Synthesis of novel ion-conducting materials for fuel cell...
Transcript of Synthesis of novel ion-conducting materials for fuel cell...
Synthesis of novel ion-conducting materials for fuel cell application
Nodar Dumbadze
Agricultural University of Georgia
Institute of Chemistry and Molecular Engineering
23 August 2018 Page 1
Introduction
23 August 2018 Page 2
Introduction
Fuel cells
23 August 2018 Page 3
Introduction
Fuel cells
23 August 2018
1. Higher energy efficiency;
2. Less CO2 emissions.
Page 4
Introduction
Fuel cells
23 August 2018
1. Higher energy efficiency;
2. Less CO2 emissions.
0 100 200 300 400 500
Water vapor, g/mile
CO, g/mile
NOx, g/mile
Hydrocarbons, g/mile
Emissions from Vehicles
Hydrogen Fuel Cell Vehicle Methanol Fuel Cell Vehicle
Gasoline ICE Light Truck Gasoline ICE Passenger Car
CO2, g/mile
Page 5
Introduction
23 August 2018 Page 6
Introduction
Fuel cells
23 August 2018
1. Polymer electrolyte membrane/proton exchange membrane fuel cells (PEMFC);
2. Phosphoric acid fuel cells (PAFC);
3. Alkaline fuel cells (AFC);
4. Solid oxide fuel cells (SOFC);
5. Molten carbonate fuel cells (MCFC).
Page 7
Introduction
Proton exchange membrane fuel cells (PEMFC)
23 August 2018 Page 8
Introduction
Proton exchange membrane fuel cells (PEMFC)
23 August 2018
• Low operation temperature;
• Higher energy density compared to batteries;
• Quiet operation;
• Fast startup;
• Zero local pollutant emission;
• High energy conversion efficiency.
Page 9
Proton exchange membrane fuel cells (PEMFC)
23 August 2018
• Anode: • Cathode:
Page 10
Proton exchange membrane fuel cells (PEMFC)
23 August 2018
Overall reaction:
Page 11
23 August 2018
Chemical structure of Nafion®
Disadvantages:
Low operation temperature (< 90 °C);
Environmental incompatibility;
High gas permeability;
High electroosmotic drag of water
from the anode to the cathode;
Deterioration of mechanical properties
at high temperature and low humidity.
Proton exchange membrane fuel cells (PEMFC)
Advantages:
Good mechanical properties (< 90 °C);
Chemical stability;
High proton conductivity.
Page 12
23 August 2018
Chemical structures of sulfonated aromatic polymers
Proton exchange membrane fuel cells (PEMFC)
Page 13
23 August 2018
Advantages:
High IECs and proton conductivities compared to
fluorinated ionomers (PFSAs);
Oxidative stability;
Thermal stability;
Low electroosmotic drag of water from the anode
to the cathode;
Good mechanical properties at moderate humidity.
Chemical structure of sPSO2-360
Proton exchange membrane fuel cells (PEMFC)
Disadvantages:
Brittleness in the dry state;
Unsatisfactory mechanical
properties at high humidity.
Page 14
23 August 2018
Blend of sPSO2-360 with PSU
+
Proton exchange membrane fuel cells (PEMFC)
Page 15
23 August 2018
Specific interactions between macromolecules
Proton exchange membrane fuel cells (PEMFC)
Increa
sing b
on
d stren
gth
Page 16
23 August 2018
Blend of sPSO2-360 with PSU-py
+
Proton exchange membrane fuel cells (PEMFC)
Page 17
23 August 2018
Blend of sPSO2-360 with PBI-OO
+
Proton exchange membrane fuel cells (PEMFC)
Page 18
23 August 2018
Scheme of ionic crosslinking of a sPSO2-360 (red) with a PBI-OO (blue)
Proton exchange membrane fuel cells (PEMFC)
Increase of mechanical strength;
Decrease of proton conductivity;
Decrease of ion exchange capacity. Page 19
23 August 2018
Synthesis of monomer and polyelectrolyte
with high sulfonation degree
Research objective:
Proton exchange membrane fuel cells (PEMFC)
Page 20
23 August 2018
Synthesis scheme of sodium 5,5'-((3-sulfonatophenyl)phosphoryl)bis(2-fluorobenzenesulfonate)1,2
1. X. Ma, C. Zhang, G. Xiao, D. Yan, G. Sun, Synthesis and characterization of sulfonated poly(phthalazinone ether phosphine oxide)s by direct polycondensation for
proton exchange membranes, J. Polym. Sci. Part A Pol. Chem. 46 (2008) 1758-1769;
2. Liao, H.; Zhang, K.; Tong, G.; Xiao, G.; Yan, D. Sulfonated Poly(arylene Ether Phosphine Oxide)s with Various Distributions and Contents of Pendant Sulfonic Acid
Groups Synthesized by Direct Polycondensation. Polym. Chem. 2014, 5, 412–422.
