Magnetothermal Microfluidic-Assisted Hierarchical Microfibers for Ultrahigh-Energy-Density Supercapacitors

Chemical architectures with an ordered porous backbone and high charge transfer are significant for fiber-shaped supercapacitors (FSCs). However, owing to the sluggish ion kinetic diffusion and storage in compacted fibers, achieving high energy density remains a challenge. An innovative magnetothermal microfluidic method is now proposed to design hierarchical carbon polyhedrons/holey graphene (CP/HG) core–shell microfibers. Owing to highly magnetothermal etching and microfluidic reactions, the CP/HG fibers maintain an open inner-linked ionic pathway, large specific surface area, and moderate nitrogen active site, facilitating more rapid ionic dynamic transportation and accommodation. The CP/HG FSCs show an ultrahigh energy density (335.8 μWh cm⁻²) and large areal capacitance (2760 mF cm⁻²). A self-powered endurance application with the integration of chip-based FSCs is designed to profoundly drive the durable motions of an electric car and walking robot.     

Hierarchical Micro‐Mesoporous Carbon‐Framework‐Based Hybrid Nanofibres for High‐Density Capacitive Energy Storage

Advanced methods, allowing the controllable synthesis of ordered structural nanomaterials with favourable charges transfer and storage, are highly important to achieve ideal supercapacitors with high energy density. Herein, we report a microliter droplet‐based method to synthesize hierarchical‐structured metal–organic framework/graphene/carbon nanotubes hybrids. The confined ultra‐small‐volume reaction, give well‐defined hybrids with a large specific‐surface‐area (1206 m² g^?1), abundant ionic‐channels (narrow pore of 0.86 nm), and nitrogen active‐sites (10.63 %), resulting in high pore‐size utilization (97.9 %) and redox‐activity (32.3 %). We also propose a scalable microfluidic‐blow‐spinning method to consecutively generate nanofibre‐based flexible supercapacitor electrodes with striking flexibility and mechanical strength. The supercapacitors display large volumetric energy density (147.5 mWh cm^?3), high specific capacitance (472 F cm^?3) and stably deformable energy‐supply.     

Realizing both High Energy and High Power Densities by Twisting Three Carbon‐Nanotube‐Based Hybrid Fibers

Energy storage devices, such as lithium‐ion batteries and supercapacitors, are required for the modern electronics. However, the intrinsic characteristics of low power densities in batteries and low energy densities in supercapacitors have limited their applications. How to simultaneously realize high energy and power densities in one device remains a challenge. Herein a fiber‐shaped hybrid energy‐storage device (FESD) formed by twisting three carbon nanotube hybrid fibers demonstrates both high energy and power densities. For the FESD, the energy density (50 mWh cm^?3 or 90 Wh kg^?1) many times higher than for other forms of supercapacitors and approximately 3 times that of thin‐film batteries; the power density (1 W cm^?3 or 5970 W kg^?1) is approximately 140 times of thin‐film lithium‐ion battery. The FESD is flexible, weaveable and wearable, which offers promising advantages in the modern electronics.     

Synthesis of Hierarchically Porous Sandwich‐Like Carbon Materials for High‐Performance Supercapacitors

For the first time, hierarchically porous carbon materials with a sandwich‐like structure are synthesized through a facile and efficient tri‐template approach. The hierarchically porous microstructures consist of abundant macropores and numerous micropores embedded into the crosslinked mesoporous walls. As a result, the obtained carbon material with a unique sandwich‐like structure has a relatively high specific surface (1235 m² g^?1), large pore volume (1.30 cm³ g^?1), and appropriate pore size distribution. These merits lead to a comparably high specific capacitance of 274.8 F g^?1 at 0.2 A g^?1 and satisfying rate performance (87.7 % retention from 1 to 20 A g^?1). More importantly, the symmetric supercapacitor with two identical as‐prepared carbon samples shows a superior energy density of 18.47 Wh kg^?1 at a power density of 179.9 W kg^?1. The asymmetric supercapacitor based on as‐obtained carbon sample and its composite with manganese dioxide (MnO₂) can reach up to an energy density of 25.93 Wh kg^?1 at a power density of 199.9 W kg^?1. Therefore, these unique carbon material open a promising prospect for future development and utilization in the field of energy storage.     

