Hierarchical Ordered Dual‐Mesoporous Polypyrrole/Graphene Nanosheets as Bi‐Functional Active Materials for High‐Performance Planar Integrated System of Micro‐Supercapacitor and Gas Sensor

Planar integrated systems of micro‐supercapacitors (MSCs) and sensors are of profound importance for 3C electronics, but usually appear poor in compatibility due to the complex connections of device units with multiple mono‐functional materials. Herein, 2D hierarchical ordered dual‐mesoporous polypyrrole/graphene (DM‐PG) nanosheets are developed as bi‐functional active materials for a novel prototype planar integrated system of MSC and NH₃ sensor. Owing to effective coupling of conductive graphene and high‐sensitive pseudocapacitive polypyrrole, well‐defined dual‐mesopores of ≈7 and ≈18 nm, hierarchical mesoporous network, and large surface area of 112 m² g^?1, the resultant DM‐PG nanosheets exhibit extraordinary sensing response to NH₃ as low as 200 ppb, exceptional selectivity toward NH₃ that is much higher than other volatile organic compounds, and outstanding capacitance of 376 F g^?1 at 1 mV s^?1 for supercapacitors, simultaneously surpassing single‐mesoporous and non‐mesoporous counterparts. Importantly, the bi‐functional DM‐PG‐based MSC‐sensor integrated system represents rapid and stable response exposed to 10–40 ppm of NH₃ after only charging for 100 s, remarkable sensitivity of NH₃ detection that is close to DM‐PG‐based MSC‐free sensor, impressive flexibility with ≈82% of initial response value even at 180°, and enhanced overall compatibility, thereby holding great promise for ultrathin, miniaturized, body‐attachable, and portable detection of NH₃.     

Layered Silicon‐Based Nanosheets as Electrode for 4 V High‐Performance Supercapacitor

Silicon‐based materials have shown great potential and been widely studied in various fields. Unlike its unparalleled theoretical capacity as anodes for batteries, few investigations have been reported on silicon‐based materials for applications in supercapacitors. Here, an electrode composed of layered silicon‐based nanosheets, obtained through oxidation and exfoliation, for a supercapacitor operated up to 4 V is reported. These silicon‐based nanosheets show an areal specific capacitance of 4.43 mF cm^?2 at 10 mV s^?1 while still retaining a specific capacitance of 834 µF cm^?2 even at an ultrahigh scan rate of 50 000 mV s^?1. The volumetric energy and power density of the supercapacitor are 7.65 mWh cm^?3 and 9312 mW cm^?3, respectively, and the electrode can operate for 12000 cycles in a potential window of 4 V at 2 A g^?1, while retaining 90.6% capacitance. These results indicate that the silicon‐based nanosheets can be a competitive candidate as the supercapacitor electrode material.     

Microstructure Design of Carbonaceous Fibers: A Promising Strategy toward High‐Performance Weaveable/Wearable Supercapacitors

Fiber‐based supercapacitors (FSCs) possess great potential as an ideal type of power source for future weaveable/wearable electronics and electronic‐textiles. The performance of FSCs is, without doubt, primarily determined by the properties of fibrous electrodes. Carbonaceous fibers, e.g., commercial carbon fibers, newly developed graphene fibers, and carbon nanotube fibers, are deemed as promising materials for weaveable/wearable supercapacitors owing to their exotic properties including high tensile strength and robustness, excellent electrical conductivity, good flexibility, and environmental stability. Nevertheless, bare carbonaceous fiber normally exhibits low capacitance originating from electric double‐layer capacitance, which remains unsatisfactory for efficiently powering wearable and portable devices. Numerous efforts have been devoted to tailoring fiber properties by hybridizing pseudocapacitive materials, and impressive progress has been achieved thus far. Herein, the microstructures of pristine carbonaceous fibers are introduced in detail, and the recent advances in rational nano/microstructure design of their hybrids, which provides the feasibility to achieve the synergistic interaction between conductive agents and pseudocapacitive nanomaterials but are normally overlooked, are comprehensively reviewed. Besides, the challenges in developing high‐performance fibrous electrodes are also elaborately discussed.     

