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.     

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.     

Achieving Insertion‐Like Capacity at Ultrahigh Rate via Tunable Surface Pseudocapacitance

The insertion/deinsertion mechanism enables plenty of charge‐storage sites in the bulk phase to be accessible to intercalated ions, giving rise to at least one more order of magnitude higher energy density than the adsorption/desorption mechanism. However, the sluggish ion diffusion in the bulk phase leads to several orders of magnitude slower charge‐transport kinetics. An ideal energy‐storage device should possess high power density and large energy density simultaneously. Herein, surface‐modified Fe₂O₃ quantum dots anchored on graphene nanosheets are developed and exhibit greatly enhanced pseudocapacitance via fast dual‐ion‐involved redox reactions with both large specific capacity and fast charge/discharge capability. By using an aqueous Na₂SO₃ electrolyte, the oxygen‐vacancy‐tuned Fe₂O₃ surface greatly enhances the absorption of SO₃^2? anions that majorly increase the surface pseudocapacitance. Significantly, the Fe₂O₃‐based electrode delivers a high specific capacity of 749 C g^?1 at 5 mV s^?1 and retains 290 C g^?1 at an ultrahigh scan rate of 3.2 V s^?1. With a novel dual‐electrolyte design, a 2 V Fe₂O₃/Na₂SO₃//MnO₂/Na₂SO₄ asymmetric supercapacitor is constructed, delivering a high energy density of 75 W h kg^?1 at a power density of 3125 W kg^?1.     

An Integrated Approach Toward Renewable Energy Storage Using Rechargeable Ag@Ni0.67Co0.33S‐Based Hybrid Supercapacitors

Self‐powered charging systems in conjunction with renewable energy conversion and storage devices have attracted promising attention in recent years. In this work, a prolific approach to design a wind/solar‐powered rechargeable high‐energy density pouch‐type hybrid supercapacitor (HSC) is proposed. The pouch‐type HSC is fabricated by engineering nature‐inspired nanosliver (nano‐Ag) decorated Ni_0.67Co_0.33S forest‐like nanostructures on Ni foam (nano‐Ag@NCS FNs/Ni foam) as a battery‐type electrode and porous activated carbon as a capacitive‐type electrode. Initially, the core–shell‐like NCS FNs/Ni foam is prepared via a single‐step wet‐chemical method, followed by a light‐induced growth of nano‐Ag onto it for enhancing the conductivity of the composite. Utilizing the synergistic effects of forest‐like nano‐Ag@NCS FNs/Ni foam as a composite electrode, the fabricated device shows a maximum capacitance of 1104.14 mF cm^?2 at a current density of 5 mA cm^?2 and it stores superior energy and power densities of 0.36 mWh cm^?2 and 27.22 mW cm^?2, respectively along with good cycling stability, which are higher than most of previous reports. The high‐energy storage capability of HSCs is further connected to wind fans and solar cells to harvest renewable energy. The wind/solar charged HSCs can effectively operate various electronic devices for a long time, enlightening its potency for the development of sustainable energy systems.     

Highly Conductive Ti3C2Tx MXene Hybrid Fibers for Flexible and Elastic Fiber‐Shaped Supercapacitors

Fiber‐shaped supercapacitors (FSCs) are promising energy storage solutions for powering miniaturized or wearable electronics. However, the scalable fabrication of fiber electrodes with high electrical conductivity and excellent energy storage performance for use in FSCs remains a challenge. Here, an easily scalable one‐step wet‐spinning approach is reported to fabricate highly conductive fibers using hybrid formulations of Ti₃C₂T_x MXene nanosheets and poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate. This approach produces fibers with a record conductivity of ≈1489 S cm^?1, which is about five times higher than other reported Ti₃C₂T_x MXene‐based fibers (up to ≈290 S cm^?1). The hybrid fiber at ≈70 wt% MXene shows a high volumetric capacitance (≈614.5 F cm^?3 at 5 mV s^?1) and an excellent rate performance (≈375.2 F cm^?3 at 1000 mV s^?1). When assembled into a free‐standing FSC, the energy and power densities of the device reach ≈7.13 Wh cm^?3 and ≈8249 mW cm^?3, respectively. The excellent strength and flexibility of the hybrid fibers allow them to be wrapped on a silicone elastomer fiber to achieve an elastic FSC with 96% capacitance retention when cyclically stretched to 100% strain. This work demonstrates the potential of MXene‐based fiber electrodes and their scalable production for fiber‐based energy storage applications.