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Towards alkali-stable polymers and hydroxide exchange membranes functionalized with alicyclic quaternary ammonium cations

Pham, Thanh Huong LU (2019)
Abstract
In the current work, cationic polymers functionalized with N-alicyclic quaternary ammonium (QA) cations were synthesized and characterized as potential hydroxide exchange membranes (HEMs) for application in fuel cells. Three different polymers, namely poly(arylene ether sulfone), spiro-ionene and poly(arylene alkylene), were explored as polymer backbones for the HEMs. Various mono- and spirocyclic QA cations were incorporated either within the backbone, directly on the backbone or via spacers. The synthesis of these
polymers was a great challenge which was overcome with the help of numerous synthetic methods. Radical bromination, hydroboration and Suzuki coupling were employed when synthesizing the monomers. The backbone polymers were... (More)
In the current work, cationic polymers functionalized with N-alicyclic quaternary ammonium (QA) cations were synthesized and characterized as potential hydroxide exchange membranes (HEMs) for application in fuel cells. Three different polymers, namely poly(arylene ether sulfone), spiro-ionene and poly(arylene alkylene), were explored as polymer backbones for the HEMs. Various mono- and spirocyclic QA cations were incorporated either within the backbone, directly on the backbone or via spacers. The synthesis of these
polymers was a great challenge which was overcome with the help of numerous synthetic methods. Radical bromination, hydroboration and Suzuki coupling were employed when synthesizing the monomers. The backbone polymers were obtained by polyetherification, cyclo-polycondensation and super acid-mediated
polyhydroxyalkylation. The mono- and spirocyclic QA cations were incorporated by quaternization and cycloquaternization, respectively.
The HEMs were characterized with regard to morphology, hydroxide conductivity, water uptake, thermal and thermochemical stability, i.e., the key properties that determine the performance and durability of the HEMs as electrolytes for hydroxide exchange membrane fuel cells. Studying the change in the properties as different chemical and structural features of the HEMs varied gave valuable insights into the structure-property relationships of theses materials, paving the way for further development of high performance HEMs for FC applications.
In this work, HEMs based on poly(arylene alkylene) functionalized with dimethylpiperidinium via spacers were found to possess the most attractive combination of properties. They had high hydroxide conductivities (103-
146 mS cm-1) and still maintained a reasonable water uptake (73-103%). Most importantly, they were exceptionally stable under alkaline conditions at elevated temperatures, with less than 5% ionic loss after 720 h of storage in 2 M NaOH solution at 90 °C. (Less)
Please use this url to cite or link to this publication:
author
supervisor
opponent
  • Dr. Meier-Haack, Jochen, Leibnitz Institute of Polymer Research, Germany
organization
publishing date
type
Thesis
publication status
submitted
keywords
hydroxide exchange membrane, fuel cell, alicyclic quaternary ammonium, alkali-stable, high hydroxide conductivity, structure-property relationship
pages
172 pages
publisher
Centre for Analysis and Synthesis, Department of Chemistry, Lund University
defense location
Lecture hall KC:B Kemicentrum, Naturvetarvägen 14, Lund University, Faculty of Engineering LTH
defense date
2019-10-24 10:15
ISBN
978-91-7422-687-4
978-91-7422-686-7
language
English
LU publication?
yes
id
4f90f71f-d138-48d6-8a02-bc12e8b8bafe
date added to LUP
2019-09-20 16:08:38
date last changed
2019-09-30 10:13:43
@phdthesis{4f90f71f-d138-48d6-8a02-bc12e8b8bafe,
  abstract     = {In the current work, cationic polymers functionalized with N-alicyclic quaternary ammonium (QA) cations were synthesized and characterized as potential hydroxide exchange membranes (HEMs) for application in fuel cells. Three different polymers, namely poly(arylene ether sulfone), spiro-ionene and poly(arylene alkylene), were explored as polymer backbones for the HEMs. Various mono- and spirocyclic QA cations were incorporated either within the backbone, directly on the backbone or via spacers. The synthesis of these<br/>polymers was a great challenge which was overcome with the help of numerous synthetic methods. Radical bromination, hydroboration and Suzuki coupling were employed when synthesizing the monomers. The backbone polymers were obtained by polyetherification, cyclo-polycondensation and super acid-mediated<br/>polyhydroxyalkylation. The mono- and spirocyclic QA cations were incorporated by quaternization and cycloquaternization, respectively.<br/>The HEMs were characterized with regard to morphology, hydroxide conductivity, water uptake, thermal and thermochemical stability, i.e., the key properties that determine the performance and durability of the HEMs as electrolytes for hydroxide exchange membrane fuel cells. Studying the change in the properties as different chemical and structural features of the HEMs varied gave valuable insights into the structure-property relationships of theses materials, paving the way for further development of high performance HEMs for FC applications.<br/>In this work, HEMs based on poly(arylene alkylene) functionalized with dimethylpiperidinium via spacers were found to possess the most attractive combination of properties. They had high hydroxide conductivities (103-<br/>146 mS cm-1) and still maintained a reasonable water uptake (73-103%). Most importantly, they were exceptionally stable under alkaline conditions at elevated temperatures, with less than 5% ionic loss after 720 h of storage in 2 M NaOH solution at 90 °C.},
  author       = {Pham, Thanh Huong},
  isbn         = {978-91-7422-687-4},
  keyword      = {hydroxide exchange membrane,fuel cell,alicyclic quaternary ammonium,alkali-stable,high hydroxide conductivity,structure-property relationship},
  language     = {eng},
  pages        = {172},
  publisher    = {Centre for Analysis and Synthesis, Department of Chemistry, Lund University},
  school       = {Lund University},
  title        = {Towards alkali-stable polymers and hydroxide exchange membranes functionalized with alicyclic quaternary ammonium cations},
  year         = {2019},
}