Enhancing ion transport in charged block copolymers by stabilizing low symmetry morphology: Electrostatic control of interfaces.

Recently, the interest in charged polymers has been rapidly growing due to their uses in energy storage and transfer devices. Yet, polymer electrolyte-based devices are not on the immediate horizon because of the low ionic conductivity. In the present study, we developed a methodology to enhance the ionic conductivity of charged block copolymers comprising ionic liquids through the electrostatic control of the interfacial layers. Unprecedented reentrant phase transitions between lamellar and A15 structures were seen, which cannot be explained by well-established thermodynamic factors. X-ray scattering experiments and molecular dynamics simulations revealed the formation of fascinating, thin ionic shell layers composed of ionic complexes. The ionic liquid cations of these complexes predominantly presented near the micellar interfaces if they had strong binding affinity with the charged polymer chains. Therefore, the interfacial properties and concentration fluctuations of the A15 structures were crucially dependent on the type of tethered acid groups in the polymers. Overall, the stabilization energies of the A15 structures were greater when enriched, attractive electrostatic interactions were present at the micellar interfaces. Contrary to the conventional wisdom that block copolymer interfaces act as "dead zone" to significantly deteriorate ion transport, this study establishes a prospective avenue for advanced polymer electrolyte having tailor-made interfaces.

Enhanced ionic conductivity in block copolymer electrolytes through interfacial passivation using mixed ionic liquids.

We present a strategic approach for enhancing the ionic conductivity of block copolymer electrolytes. This was achieved by introducing mixed ionic liquids (ILs) with varying molar ratios, wherein the imidazolium cation was paired with either tetrafluoroborate (BF4) anion or bis(trifluoromethylsulfonyl)imide (TFSI) anion. Two polymer matrices, poly(4-styrenesulfonate)-b-polymethylbutylene (SSMB) and poly(4-styrenesulfonyl (trifluoromethanesulfonyl)imide)-b-polymethylbutylene (STMB), were synthesized for this purpose. All the SSMB and STMB containing mixed ILs showed hexagonal cylindrical structures, but the type of tethered acid group significantly influenced the interfacial properties. STMB electrolytes demonstrated enhanced segregation strength, which was attributed to strengthened Coulomb and hydrogen bonding interactions in the ionic domains, where the ILs were uniformly distributed. In contrast, the SSMB electrolytes exhibited increased concentration fluctuations because the BF4 anions were selectively sequestered at the block interfaces. This resulted in the effective confinement of imidazolium TFSI along the ionic domains, thereby preventing ion trapping in dead zones and facilitating rapid ion diffusion. Consequently, the SSMB electrolytes with mixed ILs demonstrated significantly improved ionic conductivities, surpassing the expected values based on the arithmetic average of the conductivities of each IL, whereas the ionic conductivity of the STMB was aligned with the expected average. The methodology explored in this study holds great promise for the development of solid-state polymer electrolytes.

Charged Block Copolymers: From Fundamentals to Electromechanical Applications.

Charged block copolymers are promising materials for next-generation battery technologies and soft electronics. Although once it was only possible to prepare randomly organized structures, nowadays, well-ordered charged block copolymers can be prepared. In addition, theoretical and experimental analyses of the thermodynamic properties of charged polymers have provided insights into how to control nanostructures via electrostatic interactions and improve the ionic conductivity without compromising mechanical strength, which is crucial for practical applications. In this Account, we discuss methods to control the self-assembly and ion diffusion behavior of charged block copolymers by varying the type of tethered ionic moieties, local concentration of embedded ions with controlled electrostatic interactions, and nanoscale morphology. We discuss with particular emphasis on the structure-transport relationship of charged block copolymers using various ionic additives to control the phase behavior electrostatically as well as the ion transport properties. Through this, we establish the role of interconnected ionic channels in promoting ion-conduction and the importance of developing three-dimensional interconnected morphologies such as gyroid, orthorhombic Fddd (O70) networks, body-centered cubic (bcc), face-centered cubic (fcc), and A15 structures with well-defined interfaces in creating less tortuous ion-conduction pathways. Our prolonged surge and synthetic advances are pushing the frontiers of charged block copolymers to have virtually homogeneous ionic domains with suppressed ion agglomeration via the nanoconfinement of closely bound ionic moieties, resulting in efficient ion conduction and high mechanical strength.Subsequently, we discuss how, by using zwitterions, we have radically improved the ionic conductivity of single-ion conducting polymers, which have potential for use in next-generation electrochemical devices owing to the constrained anion depletion. Key to the improvement stems from hierarchically ordered ionic crystals in nanodomains of the single-ion block copolymers through the self-organization of the dipolar/ionic moieties under confinement. By precisely tuning the distances between ionic sites and the dipolar orientation in the ionic domains with varied zwitterion contents, unprecedented dielectric constants close to those of aqueous electrolytes have been achieved, leading to the development of high-conductivity solid-state single-ion conducting polymers with leak-free characteristics. Further, using these materials, low-voltage-driven artificial muscles have been prepared that show a large bending strain and millisecond-scale mechanical deformations at 1 V in air without fatigue, exceeding the performance of previously reported polymer actuators. Finally, smart multiresponsive actuators based on tailor-made charged polymers capable of programmable deformation with high force and self-locking without power consumption are suggested as candidates for use in soft robotics.

