Rational design of conductive metal-organic frameworks and aligned carbon nanofibers for enhancing the performance of flexible supercapacitors.

Carbonaceous materials are attractive active materials for the manufacture of flexible electrochemical double-layer capacitors (EDLCs) because of their high electrical conductivity, large surface area, and inherent resilience against deformation. However, compared to pseudocapacitors, which store electrochemical energy via faradaic redox reactions, EDLCs generally exhibit inferior energy density. One potential approach to addressing this issue is to incorporate highly porous and electrically conductive materials into carbonaceous material-based EDLCs. In this paper, we present a hybrid electrode consisting of a conductive metal-organic framework (c-MOF) with high electrical conductivity and unique porous structure combined with a mat of aligned carbon nanofibers (ACNFs). Its highly ordered structure facilitates electronic/ionic transport, increasing the areal capacitance by up to 3.9 times compared to randomly-oriented carbon nanofibers (RCNFs). An additional increase in areal capacitance (+64%) is achieved by introducing c-MOF (RCNFs: 25.4 mF cm-2; ACNFs: 98.7 mF cm-2; c-MOF/ACNF: 161.8 mF cm-2). Additionally, an ACNF mat exhibits excellent mechanical flexibility and electrochemical reliability, making it highly suitable for the assembly of freestanding flexible supercapacitors. By optimizing the electrochemical performance of c-MOF/ACNF and its suitability for utilization in flexible energy storage systems, this study presents a promising avenue for the practical implementation of c-MOF-based supercapacitors.

Boron-Doped Activated Carbon Supports for Cobalt-Catalyzed Oxygen Evolution in Alkaline Electrolyte.

Activated carbons (ACs) are the most widely used and attractive support materials for electrocatalytic applications because of their significant surface areas, high electrical conductivities, and moderate affinities toward supported metal catalysts. However, the corrosive behavior of ACs at oxidative potentials causes an inevitable reduction in the active surface area of supported catalysts, resulting in the continuous deterioration of their electrocatalytic performance. Therefore, the introduction of corrosion-resistant durable catalyst supports is essential for sustainable and efficient electrocatalysis. Here, we modified ACs to obtain different boron (B)-doped structures via doping-temperature controls to investigate the corrosion resistance of B-doped ACs. With increasing doping temperature, the B-doped ACs exhibited a decreased defect density and enhanced crystallinity owing to the accelerating dopant-induced graphitization. We found that the substitution of B atoms into the carbon lattice improved the structural integrity of the carbon structure, and cyclic voltammetry (CV) tests suggested that the highly B-substituted structures caused electrochemical surface passivation against carbon corrosion. Moreover, B-doped ACs significantly contributed to the increase in loading mass of cobalt (Co)-based catalyst on them and the electrochemical durability toward the oxygen evolution reaction as catalyst-support hybrid. The B22 (B-doped AC obtained at a 2200 °C B-doping temperature)-supported Co catalyst with the lowest oxidation current exhibited a voltage change of 32 mV at a current density of 10 mA/cm2 (ΔEj=10) after 10,000 cycles, which was a factor of ∼7 higher cycle durability and stability than that of the conventional IrO2 catalyst (ΔEj=10 = 205 mV). Here, we propose that surface engineering by B-doping to improve the structural integrity of ACs is an attractive method for designing durable electrocatalytic support materials.

Chemo-Mechanical Energy Harvesters with Enhanced Intrinsic Electrochemical Capacitance in Carbon Nanotube Yarns.

