Scalable 3D Self-Assembly of MXene Films for Flexible Sandwich and Microsized Supercapacitors

The self-assembly of large-area MXene films is the main step to realize their applications in various energy storage devices. However, the scalable self-assembly of flexible thin MXene films with high conductivity as well as excellent mechanical and electrochemical properties is still a challenge. Herein, a synchronous reduction and self-assembly strategy to fabricate flexible MXene films is developed, where MXene films are synchronously reduced and self-assembled on the Zn foil surface. Furthermore, the self-assembly of MXene films can be scaled up by controlling the area of Zn substrates. By adjusting the patterns of Zn substrates, the interdigital MXene patterns can also be obtained via a selectively reducing/assembling process. The resultant MXene films demonstrate high electrical conductivity, large specific surface area, and excellent mechanical properties. Thus they can serve as the electrodes of flexible supercapacitor devices directly. As a proof of concept, flexible sandwich and microsized supercapacitors are designed based on the above MXene film electrodes. Both sandwich and microsized supercapacitors display stable electrochemical performance under various bending states. This study provides a route to achieve large-area MXene-based films or microsized structures for applications in the field of energy storage.     

Foldable All‐Solid‐State Supercapacitors Integrated with Photodetectors

Recent development in flexible electronics has promoted the increasing demand for their energy storage systems that will be lightweight, thin, flexible, and even foldable. Although various flexible supercapacitors recently have been successfully developed, the design and assembly of highly foldable supercapacitors have received less attention. Furthermore, foldable supercapacitors are in general operated independently with other electronics, resulting in some space and energy consumption from the external connection system. Therefore, the authors fabricate the foldable all‐solid‐state integrated devices with supercapacitor and photodetector functions in a simplified and compact configuration based on single‐walled carbon nanotube films and TiO₂ nanoparticles. The integrated devices not only retain the intrinsic capacitance behavior but also show excellent sensitivity of detecting white light. More importantly, the capacitance behavior of integrated devices remains almost unchanged and the photodetector behavior is quite stable even folded by 180° due to their unique integrated configuration. Such rational design of all‐solid‐state integrated devices will pave the way for assembling energy storage devices and other electronics into highly flexible and foldable integrated devices.     

High‐Performance Polypyrrole/Graphene/SnCl2 Modified Polyester Textile Electrodes and Yarn Electrodes for Wearable Energy Storage

Flexible supercapacitors have potential for wearable energy storage due to their high energy/power densities and long operating lifetimes. High electrochemical performance with robust mechanical properties is highly desired for flexible supercapacitor electrodes. Usually, the mechanical properties are improved by choosing high flexible textile substrates but at the much expense of electrochemical performance due to the nonideal contact between conductive materials and textile substrates. Herein, the authors present an efficient, scalable, and general strategy for the simultaneous fabrication of high‐performance textile electrodes and yarn electrodes. It is interesting to find that the conformal reduced graphene oxide (RGO) layer is uniformly and successively painted on the surface of SnCl₂ modified polyester fibers (M‐PEF) via a repeated “dyeing and drying” strategy. The large‐area textile electrodes and ultralong yarn electrodes are fabricated by using RGO/M‐PEF as substrate with subsequent deposition of polypyrrole. This work provides new opportunities for developing high flexible textile electrodes and yarn electrodes with further increased electrochemical performance and scalable production.     

Stretchable Supercapacitor with Adjustable Volumetric Capacitance Based on 3D Interdigital Electrodes

Reduced graphene oxide (rGO)‐based materials have shown good performance as electrodes in flexible energy storage devices owing to their physical properties, high specific surface area, and excellent electrical conductivity. Here, a novel road is reported for fabricating high‐performance supercapacitors based on 3D rGO electrodes and solid electrolyte multilayers via pressure spray printing and machine coating. These supercapacitors demonstrate high and adjustable volumetric capacitance, excellent flexibility, and stretchability. The results show that this commercial strategy has its essential merits such as low‐cost, inexpensive, and simple fabrication for large area production. These properties are in the favor of fabricating high‐performance supercapacitor to meet the practical energy demands in devices, especially flexible electronic devices. Furthermore, this novel 3D interdigital electrode concept can be widely applied to other energy devices for enhancing performances and to other micro devices for reducing cost.     