Freestanding 1T‐MnxMo1–xS2–ySey and MoFe2S4–zSez Ultrathin Nanosheet‐Structured Electrodes for Highly Efficient Flexible Solid‐State Asymmetric Supercapacitors

Fabrication of hierarchical nanosheet arrays of 1T phase of transition‐metal dichalcogenides is indeed a critical task, but it holds immense potential for energy storage. A single‐step strategy is employed for the fabrication of stable 1T‐Mn_xMo_1–xS_2–ySe_y and MoFe₂S_4–zSe_z hierarchical nanosheet arrays on carbon cloth as positive and negative electrodes, respectively. The flexible asymmetric supercapacitor constructed with these two electrodes exhibits an excellent electrochemical performance (energy density of ≈69 Wh kg^?1 at a power density of 0.985 kW kg^?1) with ultralong cyclic stability of ≈83.5% capacity retention, after 10 000 consecutive cycles. Co‐doping of the metal and nonmetal boosts the charge storage ability of the transition‐metal chalcogenides following enrichment in the metallic 1T phase, improvement in the surface area, and expansion in the interlayer spacing in tandem, which is the key focus of the present study. This study explicitly demonstrates the exponential enhancement of specific capacity of MoS₂ following intercalation and doping of Mn and Se, and Fe₂S₃ following doping of Mo and Se could be an ideal direction for the fabrication of novel energy‐storage materials with high‐energy storage ability.     

Cucurbit[6]uril‐Derived Sub‐4 nm Pores‐Dominated Hierarchical Porous Carbon for Supercapacitors: Operating Voltage Expansion and Pore Size Matching

The intrinsic properties of carbon‐based material and the voltage window of electrolyte are the two key barriers to restrict the energy density of carbon‐based supercapacitors (SCs). Herein, a cucurbit[6]uril‐derived nitrogen‐doped hierarchical porous carbon (CBCx) with unique pore structure characteristics is synthesized and successfully applied to construct SCs based on different electrolyte systems. Owing to narrow pore size distribution (0.5–4 nm), colossal ion‐accessible pore volume, prominent supermesopore volume, and reasonable heteroatom configuration, the CBCx‐based SCs demonstrate excellent electrochemical performances with high operating voltages in two distinct systems. The optimal SCs can output a maximum energy/power density of 18 Wh kg^?1 (11.1 Wh L^?1)/20 kW kg^?1 (12.3 kW L^?1) with an operating voltage of 1.2 V in potassium hydroxide aqueous electrolyte, as well as an ultralong cycle life of up to 50 000 cycles (0.046% decay per 100 cycles). Furthermore, the optimal SCs deliver an exceptionally high energy/power density of 95 Wh kg^?1 (58.4 Wh L^?1)/70 kW kg^?1 (43 kW L^?1) with an ultrahigh operating voltage of 3.5 V in 1‐ethyl‐3‐methylimidazolium tetrafluoroborate electrolyte. This work opens up a new application field for cucurbit[6]uril and provides an alternative avenue for optimizing the performances of carbon‐based materials for SCs.     

Coupling PEDOT on Mesoporous Vanadium Nitride Arrays for Advanced Flexible All‐Solid‐State Supercapacitors

Tailored construction of advanced flexible supercapacitors (SCs) is of great importance to the development of high‐performance wearable modern electronics. Herein, a facile combined wet chemical method to fabricate novel mesoporous vanadium nitride (VN) composite arrays coupled with poly(3,4‐ethylenedioxythiophene) (PEDOT) as flexible electrodes for all‐solid‐state SCs is reported. The mesoporous VN nanosheets arrays prepared by the hydrothermal–nitridation method are composed of cross‐linked nanoparticles of 10–50 nm. To enhance electrochemical stability, the VN is further coupled with electrodeposited PEDOT shell to form high‐quality VN/PEDOT flexible arrays. Benefiting from high intrinsic reactivity and enhanced structural stability, the designed VN/PEDOT flexible arrays exhibit a high specific capacitance of 226.2 F g^?1 at 1 A g^?1 and an excellent cycle stability with 91.5% capacity retention after 5000 cycles at 10 A g^?1. In addition, high energy/power density (48.36 Wh kg^?1 at 2 A g^?1 and 4 kW kg^?1 at 5 A g^?1) and notable cycling life (91.6% retention over 10 000 cycles) are also achieved in the assembled asymmetric flexible supercapacitor cell with commercial nickel–cobalt–aluminum ternary oxides cathode and VN/PEDOT anode. This research opens up a way for construction of advanced hybrid organic–inorganic electrodes for flexible energy storage.     