Extraordinary Supercapacitor Performance of a Multicomponent and Mixed‐Valence Oxyhydroxide

We report a novel multicomponent mixed‐valence oxyhydroxide‐based electrode synthesized by electrochemical polarization of a de‐alloyed nanoporous NiCuMn alloy. The multicomponent oxyhydroxide has a high specific capacitance larger than 627 F cm^?3 (1097±95 F g^?1) at a current density of 0.25 A cm^?3, originating from multiple redox reactions. More importantly, the oxyhydroxide electrode possesses an extraordinarily wide working‐potential window of 1.8 V in an aqueous electrolyte, which far exceeds the theoretically stable window of water. The realization of both high specific capacitance and high working‐potential windows gives rise to a high energy density, 51 mWh cm^?3, of the multicomponent oxyhydroxide‐based supercapacitor for high‐energy and high‐power applications.     

Thermodynamic and Structural Characterization of the Transformation from a Metastable Low‐Density to a Very High‐Density Form of Supercooled TIP4P‐Ew Model Water

We explore the phase diagram of the metastable TIP4P‐Ew liquid model water from 360 K down to 150 K at densities ranging from 0.950 to 1.355 g cm^?3. In addition to the low‐density/high‐density (LDL/HDL) liquid–liquid transition, we observe a structural high‐density/very high‐density (HDL/VHDL) transformation for the lowest temperatures at 1.30 g cm^?3. The characteristics of the isobars and isotherms suggest the presence of a stepwise HDL/VHDL transition with first‐order‐like appearance. In addition, we also identify an apparent pretransition at 1.24 g cm^?3, which suggests that the experimentally detected LDA/VHDA transformation might evolve into a multiple‐step process with different local structures representing local minima in the free‐energy landscape. Such a scenario is supported by a pronounced correlation between the isothermal density dependence of the pressure, with a stepwise increase of the oxygen coordination number, due to the appearance of interstitial water molecules.     

Three‐Dimensional NiMoO4 Nanosheets Supported on a Carbon Fibers@Pre‐Treated Ni Foam (CF@PNF) Substrate as Advanced Electrodes for Asymmetric Supercapacitors

Herein, we report a nanoarchitectured nickel molybdate/carbon fibers@pre‐treated Ni foam (NiMoO₄/CF@PNF) electrode for supercapacitors. The synthesis of NiMoO₄/CF@PNF mainly consists of a direct chemical vapor deposition (CVD) growth of dense carbon fibers (CFs) onto pre‐treated Ni foam (PNF) as the substrate, followed by in situ growth of NiMoO₄ nanosheets (NSs) on the CF@PNF substrate by means of a hydrothermal process. The NiMoO₄/CF@PNF electrode exhibits a high areal capacitance (5.14 F cm^?2 at 4 mA cm^?2) and excellent cycling stability (97 % capacitance retention after 2000 cycles at 10 mA cm^?2). Furthermore, we have successfully assembled NiMoO₄ NSs//activated carbon (AC) asymmetric supercapacitors, which can achieve an energy density of 45.6 Wh kg^?1 at 674 W kg^?1, and excellent stability with 93 % capacitance retention after 2000 cycles at 5 mA cm^?2. These superior properties hold great promise for energy‐storage applications.     

