RESUMEN
Hierarchical superstructures have novel shape-dependent properties, but well-defined anisotropic carbon superstructures with controllable size, shape, and building block dimensionality have rarely been accomplished thus far. Here, a hierarchical assembly technique is presented that uses spinodal decomposition (SD) to synthesize anisotropic oblate particles of mesoporous carbon superstructure (o-MCS) with nanorod arrays by integrating block-copolymer (BCP) self-assembly and polymer-polymer interface behaviors in binary blends. The interaction of major and minor phases in binary polymer blends leads to the formation of an anisotropic oblate particle, and the BCP-rich phase enables ordered packing and unidirectional alignment of carbon nanorods. Consequently, this approach enables precise control over particles' size, shape, and over the dimensionality of their components. Exploiting this functional superstructure, o-MCS are used as an anode material in potassium-ion batteries, and achieve a notable specific capacity of 156 mA h g-1 at a current density of 2 A g-1, and long-term stability for 3000 cycles. This work presents a significant advancement in the field of hierarchical superstructures, providing a promising strategy for the design and synthesis of anisotropic carbon materials with controlled properties, offering promising applications in energy storage and beyond.
RESUMEN
Anisotropic lens-shaped nitrogen-doped carbon (Lens-NMC) with unidirectionally aligned mesopores was achieved via perpendicular block copolymer self-assembly at the polymer interface. Lens-NMC is applied as a potassium-ion battery anode material as a next-generation battery system.
RESUMEN
ConspectusMesoporous inorganic materials (MIMs) directed by block copolymers (BCPs) have attracted tremendous attention due to their high surface area, large pore volume, and tunable pore size. The structural hierarchy of inorganic materials with designed meso- and macrostructures combines the benefits of mesoporosity and tailored macrostructures in which macropores have increased ion/mass transfer and large capacity to carry guest material and have a macroscale particle morphology that permits close packing and a low surface energy. Existing methods for hierarchically structured MIMs require complicated multistep procedures including preparation of sacrificial macrotemplates (e.g., foams and colloidal spheres). Despite considerable efforts to control the macrostructures of mesoporous materials, major challenges remain in the formation of a structural hierarchy with ordered mesoporosity.In polymer science, spinodal decomposition (SD) is a physical phenomenon that spontaneously produces a wide variety of macroscale heterostructures from interconnected networks to isolated droplets. Exploitation of SD is a promising method to achieve precise control of the macrostructure (e.g., macropore, particle morphology) and mesostructure (e.g., pore size and structure, composition) of inorganic materials. However, this approach for tailoring the structural hierarchy of MIMs is unexplored due to the lack of effective systems that can control the complex thermodynamic interactions of inorganic precursor/polymer blends and the phase-separation kinetics.In this Account, we present our recent research progress on the development of synthesis systems that combine unique SD behaviors and BCP self-assembly in polymer blends. To generate macropores in MIMs, we have exploited interconnected macrostructures of SD induced by designed quench conditions of multicomponent blends containing BCP. These strategies enable control of the size of the macropores of the nanostructures independently and can be extended to various compositions (e.g., carbon, SiO2, TiO2, WO3, TiNb2O7, TiN). We also control the macroscopic morphology of the MIMs into spherical particles (e.g., solid and hollow mesoporous spheres) by using SD induced by increasing the mixing entropy penalty of polymer blends that consist BCP, homopolymer(s), and inorganic precursors. Furthermore, interfacial tension between polymers determines the macroscopic morphology of MIMs, from isotropic to anisotropic mesoporous particles (e.g., oblate, bowl, 2D nanosheet). The interfacial states of the homopolymer determine the pore orientation and particle morphology of BCP-directed MIMs.We also highlight the application of the hierarchically structured MIMs in energy storage devices. Generated macropores facilitate ion/mass transfer in lithium-ion batteries and stable accommodation of a large amount of sulfur in lithium-sulfur batteries. Designed morphologies of MIMs are beneficial to achieve high packing density as electrode materials in potassium-ion batteries and thereby achieve high volumetric capacities.Recent advances in SD-driven synthesis for the structural hierarchy of MIMs will inspire how polymer science can be used as a platform for preparing the designed inorganic materials. Additionally, broadening the polymer and composition repertoire will guide in novel frontiers in the design and applications of MIMs in various fields.
RESUMEN
Two-dimensional (2D) porous inorganic nanomaterials have intriguing properties as a result of dimensional features and high porosity, but controlled production of circular 2D shapes is still challenging. Here, we designed a simple approach to produce 2D porous inorganic nanocoins (NCs) by integrating block copolymer (BCP) self-assembly and orientation control of microdomains at polymer-polymer interfaces. Multicomponent blends containing BCP and homopoly(methyl methacrylate) (hPMMA) are designed to undergo macrophase separation followed by microphase separation. The balanced interfacial compatibility of BCP allows perpendicularly oriented lamellar-assembly at the interfaces between BCP-rich phase and hPMMA matrix. Disassembly of lamellar structures and calcination yield ultrathin 2D inorganic NCs that are perforated by micropores. This approach enables control of the thickness, size, and chemical composition of the NCs. 2D porous and acidic aluminosilicate NC (AS-NC) is used to fabricate an ultrathin and lightweight functional separator for lithium-sulfur batteries. The AS-NC layer acts as an ionic sieve to selectively block lithium polysulfides. Abundant acid sites chemically capture polysulfides, and micropores physically exclude them, so sulfur utilization and cycle stability are increased.