Mechanochemical‐Assisted Synthesis of High‐Entropy Metal Nitride via a Soft Urea Strategy

Crystalline high‐entropy ceramics (CHC), a new class of solids that contain five or more elemental species, have attracted increasing interest because of their unique structure and potential applications. Up to now, only a couple of CHCs (e.g., high‐entropy metal oxides and diborides) have been successfully synthesized. Here, a new strategy for preparing high‐entropy metal nitride (HEMN‐1) is proposed via a soft urea method assisted by mechanochemical synthesis. The as‐prepared HEMN‐1 possesses five highly dispersed metal components, including V, Cr, Nb, Mo, Zr, and simultaneously exhibits an interesting cubic crystal structure of metal nitrides. By taking advantage of these unique features, HEMN‐1 can function as a promising candidate for supercapacitor applications. A specific capacitance of 78 F g^?1 is achieved at a scan rate of 100 mV s^?1 in 1 m KOH. In addition, such a facile synthetic strategy can be further extended to the fabrication of other types of HEMNs, paving the way for the synthesis of HEMNs with attractive properties for task‐specific applications.     

Editable Supercapacitors with Customizable Stretchability Based on Mechanically Strengthened Ultralong MnO2 Nanowire Composite

Although some progress has been made on stretchable supercapacitors, traditional stretchable supercapacitors fabricated by predesigning structured electrodes for device assembling still lack the device‐level editability and programmability. To adapt to wearable electronics with arbitrary configurations, it is highly desirable to develop editable supercapacitors that can be directly transferred into desirable shapes and stretchability. In this work, editable supercapacitors for customizable shapes and stretchability using electrodes based on mechanically strengthened ultralong MnO₂ nanowire composites are developed. A supercapacitor edited with honeycomb‐like structure shows a specific capacitance of 227.2 mF cm^?2 and can be stretched up to 500% without degradation of electrochemical performance, which is superior to most of the state‐of‐the‐art stretchable supercapacitors. In addition, it maintains nearly 98% of the initial capacitance after 10 000 stretch‐and‐release cycles under 400% tensile strain. As a representative of concept for system integration, the editable supercapacitors are integrated with a strain sensor, and the system exhibits a stable sensing performance even under arm swing. Being highly stretchable, easily programmable, as well as connectable in series and parallel, an editable supercapacitor with customizable stretchability is promising to produce stylish energy storage devices to power various portable, stretchable, and wearable devices.     

Porous Graphene Films with Unprecedented Elastomeric Scaffold‐Like Folding Behavior for Foldable Energy Storage Devices

The development of fully foldable energy storage devices is a major science and engineering challenge, but one that must be overcome if next‐generation foldable or wearable electronic devices are to be realized. To overcome this challenge, it is necessary to develop new electrically conductive materials that exhibit superflexibility and can be folded or crumpled without plastic deformation or damage. Herein, a graphene film with engineered microvoids is prepared by reduction (under confinement) of its precursor graphene oxide film. The resultant porous graphene film can be single folded, double folded, and even crumpled, but springs back to its original shape without yielding or plastic deformation akin to an elastomeric scaffold after the applied stress is removed. Even after thermal annealing at ≈1300 °C, the folding performance of the porous graphene film is not compromised and the thermally annealed film exhibits complete foldability even in liquid nitrogen. A solid‐state foldable supercapacitor is demonstrated with the porous graphene film as the device electrode. The capacitance performance is nearly identical after 2000 cycles of single‐folding followed by another 2000 cycles of double folding.