Predicting and preventing disasters in difficult-to-access environments, such as oceans, requires self-powered monitoring devices. Since the need to periodically charge and replace batteries is an economic and environmental concern, energy harvesting from external stimuli to supply electricity to batteries is increasingly being considered. Especially, in aqueous environments including electrolytes, coiled carbon nanotube (CNT) yarn harvesters have been reported as an emerging approach for converting mechanical energy into electrical energy driven by large and reversible capacitance changes under stretching and releasing. To realize enhanced harvesting performance, experimental and computational approaches to optimize structural homogeneity and electrochemical accessible area in CNT yarns to maximize intrinsic electrochemical capacitance (IEC) and stretch-induced changes are presented here. Enhanced IEC further enables to decrease matching impedance for more energy efficient circuits with harvesters. In an ocean-like environment with a frequency from 0.1 to 1 Hz, the proposed harvester demonstrates the highest volumetric power (1.6-10.45 mW cm-3 ) of all mechanical harvesters reported in the literature to the knowledge of the authors. Additionally, a high electrical peak power of 540 W kg-1 and energy conversion efficiency of 2.15% are obtained from torsional and tensile mechanical energy.

Rational Process Design for Facile Fabrication of Dual Functional Hybrid Membrane of MOF and Electrospun Nanofiber towards High Removal Efficiency of PM2.5 and Toxic Gases.

The application of nanofiber (NF) and porous metal-organic framework (MOF) has increasingly attracted attention for the protection of public health. This composite platform provides the physical sieving of particulate matters (PMs) and capturing gases, serving as an outstanding filtering medium with lightweight and multifunctionality. Herein, process design and optimization are performed to produce a multifunctional membrane comprised NFs and MOF particles. Electrospinning/electrospray techniques are used to fabricate a hybrid membrane of poly(vinyl alcohol) NF and Fe-BTC as an adsorptive MOF on a macroporous nonwoven (NW). Three types of filters are prepared by varying the order of processing steps, that is, MOF/NF/NW, MOF+NF/NW, and NF/MOF/NW, to elucidate the effect of the fabrication process in the filtration of air pollutant. The optimal filtration performance is achieved in MOF+NF/NW system: the highest filtration efficiency (97%) and outstanding gas capturing efficiencies (≈60% and ≈35% decreases from initial NH3 and H2 S concentrations, respectively). However, when air permeability and filtration efficiency are considered, the most desirable configuration for personal protection equipment (PPE) is NF/MOF/NW system, which effectively enabled comfortable breathing without compromising the lightweight and multifunctional performance.

Single-Step Fabrication of Polymeric Composite Membrane via Centrifugal Colloidal Casting for Fuel Cell Applications.

Recent interest in polymer electrolyte membranes (PEMs) for fuel cell systems has spurred the development of infiltration technology by which to insert ionomers into mechanically robust reinforcement structures by solution casting in order to produce a cost effective and highly efficient electrolyte. However, the results of the fabrication process often continue to present challenges related to the structural complexity and self-assembly dynamics between the hydrophobic and hydrophilic parts of the constituents which in turn, necessitates additional processing steps and increases production costs. Here, a single-step process is reported for highly compact polymeric composite membranes (PCMs), fabricated using a centrifugal colloidal casting (C3) method. Combined structural analyses as well as coarse-grained molecular dynamics simulations are employed to determine the micro-/macroscopic structural characteristics of the fabricated PCMs. These findings indicate that the C3 method is capable of forming highly dense ionomer matrix-reinforcement composites consisting of microphase-separated ionomer structures with tailored crystallinity and ionic cluster sizes. An outcome that is very unlikely with the single-step coating steps in conventional methods. These structural attributes ensure PCMs with better proton conductivity, greater strain stability, and lower gas crossover properties compared to commercial pristine membranes, expanding their possible range of applicability to PEMs.

Black Tungsten Oxide Nanofiber as a Robust Support for Metal Catalysts: High Catalyst Loading for Electrochemical Oxygen Reduction.

