Local Built-In Field at the Sub-nanometric Heterointerface Mediates Cascade Electrochemical Conversion of Lithium-sulfur Batteries.

Heterogeneous catalytic mediators have been proposed to play a vital role in enhancing the multiorder reaction and nucleation kinetics in multielectron sulfur electrochemistry. However, the predictive design of heterogeneous catalysts is still challenging, owing to the lack of in-depth understanding of interfacial electronic states and electron transfer on cascade reaction in Li-S batteries. Here, a heterogeneous catalytic mediator based on monodispersed titanium carbide sub-nanoclusters embedded in titanium dioxide nanobelts is reported. The tunable catalytic and anchoring effects of the resulting catalyst are achieved by the redistribution of localized electrons caused by the abundant built-in fields in heterointerfaces. Subsequently, the resulting sulfur cathodes deliver an areal capacity of 5.6 mAh cm-2 and excellent stability at 1 C under sulfur loading of 8.0 mg cm-2 . The catalytic mechanism especially on enhancing the multiorder reaction kinetic of polysulfides is further demonstrated via operando time-resolved Raman spectroscopy during the reduction process in conjunction with theoretical analysis.

MOF-Enabled Ion-Regulating Gel Electrolyte for Long-Cycling Lithium Metal Batteries Under High Voltage.

High-voltage lithium metal batteries (LMBs) are a promising high-energy-density energy storage system. However, their practical implementations are impeded by short lifespan due to uncontrolled lithium dendrite growth, narrow electrochemical stability window, and safety concerns of liquid electrolytes. Here, a porous composite aerogel is reported as the gel electrolyte (GE) matrix, made of metal-organic framework (MOF)@bacterial cellulose (BC), to enable long-life LMBs under high voltage. The effectiveness of suppressing dendrite growth is achieved by regulating ion deposition and facilitating ion conduction. Specifically, two hierarchical mesoporous Zr-based MOFs with different organic linkers, that is, UiO-66 and NH2 -UiO-66, are embedded into BC aerogel skeletons. The results indicate that NH2 -UiO-66 with anionphilic linkers is more effective in increasing the Li+ transference number; the intermolecular interactions between BC and NH2 -UiO-66 markedly increase the electrochemical stability. The resulting GE shows high ionic conductivity (≈1 mS cm-1 ), high Li+ transference number (0.82), wide electrochemical stability window (4.9 V), and excellent thermal stability. Incorporating this GE in a symmetrical Li cell successfully prolongs the cycle life to 1200 h. Paired with the Ni-rich LiNiCoAlO2 (Ni: Co: Al = 8.15:1.5:0.35, NCA) cathode, the NH2 -UiO-66@BC GE significantly improves the capacity, rate performance, and cycle stability, manifesting its feasibility to operate under high voltage.

Spectral Stable Blue-Light-Emitting Diodes via Asymmetric Organic Diamine Based Dion-Jacobson Perovskites.

The spectral instability issue is a challenge in blue perovskite light-emitting diodes (PeLEDs). Dion-Jacobson (DJ) phase perovskites are promising alternatives to achieve high-quality blue PeLEDs. However, the current exploration of DJ phase perovskites is focused on symmetric divalent cations, and the corresponding efficiency of blue PeLEDs is still inferior to that of green and red ones. In this work, we report a new type of DJ phase CsPb(Br/Cl)3 perovskite via introduction of an asymmetric molecular configuration as the organic spacer cation in perovskites. The primary and tertiary ammonium groups on the asymmetric cations bridge with the lead halide octahedra forming the DJ phase structures. Stable photoluminescence spectra were demonstrated in perovskite films owing to the suppressed halide segregation. Meanwhile, the radiative recombination efficiency of charges is improved significantly as a result of the confinement effects and passivation of charge traps. Finally, we achieved an external quantum efficiency of 2.65% in blue PeLEDs with stable spectra emission under applied bias voltages. To our best knowledge, this is the first report of asymmetric cations used in PeLEDs, which provides a facile solution to the halide segregation issue in PeLEDs.