Ten-Minute Synthesis of Highly Conductive Polymer Nanosheets on Ice Surfaces: Role of Ice Crystallinity.

Conducting polymers have been studied widely over the past decades for use as organic electrode materials owing to their high electrical conductivity and low-cost synthesis. Among the various synthesis methods reported, the recently established ice-assisted approach for developing conducting polymer nanosheets is regarded as an advanced technology that allows for easy fabrication in an eco-friendly manner. However, the role of the crystallinity of the underlying ice surface in determining the physicochemical properties of the conducting polymers remains unclear. Here, the electronic properties and packing structures of polyaniline (PANI) nanosheets formed on ice surfaces are studied by controlling the ice crystallinity. Intriguingly, the crystallinity of the PANI nanosheets resembles that of the ice surfaces, in that the anisotropic growth of the PANI crystals with a face-on orientation occurs preferentially on high-crystalline ice surfaces. In addition, it is found that the development of highly crystalline PANI nanosheets results in efficient charge transport, owing to polaron delocalization in PANI with extended chain conformations and the improvement in the degree of backbone ordering because of the preorganized aniline moieties on the ice surface.

Triazenyl Radicals Stabilized by N-Heterocyclic Carbenes.

Notwithstanding the notable progress in the synthesis of N-heterocyclic carbene-stabilized radicals, aminyl radicals, supported by NHCs or otherwise, have been scarcely studied due to synthetic challenges. Triazenyl radical is a particular form of aminyl radical that contains three adjacent nitrogen atoms, and offers intriguing possibilities for unique reactivity and physical properties stemming from expected delocalization of the spin density over the NNN moiety and its conjugated substituents. Here, we report the synthesis and full characterization of the first NHC-stabilized triazenyl radicals, obtained by one-electron reduction of the corresponding triazenyl cations with potassium metal. These radicals reversibly oxidize back to the cations upon treatment with transition metal sources or electrophiles, and abstract H atom from xanthene to form a new N-H bond at the center nitrogen atom. Potential application of the redox couple between triazenyl cation and triazenyl radical was demonstrated as cathode active materials in lithium ion batteries.

Thermodynamics and phase behavior of acid-tethered block copolymers with ionic liquids.

We investigate the phase behavior of acid-tethered block copolymers with and without ionic liquids. Two phosphonated block copolymers and their sulfonated analogs were synthesized by fine-tuning the degree of polymerization and the acid content. The block copolymers carrying acid groups with ionic liquids exhibited rich phase sequences, i.e., disorder-lamellae (LAM), gyroid-LAM, gyroid-hexagonal cylinder (HEX), and gyroid-A15 lattice, and the cation/anion ratio in the ionic liquid exerted profound effects on the segregation strength and topology of the self-assembled structures. Additionally, using ionic liquids with excessive cation content was found to enhance the effective Flory-Huggins interaction parameter, χeff, of the samples. However, as the anion content of the ionic liquids increased the segregation strength decreased. This is attributed to the packing frustration accompanied by the prevailing repulsive electrostatic interactions of the anions in the ionic liquid and the polymer matrix. As the hydrophobicity of the ionic liquids increased, well-defined ordered phases emerged in the phosphonated block copolymers with increased anion content, contrary to the disordered phases of the sulfonated samples. Thus, the balance between solvation energy of the anions and the electrostatic interactions is a key determinant of the thermodynamics of acid-tethered block copolymers containing ionic liquids.

Ion Transport in Nanostructured Phosphonated Block Copolymers Containing Ionic Liquids.

