Comb-shaped polymers to enhance hydroxide transport in anion exchange membranes

Li, Nanwen; Yan, Tingzi; Li, Zheng; Thurn‐Albrecht, Thomas; Binder, Wolfgang H.

doi:10.1039/c2ee22050d

Cited by 340 publications

(254 citation statements)

References 39 publications

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“…As shown in Figure 14a, comb-shaped poly(2,6-dimethyl-1,4-phenylene oxide)s (PPO) with quaternary ammonium (QA) groups 30 and long alkyl side chains have been synthesized by bromination and amination reaction from inexpensive starting materials. 17,119 The unique polymer architecture results in nanophase separation between the conducting (quaternized PPO) and nonconducting domains (grafted alkyl chains) as confirmed by small-angle X-ray scattering (SAXS) ( Figure 14c) 119 and thus gives rise to high anion conductivities. An important characteristic is that the comb-shaped membranes exhibited a much lower water uptake (10−20 wt %) but a comparable conductivity compared with the values reported for many QA-AEMs in the hydroxide form.…”

Section: Anion Exchange Membranesmentioning

confidence: 99%

“…A number of well-defined copolymer architectures having nanochannels for anionic transport (block, 16 graft copolymers 17,119 ) have been reported in the literature. For practical applications, an anionic conductivity of >50 mS cm at 80°C needs to be achieved.…”

Section: Outlook and Future Prospectsmentioning

confidence: 99%

“…Li et al 17,119 prepared highly stable comb-shaped anion exchange membranes with improved anionic conductivities. As shown in Figure 14a, comb-shaped poly(2,6-dimethyl-1,4-phenylene oxide)s (PPO) with quaternary ammonium (QA) groups 30 and long alkyl side chains have been synthesized by bromination and amination reaction from inexpensive starting materials.…”

Section: Anion Exchange Membranesmentioning

confidence: 99%

“…Several key membrane hurdles must be overcome, namely, improving chemical, dimensional, and mechanical stability and hydroxide conductivity in membranes, to produce high power density devices with long operational lifetimes. 3,4 Therefore, the control of morphology and thus improvement of ionic transport in both aromatic copolymer-based PEMs 2,14 and AEMs 16,17 have been under intense investigation. In this Perspective, we highlight the morphological development in sulfonated and quaternized aromatic copolymers and observations on their solid-state structures.…”

Section: Introductionmentioning

confidence: 99%

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Ion Transport by Nanochannels in Ion-Containing Aromatic Copolymers

2014

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/npsi/ctrl?lang=en http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/ctrl?lang=fr Access and use of this website and the material on it are subject to the Terms and Conditions set forth at http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/jsp/nparc_cp.jsp?lang=en NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur. For the publisher's version, please access the DOI link below./ Pour consulter la version de l'éditeur, utilisez le lien DOI ci-dessous.http://dx.doi.org/10.1021/ma402254h Macromolecules, 47, 7, pp. 2175Macromolecules, 47, 7, pp. -2198Macromolecules, 47, 7, pp. , 2014 Ion transport by nanochannels in ion-containing aromatic copolymers Li, Nanwen; Guiver, Michael D. Ion Transport by Nanochannels in Ion-Containing Aromatic CopolymersThe search for the next generation of highly ion-conducting polymer electrolyte membranes has been a subject of intense research because of their potential applications in energy storage and transformation devices, such as fuel cells, vanadium flow batteries, membrane-based artificial photosynthesis, water electrolysis, or water treatment processes such as electrodialysis desalination. Nanochannels that contain ionic groups, through which "hydrated" ions can pass, are believed to be of key importance for efficient ion transport in polymer electrolytes membranes. In this Perspective, we present an overview of the approaches to induce ion-conducting nanochannel formation by selfassembly, using polymer architecture such as block or combshaped copolymers. The transport properties of ion-containing aromatic copolymers are examined to obtain an insight into the fundamental behavior of these materials, which are targeted toward applications in fuel cells and other electrochemical devices. Challenges in obtaining well-defined nanochannel morphologies, and possible strategies to improve transport properties in aromatic copolymers having structures with the potential to withstand operation in electrochemical/chemical devices, are discussed. Opportunities for the application of ion-containing aromatic copolymer membranes in fuel cells, vanadium flow batteries, membrane-based artificial photosynthesis, electrolysis, and electrodialysis are also reviewed. Research needs for further improvements in ionic conductivity and durability, and their applications are identified.

