chamber 3. Anode (Pt) 4. Electrolyte (PEM) 5. Cathode (Pt/C) (Anode, Pt) (Cathode, Pt) (Overall) Advantages  Efficient Power Generation  Environmental Friendly  Automobile  Distributed Power Gen.  Portable Electronics Eqpt. Department of Chemical Engineering Indian Institute of Technology-Delhi, New Delhi 110 016, India
  • Polymer Electrolyte Membrane (PEM) Perfluro-sulphonic Acid Membrane PEM Anode MEA Cathode 70 oC, 1 Bar Hydrophilic part Hydrophobic part PEM Department of Chemical Engineering Indian Institute of Technology-Delhi, New Delhi 110 016, India
  • Advantages of High Temperature PEM  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 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
  • Experimental 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 N2 gas purged for 15 min. 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 Department of Chemical Engineering Indian Institute of Technology-Delhi, New Delhi 110 016, India
  • Reaction Schemen: Synthesis of Poly(AAc-coDMAPMA) Hydrogel Membrane H H2C C + C O H (AAc) CH3 H2C APS-TEMED 41±1°C, 24 h C C O CH3 O NH (CH2)3 ( H2C CH ) m CO2H ( H2C C )n C O NH N (CH2)3 CH3 CH3 N (DMAPMA) CH3 CH3 Poly(AAc-co-DMAPMA) 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 No fracture of membrane was observed  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 Department of Chemical Engineering Indian Institute of Technology-Delhi, New Delhi 110 016, India
  • Ionic Conductivity of PADMA Membranes 1.E+00 PADMA; Temp = 25 °C PADMA; Temp = 60 °C Nafion; Temp = 60 °C Nafion; Temp = 80 °C Conductivity (S/cm) PADMA; Temp = 80 °C Nafion; Temp = 25 °C 1.E-01 PADMA; Temp = 40 °C Heat treated PADMA; Temp = 80 °C  EIS: 100 Hz and 30 kHz  PADMA : 625 mm thick  Nafion®512: 133 mm thick 1.E-02 1.E-03 Water starved condition: RH = 39% 1.E-04 1.E-05 1.E-06 1 3 5 7 9 11 pH 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. Department of Chemical Engineering Indian Institute of Technology-Delhi, New Delhi 110 016, India
  • pH Effect Predominant molecular composition of PADMA membrane in buffers of various pH values: a) pH < 3.5; b) pH=3.5; c) pH > 3.5. a b CH3 ( CH2 CH )m ( CH2 C )n ( CH2 CH )m ( CH C 2 CO CO2H O + CH3 H ( CH2 CH )m ( CH 2 O- O N CH3 C pH=3.5 CH3 H )n CO C HN + N pH<3.5 )n CH3 CO C HN c CH3 O- HN N CH3 Poly(AAc-co-DMAPMA) Department of Chemical Engineering Indian Institute of Technology-Delhi, New Delhi 110 016, India pH>3.5 CH3 CH3
  • 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 Ph.D Students Post-Doctoral Fellows Varagunapandiyan N Rajelakshmi pillai Debika Basu Pankaj Kumar Tiwari Rahul Pal Gurpreet Kaur Merajul Islam Jyoti Goel Dyuti Pandey Shaneeth (part time) Mridul Kumar Amandeep Jindal Harikrishnan N Neetu Kumari Department of Chemical Engineering Indian Institute of Technology-Delhi, New Delhi 110 016, India