Ultralight and Binder‐Free All‐Solid‐State Flexible Supercapacitors for Powering Wearable Strain Sensors

Flexible energy storage devices play a pivotal role in realizing the full potential of flexible electronics. This work presents high‐performance, all‐solid‐state, flexible supercapacitors by employing an innovative multilevel porous graphite foam (MPG). MPGs exhibit superior properties, such as large specific surface area, high electric conductivity, low mass density, high loading efficiency of pseudocapacitive materials, and controlled corrugations for accommodating mechanical strains. When loaded with pseudocapacitive manganese oxide (Mn₃O₄), the MPG/Mn₃O₄ (MPGM) composites achieve a specific capacitance of 538 F g^?1 (1 mV s^?1) and 260 F g^?1 (1 mV s^?1) based on the mass of pure Mn₃O₄ and entire electrode composite, respectively. Both are among the best of Mn₃O₄‐based supercapacitors. The MPGM is mechanically robust and can go through 1000 mechanical bending cycles with only 1.5% change in electric resistance. When integrated as all‐solid‐state symmetric supercapacitors, they offer a full cell specific capacitance as high as 53 F g^?1 based on the entire electrode and retain 80% of capacitance after 1000 continuous mechanical bending cycles. Furthermore, the all‐solid‐state flexible supercapacitors are incorporated with strain sensors into self‐powered flexible devices for detection of both coarse and fine motions on human skins, i.e., those from finger bending and heart beating.     

Engineering 3D Ion Transport Channels for Flexible MXene Films with Superior Capacitive Performance

2D MXene materials are of considerable interest for future energy storage. A MXene film could be used as an effective flexible supercapacitor electrode due to its flexibility and, more importantly, its high specific capacitance. However, although it has excellent electronic conductivity, sluggish ionic kinetics within the MXene film becomes a fundamental limitation to the electrochemical performance. To compensate for the relative deficiency, MXene films are frequently reduced to several micrometer dimensions with low mass loading (<1 mg cm^?2), to the point of detriment of areal performance and commercial value. Herein, for the first time, the design of a 3D porous MXene/bacterial cellulose (BC) self‐supporting film is reported for ultrahigh capacitance performance (416 F g^?1, 2084 mF cm^?2) with outstanding mechanical properties and high flexibility, even when the MXene loading reaches 5 mg cm^?2. The highly interconnected MXene/BC network enables both excellent electron and ion transport channel. Additionally, a maximum energy density of 252 µWh cm^?2 is achieved in an asymmetric supercapacitor, higher than that of all ever‐reported MXene‐based supercapacitors. This work exploits a simple route for assembling 2D MXene materials into 3D porous films as state‐of‐the‐art electrodes for high performance energy storage devices.     

General Method for Large‐Area Films of Carbon Nanomaterials and Application of a Self‐Assembled Carbon Nanotube Film as a High‐Performance Electrode Material for an All‐Solid‐State Supercapacitor

Rational assembly of carbon nanostructures into large‐area films is a key step to realize their applications in ubiquitous electronics and energy devices. Here, a self‐assembly methodology is devised to organize diverse carbon nanostructures (nanotubes, dots, microspheres, etc.) into homogeneous films with potentially infinite lateral dimensions. On the basis of studies of the redox reactions in the systems and the structures of films, the spontaneous deposition of carbon nanostructures onto the surface of the copper substrate is found to be driven by the electrical double layer between copper and solution. As a notable example, the as‐assembled multiwalled carbon nanotube (MWCNT) films display exceptional properties. They are a promising material for flexible electronics with superior electrical and mechanical compliance characteristics. Finally, two kinds of all‐solid‐state supercapacitors based on the self‐assembled MWCNT films are fabricated. The supercapacitor using carbon cloth as the current collector delivers an energy density of 3.5 Wh kg^?1 and a power density of 28.1 kW kg^?1, which are comparable with the state‐of‐the‐art supercapacitors fabricated by the costly single‐walled carbon nanotubes and arrays. The supercapacitor free of foreign current collector is ultrathin and shows impressive volumetric energy density (0.58 mWh cm^?3) and power density (0.39 W cm^?3) too.     

