Ion transport in sulfonated polymers

Park, Moon Jeong; Kim, Sung Yeon

doi:10.1002/polb.23257

Cited by 33 publications

(48 citation statements)

References 90 publications

(240 reference statements)

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“…At 30°C and low relative humidity (30,45, and 60% RH), the block copolymer at 50.0 vol % PIL has conductivities ∼92% higher than that of the homopolymer; however, the block copolymers at all other PIL compositions have lower hydroxide conductivities compared to the homopolymer at these humidities. Interestingly, at 30°C and 90% RH, the block copolymer at 50.0 vol % PIL has a lower conductivity than the homopolymer (∼52% less), while the block copolymer at 36.7 vol % PIL has higher conductivity (∼38% higher) than the homopolymer.…”

Section: ■ Experimental Sectionmentioning

confidence: 91%

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Bromide and Hydroxide Conductivity–Morphology Relationships in Polymerized Ionic Liquid Block Copolymers

Meek

Sharick

et al. 2015

Macromolecules

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A polymerized ionic liquid (PIL) diblock copolymer, poly (MMA-b-MEBIm-Br), was synthesized at various compositions from an ionic liquid monomer, (1-[(2-methacryloyloxy)ethyl]-3-butylimidazolium bromide) (MEBIm-Br), and a nonionic monomer, methyl methacrylate (MMA), via the reverse addition−fragmentation chain transfer (RAFT) polymerization technique. A hydroxide-conducting PIL diblock copolymer, poly(MMA-b-MEBIm-OH), was also prepared via anion exchange metathesis of the bromide-conducting block copolymer. In a former study, the conductivity and morphology of the bromide-and hydroxide-conducting PIL diblock copolymer were examined at one fixed PIL composition: 17.3 mol %. In this study, additional PIL compositions of (6.6, 11.9, and 26.5 mol %) were explored to fully understand the previous unusual conductivity results. Both bromide and hydroxide conductivities were higher in the PIL block copolymer at PIL compositions of 11.9, 17.3, and 26.5 mol % compared to the PIL homopolymer under the same experimental conditions, even though the homopolymer possessed a higher water and ionic content compared to the block copolymers. These unusual results suggest that the confinement of the PIL microdomain within the block copolymer morphology enhances ion transport compared to its predicted value. Morphology factors (or normalized ionic conductivity, f) were as high as >3 at some conditions, which is much higher than the maximum theoretical limit for randomly oriented lamellar domains (f = 2/3). Application of percolation theory revealed a 3−4-fold enhancement of conductivity when comparing the inherent conductivity to the measured PIL homopolymer conductivity. Both morphology factor analysis and percolation theory corroborate with the absolute conductivity results and the hypothesis that PIL domain confinement in PIL block copolymers enhances conductivity over its bulk properties. ■ INTRODUCTIONPolymerized ionic liquid (PIL) block copolymers are a relatively new class of polymer electrolytes, where the cation of the ionic liquid is covalently attached to one of the polymers in a block copolymer and the benefits of both PILs and block copolymers are combined. PILs possess unique properties, such as high solid-state ionic conductivity, high chemical, electrochemical, and thermal stability, and a widely tunable chemical platform, where significant changes in physical properties have been observed with subtle changes in chemistry. 1−5 When PILs are incorporated into the block copolymer, the resulting PIL block copolymer can possess orthogonal properties, such as high modulus (from the nonionic polymer) and high conductivity or transport (from the ionic polymer or PIL) through the self-assembly of two distinct polymers into welldefined nanostructures of long-range order with tunable morphology and domain size. 1,3,6−10 This has promoted the investigation of PIL block copolymers as thin films for organic electronic devices, 11−14 gas permeation membranes for CO 2 separations, 15,16 and solid-state polymer electrolytes for use in...

