Gyroid structured aqua-sheets with sub-nanometer thickness enabling 3D fast proton relay conduction

Kobayashi, Tetsuo; Li, Yaxin; Ono, Ayaka; Zeng, Xiangbing; Ichikawa, Takahiro

doi:10.1039/c9sc00131j

Cited by 39 publications

(71 citation statements)

References 72 publications

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“…As anion species, tetrafluoroborate (BF 4 ), trifluoromethanesulfonate (Tf), and bis(trifluoromethane)sulfonimide (Tf 2 N) have been selected because they are known as useful anions for designing ionic liquids with a low glass transition temperature (T g ) [32]. As a cation part, a pyridinium cation has been employed since there have been several reports on the exhibition of Cub bi phases for pyridinium-based amphiphiles [33][34][35][36][37]. As a linker, we have selected a hexyl chain according to several researches on gemini-type amphiphiles [26][27][28][29][30][31].…”

Section: Resultsmentioning

confidence: 99%

Design of Ionic Liquid Crystals Forming Normal-Type Bicontinuous Cubic Phases with a 3D Continuous Ion Conductive Pathway

et al. 2019

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We have prepared a series of pyridinium-based gemini amphiphiles. They exhibit thermotropic liquid–crystalline behavior depending on their alkyl chain lengths and anion species. By adjusting the alkyl chain lengths and selecting suitable anions, we have obtained an ionic amphiphile that exhibits a normal-type bicontinuous cubic phase from 38 °C to 12 °C on cooling from an isotropic phase. In the bicontinuous cubic liquid–crystalline assembly, the pyridinium-based ionic parts align along a gyroid minimal surface forming a 3D continuous ionic domain while their ionophobic alkyl chains form 3D branched nanochannel networks. This ionic compound can form homogeneous mixtures with a lithium salt and the resultant mixtures keep the ability to form normal-type bicontinuous cubic phases. Ion conduction measurements have been performed for the mixtures on cooling. It has been revealed that the formation of the 3D branched ionophobic nanochannels does not disturb the ion conduction behavior in the ionic domain while it results in the conversion of the state of the mixtures from fluidic liquids to quasi-solids, namely highly viscous liquid crystals. Although the ionic conductivity of the mixtures is in the order of 10–7 S cm–1 at 40 °C, which is far lower than the values for practical use, the present material design has a potential to pave the way for developing advanced solid electrolytes consisting of two task-specific nanosegregated domains: One is an ionic liquid nano-domain with a 3D continuity for high ionic conductivity and the other is ionophobic nanochannel network domains for high mechanical strength.

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Section: Resultsmentioning

confidence: 99%

Design of Ionic Liquid Crystals Forming Normal-Type Bicontinuous Cubic Phases with a 3D Continuous Ion Conductive Pathway

et al. 2019

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“…Recently, Ichikawa and coworkers developed proton-conductive bicontinuous cubic LC polymer films, based on the self-assembly of polymerizable zwitterionic molecules and HTFSI in the presence of water [16]. The three-dimensionally continuous channel structures allowed significantly higher proton conduction of 9.9 × 10 −2 S cm −1 at 70 • C and lower activation energy of 2.2 kJ mol −1 attributable to proton conduction via the Grotthuss mechanism.…”

Section: Discussionmentioning

confidence: 99%

“…The binary mixtures of solid imidazolium-based zwitterionic salt and liquids by Yoshizawa and Ohno [12]. This concept was further extended to the design of high protonconductive thermotropic and lyotropic LC materials [13][14][15][16]. In addition, Watanabe and coworkers developed high proton-conducting protic ionic liquids by the neutralization of imidazole and HTFSI, which can be applicable to fuel cell electrolytes [17].…”

Section: Introductionmentioning

confidence: 99%

Ion-Conductive Nanostructured Polymer Films Formed by Photopolymerization of Lyotropic Columnar Liquid-Crystalline Monomers, Composed of a Zwitterionic Compound and a Protic Ionic Liquid

2020

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Here, we report on a new family of columnar nanostructured polymer films forming protic nanochannels that exhibit good ionic conductivities in the order of 10−4–10−3 S cm−1 at ambient temperature. These polymer films were obtained by the in situ photopolymerization of lyotropic columnar liquid crystals, consisting of a polymerizable taper-shaped zwitterionic compound and a protic ionic liquid (imidazolium bis(trifluoromethylsulfonyl)imide), in the presence of 15 wt% water. The composition of the protic ionic liquid in the mixture was changed from 40 to 60 mol%. The ionic conductivities were measured by an alternating current impedance method. The ionic conductivity increased with the increase of the protic ionic liquid. The conductivities of columnar nanostructured polymer films were about 2–3 orders of magnitude higher than those of amorphous polymer films prepared by photopolymerization of the corresponding monomers in an isotropic liquid state. The formation of nanochannels in the polymer matrices significantly enhanced the ion conduction. The present two-component lyotropic liquid-crystalline self-assembly followed by photopolymerization is a promising approach to the development of high ion-conductive polymer membranes.

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“…The conductivities of POPM are comparable and even superior to those in reported proton‐conductive materials. [ 21,35,36 ] The increment of proton conductivity with hydration level is mainly attributed that higher level of water adsorption creates more hydrogen‐bonded pathways for proton transfer. [ 36 ] As comparison, proton conductivity of POPM without phosphoric acid was measured at 25 °C under 98% RH.…”

Section: Figurementioning

confidence: 99%

Flexible Porous Organic Polymer Membranes for Protonic Field‐Effect Transistors

Zhong

et al. 2020

Advanced Materials

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Artificial transistors represent an ideal means for meeting the requirements in interfacing with biological systems. It is pivotal to develop new proton‐conductive materials for the transduction between biochemical events and electronic signals. Herein, the first demonstration of a porous organic polymer membrane (POPM) as a proton‐conductive material for protonic field‐effect transistors is presented. The POPM is readily prepared through a thiourea‐formation condensation reaction. Under hydrated conditions and at room temperature, the POPM delivers a proton mobility of 5.7 × 10−3 cm2 V−1 s−1; the charge carrier densities are successfully modulated from 4.3 × 1017 to 14.1 × 1017 cm−3 by the gate voltage. This study provides a type of promising modular proton‐conductive materials for bioelectronics application.

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Gyroid structured aqua-sheets with sub-nanometer thickness enabling 3D fast proton relay conduction

Abstract: We have succeeded in creating gyroid-nanostructured polymer films having a 3D continuous proton conduction pathway.

Cited by 39 publications

References 72 publications

Design of Ionic Liquid Crystals Forming Normal-Type Bicontinuous Cubic Phases with a 3D Continuous Ion Conductive Pathway

Design of Ionic Liquid Crystals Forming Normal-Type Bicontinuous Cubic Phases with a 3D Continuous Ion Conductive Pathway

Ion-Conductive Nanostructured Polymer Films Formed by Photopolymerization of Lyotropic Columnar Liquid-Crystalline Monomers, Composed of a Zwitterionic Compound and a Protic Ionic Liquid

Flexible Porous Organic Polymer Membranes for Protonic Field‐Effect Transistors

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