Thesis etd-01102011-112943 |
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Thesis type
Tesi di dottorato di ricerca
Author
FILPI, ANTONIO
URN
etd-01102011-112943
Thesis title
Synthesis and Physico-Chemical characterization of anion-exchange polymeric materials for electrochemical applications
Academic discipline
CHIM/05
Course of study
SCIENZE CHIMICHE
Supervisors
tutor Prof. Ciardelli, Francesco
Keywords
- AMFC
- electrochemistry
- Fuel Cell
- ion-exchange
- PEMFC
- SBS
Graduation session start date
27/01/2011
Availability
Full
Summary
In the last few years a number of new anion-exchange polymers have been developed, offering the possibility of assembling Membrane Electrode Assemblies (MEAs) to develop Anion-exchange Membrane Fuel Cells (AMFCs) and Anion-exchange Membrane-based Electrolyzers (AMEs).
The current technologies of Anion Exchange Materials (AMs) for electrochemical application shows several limitations relate to the possibility of obtaining a reasonable low cost membrane having: high ionic conductivity, chemical stability in strong alkaline media, low permeability, low water swelling and good mechanical properties.
The purpose of this study was to develop and characterize AMs based on Styrene–butadiene–styrene (SBS) copolymer, a thermoplastic material with a block structure widely employed in the rubber industry. In the present work is reported a controlled radical functionalization, initiated by benzoyl peroxide (BPO), of SBS with 4-vinylbenzyl chloride (VBC). The resulting thermoplastic polymer was converted into an anion exchange membrane via quaternization reaction with aliphatic amines, such as trimethylamine or
1,4-diazabicyclo[2.2.2]octane (DABCO). Electrochemical properties of these materials were measured and correlated with synthetic parameters. Correlations between transport properties and synthetic parameters were explained in terms of Cluster-Network morphological model. Performance of the synthesized SBS-based AMs were then evaluated in a working AMFC and compared with commercial materials. Diagnostics on AMFCs, by means of electrochemical impedance spectroscopy (EIS), were performed in order to evaluate measured performances.
The current technologies of Anion Exchange Materials (AMs) for electrochemical application shows several limitations relate to the possibility of obtaining a reasonable low cost membrane having: high ionic conductivity, chemical stability in strong alkaline media, low permeability, low water swelling and good mechanical properties.
The purpose of this study was to develop and characterize AMs based on Styrene–butadiene–styrene (SBS) copolymer, a thermoplastic material with a block structure widely employed in the rubber industry. In the present work is reported a controlled radical functionalization, initiated by benzoyl peroxide (BPO), of SBS with 4-vinylbenzyl chloride (VBC). The resulting thermoplastic polymer was converted into an anion exchange membrane via quaternization reaction with aliphatic amines, such as trimethylamine or
1,4-diazabicyclo[2.2.2]octane (DABCO). Electrochemical properties of these materials were measured and correlated with synthetic parameters. Correlations between transport properties and synthetic parameters were explained in terms of Cluster-Network morphological model. Performance of the synthesized SBS-based AMs were then evaluated in a working AMFC and compared with commercial materials. Diagnostics on AMFCs, by means of electrochemical impedance spectroscopy (EIS), were performed in order to evaluate measured performances.
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