The morphology and conductivity of poly(styrenephosphonate-b-methylbutylene) block copolymers containing ionic liquids are investigated. The block copolymers display a series of well-defined self-assembled morphologies, i.e., lamellae, gyroid, hexagonal cylinder (HEX), body-centered cubic, and A15 lattice, in the absence and presence of ionic liquids. The observation of an equilibrium A15 lattice for linear diblock copolymers, in contrast to a number of theoretical studies, is ascribed to the packing frustration accompanied by prevailing electrostatic interactions. The samples having the A15 lattice show a substantially higher morphology factors (0.83-0.96) than those with the HEX phases (0.42-0.69). This indicates the structural advantage of the A15 lattice with a well-defined 3D symmetry over the 2D HEX structure for constructing less tortuous ion-conduction pathways. This unprecedented study portends the rational design of nanostructured phosphonated polymer membranes with improved conductivity.

High-Conductivity Two-Dimensional Polyaniline Nanosheets Developed on Ice Surfaces.

A new method to develop two-dimensional PANI nanosheets using ice as a removable hard template is presented. Distinctly high current flows of 5.5 mA at 1 V and a high electrical conductivity of 35 S cm(-1) were obtained for the polyaniline (PANI) nanosheets, which marked a significant improvement from previously values on other PANIs reported over the past decades. These improved electrical properties of ice-templated PANI nanosheets were attributed to the long-range ordered edge-on π-stacking of the quinoid ring, ascribed to the ice surface-assisted vertical growth of PANI. The unprecedented advantages of the ice-templated PANI nanosheets are two-fold. First, the PANI nanosheet can be easily transferred onto various types of substrates via float-off from the ice surfaces. Second, PANI can be patterned into any shape using predetermined masks, and this is expected to facilitate the eventual convenient and inexpensive application of conducting polymers in versatile electronic device forms.

Nanotopography-guided migration of T cells.

T cells navigate a wide variety of tissues and organs for immune surveillance and effector functions. Although nanoscale topographical structures of extracellular matrices and stromal/endothelial cell surfaces in local tissues may guide the migration of T cells, there has been little opportunity to study how nanoscale topographical features affect T cell migration. In this study, we systematically investigated mechanisms of nanotopography-guided migration of T cells using nanoscale ridge/groove surfaces. The velocity and directionality of T cells on these nanostructured surfaces were quantitatively assessed with and without confinement, which is a key property of three-dimensional interstitial tissue spaces for leukocyte motility. Depending on the confinement, T cells exhibited different mechanisms for nanotopography-guided migration. Without confinement, actin polymerization-driven leading edge protrusion was guided toward the direction of nanogrooves via integrin-mediated adhesion. In contrast, T cells under confinement appeared to migrate along the direction of nanogrooves purely by mechanical effects, and integrin-mediated adhesion was dispensable. Therefore, surface nanotopography may play a prominent role in generating migratory patterns for T cells. Because the majority of cells in periphery migrate along the topography of extracellular matrices with much lower motility than T cells, nanotopography-guided migration of T cells would be an important strategy to efficiently perform cell-mediated immune responses by increasing chances of encountering other cells within a given amount of time.

Thermodynamically stable plumber's nightmare structures in block copolymers.

Block copolymer self-assembly affords diverse nanostructures, spanning from spheres and cylinders to networks, offering meticulous control over properties and functionalities at the nanoscale. However, creating thermodynamically stable network structures with high packing frustration remains a challenge. In this study, we report a methodology to access diverse network structures such as gyroid, diamond, and primitive phases from diblock copolymers using end group and linker chemistry. The stability of the medial packing of polymer chain ends (plumber's nightmare structure) over skeletal aggregation (gyroid) is attributed to the interplay between the strength of the end-end interactions and the initial shape of the curvature. Our study establishes an approach to develop tailored network structures from block copolymers, providing an important platform for using block copolymers in nanotechnology applications.

All-solid-state lithium-sulfur batteries enabled by single-ion conducting binary nanoparticle electrolytes.

We designed solid-state hybrid electrolytes with single-ion conducting properties by co-assembling binary core-shell polymer nanoparticles. By controlling the nanoparticle size and number, we created superlattices that optimized the Li+ concentration and transport. The electrolytes exhibited a remarkable ionic conductivity (10-4 S cm-1), lithium transference number (0.94), electrochemical stability (up to 6 V), and modulus (0.12 GPa) at 25 °C. The mechanical strength of these electrolytes depended minimally on temperature at 25-150 °C because of the robustness of the cores. When implemented in Li-S batteries with no liquids, they demonstrated an initial discharge capacity of 1090 mA h g-1 at 0.05C, a cycle life of over 200 cycles, and a rate capability with a discharge capacity of 627 mA h g-1 at 3C.

Superionic Bifunctional Polymer Electrolytes for Solid-State Energy Storage and Conversion.