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Section: ■ Experimental Sectionmentioning

confidence: 91%

“…6,8,28,42,44,45 Weber et al 6 determined morphology factors in the range of 0.41−0.61 for a PIL composition of ϕ c = 0.5 with a lamellar morphology. This was slightly lower than the predicted f = 2/3 for randomly oriented lamellae.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Bromide and Hydroxide Conductivity–Morphology Relationships in Polymerized Ionic Liquid Block Copolymers

Meek

Sharick

et al. 2015

Macromolecules

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“…2a, the largest average d-value exceeding 5.2 mm (corresponding to e ¼ 2%) was achieved with a cycle time of 20 s for the actuator composed of the ionic liquid-integrated P17(75) copolymer, whereas 1.7 mm and 0.6 mm were obtained with the use of P17 (30) and P17 (20) copolymers, respectively. Without doubt, we can conclude that the increased amount of -SO 3 H groups promoted the dissociation of ionic liquids, thereby offering the capability to improve the actuator performance by facilitating ion transport in the polymer layer 44 . The displacements obtained for different ionic liquid concentrations are presented in Supplementary Fig.…”

Section: Resultsmentioning

confidence: 99%

Fast low-voltage electroactive actuators using nanostructured polymer electrolytes

2013

Self Cite

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Electroactive actuators have received enormous interest for a variety of biomimetic technologies ranging from robotics and microsensors to artificial muscles. Major challenges towards practically viable actuators are the achievement of large electromechanical deformation, fast switching response, low operating voltage and durable operation. Here we report a new electroactive actuator composed of self-assembled sulphonated block copolymers and ionic liquids. The new actuator demonstrated improvements in actuation properties over other polymer actuators reported earlier, large generated strain (up to 4%) without any signs of back relaxation. In particular, the millimetre-scale displacements obtained for the actuators, with rapid response (o1 s) at sub-1-V conditions over 13,500 cycles in air, have not been previously reported in the literature. The key to success stems from the evolution of the unique hexagonal structure of the polymer layer with domain size gradients beneath the cathode during actuation, which promotes the bending motion of the actuators.

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“…Proton exchange membrane (PEM) acts as a key component of PEMFC, which will directly dominate the performance and lifetime of the PEMFC [2].…”

Section: Introductionmentioning

confidence: 99%

Experiment and simulation studies on SPEEK PEM with different sulfonation degrees

Wang

2017

IOP Conf. Ser.: Earth Environ. Sci.

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Free-volume structure of fluoropolymerbased radiation-grafted electrolyte membranes investigated by positron annihilation lifetime spectroscopy S Sawada, A Kawasuso, M Maekawa et al. - Recent citationsPolymer coatings based on sulfonatedpoly-ether-ether-ketone films for implant dentistry applications R. S. Abstract. Effects of degrees of sulfonation (DS) on the cluster aggregation, proton conductivity and mechanical properties of sulfonated poly ether ether ketone (SPEEK) proton exchange membranes (PEMs) were investigated by experiment and simulation studies. SPEEK materials with different DS and the corresponding PEMs had been prepared by sulfonation and solution casting. The water uptake, swelling ratio, proton conductivity and mechanical properties of SPEEK PEMs were greatly affected by DS. And the hydrophilic cluster aggregation in SPEEK of different DS was revealed by molecular simulation. The relationship between structure and performance of SPEEK membrane provides theoretical guidance for the preparation of high performance proton exchange membranes. IntroductionBecause of high efficiency and zero emission, proton exchange membrane fuel cell (PEMFC) is believed to be alternative energy conversion devices in mobile vehicles and power generations [1]. Proton exchange membrane (PEM) acts as a key component of PEMFC, which will directly dominate the performance and lifetime of the PEMFC [2]. Compared with other commonly used PEM materials in PEMFC, sulfonated poly ether ether ketone (SPEEK), a kind of non-fluorinated material, possesses good chemical stability and thermal stability, low cost, and high mechanical stability. However, as is the case with most non-fluorinated material, SPEEK PEMs are limited by poor hydrophilic cluster morphology and insufficient proton conductivity, resulting from low hydrophilic/hydrophobic difference and rigidity of the polymer backbone [3]. It's well known that the increase of degrees of sulfonation (DS) would improve the hydrophilic cluster morphology and the proton conductivity as well. Nevertheless, serious deterioration in swelling and mechanical properties will be yielded by high DS. This study aim to investigate the effects of DS on the cluster aggregation, proton conductivity and mechanical properties of SPEEK PEMs by experiment and simulation studies.

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Ion transport in sulfonated polymers

Cited by 33 publications

References 90 publications

Bromide and Hydroxide Conductivity–Morphology Relationships in Polymerized Ionic Liquid Block Copolymers

Bromide and Hydroxide Conductivity–Morphology Relationships in Polymerized Ionic Liquid Block Copolymers

Fast low-voltage electroactive actuators using nanostructured polymer electrolytes

Experiment and simulation studies on SPEEK PEM with different sulfonation degrees

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