Tetrathiafulvalene‐amido‐2‐pyridine‐N‐oxide as Efficient Charge‐Transfer Antenna Ligand for the Sensitization of YbIII Luminescence in a Series of Lanthanide Paramagnetic Coordination Complexes

The tetrathiafulvalene‐amido‐2‐pyridine‐N‐oxide ( L ) ligand has been employed to coordinate 4f elements. The architecture of the complexes mainly depends on the ionic radii of the lanthanides. Thus, the reaction of L in the same experimental protocol leads to three different molecular structure series. Binuclear [Ln₂(hfac)₅(O₂CPhCl)( L )₃] ? 2 H₂O (hfac^?=1,1,1,5,5,5‐hexafluoroacetylacetonate anion, O₂CPhCl^?=3‐chlorobenzoate anion) and mononuclear [Ln(hfac)₃( L )₂] complexes were obtained by using rare‐earth ions with either large (Ln^III=Pr, Gd) or small (Ln^III=Y, Yb) ionic radius, respectively, whereas the use of Tb^III that possesses an intermediate ionic radius led to the formation of a binuclear complex of formula [Tb₂(hfac)₄(O₂CPhCl)₂( L )₂]. Antiferromagnetic interactions have been observed in the three dinuclear compounds by using an extended empirical method. Photophysical properties of the coordination complexes have been studied by solid‐state absorption spectroscopy, whereas time‐dependent density functional theory (TD‐DFT) calculations have been carried out on the diamagnetic Y^III derivative to build a molecular orbital diagram and to reproduce the absorption spectrum. For the [Yb(hfac)₃( L )₂] complex, the excitation at 19 600 cm^?1 of the HOMO→LUMO+1/LUMO+2 charge‐transfer transition induces both line‐shape emissions in the near‐IR spectral range assigned to the ²F_5/2→²F_7/2 (9860 cm^?1) ytterbium‐centered transition and a residual charge‐transfer emission around 13 150 cm^?1. An efficient antenna effect that proceeds through energy transfer from the singlet excited state of the tetrathiafulvalene‐amido‐2‐pyridine‐N‐oxide chromophore is evidence of the Yb^III sensitization.     

Large‐Scale Synthesis of MOF‐Derived Superporous Carbon Aerogels with Extraordinary Adsorption Capacity for Organic Solvents

Carbon aerogels (CAs) with 3D interconnected networks hold promise for application in areas such as pollutant treatment, energy storage, and electrocatalysis. In spite of this, it remains challenging to synthesize high‐performance CAs on a large scale in a simple and sustainable manner. We report an eco‐friendly method for the scalable synthesis of ultralight and superporous CAs by using cheap and widely available agarose (AG) biomass as the carbon precursor. Zeolitic imidazolate framework‐8 (ZIF‐8) with high porosity is introduced into the AG aerogels to increase the specific surface area and enable heteroatom doping. After pyrolysis under inert atmosphere, the ZIF‐8/AG‐derived nitrogen‐doped CAs show a highly interconnected porous mazelike structure with a low density of 24 mg cm^?3, a high specific surface area of 516 m² g^?1, and a large pore volume of 0.58 cm^?3 g^?1. The resulting CAs exhibit significant potential for application in the adsorption of organic pollutants.     

Free‐Standing Conducting Polymer Films for High‐Performance Energy Devices

Thick, uniform, easily processed, highly conductive polymer films are desirable as electrodes for solar cells as well as polymer capacitors. Here, a novel scalable strategy is developed to prepare highly conductive thick poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate (HCT‐PEDOT:PSS) films with layered structure that display a conductivity of 1400 S cm^?1 and a low sheet resistance of 0.59 ohm sq^?1. Organic solar cells with laminated HCT‐PEDOT:PSS exhibit a performance comparable to the reference devices with vacuum‐deposited Ag top electrodes. More importantly, the HCT‐PEDOT:PSS film delivers a specific capacitance of 120 F g^?1 at a current density of 0.4 A g^?1. All‐solid‐state flexible symmetric supercapacitors with the HCT‐PEDOT:PSS films display a high volumetric energy density of 6.80 mWh cm^?3 at a power density of 100 mW cm^?3 and 3.15 mWh cm^?3 at a very high power density of 16160 mW cm^?3 that outperforms previous reported solid‐state supercapacitors based on PEDOT materials.     