Flexible Solid‐State Supercapacitors with Enhanced Performance from Hierarchically Graphene Nanocomposite Electrodes and Ionic Liquid Incorporated Gel Polymer Electrolyte

High energy density, durability, and flexibility of supercapacitors are required urgently for the next generation of wearable and portable electronic devices. Herein, a novel strategy is introduced to boost the energy density of flexible soild‐state supercapacitors via rational design of hierarchically graphene nanocomposite (GNC) electrode material and employing an ionic liquid gel polymer electrolyte. The hierarchical graphene nanocomposite consisting of graphene and polyaniline‐derived carbon is synthesized as an electrode material via a scalable process. The meso/microporous graphene nanocomposites exhibit a high specific capacitance of 176 F g^?1 at 0.5 A g^?1 in the ionic liquid 1‐ethyl‐3‐methylimidazolium tetrafluoroborate (EMIBF₄) with a wide voltage window of 3.5 V, good rate capability of 80.7% in the range of 0.5–10 A g^?1 and excellent stability over 10 000 cycles, which is attributed to the superior conductivity (7246 S m^?1), and quite large specific surface area (2416 m² g^?1) as well as hierarchical meso/micropores distribution of the electrode materials. Furthermore, flexible solid‐state supercapacitor devices based on the GNC electrodes and gel polymer electrolyte film are assembled, which offer high specific capacitance of 180 F g^?1 at 1 A g^?1, large energy density of 75 Wh Kg^?1, and remarkable flexible performance under consecutive bending conditions.     

Fabrication of Hybrid Supercapacitor by MoCl5 Precursor-Assisted Carbonization with Ultrafast Laser for Improved Capacitance Performance

Hybrid supercapacitors use electric double-layer capacitance and Faradaic pseudocapacitance as energy storage mechanisms. This type of supercapacitor is becoming a prime candidate for next-generation energy storage devices, with advantages in terms of energy density, specific capacitance, and life cycle. However, reducing the electrode area and increasing the specific capacitance of hybrid supercapacitors remain challenging. In this study, a MoCl₅ Precursor-assisted Ultrafast Laser Carbonization (MPAULC) method to fabricate symmetric hybrid supercapacitors with improved capacitance and reduced size is proposed. The method uses an ultrafast laser to induce the formation of carbon/MoO₃ composite with the assistance of the MoCl5 precursor. This ultrafast laser carbonization method exhibited high processing precision. The role of the precursor in laser processing is studied using time-resolved imaging and temperature calculations. The specific area capacitance of the C/MoO₃ hybrid supercapacitor is 11.85 mF cm⁻², 9.2 times higher than that of the laser-induced carbon supercapacitor without precursor. The MPAULC method provides a reliable pathway for fabricating miniaturized hybrid supercapacitors with carbon/metal oxide composite electrodes on polymer substrates.     

Multilayer‐Folded Graphene Ribbon Film with Ultrahigh Areal Capacitance and High Rate Performance for Compressible Supercapacitors

Limited by 2D geometric morphology and low bulk packing density, developing graphene‐based flexible/compressible supercapacitors with high specific capacitances (gravimetric/volumetric/areal), especially at high rates, is an outstanding challenge. Here, a strategy for the synthesis of free‐standing graphene ribbon films (GRFs) for high‐performance flexible and compressible supercapacitors through blade‐coating of interconnected graphene oxide ribbons and a subsequent thermal treatment process is reported. With an ultrahigh mass loading of 21 mg cm^?2, large ion‐accessible surface area, efficient electron and ion transport pathways as well as high packing density, the compressed multilayer‐folded GRF films (F‐GRF) exhibit ultrahigh areal capacitance of 6.7 F cm^?2 at 5 mA cm^?2, high gravimetric/volumetric capacitances (318 F g^?1, 293 F cm^?3), and high rate performance (3.9 F cm^?2 at 105 mA cm^?2), as well as excellent cycling stability (109% of capacitance retention after 40 000 cycles). Furthermore, the assembled F‐GRF symmetric supercapacitor with compressible and flexible characteristics, can deliver an ultrahigh areal energy density of 0.52 mWh cm^?2 in aqueous electrolyte, almost two times higher than the values obtained from symmetric supercapacitors with comparable dimensions.     