Superresilient Hard Carbon Nanofabrics for Sodium-Ion Batteries.

Developing supermechanically resilient hard carbon materials that can quickly accommodate sodium ions is highly demanded in fabricating durable anodes for wearable sodium-ion batteries. Here, an interconnected spiral nanofibrous hard carbon fabric with both remarkable resiliency (e.g., recovery rate as high as 1200 mm s-1 ) and high Young's modulus is reported. The hard carbon nanofabrics are prepared by spinning and then carbonizing the reaction product of polyacrylonitrile and polar molecules (melamine). The resulting unique hard carbon possesses a highly disordered carbonaceous structure with enlarged interlayer spacing contributed from the strong electrostatic repulsion of dense pyrrolic nitrogen atoms. Its excellent resiliency remains after intercalation/deintercalation of sodium ions. The outstanding sodium-storage performance of the derived anode includes excellent gravimetric capacity, high-power capability, and long-term cyclic stability. More significantly, with a high loading mass, the hard carbon anode displays a high-power capacity (1.05 mAh cm-2 at 2 A g-1 ) and excellent cyclic stability. This study provides a unique strategy for the design and fabrication of new hard carbon materials for advanced wearable energy storage systems.

A Bimodal Protein Fabric Enabled via In Situ Diffusion for High-Performance Air Filtration.

Design and fabrication of bimodal structures are essential for successful development of advanced air filters with ultralow airflow resistance. To realize this goal, simplified processing procedures are necessary for meeting the practical needs. Here, a bimodal protein fabric with high-performance air filtration, and effectively lowered airflow resistance is reported. The various functional groups of proteins provide versatile interactions with pollutants. By utilizing a novel and cost-effective "cross-axial" configuration with an optimized condition (75° of contacting angle between solution nozzle and cospinning solvent nozzle), the diffusion in Taylor cone is in situ controlled, which results in the successful production of bimodal protein fabric. The bimodal protein fabric (16.7 g/m2 areal density) is demonstrated to show excellent filtration performance for removing particulate matter (PM) pollutants and only causes 17.1 Pa air pressure drop. The study of multilayered protein fabric air filters shows a further improvement in filtration performance of removing 97% of PM0.3 and 99% of PM2.5 with a low airflow resistance (34.9 Pa). More importantly, the four-layered bimodal protein fabric shows an exceptional long-term performance and maintains a high removal efficiency in the humid environment. This study presents an effective and viable strategy for fabricating bimodal fibrous materials for advanced air filtration.

Mitigating the Trade-Off between Non-Radiative Recombination and Charge Transport to Enable Efficient Ternary Organic Solar Cells.

Ternary organic solar cells (OSCs) have attracted intensive studies due to their promising potential for attaining high-performing photovoltaics, whereas there has been an opening challenge in minimizing the open circuit voltage (Voc) loss while retaining the optimal carrier extraction in the multiple mixture absorbers. Here, we systemically investigate a ternary absorber comprised of two acceptors and a donor, in which the resultant Voc and fill factor are varied and determined by the ratios of acceptor components as a result of the unbalance of non-radiative recombination rates and charge transport. The transient absorption spectroscopy and electroluminescence techniques verify two distinguishable charge-transfer (CT) states in the ternary absorber, and the mismatch of non-radiative recombination rates of those two CT states is demonstrated to be associated with the Voc deficit, whilst the high-emissive acceptor molecule delivers inferior electron mobility, resulting in poor charge transport and a subpar fill factor. These findings enable us to optimize the mixture configuration for attaining the maximal-performing devices. Our results not only provide insight into maximizing the photovoltage of organic solar cells but can also motivate researchers to further unravel the photophysical mechanisms underlying the intermolecular electronic states of organic semiconductors.

Graphene-Like Conjugated Molecule as Hole-Selective Contact for Operationally Stable Inverted Perovskite Solar Cells and Modules.

