Nanoparticle-Driven Assembly of Highly Conducting Hybrid Block Copolymer Electrolytes

Villaluenga, Irune; Chen, X. Chelsea; Devaux, Didier; Hallinan, Daniel T.; Balsara, Nitash P.

doi:10.1021/ma502234y

Cited by 71 publications

(87 citation statements)

References 27 publications

(41 reference statements)

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“…13-nm and 9-nm domain sizes for HR- [1] [2] 200 , and the segregated domains observed in TEM imaging are too large for a corresponding peak, if present, to be resolved in these SAXS profiles. As stated in other reports (71)(72)(73), the synthesis of block copolymers alone is not enough to ensure high ionic conductivity in AAEMs. It is also necessary to optimize membrane processing conditions to produce AAEMs with microphase separations that provide continuous ion transport channels.…”

Section: Resultsmentioning

confidence: 81%

Highly conductive and chemically stable alkaline anion exchange membranes via ROMP of trans -cyclooctene derivatives

You

Padgett

MacMillan

et al. 2019

Proc. Natl. Acad. Sci. U.S.A.

125

107

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Alkaline anion exchange membranes (AAEMs) are an important component of alkaline exchange membrane fuel cells (AEMFCs), which facilitate the efficient conversion of fuels to electricity using nonplatinum electrode catalysts. However, low hydroxide conductivity and poor long-term alkaline stability of AAEMs are the major limitations for the widespread application of AEMFCs. In this paper, we report the synthesis of highly conductive and chemically stable AAEMs from the living polymerization of trans-cyclooctenes. A trans-cyclooctene-fused imidazolium monomer was designed and synthesized on gram scale. Using these highly ring-strained monomers, we produced a range of block and random copolymers. Surprisingly, AAEMs made from the random copolymer exhibited much higher conductivities than their block copolymer analogs. Investigation by transmission electron microscopy showed that the block copolymers had a disordered microphase segregation which likely impeded ion conduction. A cross-linked random copolymer demonstrated a high level of hydroxide conductivity (134 mS/cm at 80°C). More importantly, the membranes exhibited excellent chemical stability due to the incorporation of highly alkaline-stable multisubstituted imidazolium cations. No chemical degradation was detected by 1 H NMR spectroscopy when the polymers were treated with 2 M KOH in CD 3 OH at 80°C for 30 d.alkaline anion exchange membrane | trans-cyclooctene | block and random copolymer | cross-linked polymer | transmission electron microscopy A lkaline anion exchange membranes (AAEMs) are a class of polymer electrolytes constructed from immobilized cations with hydroxide counteranions (1-3). AAEMs have been widely used for a variety of electrochemical applications, such as redox flow batteries, electrodialysis, and water electrolysis (4-7). One of the most important applications for AAEMs is their use as polyelectrolytes in alkaline exchange membrane fuel cells (AEMFCs). These devices can efficiently convert chemical energy in fuels (e.g., H 2 , hydrazine, and direct alcohols) into electricity. In comparison with proton exchange membrane fuel cells and aqueous alkaline fuel cells, AEMFCs are advantageous because they allow for rapid reduction of oxygen at the cathode, limit fuel cross-over, prevent the formation of carbonate precipitates, and are compatible with nonnoble electrocatalysts (8-12). Because of their essential role in AEMFCs, AAEMs have been extensively studied to optimize their performance and, in particular, to improve their hydroxide conductivity and alkaline stability.Hydroxide conductivity is one of the most important parameters used to evaluate AAEMs, because it is directly related to the ohmic resistance and power density of an AEMFC (9). There are several strategies to enhance the hydroxide conductivity of AAEMs. The most straightforward method is to increase the ion exchange capacity (IEC), such that more ions are present in AAEMs. However, a higher IEC typically results in higher water uptake. While the presence of water facilitates h...

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Section: Resultsmentioning

confidence: 81%

Highly conductive and chemically stable alkaline anion exchange membranes via ROMP of trans -cyclooctene derivatives

You

Padgett

MacMillan

et al. 2019

Proc. Natl. Acad. Sci. U.S.A.