Dual‐Template Pore Engineering of Whey Powder‐Derived Carbon as an Efficient Oxygen Reduction Reaction Electrocatalyst for Primary Zinc‐Air Battery

Cost‐effective and high‐performance electrocatalysts for oxygen reduction reactions (ORR) are needed for many energy storage and conversion devices. Here, we demonstrate that whey powder, a major by‐product in the dairy industry, can be used as a sustainable precursor to produce heteroatom doped carbon electrocatalysts for ORR. Rich N and S compounds in whey powders can generate abundant catalytic active sites. However, these sites are not easily accessible by reactants of ORR. A dual‐template method was used to create a hierarchically and interconnected porous structure with micropores created by ZnCl₂ and large mesopores generated by fumed SiO₂ particles. At the optimum mass ratio of whey power: ZnCl₂ : SiO₂ at 1 : 3 : 0.8, the resulting carbon material has a large specific surface area close to 2000 m² g^?1, containing 4.6 at.% of N with 39.7% as pyridinic N. This carbon material shows superior electrocatalytic activity for ORR, with an electron transfer number of 3.88 and a large kinetic limiting current density of 45.40 mA cm^?2. They were employed as ORR catalysts to assemble primary zinc‐air batteries, which deliver a power density of 84.1 mW cm^?2 and a specific capacity of 779.5 mAh g^?1, outperforming batteries constructed using a commercial Pt/C catalyst. Our findings open new opportunities to use an abundant biomaterial, whey powder, to create high‐value‐added carbon electrocatalysts for emerging energy applications.     

Constant Electricity Generation in Nanostructured Silicon by Evaporation‐Driven Water Flow

Recently, hydrovoltaic technology emerged as a novel renewable energy harvesting method, which dramatically extends the capability to harvest water energy. However, the urgent issue restricting its device performance is poor carrier transport properties of the solid surface if large charged interface is considered simultaneously. Herein, a hydrovoltaic device based on silicon nanowire arrays (SiNWs), which provide large charged surface/volume ratio and excellent carrier transport properties, yields sustained electricity by a carrier concentration gradient induced by evaporation‐induced water flow inside nanochannels. The device can yield direct current with a short‐circuit current density of over 55 μA cm^?2, which is three orders larger than a previously reported analogous device (approximately 40 nA cm^?2). Moreover, it exhibits a constant output power density of over 6 μW cm^?2 and an open‐circuit voltage of up to 400 mV. Our finding may pave a way for developing energy‐harvesting devices from ubiquitous evaporation‐driven internal water flow in nature with semiconductor material of silicon.     

Multiscale Dot-Wire-Sheet Heterostructured Nitrogen-Doped Carbon Dots-Ti3C2Tx/Silk Nanofibers for High-Performance Fiber-Shaped Supercapacitors

Fiber-shaped supercapacitors (FSCs) have become one of the significantly strategical flexible energy-storage materials towards future wearable textile electronics and metaverse technologies. Here, we develop the high-performance FSCs based on multiscale dot-wire-sheet heterostructure microfiber of nitrogen-doped carbon dots-Ti₃C₂T_x/silk nanofibers (NCDs-Ti₃C₂T_x/SNFs) hybrids via microfluidic fabrication. Due to the enlarged interlayer spacing, plentiful porous channels, accelerated H⁺ ion transport dynamics, large electrical conductivity and excellent mechanical strength/flexibility, the NCDs-Ti₃C₂T_x/SNFs possesses high volumetric capacitance (2218.7 F cm⁻³) and reversible charge–discharge stability in 1 M H₂SO₄ electrolyte. Furthermore, the solid-state FSCs present high energy density (57.9 mWh cm⁻³), good capacitance (1157 F cm⁻³), long-life cycles (82.3 % capacitance retention after 40000 cycles), which realize the actual energy-supply applications (powering lamp, watch and toy car).     