A Continuous Carbon Nitride Polyhedron Assembly for High‐Performance Flexible Supercapacitors

Flexible supercapacitors with high power density, flexibility, and durability have shown enormous potential for smart electronics. Here, a continuous graphitic carbon nitride polyhedron assembly for flexible supercapacitor that is prepared by pyrolysis of carbon nanotubes wired zeolitic imidazolate framework‐8 (ZIF‐8) composites under nitrogen is reported. It exhibits a high specific capacitance of 426 F g^?1 at current density of 1 A g^?1 in 1 m H₂SO₄ and excellent stability over 10 000 cycles. The remarkable performance results from the continuous hierarchical structure with average pore size of 2.5 nm, high nitrogen‐doping level (17.82%), and large specific surface area (920 m² g^?1). Furthermore, a flexible supercapacitor is developed by constructing the assembly with interpenetrating polymer network electrolyte. Stemming from the synergistic effect of high‐performance electrode and highly ion‐conductive electrolyte, superior energy density of 59.40 Wh kg^?1 at 1 A g^?1 is achieved. The device maintains a stable energy supply under cyclic deformations, showing wide application in flexible and even wearable conditions. The work paves a new way for designing pliable electrode with excellent electronic and mechanic property for long‐lived flexible energy storage devices.     

Hierarchical Design for Fabricating Cost‐Effective High Performance Supercapacitors

The salient feature of a supercapacitor is its ability to deliver much higher power density than a battery. A hierarchical design and a cost‐effective approach to fabricate high performance supercapacitors using functional carbon nano‐particles is reported. A special arc synthesis method is used to produce amorphous/crystalline composite with nitrogen and boron co‐doped high charge density carbon nanoparticles. Upon etch removal of the amorphous phase in the composite nanoparticle, a crystalline carbon framework emerges, consisting of a mixture of nano‐graphitic sheets mostly in the middle and single nanohorns distributed around the surface of the nanoparticle. These nanoparticles have large internal/external surfaces with subnano channels and sharp nano‐tips for high speed charge transport and local charge accumulation. To deliver high power density, the internal resistance of the device is reduced by assembling the nanoparticles via electro‐spraying and compacting them into dense films (without any binder) under 700 MPa of pressure before supercapacitor assembly. Taken together, the hierarchical processed supercapacitor has a very high (compared to literature values) power density of nearly 4.5 kW cm^?3 and a respectable energy density of 2.45 mWh cm^?3. Combining these carbon nanoparticles with large area spraying coating, it can lead to a cost‐effective production of high performance supercapacitors.     

Enhancing the Capacitive Storage Performance of Carbon Fiber Textile by Surface and Structural Modulation for Advanced Flexible Asymmetric Supercapacitors

The exploration of high‐energy anodes with good mechanical properties is highly attractive for flexible asymmetric supercapacitors (ASCs) but challenging. Owing to the excellent conductivity and superior mechanical flexibility, carbon fiber textile (CFT) holds great promise as a substrate/current‐collector for fabricating flexible electrodes. Yet, it is rarely used as a flexible active electrode in terms of its low electrochemical reactivity and small accessible area. In this work, an effective surface and structural modulation strategy is developed to directly tune CFT into a highly active anode for flexible ASCs by creating hierarchical pores and numerous pseudocapacitive oxygenic groups. Arising from large surface and increased active sites, the as‐prepared activated porous CFT (APCFT) electrode not only achieves a large capacitance (1.2 F cm^?2 at 4 mA cm^?2) and fast kinetics but also shows satisfying cycling durability (no capacitance decay after 25 000 cycles). More importantly, an advanced flexible ASC device with an impressive energy density of 4.70 mWh cm^?3 is successfully assembled by employing this APCFT as an anode, outperforming most recently reported ASC devices. This dual modification strategy may throw light on the rational design of new generation advanced carbon electrodes for high‐performance flexible supercapacitors.     

Nickel–Cobalt Layered Double Hydroxide Nanosheets for High‐performance Supercapacitor Electrode Materials

A facile and novel one‐step method of growing nickel‐cobalt layered double hydroxide (Ni‐Co LDH) hybrid films with ultrathin nanosheets and porous nanostructures on nickel foam is presented using cetyltrimethylammonium bromide as nanostructure growth assisting agent but without any adscititious alkali sources and oxidants. As pseudocapacitors, the as‐obtained Ni‐Co LDH hybrid film‐based electrodes display a significantly enhanced specific capacitance (2682 F g^?1 at 3 A g^?1, based on active materials) and energy density (77.3 Wh kg^?1 at 623 W kg^?1), compared to most previously reported electrodes based on nickel‐cobalt oxides/hydroxides. Moreover, the asymmetric supercapacitor, with the Ni‐Co LDH hybrid film as the positive electrode material and porous freeze‐dried reduced graphene oxide (RGO) as the negative electrode material, exhibits an ultrahigh energy density (188 Wh kg^?1) at an average power density of 1499 W kg^?1 based on the mass of active material, which greatly exceeds the energy densities of most previously reported nickel or cobalt oxide/hydroxide‐based asymmetric supercapacitors.     