125

107

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“…ForS VP97K-2 with aS iW content of 8.4 wt %, its morphology represents atransient state between discrete and percolated ( Figure 2c). [16,19] Such structures are stable under thermal annealing at 120 8 8C for 48 h. Notably,t he phase transition is accompanied by adecrease in the P2VP/SiW domain distances,which are 61.8, 45.8, and 32.9 nm for SVP97K-1, -3, and -5, respectively ( Figure S5 b-d), which reflects an increase in the interfacial areas between the PS domain and the P2VP/SiW domain that is due to the SiW-induced electrostatic cross-linking of the P2VP chains.T he cross-linking is also indicated by the vanished glass transition of P2VP ( Figure S12). Furthermore, the SAXS profile of SVP97K-5 only features one broad primary peak without high-order peaks ( Figure S6 a), which is indicative of atypical disordered bicontinuous structure.…”

Section: Angewandte Chemiementioning

confidence: 99%

“…Furthermore, the SAXS profile of SVP97K-5 only features one broad primary peak without high-order peaks (Figure S6 a), which is indicative of atypical disordered bicontinuous structure. [16,19] Such structures are stable under thermal annealing at 120 8 8C for 48 h. Notably,t he phase transition is accompanied by adecrease in the P2VP/SiW domain distances,which are 61.8, 45.8, and 32.9 nm for SVP97K-1, -3, and -5, respectively ( Figure S5 b-d), which reflects an increase in the interfacial areas between the PS domain and the P2VP/SiW domain that is due to the SiW-induced electrostatic cross-linking of the P2VP chains.T he cross-linking is also indicated by the vanished glass transition of P2VP ( Figure S12). Theincreased interfacial areas lead to large f values for the percolated domains;for example,the f value of the P2VP/SiW domain in SVP97K-5 reaches 50.7 % ( Table 1).…”

Section: Angewandte Chemiementioning

confidence: 99%

“…[16,17] Fore xample,H illmyer,L odge,a nd co-workers reported ap olymerization-inducedp hase separation approach to obtain disordered bicontinuous polymer electrolytes by cross-linking ab lock during the growth of the block copolymer. [18,19] Although the above studies have made notable progress in fabricating bicontinuous structures,t hese strategies still require either relatively complex polymerization reactions or delicate modifications of nanoparticles.T hus af acile way to access bicontinuous structures is in high demand. [18,19] Although the above studies have made notable progress in fabricating bicontinuous structures,t hese strategies still require either relatively complex polymerization reactions or delicate modifications of nanoparticles.T hus af acile way to access bicontinuous structures is in high demand.…”

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confidence: 99%

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Inorganic‐Macroion‐Induced Formation of Bicontinuous Block Copolymer Nanocomposites with Enhanced Conductivity and Modulus

et al. 2017

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A facile and electrostatically driven approach has been developed to prepare bicontinuous polymer nanocomposites that is based on the polyoxometalate (POM) macroion induced phase transition of PS-b-P2VP from an initial lamellar phase to a stable bicontinuous phase. The multi-charged POMs can electrostatically cross-link P2VP blocks and give rise to bicontinuous phases in which the POM hybrid conductive domains occupy a large volume fraction of more than 50 %. Furthermore, the POMs can give rise to high proton conductivity and serve as nanoenhancers, endowing the bicontinuous nanocomposites with a conductivity of 0.1 mS cm and a Young's modulus of 7.4 GPa at room temperature; these values are greater than those of pristine PS-b-P2VP by two orders of magnitude and a factor of 1.8, respectively. This approach can provide a new concept based on electrostatic control to design functional bicontinuous polymer materials.

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“…Recently, it has been shown that the bicontinuous gyroidal phase is the optimal phase for Li + ion conduction. 214 We envision achieving such bicontinuous structures through the assembly of polymer nanoparticles. For example, it has been shown that particle films derived from latex particles containing poly(styrenesulfonic acid) show superior proton conductivity compared to polymer membranes with similar charge content.…”

Section: Impact On Functional Materialsmentioning

confidence: 99%

Polymer Nanoparticle Assemblies: A Versatile Route to Functional Mesostructures

et al. 2015

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Fabricating macromolecular mesoscale assemblies containing disparate components with targeted molecular order for each of the components on the nanoscale and targeted assembly of the components in the mesoscale is a challenge. In this Perspective, we explore the self-assembly of polymer nanoparticles as a viable route to obtain tunable mesostructured materials. We describe the state-of-the-art methods available for and the challenges to obtain spherical and nonspherical polymer nanoparticles. We discuss the predicted ordered assemblies and disordered assemblies of nanoparticles and the challenges to obtain these assemblies in polymer nanoparticles. We also comment on the rich and future opportunities in the burgeoning field of polymer nanoparticle assemblies.

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Nanoparticle-Driven Assembly of Highly Conducting Hybrid Block Copolymer Electrolytes

Cited by 71 publications

References 27 publications

Highly conductive and chemically stable alkaline anion exchange membranes via ROMP of trans -cyclooctene derivatives

Highly conductive and chemically stable alkaline anion exchange membranes via ROMP of trans -cyclooctene derivatives

Inorganic‐Macroion‐Induced Formation of Bicontinuous Block Copolymer Nanocomposites with Enhanced Conductivity and Modulus

Polymer Nanoparticle Assemblies: A Versatile Route to Functional Mesostructures

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