Further enhancing the operational lifetime of inverted-structure perovskite solar cells (PSCs) is crucial for their commercialization, and the design of hole-selective contacts at the illumination side plays a key role in operational stability. In this work, the self-anchoring benzo[rst]pentaphene (SA-BPP) is developed as a new type of hole-selective contact toward long-term operationally stable inverted PSCs. The SA-BPP molecule with a graphene-like conjugated structure shows a higher photostability and mobility than that of the frequently-used triphenylamine and carbazole-based hole-selective molecules. Besides, the anchoring groups of SA-BPP promote the formation of a large-scale uniform hole contact on ITO substrate and efficiently passivate the perovskite absorbers. Benefiting from these merits, the champion efficiencies of 22.03% for the small-sized cells and 17.08% for 5 × 5 cm2 solar modules on an aperture area of 22.4 cm2 are achieved based on this SA-BPP contact. Also, the SA-BPP-based device exhibits promising operational stability, with an efficiency retention of 87.4% after 2000 h continuous operation at the maximum power point under simulated 1-sun illumination, which indicates an estimated T80 lifetime of 3175 h. This novel design concept of hole-selective contacts provides a promising strategy for further improving the PSC stability.

Steered polymorphic nanodomains in TiO2 to boost visible-light photocatalytic oxidation.

A breakthrough in enhancing visible-light photocatalysis of wide-bandgap semiconductors such as prototypical titania (TiO2) via cocatalyst decoration is still challenged by insufficient heterojunctions and inevitable interfacial transport issues. Herein, we report a novel TiO2-based composite material composed of in situ generated polymorphic nanodomains including carbon nitride (C3N4) and (001)/(101)-faceted anatase nanocrystals. The introduction of ultrafine C3N4 results in the generation of many oxygen vacancies in the TiO2 lattice, and simultaneously induces the exposure and growth of anatase TiO2(001) facets with high surface energy. The photocatalytic performance of C3N4-induced TiO2 for degradation of 2,4-dichlorophenol under visible-light irradiation was tested, its apparent rate being up to 1.49 × 10-2 min-1, almost 3.8 times as high as that for the pure TiO2 nanofibers. More significantly, even under low operation temperature and after a long-term photocatalytic process, the composite still exhibits exceptional degradation efficiency and stability. The normalized degradation efficiency and effective lifespan of the composite photocatalyst are far superior to other reported modified photocatalysts.

Building bimodal structures by a wettability difference-driven strategy for high-performance protein air-filters.

Building bimodal structures for air-filters is promising to reduce the airflow resistance without sacrificing the filtration efficiency. To do so, multi-jet electrospinning is among the most broadly used methods, yet the interplay between single fibers in electrospinning, which is significant to their morphologies, is overlooked. In this study, we report a wettability difference-driven strategy to fabricate a bimodal protein fabric with superior filtration performance. We surprisingly find that only by co-spinning of two proteins, zein and gelatin, with different wettability between them, a drastic change of fiber diameters is spontaneously achieved. The generated protein-blend fabric possesses bimodally distributed diameters of 270 nm for gelatin fibers and of 1.12 µm for zein fibers; both pure protein fabrics via single-jet electrospinning have diameters unimodally distributed in the range of 500-700 nm. The bimodal protein-blend fabric delivers exceptional removal efficiencies of 99.67% for PM2.5 and 98.80% for PM0.3, yielding an ultra-low airflow resistance of 38 Pa. The PM2.5 removal efficiency retains to be 96.04% after filtering 1000 L polluted air, indicating a good long-term performance. This study brings about a new insight into fabrication of bimodal structures using multi-jet electrospinning method and promotes the development of natural products for broad applications.

A Super-breathable "Woven-like" Protein Nanofabric.