Black valve metal oxides with low oxygen vacancies are identified to be promising for various industrial applications, such as in gas sensing, photocatalysis, and rechargeable batteries, owing to their high reducibility and stability, as well as considerable fractions of low-valent metal species and oxygen vacancies in their lattices. Herein, the nanofiber (NF) of black oxygen-deficient tungsten trioxide (WO3- x ) is presented as a versatile and robust support for the direct growth of a platinum catalyst for oxygen reduction reaction (ORR). The nonstoichiometric, poorly crystallized black WO3- x NFs are prepared by electrospinning the W precursor into NFs followed by their low-temperature (650 °C) reductive calcination. The black WO3- x NFs have adequate electrical conductivity owing to their decreased bandgap and amorphous structure. Remarkably, the oxygen-deficient surface (surface O/W = 2.44) facilitates the growth of small Pt nanoparticles, which resist aggregation, as confirmed by structural characterization and computational analysis. The Pt-loaded black WO3- x NFs outperform the Pt-loaded crystalline white WO3- x NFs in both the electrochemical ORR activity and the accelerated durability test. This study can inspire the use of oxygen-deficient metal oxides as supports for other electrocatalysts, and can further increase the versatility of oxygen-deficient metal oxides.

Hierarchically Assembled Cobalt Oxynitride Nanorods and N-Doped Carbon Nanofibers for Efficient Bifunctional Oxygen Electrocatalysis with Exceptional Regenerative Efficiency.

Oxygen-based electrocatalysis is an integral aspect of a clean and sustainable energy conversion/storage system. The development of economic bifunctional electrocatalysts with high activity and durability during reversible reactions remains a great challenge. The tailored porous structure and separately presented active sites for oxygen reduction and oxygen evolution reactions (ORR and OER) without mutual interference are most crucial for achieving desired bifunctional catalysts. Here, we report a hybrid composed of sheath-core cobalt oxynitride (CoOx@CoNy) nanorods grown perpendicularly on N-doped carbon nanofiber (NCNF). The brush-like CoOx@CoNy nanorods, composed of metallic Co4N cores and oxidized surfaces, exhibit excellent OER activity (E = 1.69 V at 10 mA cm-2) in an alkaline medium. Although pristine NCNF or CoOx@CoNy alone had poor catalytic activity in the ORR, the hybrid showed dramatically enhanced ORR performance (E = 0.78 V at -3 mA cm-2). The experimental results coupled with a density functional theory (DFT) simulation confirmed that the broad surface area of the CoOx@CoNy nanorods with an oxidized skin layer boosts the catalytic OER, while the facile adsorption of ORR intermediates and a rapid interfacial charge transfer occur at the interface between the CoOx@CoNy nanorods and the electrically conductive NCNF. Furthermore, it was found that the independent catalytic active sites in the CoOx@CoNy/NCNF catalyst are continuously regenerated and sustained without mutual interference during the round-trip ORR/OER, affording stable operation of Zn-air batteries.

Synergistic Interactions of Different Electroactive Components for Superior Lithium Storage Performance.

The fusion of different electroactive components of lithium-ion batteries (LIBs) sometimes brings exceptional electrochemical properties. We herein report the reduced graphene-oxide (rGO)-coated Zn2SnO4z@NiO nanofibers (ZSO@NiO@G NFs) formed by the synergistic fusion of three different electroactive components including ZnO, SnO2, and NiO that exhibit exceptional electrochemical properties as negative electrodes for LIBs. The simple synthetic route comprised of electrospinning and calcination processes enables to form porous one-dimensional (1D) structured ZSO, which is the atomic combination between ZnO and SnO2, exhibiting effective strain relaxation during battery operation. Furthermore, the catalytic effect of Ni converted from the surface-functional NiO nanolayer on ZSO significantly contributes to improved reversible capacity. Finally, rGO sheets formed on the surface of ZSO@NiO NFs enable to construct electrically conductive path as well as a stable SEI layer, resulting in excellent electrochemical performances. Especially, exceptional cycle lifespan of more than 1600 cycles with a high capacity (1060 mAh g-1) at a high current density (1000 mA g-1), which is the best result among mixed transition metal oxide (stannates, molybdates, cobaltates, ferrites, and manganates) negative electrodes for LIBs, is demonstrated.

Colorimetric Dye-Loaded Nanofiber Yarn: Eye-Readable and Weavable Gas Sensing Platform.

