Perfluorocyclobutyl-containing multiblock copolymers to induce enhanced hydrophilic/hydrophobic phase separation and high proton conductivity at low humidity

Ahn, Su Min; Kim, Tae Hyeong; Yuk, Jinok; Jeong, Hwan Yeop; Yu, Duk Man; Hong, Sung–Kwon; Hong, Yong Taik; Lee, Jong-Chan; Kim, Sang Woo

doi:10.1016/j.memsci.2021.119892

Cited by 18 publications

(4 citation statements)

References 81 publications

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“…Fluorine-containing multiblock copolymers are being actively studied as ion-conducting media, such as proton exchange membranes [25,26]. The introduction of fluorine atoms considerably increases the contrast between hydrophilic and hydrophobic moieties, thus promoting a well-developed microphase separation [27][28][29]. Of interest are also fluorocopolymers containing blocks with different degrees of flexibility that are prone to the liquid-crystalline type of self-assembly [30].…”

Section: Introductionmentioning

confidence: 99%

Effect of Chain Structure on the Various Properties of the Copolymers of Fluorinated Norbornenes with Cyclooctene

et al. 2023

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Fluorinated polymers are attractive due to their special thermal, surface, gas separation, and other properties. In this study, new diblock, multiblock, and random copolymers of cyclooctene with two fluorinated norbornenes, 5-perfluorobutyl-2-norbornene and N-pentafluorophenyl-exo-endo-norbornene-5,6-dicarboximide, are synthesized by ring-opening metathesis copolymerization and macromolecular cross-metathesis in the presence of the first- to third-generation Grubbs’ Ru-catalysts. Their thermal, surface, bulk, and solution characteristics are investigated and compared using differential scanning calorimetry, water contact angle measurements, gas permeation, and light scattering, respectively. It is demonstrated that they are correlated with the chain structure of the copolymers. The properties of multiblock copolymers are generally closer to those of diblock copolymers than of random ones, which can be explained by the presence of long blocks capable of self-organization. In particular, diblock and multiblock fluorine-imide-containing copolymers show a tendency to form micelles in chloroform solutions well below the overlap concentration. The results obtained may be of interest to a wide range of researchers involved in the design of functional copolymers.

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Section: Introductionmentioning

confidence: 99%

Effect of Chain Structure on the Various Properties of the Copolymers of Fluorinated Norbornenes with Cyclooctene

et al. 2023

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“…Hence, recent advances focus on the architecture optimization of aromatic-based PEMs to construct efficient proton nanochannels. For example, Holdcroft, Pang, and Guiver et al have reported a series of densely grafted and comb-shaped aromatic PEMs, and these studies favored optimizing the ionic functional side chains. − Guiver and Kim et al reported that the block copolymers facilitate the micromorphology regulation due to the intrinsic polarity discrimination between different segments. , Notwithstanding these laboratory-scale efforts, most of them commonly employed complex preparation routes (multistep reactions) and harsh reaction conditions (high temperature, metal catalyst, etc.). Hence quantity production is still in desired.…”

Section: Introductionmentioning

confidence: 99%

“…15−18 ments. 19,20 Notwithstanding these laboratory-scale efforts, most of them commonly employed complex preparation routes (multistep reactions) and harsh reaction conditions (high temperature, metal catalyst, etc.). Hence quantity production is still in desired.…”

Section: Introductionmentioning

confidence: 99%

Development of a High-Performance Proton Exchange Membrane: From Structural Optimization to Quantity Production

Zhang

et al. 2022

Ind. Eng. Chem. Res.

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Quantity production of low-cost and high-performance proton exchange membranes (PEMs) used in hydrogen fuel cells is the centerpiece step toward the hydrogen future. Herein, we developed a facile synthesis approach for this task. The prepared PEM breaks through the unfavorable trade-off between thermaldimensional stability and proton conductivity due to the adequately designed hierarchical polymer structure composed of flexible ionic side-chains anchored onto twisted rigid backbone. Microscale topology structure analyses and molecular dynamics simulations indicate that the hydrated ionic groups self-assemble to form well-connected proton nanochannels. More importantly, the quantity production of the PEM is allowed with a pilot-scale production line. The PEM reaches a peak power density of 1.2 W cm −2 under the realistic low fuel gas flow in a single-cell of H 2 /O 2 fuel cell. Additionally, the PEM maintains profitable fuel cell performance under lower relative humidity (1.1 and 0.9 W cm −2 peak power density at 80 and 60% relative humidity, respectively). In short, we report that a canonical form from the structural optimization of a PEM to the pilot-scale production in which the micromorphology-proton conduction relationship is fully explored.

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“…Permeability is also affected by the liquid water being subjected to PEMWE, which functions as a plasticizer, lowering T g and increasing PEM permeability . The amphiphilic nature of a PEM induces a hydrophilic/hydrophobic phase separation, where the proton is transported through hydrophilic channels. , Although hydrogen permeation occurs in both the hydrophilic and hydrophobic domains of a PEM, hydrogen permeates through the water-bearing hydrophilic domains with lower activation energy. , Therefore, designing the PEM morphology by promoting high σ while maintaining low hydrogen permeability ( P H2 ) is the key to achieving PEMWE with efficient performance, durability, and safety.…”

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confidence: 99%

Highly Sulfonated Aromatic Graft Polymer with Very High Proton Conductivity and Low Hydrogen Permeability for Water Electrolysis

et al. 2022

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An aromatic graft polymer was synthesized for a proton exchange membrane (PEM) by grafting a highly sulfonated poly(phenylene sulfide sulfone) side chain onto a poly(arylene ether sulfone) main chain, thus creating a phase-separated morphology with cocontinuous channels of small hydrophilic ion domains. The graft PEM with the distinct hydrophilic/hydrophobic-separated morphology showed low hydrogen permeability while maintaining high proton conductivity. Along with durable dimensional, mechanical, and thermohydrolytic stabilities, the graft PEM showed effective properties for PEM water electrolysis (PEMWE). The graft PEM afforded a PEMWE performance of 6000 mA cm–2 at 1.9 V, which was 2.1-fold higher than that of N212, and showed a durable performance without loss for 50 h at a high current density (1000 mA cm–2).

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Perfluorocyclobutyl-containing multiblock copolymers to induce enhanced hydrophilic/hydrophobic phase separation and high proton conductivity at low humidity

Cited by 18 publications

References 81 publications

Effect of Chain Structure on the Various Properties of the Copolymers of Fluorinated Norbornenes with Cyclooctene

Effect of Chain Structure on the Various Properties of the Copolymers of Fluorinated Norbornenes with Cyclooctene

Development of a High-Performance Proton Exchange Membrane: From Structural Optimization to Quantity Production

Highly Sulfonated Aromatic Graft Polymer with Very High Proton Conductivity and Low Hydrogen Permeability for Water Electrolysis

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