Porous architectures are important in determining the performance of lithium–sulfur batteries (LSBs). Among them, multiscale porous architecutures are highly desired to tackle the limitations of single‐sized porous architectures, and to combine the advantages of different pore scales. Although a few carbonaceous materials with multiscale porosity are employed in LSBs, their nonpolar surface properties cause the severe dissolution of lithium polysulfides (LiPSs). In this context, multiscale porous structure design of noncarbonaceous materials is highly required, but has not been exploited in LSBs yet because of the absence of a facile method to control the multiscale porous inorganic materials. Here, a hierarchically porous titanium nitride (h‐TiN) is reported as a multifunctional sulfur host, integrating the advantages of multiscale porous architectures with intrinsic surface properties of TiN to achieve high‐rate and long‐life LSBs. The macropores accommodate the high amount of sulfur, facilitate the electrolyte penetration and transportation of Li+ ions, while the mesopores effectively prevent the LiPS dissolution. TiN strongly adsorbs LiPS, mitigates the shuttle effect, and promotes the redox kinetics. Therefore, h‐TiN/S shows a reversible capacity of 557 mA h g−1 even after 1000 cycles at 5 C rate with only 0.016% of capacity decay per cycle.
Hierarchically porous oxide materials have immense potential for applications in catalysis, separation, and energy devices, but the synthesis of these materials is hampered by the need to use multiple templates and the associated complicated steps and uncontrollable mixing behavior. Here we report a simple one-pot strategy for the synthesis of inorganic oxide materials with multiscale porosity. The inorganic precursor and block copolymer are coassembled into an ordered mesostructure (microphase separation), while the in situ-polymerized organic precursor forms organic-rich macrodomains (macrophase separation) around which the mesostructure grows. Calcination generates hierarchical meso/macroporous SiO2 and TiO2 with three-dimensionally interconnected pore networks. The continuous 3D macrostructures were clearly visualized by nanoscale X-ray computed tomography. The resulting TiO2 was used as the anode in a lithium ion battery and showed excellent rate capability compared with mesoporous TiO2. This work is of particular importance because it (i) expands the base of BCP self-assembly from mesostructures to complex porous structures, (ii) shows that the interplay of micro- and macrophase separation can be fully exploited for the design of hierarchically porous inorganic materials, and therefore (iii) provides strategies for researchers in materials science and polymer science.
Two-dimensional
(2D) carbon nanosheets with micro- and/or mesopores
have attracted great attention due to unique physical and chemical
properties, but well-defined nanoporous carbon nanosheets with tunable
thickness and pore size have been rarely realized. Here, we develop
a polymer–polymer interfacial self-assembly strategy to achieve
hierarchically porous carbon nanosheets (HNCNSs) by integrating the
migration behaviors of immiscible ternary polymers with block copolymer
(BCP)-directed self-assembly. The balanced interfacial compatibility
of BCP allows the migration of a BCP-rich phase to the interface between
two immiscible homopolymer major phases (i.e., homopoly(methyl methacrylate)
and homopolystyrene), where the BCP-rich phase spreads thinly to a
thickness of a few nanometers to decrease the interfacial tension.
BCP-directed coassembly with organic–inorganic precursors constructs
an ordered mesostructure. Carbonization and chemical etching yield
ultrathin HNCNSs with hierarchical micropores and mesopores. This
approach enables facile control over the thickness (5.6–75
nm) and mesopore size (25–46 nm). As an anode material in a
potassium ion battery, HNCNSs show high specific capacity (178 mA
h g–1 at a current density of 1 A g–1) with excellent long-term stability (2000 cycles), by exploiting
the advantages of the hierarchical pores and 2D nanosheet morphology
(efficient ion/electron diffusion) and of the large interlayer spacing
(stable ion insertion).
Mesoporous inorganic particles and hollow spheres are of increasing interest for a broad range of applications, but synthesis approaches are typically material specific, complex, or lack control over desired structures. Here it is reported how combining mesoscale block copolymer (BCP) directed inorganic materials self-assembly and macroscale spinodal decomposition can be employed in multicomponent BCP/hydrophilic inorganic precursor blends with homopolymers to prepare mesoporous inorganic particles with controlled meso- and macrostructures. The homogeneous multicomponent blend solution undergoes dual phase separation upon solvent evaporation. Microphase-separated (BCP/inorganic precursor)-domains are confined within the macrophase-separated majority homopolymer matrix, being self-organized toward particle shapes that minimize the total interfacial area/energy. The pore orientation and particle shape (solid spheres, oblate ellipsoids, hollow spheres) are tailored by changing the kind of homopolymer matrix and associated enthalpic interactions. Furthermore, the sizes of particle and hollow inner cavity are tailored by changing the relative amount of homopolymer matrix and the rates of solvent evaporation. Pyrolysis yields discrete mesoporous inorganic particles and hollow spheres. The present approach enables a high degree of control over pore structure, orientation, and size (15-44 nm), particle shape, particle size (0.6-3 µm), inner cavity size (120-700 nm), and chemical composition (e.g., aluminosilicates, carbon, and metal oxides).
This review comprehensively summarizes the key challenges of sodium metal anodes and the recent progress in engineering the SEI layer for high energy density SMBs.
Anisotropic mesoporous inorganic materials have attracted great interest due to their unique and intriguing properties, yet their controllable synthesis still remains a great challenge. Here, we develop a simple synthesis approach toward mesoporous inorganic bowls and two-dimensional (2D) nanosheets by combining block copolymer (BCP)–directed self-assembly with asymmetric phase migration in ternary-phase blends. The homogeneous blend solution spontaneously self-assembles to anisotropically stacked hybrids as the solvent evaporates. Two minor phases—BCP/inorganic precursor and homopolystyrene (hPS)—form closely stacked, Janus domains that are dispersed/confined in the major homopoly(methyl methacrylate) (hPMMA) matrix. hPS phases are partially covered by BCP-rich phases, where ordered mesostructures develop. With increasing the relative amount of hPS, the anisotropic shape evolves from bowls to 2D nanosheets. Benefiting from the unique bowl-like morphology, the resulting transition metal oxides show promise as high-performance anodes in potassium-ion batteries.
Niobium nitride is first reported as an ultra-stable anode for KIBs. The superior electrochemical performance is attributed to large host for accommodating K ions with small-strain, and a high portion of the surface-controlled reaction.
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.
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