Porous
crystalline materials such as covalent organic frameworks
and metal–organic frameworks have garnered considerable attention
as promising ion conducting media. However, most of them additionally
incorporate lithium salts and/or solvents inside the pores of frameworks,
thus failing to realize solid-state single lithium-ion conduction
behavior. Herein, we demonstrate a lithium sulfonated covalent organic
framework (denoted as TpPa-SO
3
Li) as a new class of solvent-free, single lithium-ion
conductors. Benefiting from well-designed directional ion channels,
a high number density of lithium-ions, and covalently tethered anion
groups, TpPa-SO
3
Li exhibits an ionic conductivity of 2.7 × 10–5 S cm–1 with a lithium-ion transference number
of 0.9 at room temperature and an activation energy of 0.18 eV without
additionally incorporating lithium salts and organic solvents. Such
unusual ion transport phenomena of TpPa-SO
3
Li allow reversible and stable lithium
plating/stripping on lithium metal electrodes, demonstrating its potential
use for lithium metal electrodes.
Supramolecular self-assembly enables access to designer soft materials that typically exhibit high-symmetry packing arrangements, which optimize the interactions between their mesoscopic constituents over multiple length scales. We report the discovery of an ionic small molecule surfactant that undergoes water-induced selfassembly into spherical micelles, which pack into a previously unknown, low-symmetry lyotropic liquid crystalline Frank-Kasper σ phase. Small-angle X-ray scattering studies reveal that this complex phase is characterized by a gigantic tetragonal unit cell, in which 30 sub-2-nm quasispherical micelles of five discrete sizes are arranged into a tetrahedral close packing, with exceptional translational order over length scales exceeding 100 nm. Varying the relative concentrations of water and surfactant in these lyotropic phases also triggers formation of the related Frank-Kasper A15 sphere packing as well as a common body-centered cubic structure. Molecular dynamics simulations reveal that the symmetry breaking that drives the formation of the σ and A15 phases arises from minimization of local deviations in surfactant headgroup and counterion solvation to maintain a nearly spherical counterion atmosphere around each micelle, while maximizing counterion-mediated electrostatic cohesion among the ensemble of charged particles.self-assembly | liquid crystals | surfactants | Frank-Kasper phases | lyotropic phase M olecular self-assembly provides a facile means of constructing a plethora of multifunctional soft materials, with mesoscopic structures that dictate their tailored properties and performance applications. Driven by noncovalent interactions between constituents, block polymers (1), giant shape amphiphiles (2), thermotropic liquid crystals (LCs) (3), lyotropic liquid crystals (LLCs) (4), and colloids (5) exemplify soft matter systems that spontaneously form periodic 1D lamellar phases, 2D columnar structures, and 3D packings of spherical particles. Columnar and spherical phases are useful as templates for mesoporous heterogeneous catalysts (6) and as microscale photonic bandgap materials (7). Manipulating supramolecular self-assembly to achieve specific materials morphologies and functions requires a fundamental understanding of the interplay between the structure and symmetry of the constituents and their multibody interactions.Although the packing of spherical objects (e.g., oranges and billiard balls) seems intuitively simple, point particles form a dizzying array of periodic crystals, quasicrystals (QCs), and structurally disordered glasses. Metallic elements typically form high-symmetry body-centered cubic (BCC), hexagonally closest-packed, and facecentered cubic (FCC) structures, due to the isotropy of metallic cohesion mediated by itinerant electrons (8). A few pure elements (e.g., Mn and U) form low-symmetry crystals with large and complex unit cells that maximize metallic cohesion against local constraints, such as maximization of Fermi surface sphericity (9).Sphere-forming soft mater...
This review describes the current status and challenges of polymeric single lithium-ion conductors for all-solid-state lithium ion and metal batteries.
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