Nanofabrics made from abundant natural protein that possesses enormous amounts of functional groups may have important applications such as air filtration. However, protein nanofabrics with randomly distributed nanofibers have very low mechanical properties and high airflow resistance, both of which seriously reduce the breathability. Here, a super-breathable zein (corn protein) fabric having a unique "woven-like" nanofibrous structure (w-PNF) via the accumulation effect between the charged nanofibers and the collector during electrospinning is reported. The resulting w-PNF exhibits remarkable tensile strength and modulus, which are 3 and 9 times, respectively, higher than the random protein nanofibrous materials. The filtration tests indicate that w-PNF presents super-breathable performance, including ultralow airflow resistance (1/12 of that of the nonwoven nanofabric) and high filtration efficiency for capturing PM2.5. As compared with the reported nanofabrics, w-PNF maintains the same airflow resistance at up to 4 times higher airflow rate. In addition, w-PNF presents visible-light transparency (80%) and high resolution even in microareas. This work provides a significant strategy for designing and fabricating nanofabrics for boosting the development of biological nanomaterials.

An Ultra-microporous Carbon Material Boosting Integrated Capacitance for Cellulose-Based Supercapacitors.

A breakthrough in advancing power density and stability of carbon-based supercapacitors is trapped by inefficient pore structures of electrode materials. Herein, an ultra-microporous carbon with ultrahigh integrated capacitance fabricated via one-step carbonization/activation of dense bacterial cellulose (BC) precursor followed by nitrogen/sulfur dual doping is reported. The microporous carbon possesses highly concentrated micropores (~ 2 nm) and a considerable amount of sub-micropores (< 1 nm). The unique porous structure provides high specific surface area (1554 m2 g-1) and packing density (1.18 g cm-3). The synergistic effects from the particular porous structure and optimal doping effectively enhance ion storage and ion/electron transport. As a result, the remarkable specific capacitances, including ultrahigh gravimetric and volumetric capacitances (430 F g-1 and 507 F cm-3 at 0.5 A g-1), and excellent cycling and rate stability even at a high current density of 10 A g-1 (327 F g-1 and 385 F cm-3) are realized. Via compositing the porous carbon and BC skeleton, a robust all-solid-state cellulose-based supercapacitor presents super high areal energy density (~ 0.77 mWh cm-2), volumetric energy density (~ 17.8 W L-1), and excellent cyclic stability.

Ultralight Programmable Bioinspired Aerogels with an Integrated Multifunctional Surface for Self-Cleaning, Oil Absorption, and Thermal Insulation via Coassembly.

Creating a configurable and controllable surface for structure-integrated multifunctionality of ultralight aerogels is of significance but remains a huge challenge because of the critical limitations of mechanical vulnerability and structural processability. Herein, inspired by Salvinia minima, the facile and one-step coassembly approach is developed to allow the structured aerogels to spontaneously replicate Salvinia-like textures for function-adaptable surfaces morphologically. The in situ superimposed construction of bioinspired topography and intrinsic topology is for the first time performed for programmable binary architectures with multifunctionality without engendering structural vulnerability and functional disruption. By introducing the binding groups for hydrophobicity tailoring, functionalized nanocellulose (f-NC) is prepared via mechanochemistry as a structural, functional, and topographical modifier for a multitasking role. The self-generated bioinspired surface with f-NC greatly maintains the structural unity and mechanical robustness, which enable self-adaptability and self-supporting of surface configurations. With fine-tuning of nucleation-driving, the binary microstructures can be controllably diversified for structure-adaptable multifunctionalities. The resulting ultralight S. minima-inspired aerogels (e.g., 0.054 g cm-3) presented outstanding temperature-endured elasticity (e.g., 90.7% high-temperature compress-recovery after multiple cycles), durable superhydrophobicity, anti-icing properties, oil absorbency efficiency (e.g., 60.2 g g-1), and thermal insulating (e.g., 0.075 W mK-1), which are superior to these reported on the overall performance. This coassembly strategy offers the opportunities for the design of ultralight materials with topography- and function-tailorable features to meet the increasing demands in many fields such as smart surfaces and self-cleaning coatings.