Maximum Compaction of Ionic Organic Explosives: Bis(hydroxylammonium) 5,5′‐Dinitromethyl‐3,3′‐bis(1,2,4‐oxadiazolate) and its Derivatives

Within this contribution on bis(oxadiazoles) we report on bis‐hydroxylammonium 5,5′‐dinitro‐methyl‐3,3′‐bis(1,2,4‐oxadiazolate), which (to the best of our knowledge) shows the highest density (2.00 g cm^?3 at 92 K, 1.95 g cm^?3 at RT) ever reported for an ionic CHNO explosive. Also the corresponding bis(ammonium) salt shows an outstanding density of 1.95 g cm^?3 (173 K). The reaction of the 3,3′‐bis(1,2,4‐oxadiazolyl)‐5,5′‐bis(2,2′‐dinitro)‐diacetic acid diethyl ester with different nitrogen‐rich bases, such as ammonia, hydrazine, hydroxylamine, and triaminoguanidine causes decarboxylation followed by the formation of the corresponding salts (cation/anion stoichiometry 2:1). The reactions are performed at ambient temperature in H₂O/MeOH mixtures and furnish qualitatively pure products showing characteristics of typical secondary explosives. The obtained compounds were characterized by multinuclear NMR spectroscopy, IR and Raman spectroscopy, as well as mass spectrometry. Single‐crystal X‐ray diffraction studies were performed and the structures of all compounds were determined at low temperatures. The thermal stability was measured by differential scanning calorimetry (DSC). The sensitivities were explored by using the BAM drophammer and friction test. The heats of formation were calculated by the atomization method based on CBS‐4M enthalpies. With these values and the X‐ray densities, several detonation parameters such as the detonation pressure, velocity, energy, and temperature were computed using the EXPLO5 code.     

Porous Nitrogen‐Doped Carbon Nanotubes Derived from Tubular Polypyrrole for Energy‐Storage Applications

Porous nitrogen‐doped carbon nanotubes (PNCNTs) with a high specific surface area (1765 m² g^?1) and a large pore volume (1.28 cm³ g^?1) have been synthesized from a tubular polypyrrole (T‐PPY). The inner diameter and wall thickness of the PNCNTs are about 55 nm and 22 nm, respectively. This material shows extremely promising properties for both supercapacitors and for encapsulating sulfur as a superior cathode material for high‐performance lithium–sulfur (Li‐S) batteries. At a current density of 0.5 A g^?1, PNCNT presents a high specific capacitance of 210 F g^?1, as well as excellent cycling stability at a current density of 2 A g^?1. When the S/PNCNT composite was tested as the cathode material for Li‐S batteries, the initial discharge capacity was 1341 mAh g^?1 at a current rate of 1 C and, even after 50 cycles at the same rate, the high reversible capacity was retained at 933 mAh g^?1. The promising electrochemical energy‐storage performance of the PNCNTs can be attributed to their excellent conductivity, large surface area, nitrogen doping, and unique pore‐size distribution.     

Maximization of Spatial Charge Density: An Approach to Ultrahigh Energy Density of Capacitive Charge Storage

Capacitive energy storage has advantages of high power density, long lifespan, and good safety, but is restricted by low energy density. Inspired by the charge storage mechanism of batteries, a spatial charge density (SCD) maximization strategy is developed to compensate this shortage by densely and neatly packing ionic charges in capacitive materials. A record high SCD (ca. 550 C cm^?3) was achieved by balancing the valance and size of charge‐carrier ions and matching the ion sizes with the pore structure of electrode materials, nearly five times higher than those of conventional ones (ca. 120 C cm^?3). The maximization of SCD was confirmed by Monte Carlo calculations, molecular dynamics simulations, and in situ electrochemical Raman spectroscopy. A full‐cell supercapacitor was further constructed; it delivers an ultrahigh energy density of 165 Wh L^?1 at a power density of 150 WL^?1 and retains 120 Wh L^?1 even at 36 kW L^?1, opening a pathway towards high‐energy‐density capacitive energy storage.     