Achieving superionic conductivity from solid-state polymer electrolytes is an important task in the development of future energy storage and conversion technologies. Herein, a platform for innovative electrolyte technologies based on a bifunctional polymer, poly(3-hydroxy-4-sulfonated styrene) (PS-3H4S), is presented. By incorporating OH and SO3 H functional groups at adjacent positions in the styrene repeating unit, "intra-monomer" hydrogen bonds are formed to effectively weaken the electrostatic interactions of the SO3 - moieties in the polymer matrix with embedded ions, promoting rich structural and dynamic heterogeneity in the PS-3H4S electrolyte. Upon the incorporation of an ionic liquid, interconnected rod-like ion channels, which allow the decoupling of ion relaxation from polymer relaxation, are formed in the stiff motif of the polymeric domains passivated by interfacial ionic layers. This results in accelerated proton hopping through the glassy polymer matrix, and proton hopping becomes more pronounced at cryogenic temperatures down to -35 °C. The PS-3H4S/ionic liquid composite electrolytes exhibit a high ionic conductivity of 10-3 S cm-1 and high storage modulus of ≈100 MPa at 25 °C, and can be successfully applied in soft actuators and lithium-metal batteries.

Porous charged polymer nanosheets formed via microplastic removal from frozen ice for virus filtration and detection.

We developed a method for producing porous charged polymer nanosheets using frozen ice containing microplastics. Upon assessing SARS-CoV-2 filtration using nanosheets with 100 nm-sized pores, a high rejection rate of 96% was achieved. The charged surfaces of nanosheets further enabled the electrophoretic capture of the virus using a portable battery with additional real-time sensing capability.

Gate-tunable quantum pathways of high harmonic generation in graphene.

Under strong laser fields, electrons in solids radiate high-harmonic fields by travelling through quantum pathways in Bloch bands in the sub-laser-cycle timescales. Understanding these pathways in the momentum space through the high-harmonic radiation can enable an all-optical ultrafast probe to observe coherent lightwave-driven processes and measure electronic structures as recently demonstrated for semiconductors. However, such demonstration has been largely limited for semimetals because the absence of the bandgap hinders an experimental characterization of the exact pathways. In this study, by combining electrostatic control of chemical potentials with HHG measurement, we resolve quantum pathways of massless Dirac fermions in graphene under strong laser fields. Electrical modulation of HHG reveals quantum interference between the multi-photon interband excitation channels. As the light-matter interaction deviates beyond the perturbative regime, elliptically polarized laser fields efficiently drive massless Dirac fermions via an intricate coupling between the interband and intraband transitions, which is corroborated by our theoretical calculations. Our findings pave the way for strong-laser-field tomography of Dirac electrons in various quantum semimetals and their ultrafast electronics with a gate control.

Facile one-pot synthesis of functional gold nanoparticle-polymer hybrids using ionic block copolymers as a nanoreactor.

A highly versatile approach to fabricate functional gold nanoparticle (AuNP)-polymer hybrids is demonstrated by employing sulfonated block copolymers. The 3-5 nm sized ionic domain of the sulfonated poly(styrene-block-methylbutylene) (S(n) MB(m) ) copolymers can be utilized as a nanoreactor where the Au ions can be selectively sequestered and reduced to AuNPs using a simple photochemical method. The size of the AuNPs can be adjusted in fine-steps from 2.0 ± 0.3 to 3.9 ± 0.5 nm by changing the sulfonation levels of the S(n) MB(m) copolymers. Remarkably, significantly improved methanol oxidation properties are achieved with the hybrid materials owing to the ion conducting-SO(3) H groups and the interconnected network of AuNPs confined within the self-assembled microstructures, which provides electronic conductivity.

Smart Bioinspired Actuators: Crawling, Linear, and Bending Motions through a Multilayer Design.

To fulfill the insatiable demand for wearable technologies, ionic electroactive polymer actuators have been entrenched as promising candidates that can convert low-input-voltage energy into high mechanical throughput. However, a ubiquitous trilayer design of actuators allows exclusively bending deformation and their highly nonlinear response restricts the true potential of low-voltage actuators for next-generation technology. Herein, we report an unprecedented multilayer design for soft actuators that enables complex deformations shown by skeletal muscles, mechanoreceptors, and plant roots in response to various environmental stimuli. Hierarchically ordered pores in a stretchable interlayer provide excellent electromechanical properties and fast charging kinetics, which enable linear motion by soft actuators at 3 V and under ambient conditions. Our actuators demonstrate astonishing levels of performance, including a 6.5% linear actuation strain, 0.8 s rapid switching speed, and 5000 cycle stable performance in air, producing a 4.2 mN linear blocking force at a ±3 V alternating square-wave voltage. This actuator design demonstrating a walkable spider capable of controlled back-and-forth propelling motion at low driving voltages provides the platform to envision a complex functionality using a portable battery as a power source for soft robotics, wearable exosuits, and biomimetic technologies.