The colorimetric gas sensor offers an opportunity for the simple and rapid detection of toxic gaseous substances based on visually discernible changes in the color of the sensing material. In particular, the accurate detection of trace amounts of certain biomarkers in a patient's breath provides substantial clues regarding specific diseases, for example, hydrogen sulfide (H2S) for halitosis and ammonia (NH3) for kidney disorder. However, conventional colorimetric sensors often lack the sensitivity, selectivity, detection limit, and mass-productivity, impeding their commercialization. Herein, we report an inexpensive route for the meter-scale synthesis of a colorimetric sensor based on a composite nanofiber yarn that is chemically functionalized with an ionic liquid as an effective H2S adsorbent and lead acetate as a colorimetric dye. As an eye-readable and weavable sensing platform, the single-strand yarn exhibits enhanced sensitivity supported by its high surface area and well-developed porosity to detect the breath biomarker (1 ppm of H2S). Alternatively, the yarn loaded with lead iodide dyes could reversibly detect NH3 gas molecules in the ppm-level, demonstrating the facile extensibility. Finally, we demonstrated that the freestanding yarns could be sewn into patterned textiles for the fabrication of a wearable toxic gas alarm system with a visual output.

Lithium-Air Batteries: Air-Breathing Challenges and Perspective.

Lithium-oxygen (Li-O2) batteries have been intensively investigated in recent decades for their utilization in electric vehicles. The intrinsic challenges arising from O2 (electro)chemistry have been mitigated by developing various types of catalysts, porous electrode materials, and stable electrolyte solutions. At the next stage, we face the need to reform batteries by substituting pure O2 gas with air from Earth's atmosphere. Thus, the key emerging challenges of Li-air batteries, which are related to the selective filtration of O2 gas from air and the suppression of undesired reactions with other constituents in air, such as N2, water vapor (H2O), and carbon dioxide (CO2), should be properly addressed. In this review, we discuss all key aspects for developing Li-air batteries that are optimized for operating in ambient air and highlight the crucial considerations and perspectives for future air-breathing batteries.

High-yield electrochemical hydrogen peroxide production from an enhanced two-electron oxygen reduction pathway by mesoporous nitrogen-doped carbon and manganese hybrid electrocatalysts.

Electrochemical hydrogen peroxide (H2O2) production by the direct two-electron (2e-) oxygen reduction reaction (ORR) has received much attention as a promising alternative to the industrially developed anthraquinone fabrication process. Transition metal (M) and nitrogen doped carbon (M-N-C, M = Fe or Co) catalysts are known to be active for four electron ORR pathways via two + two electron transfer, where the former is for the ORR and the latter for the peroxide reduction reaction (PRR). Here, we report mesoporous N-doped carbon/manganese hybrid electrocatalysts composed of MnO and Mn-Nx coupled with N-doped carbons (Mn-O/N@NCs), which have led to the development of electrocatalysis towards the 2e- ORR route. Based on the structural and electrochemical characterization, the number of transferred electrons during the ORR on the Mn-O/N@NCs was found to be close to the theoretical value of the 2e- process, indicating their high activity toward H2O2. The favored ORR process arose due to the increased number of Mn-Nx sites within the mesoporous N-doped carbon materials. Furthermore, there was a strong indication that the PRR is significantly suppressed by adjacent MnO species, demonstrating its highly selective production of H2O2 (>80%) from the oxygen electrochemical process. The results of a real fuel cell device test demonstrated that an Mn-O/N@NC catalyst sustains a very stable current, and we attributed its outstanding activity to a combination of site-dependent facilitation of 2e- transfer and a favorable porosity for mass transport.

Three-Dimensional Nanofibrous Air Electrode Assembled With Carbon Nanotubes-Bridged Hollow Fe2O3 Nanoparticles for High-Performance Lithium-Oxygen Batteries.

