Comparing Ammonium and Tetraaminophosphonium Anion-Exchange Membranes Derived from Vinyl-Addition Polynorbornene Copolymers
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- Department of Chemistry, Carnegie Mellon University, 4400 Fifth Ave, Pittsburgh, Pennsylvania 15213, United States
- Chemistry and Nanoscience Center, National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401, United States
- School of Applied and Engineering Physics, Cornell University, Ithaca, New York 14853, United States
- Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853, United States
Herein, we systematically examined how composition influenced the properties of vinyl addition polynorbornene anion exchange membranes (AEMs) prepared from 5-n-hexyl-2-norbornene and 5-(4-bromobutyl)-2-norbornene. Copolymerization kinetics revealed that 5-n-hexyl-2-norbornene is consumed faster than 5-(4-bromobutyl)-2-norbornene, leading to a portion of the chain being richer in bromoalkyl groups. The alkyl halide pendants can then be converted to either trimethylammonium or tetrakis(dialkylamino)phosphonium cations through straightforward substitution with trimethylamine or a tris(dialkylamino)phosphazene. A series of cationic ammonium polymers were synthesized first, where conductivity and water uptake increased as a function of increasing ionic content in the polymer. The optimized copolymer had a hydroxide conductivity of 95 ± 6 mS/cm at 80 °C. The living polymerization of the two monomers catalyzed by a cationic tert-butylphosphine palladium catalyst also enabled precise changes in the molecular weight while keeping the functional group concentration constant. Molecular weight did not have a significant impact on hydroxide conductivity over the range of ~60–190 kg/mol (Mn). The optimized tetraaminophosphonium AEM had the highest conductivity for any tetraaminophosphonium polymer to date (70 ± 3 mS/cm at 80 °C). Clear phase separation and larger domains were observed for the phosphonium-based AEM compared to the ammonium at an identical composition, which is attributed to the larger occupied volume of the phosphorus cation. Fuel cell studies with the two membranes resulted in peak power densities of 1.59 and 0.79 W/cm2 for the ammonium and tetraaminophosphonium membrane electrode assemblies, respectively. The ammonium-based membrane was more water permeable as evidenced by water limiting current studies, which likely contributed to the improved performance.
- Research Organization:
- National Renewable Energy Laboratory (NREL), Golden, CO (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- Grant/Contract Number:
- SC0019445; AC36-08GO28308; DMR-1719875
- OSTI ID:
- 2301753
- Alternate ID(s):
- OSTI ID: 2324799
- Report Number(s):
- NREL/JA-5900-86720
- Journal Information:
- ACS Applied Energy Materials, Journal Name: ACS Applied Energy Materials Vol. 7 Journal Issue: 4; ISSN 2574-0962
- Publisher:
- American Chemical SocietyCopyright Statement
- Country of Publication:
- United States
- Language:
- English
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