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Section: Anion Exchange Membranesmentioning

confidence: 99%

Section: Outlook and Future Prospectsmentioning

confidence: 99%

Section: Anion Exchange Membranesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Ion Transport by Nanochannels in Ion-Containing Aromatic Copolymers

2014

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“…More recently, Li et al showed that changing the cation from quaternary benzyl trimethylammonium (TMA + ) to quaternary benzyl N,N-F687 dimethylhexylammonium (DMH + ) on a PPO backbone mitigated the backbone hydrolysis degradation mode. 36,37 Additionally, crosslinking PPO with quaternary benzyl DMH + cations further enhanced AEM mechanical stability in alkaline solutions. 18 We found these results surprising given that we had shown that changing the electron donating character of cation group at the benzyl position on a PSF backbone did not influence cleavage of the polymer backbone.…”

mentioning

confidence: 99%

Mechanically Stable Poly(arylene ether) Anion Exchange Membranes Prepared from Commercially Available Polymers for Alkaline Electrochemical Devices

Arges

Wang

Jung

et al. 2015

J. Electrochem. Soc.

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The alkaline stability of poly(arylene ether) backbones in anion exchange polymer electrolyte membranes (AEMs) derivatized with quaternary benzyl N, N-dimethylhexylammmonium (DMH + ) and trimethylammonium (TMA + ) cation groups were investigated in poly(2,6-dimethyl 1,4-phenylene) oxide (PPO) and Udel polysulfone (PSF) polymers. Previous studies have demonstrated that quaternary ammonium and phosphonium groups trigger backbone degradation in commercially available poly(arylene ether)-based AEMs, despite the base polymers being resilient to alkaline solutions. Herein, we demonstrate that the electron withdrawing or donating character in the poly(arylene ether) backbone ultimately decides whether or not the prepared AEMs will become brittle in alkaline media due to cation triggered backbone degradation. Mitigation of cation triggered backbone degradation was only achieved when electron withdrawing substituents (not including the cation), such as sulfone or bromine groups, were eliminated from the polymer backbone (or, alternately, when electron donating groups were present). Hence, PPO AEMs prepared through chloromethylation, as opposed to free radical bromination, were resistant to backbone hydrolysis in alkaline media because each cation-functionalized repeat unit had two electron donating methyl groups rather than a single methyl group. In summary, this paper presents some design rules for preparing mechanically stable poly(arylene ether) AEMs from low cost, commercially available polymers for alkaline electrochemical devices.

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Electrospun Ionomeric Fibers with Anion Conducting Properties

Mann‐Lahav

Halabi

Shter

et al. 2019

Adv Funct Materials

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Anion conductive nanofiber mats from FAA-3 ionomers are obtained by electrospinning. Depending on the solvent used in the precursor solution, nanofibers with either nonhollow cylindrical or flat ribbon-like cross-sections are prepared. The anion conductivity and water uptake of the ionomeric nanofiber mats are measured as a function of the relative humidity in the 10-90% range and compared to that of a solid membrane cast from the same ionomer. In addition, the anion conductivity of an isolated single fiber of the ionomer is measured for the first time. The anion conductivity of the electrospun single fiber is found to be higher than that of the mats, which is, in turn, one order of magnitude higher than that of the solid ionomer membrane. The higher conductivity of the mats relative to the solid membrane (in both inplane and through-plane directions) is found to be related to the variation in water uptake, which stems from the morphological distinctions. These results increase the understanding of the electrospinning process of ionomers, toward the development and design of new anion conductive ionomer fibers, useful for high performance electrochemical devices.

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Comb-shaped polymers to enhance hydroxide transport in anion exchange membranes

Cited by 340 publications

References 39 publications

Ion Transport by Nanochannels in Ion-Containing Aromatic Copolymers

Ion Transport by Nanochannels in Ion-Containing Aromatic Copolymers

Mechanically Stable Poly(arylene ether) Anion Exchange Membranes Prepared from Commercially Available Polymers for Alkaline Electrochemical Devices

Electrospun Ionomeric Fibers with Anion Conducting Properties

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