Lithium-oxygen batteries have been considered as one of the most viable energy source options for electric vehicles due to their high energy density. However, they are still faced with technical challenges, such as low round-trip efficiency and short cycle life, which mainly originate from the cathode part of the battery. In this work, we designed a three-dimensional nanofibrous air electrode consisted of hierarchically structured carbon nanotube-bridged hollow Fe2O3 nanoparticles (H-Fe2O3/CNT NFs). Composite nanofibers consisted of hollow Fe2O3 NPs anchored by multiple CNTs offered enhanced catalytic sites (interconnected hollow Fe2O3 NPs) and fast charge-transport highway (bridged CNTs) for facile formation and decomposition of Li2O2, leading to outstanding cell performance: (1) Swagelok cell exhibited highly reversible cycling characteristics for 250 cycles with a fixed capacity of 1000 mAh g-1 at a current density of 500 mA g-1. (2) A module composed of two pouch-type cells stably powered an light-emitting diode lamp operated at 5.0 V.

Brush-Like Cobalt Nitride Anchored Carbon Nanofiber Membrane: Current Collector-Catalyst Integrated Cathode for Long Cycle Li-O2 Batteries.

To achieve a high reversibility and long cycle life for lithium-oxygen (Li-O2) batteries, the irreversible formation of Li2O2, inevitable side reactions, and poor charge transport at the cathode interfaces should be overcome. Here, we report a rational design of air cathode using a cobalt nitride (Co4N) functionalized carbon nanofiber (CNF) membrane as current collector-catalyst integrated air cathode. Brush-like Co4N nanorods are uniformly anchored on conductive electrospun CNF papers via hydrothermal growth of Co(OH)F nanorods followed by nitridation step. Co4N-decorated CNF (Co4N/CNF) cathode exhibited excellent electrochemical performance with outstanding stability for over 177 cycles in Li-O2 cells. During cycling, metallic Co4N nanorods provide sufficient accessible reaction sites as well as facile electron transport pathway throughout the continuously networked CNF. Furthermore, thin oxide layer (<10 nm) formed on the surface of Co4N nanorods promote reversible formation/decomposition of film-type Li2O2, leading to significant reduction in overpotential gap (∼1.23 V at 700 mAh g-1). Moreover, pouch-type Li-air cells using Co4N/CNF cathode stably operated in real air atmosphere even under 180° bending. The results demonstrate that the favorable formation/decomposition of reaction products and mediation of side reactions are hugely governed by the suitable surface chemistry and tailored structure of cathode materials, which are essential for real Li-air battery applications.

Formation of a Surficial Bifunctional Nanolayer on Nb2 O5 for Ultrastable Electrodes for Lithium-Ion Battery.

Safe and long cycle life electrode materials for lithium-ion batteries are significantly important to meet the increasing demands of rechargeable batteries. Niobium pentoxide (Nb2 O5 ) is one of the highly promising candidates for stable electrodes due to its safety and minimal volume expansion. Nevertheless, pulverization and low conductivity of Nb2 O5 have remained as inherent challenges for its practical use as viable electrodes. A highly facile method is proposed to improve the overall cycle retention of Nb2 O5 microparticles by ammonia (NH3 ) gas-driven nitridation. After nitridation, an ultrathin surficial layer (2 nm) is formed on the Nb2 O5 , acting as a bifunctional nanolayer that allows facile lithium (Li)-ion transport (10-100 times higher Li diffusivity compared with pristine Nb2 O5 microparticles) and further prevents the pulverization of Nb2 O5 . With the subsequent decoration of silver (Ag) nanoparticles (NPs), the low electric conductivity of nitridated Nb2 O5 is also significantly improved. Cycle retention is greatly improved for nitridated Nb2 O5 (96.7%) compared with Nb2 O5 (64.7%) for 500 cycles. Ag-decorated, nitridated Nb2 O5 microparticles and nitridated Nb2 O5 microparticles exhibit ultrastable cycling for 3000 cycles at high current density (3000 mA g-1 ), which highlights the importance of the surficial nanolayer in improving overall electrochemical performances, in addition to conductive NPs.

A High-Capacity and Long-Cycle-Life Lithium-Ion Battery Anode Architecture: Silver Nanoparticle-Decorated SnO2/NiO Nanotubes.