Two‐Dimensional Conjugated Aromatic Networks as High‐Site‐Density and Single‐Atom Electrocatalysts for the Oxygen Reduction Reaction

Two‐dimensional conjugated aromatic networks (CAN) with ultra‐thin conjugated layers (ca. 3.5 nm) and high single‐metal‐atom‐site density (mass content of 10.7 wt %, and 0.73 metal atoms per nm²) are prepared via a facile pyrolysis‐free route involving a one‐step ball milling of the solid‐phase‐synthesized polyphthalocyanine. These materials display outstanding oxygen reduction reaction (ORR) mass activity of 47 mA mg_cat.^?1 represents 1.3‐ and 6.4‐fold enhancements compared to Pt and Pt/C in benchmark Pt/C, respectively. Moreover, the primary Zn‐air batteries constructed with CAN as an air electrode demonstrate a mass/volume power density of 880 W g_cat.^?1/615 W cm_cat.^?3 and stable long‐term operation for 100 h. This strategy offers a new way to design high‐performance electrocatalysts with atomic precision for use in other energy‐storage and conversion applications.     

An Auto‐Switchable Dual‐Mode Seawater Energy Extraction System Enabled by Metal–Organic Frameworks

Harvesting energy directly in oceans by electrochemical devices is essential for driving underwater appliances such as underwater vehicles or detectors. Owing to the extreme undersea environment, it is important but difficult to use the devices with both a high energy density and power density simultaneously. Inspired by marine organisms that have switchable energy extraction modes (aerobic respiration for long‐term living or anaerobic respiration to provide instantaneously high output power for fast movement), an auto‐switchable dual‐mode seawater energy extraction system is presented to provide high energy density and power density both by initiatively choosing different solutes in seawater as electron acceptors. With assistance from metal–organic frameworks, this device had a theoretical energy density of 3960 Wh kg^?1, and a high practical power density of 100±4 mW cm^?2 with exceptional stability and low cost, making practical applications in seawater to be possible.     

Na3SbS4: A Solution Processable Sodium Superionic Conductor for All‐Solid‐State Sodium‐Ion Batteries

All‐solid‐state sodium‐ion batteries that operate at room temperature are attractive candidates for use in large‐scale energy storage systems. However, materials innovation in solid electrolytes is imperative to fulfill multiple requirements, including high conductivity, functional synthesis protocols for achieving intimate ionic contact with active materials, and air stability. A new, highly conductive (1.1 mS cm^?1 at 25 °C, E_a=0.20 eV) and dry air stable sodium superionic conductor, tetragonal Na₃SbS₄, is described. Importantly, Na₃SbS₄ can be prepared by scalable solution processes using methanol or water, and it exhibits high conductivities of 0.1–0.3 mS cm^?1. The solution‐processed, highly conductive solidified Na₃SbS₄ electrolyte coated on an active material (NaCrO₂) demonstrates dramatically improved electrochemical performance in all‐solid‐state batteries.     

General Interfacial Self‐Assembly Engineering for Patterning Two‐Dimensional Polymers with Cylindrical Mesopores on Graphene

Free‐standing 2D porous nanomaterials have attracted considerable interest as ideal candidates of 2D film electrodes for planar energy storage devices. Nevertheless, the construction of well‐defined mesopore arrays parallel to the lateral surface, which facilitate fast in‐plane ionic diffusion, is a challenge. Now, a universal interface self‐assembly strategy is used for patterning 2D porous polymers, for example, polypyrrole, polyaniline, and polydopamine, with cylindrical mesopores on graphene nanosheets. The resultant 2D sandwich‐structured nanohybrids are employed as the interdigital microelectrodes for the assembly of planar micro‐supercapacitors (MSCs), which deliver outstanding volumetric capacitance of 102 F cm^?3 and energy density of 2.3 mWh cm^?3, outperforming most reported MSCs. The MSCs display remarkable flexibility and superior integration for boosting output voltage and capacitance.