Morphological manipulation of ionic block copolymer micelles using an electric field.

We present an electric-field-triggered sphere-to-cylinder transition of negatively charged block copolymer micelles with a radically low electric field of 30 V/cm. The system investigated is dilute solutions of strong polyelectrolyte containing ionic-b-neutral block copolymers (i.e., poly(styrenesulfonate-b-methylbutylene)). We have carried out in situ small-angle X-ray scattering experiments equipped with a dc power supply, combined with electron microscopy and atomic force microscopy. The application of small electrical fields across the solutions of spherical micelles results in the transient morphology of interconnected spheres, which are eventually transformed into a cylindrical shape with time. The E-field-induced cylindrical micelles revert to spherical micelles when the E field is switched off.

100th Anniversary of Macromolecular Science Viewpoint: Block Copolymers with Tethered Acid Groups: Challenges and Opportunities.

Scientific research on advanced polymer electrolytes has led to the emergence of all-solid-state energy storage/transfer systems. Early research began with acid-tethered polymers half a century ago, and research interest has gradually shifted to high-precision polymers with controllable acid functional groups and nanoscale morphologies. Consequently, various self-assembled acid-tethered block polymer morphologies have been produced. Their ion properties are profoundly affected by the multiscale intermolecular interactions in confinements. The creation of hierarchically organized ion/dipole arrangements inside the block copolymer nanostructures has been highlighted as a future method for developing advanced single-ion polymers with decoupled ion dynamics and polymer chain relaxation. Several emerging practical applications of the acid-tethered block copolymers have been explored to draw attention to the challenges and opportunities in developing state-of-the-art electrochemical systems.

Ice-assisted synthesis of functional nanomaterials: the use of quasi-liquid layers as nanoreactors and reaction accelerators.

The discovery of peculiar quasi-liquid layers on ice surfaces marks a major breakthrough in ice-related sciences, as the facile tuning of the reactions and morphologies of substances in contact with these layers make ice-assisted chemistry a low-cost, environmentally benign, and ubiquitous methodology for the synthesis of nanomaterials with improved functionality. Ice-templated synthesis of porous materials offers the appealing features of rapid self-organization and remarkable property changes arising from confinement effects and affords materials that have found a diverse range of applications such as batteries, supercapacitors, and gas separation. Moreover, much attention has been drawn to the acceleration of chemical reactions and transformations on the ice surface due to the freeze concentration effect, fast self-diffusion of surface water, and modulated surface potential energy. Some of these results are related to the accumulation of inorganic contaminants in glaciers and the blockage of natural gas pipelines. As an emerging theme in nanomaterial design, the dimension-controlled synthesis of hybrid materials with unprecedentedly enhanced properties on ice surfaces has attracted much interest. However, a deep understanding of quasi-liquid layer characteristics (and hence, the development of cutting-edge analytical technologies with high surface sensitivity) is required to achieve the current goal of ice-assisted chemistry, namely the preparation of tailor-made materials with the desired properties.

All-Solid-State Lithium-Organic Batteries Comprising Single-Ion Polymer Nanoparticle Electrolytes.

Advances in lithium battery technologies necessitate improved energy densities, long cycle lives, fast charging, safe operation, and environmentally friendly components. This study concerns lithium-organic batteries comprising bioinspired poly(4-vinyl catechol) (P4VC) cathode materials and single-ion conducting polymer nanoparticle electrolytes. The controlled synthesis of P4VC results in a two-step redox reaction with voltage plateaus at around 3.1 and 3.5 V, as well as a high initial specific capacity of 352 mAh g-1 . The use of single-ion nanoparticle electrolytes enables high electrochemical stabilities up to 5.5 V, a high lithium transference number of 0.99, high ionic conductivities, ranging from 0.2×10-3 to 10-3  S cm-1 , and stable storage moduli of >10 MPa at 25-90 °C. Lithium cells can deliver 165 mAh g-1 at 39.7 mA g-1 for 100 cycles and stable specific capacities of >100 mAh g-1 at a high current density of 794 mA g-1 for 500 cycles. As the first successful demonstration of solid-state single-ion polymer electrolytes in environmentally benign and cost-effective lithium-organic batteries, this work establishes a future research avenue for advancing lithium battery technologies.