The combination of high-capacity and long-term cyclability has always been regarded as the first priority for next generation anode materials in lithium-ion batteries (LIBs). To meet these requirements, the Ag nanoparticle decorated mesoporous SnO2/NiO nanotube (m-SNT) anodes were synthesized via an electrospinning process, followed by fast ramping rate calcination and subsequent chemical reduction in this work. The one-dimensional porous hollow structure effectively alleviates a large volume expansion during cycling as well as provides a short lithium-ion duffusion length. Furthermore, metallic nickel (Ni) nanoparticles converted from the NiO nanograins during the lithiation process reversibly decompose Li2O during delithiation process, which significantly improves the reversible capacity of the m-SNT anodes. In addition, Ag nanoparticles uniformly decorated on the m-SNT via a simple chemical reduction process significantly improve rate capability and also contribute to long-term cyclability. The m-SNT@Ag anodes exhibited excellent cycling stability without obvious capacity fading after 500 cycles with a high capacity of 826 mAh g-1 at a high current density of 1000 mA g-1. Furthermore, even at a very high current density of 5000 mA g-1, the charge-specific capacity remained as high as 721 mAh g-1, corresponding to 60% of its initial capacity at a current density of 100 mA g-1.

Tailored Combination of Low Dimensional Catalysts for Efficient Oxygen Reduction and Evolution in Li-O2 Batteries.

The development of efficient bifunctional catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is a key issue pertaining high performance Li-O2 batteries. Here, we propose a heterogeneous electrocatalyst consisting of LaMnO3 nanofibers (NFs) functionalized with RuO2 nanoparticles (NPs) and non-oxidized graphene nanoflakes (GNFs). The Li-O2 cell employing the tailored catalysts delivers an excellent electrochemical performance, affording significantly reduced discharge/charge voltage gaps (1.0 V at 400 mA g(-1) ), and superior cyclability for over 320 cycles. The outstanding performance arises from (1) the networked LaMnO3 NFs providing ORR/OER sites without severe aggregation, (2) the synergistic coupling of RuO2 NPs for further improving the OER activity and the electrical conductivity on the surface of the LaMnO3 NFs, and (3) the use of GNFs providing a fast electronic pathway as well as improved ORR kinetics.

One-Dimensional RuO2/Mn2O3 Hollow Architectures as Efficient Bifunctional Catalysts for Lithium-Oxygen Batteries.

Rational design and massive production of bifunctional catalysts with fast oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) kinetics are critical to the realization of highly efficient lithium-oxygen (Li-O2) batteries. Here, we first exploit two types of double-walled RuO2 and Mn2O3 composite fibers, i.e., (i) phase separated RuO2/Mn2O3 fiber-in-tube (RM-FIT) and (ii) multicomposite RuO2/Mn2O3 tube-in-tube (RM-TIT), by controlling ramping rate during electrospinning process. Both RM-FIT and RM-TIT exhibited excellent bifunctional electrocatalytic activities in alkaline media. The air electrodes using RM-FIT and RM-TIT showed enhanced overpotential characteristics and stable cyclability over 100 cycles in the Li-O2 cells, demonstrating high potential as efficient OER and ORR catalysts.

Rational Design of Efficient Electrocatalysts for Hydrogen Evolution Reaction: Single Layers of WS2 Nanoplates Anchored to Hollow Nitrogen-Doped Carbon Nanofibers.

To exploit the benefits of nanostructuring for enhanced hydrogen evolution reaction (HER), we employed coaxial electrospinning to synthesize single-layered WS2 nanoplates anchored to hollow nitrogen-doped carbon nanofibers (WS2@HNCNFs) as efficient electrocatalysts. For comparison, bulk WS2 powder and single layers of WS2 embedded in nitrogen-doped carbon nanofibers (WS2@NCNFs) were synthesized and electrochemically tested. The distinctive design of the WS2@HNCNFs enables remarkable electrochemical performances showing a low overpotential with reduced charge transfer resistance, a small Tafel slope, and excellent durability. The experimental results highlight the importance of nanostructure engineering in electrocatalysts for enhanced HER.