Proton exchange membrane fuel cells (PEMFC)
Page 21
23 August 2018
1H NMR Spectra of sodium 5,5'-((3-sulfonatophenyl)phosphoryl)bis(2-fluorobenzenesulfonate)
Proton exchange membrane fuel cells (PEMFC)
Page 22
23 August 2018
13C NMR Spectra of sodium 5,5'-((3-sulfonatophenyl)phosphoryl)bis(2-fluorobenzenesulfonate)
Proton exchange membrane fuel cells (PEMFC)
Page 23
23 August 2018
Synthesis scheme of sPSO2-360
Synthesis scheme of sPSO2PO-286
Proton exchange membrane fuel cells (PEMFC)
2.78
3.49
0.00
0.50
1.00
1.50
2.00
2.50
3.00
3.50
4.00
s360 s286
IEC
, m
eq/g
Comparison of IECs of s360 and s286
Page 24
IEC increases by ≈ 25 %
23 August 2018
Proton exchange membrane fuel cells (PEMFC)
2.78
2.21 2.21
3.49
Page 25
2.78
2.21
3.49
2.21
0.00
0.50
1.00
1.50
2.00
2.50
3.00
3.50
4.00
s360 blend (s360 + PBI-OO) s286 blend (s286 + PBI-OO)
IEC
, m
eq/g
Comparison of IECs of s360 & s286 blends with PBI-OO
PBI-OO = 7.5 % PBI-OO = 15.39 %
Acknowledgments
23 August 2018
Dr. Giorgi Titvinidze;
Vakhtang Tediashvili (Master student);
Tamuna Tkeshelashvili (PhD student);
Max Planck Institute for Solid State Research (Stuttgart, Germany);
FuMaTech GmbH (Bietigheim-Bissingen, Germany);
Volkswagen Foundation (Az: 93 331) for financial support.
Page 26
References
23 August 2018
• Kreuer, K.D. (2001), “On the development of proton conducting polymer membranes for hydrogen,
methanol fuel cells”, Journal of Membrane Science, Vol. 185 No. 1, pp. 29-39;
• Kreuer, K., Paddison, S. J., Spohr, E. & Schuster, M. Transport in proton conductors for fuel-cell
applications: simulations, elementary reactions, and phenomenology. Chem. Rev. 104, 4637–4678 (2004);
• Alkire, R. C.; Gerischer, H.; Kolb, D. M.; Tobias, C. W., Eds. Advances in Electrochemical Science and
Engineering; Johy Wiley & Sons: New York, 2002;
• G. Maier, J. Meier-Haack, In Fuel Cells II; Springer-Verlag Berlin, Berlin, 216 (2008) pp. 1–62;
• J.A. Kerres, Fuel Cells 5 (2005) 230-247;
• K.-D. Kreuer, Proton conductivity: materials and applications, Chem. Mater. 8 (3) (1996) 610–641;
• S. Bose, T. Kuila, T.X.H. Nguyen, N.H. Kim, K. Lau, J.H. Lee, Polymer membranes for high temperature
proton exchange membrane fuel cell: recent advances and challenges, Prog. Polym. Sci. 36 (2011) 813-
843;
• X. Ma, C. Zhang, G. Xiao, D. Yan, G. Sun, Synthesis and characterization of sulfonated poly
(phthalazinone ether phosphine oxide)s by direct polycondensation for proton exchange membranes, J.
Polym. Sci. Part A Pol. Chem. 46 (2008) 1758-1769;
• Liao, H.; Zhang, K.; Tong, G.; Xiao, G.; Yan, D. Sulfonated Poly(arylene Ether Phosphine Oxide)s with
Various Distributions and Contents of Pendant Sulfonic Acid Groups Synthesized by Direct
Polycondensation. Polym. Chem. 2014, 5, 412–422.
Page 27
23 August 2018
Thank you for attention!
Acknowledgments
Page 28