Hierarchical NiMn Layered Double Hydroxide/Carbon Nanotubes Architecture with Superb Energy Density for Flexible Supercapacitors

A hierarchical nanostructure composed of NiMn‐layered double hydroxide (NiMn‐LDH) microcrystals grafted on carbon nanotube (CNT) backbone is constructed by an in situ growth route, which exhibits superior supercapacitive performance. The resulting composite material (NiMn‐LDH/CNT) displays a three‐dimensional architecture with tunable Ni/Mn ratio, well‐defined core‐shell configuration, and enlarged surface area. An electrochemical investigation shows that the Ni₃Mn₁‐LDH/CNT electrode is rather active, which delivers a maximum specific capacitance of 2960 F g^–1 (at 1.5 A g^–1), excellent rate capability (79.5% retention at 30 A g^–1), and cyclic stability. Moreover, an all‐solid‐state asymmetric supercapacitor (SC) with good flexibility is fabricated by using the NiMn‐LDH/CNT film and reduced graphene oxide (RGO)/CNT film as the positive and negative electrode, respectively, exhibiting a wide cell voltage of 1.7 V and largely enhanced energy density up to 88.3 Wh kg^–1 (based on the total weight of the device). By virtue of the high‐capacity of pseudocapacitive hydroxides and desirable conductivity of carbon‐based materials, the monolithic design demonstrated in this work provides a promising approach for the development of flexible energy storage systems.     

Nitrogen‐Doped Carbon Networks for High Energy Density Supercapacitors Derived from Polyaniline Coated Bacterial Cellulose

Bacterial cellulose (BC) is used as both template and precursor for the synthesis of nitrogen‐doped carbon networks through the carbonization of polyaniline (PANI) coated BC. The as‐obtained carbon networks can act not only as support for obtaining high capacitance electrode materials such as activated carbon (AC) and carbon/MnO₂ hybrid material, but also as conductive networks to integrate active electrode materials. As a result, the as‐assembled AC//carbon‐MnO₂ asymmetric supercapacitor exhibits a considerably high energy density of 63 Wh kg^?1 in 1.0 m Na₂SO₄ aqueous solution, higher than most reported AC//MnO₂ asymmetric supercapacitors. More importantly, this asymmetric supercapacitor also exhibits an excellent cycling performance with 92% specific capacitance retention after 5000 cycles. Those results offer a low‐cost, eco‐friendly design of electrode materials for high‐performance supercapacitors.     

Flexible Asymmetric Supercapacitor Based on Structure‐Optimized Mn3O4/Reduced Graphene Oxide Nanohybrid Paper with High Energy and Power Density

A highly flexible Mn₃O₄/reduced graphene oxide (rGO) nanohybrid paper with high electrical conductivity and high mass loading of Mn₃O₄ nanofibers (0.71 g cm^?3) is developed via a facile gel formation and electrochemical reduction process, which is low‐cost, environmental friendly, and easy to scale up. Confined Mn₃O₄ nanofibers are well dispersed within the rGO sheets, which demonstrate to be a promising cathode material for flexible asymmetric supercapacitors (ASCs). When coupled with an electrochemically reduced rGO paper as the anode, a flexible ASC device, based on the Mn₃O₄/rGO nanohybrid paper as the cathode, is assembled; and it demonstrates remarkable electrochemical performance: a high volumetric capacitance of 54.6 F cm^?3 (546.05 mF cm^?2), and remarkable volumetric energy and power density (0.0055 Wh cm^?3 and 10.95 W cm^?3) being achieved with excellent cycling ability. The nanohybrid paper shows great improvement for flexible energy devices in terms of electrochemical properties.     

Asymmetric Supercapacitors Based on Graphene/MnO2 Nanospheres and Graphene/MoO3 Nanosheets with High Energy Density

Asymmetric supercapacitors with high energy density are fabricated using a self‐assembled reduced graphene oxide (RGO)/MnO₂ (GrMnO₂) composite as a positive electrode and a RGO/MoO₃ (GrMoO₃) composite as a negative electrode in safe aqueous Na₂SO₄ electrolyte. The operation voltage is maximized by choosing two metal oxides with the largest work function difference. Because of the synergistic effects of highly conductive graphene and highly pseudocapacitive metal oxides, the hybrid nanostructure electrodes exhibit better charge transport and cycling stability. The operation voltage is expanded to 2.0 V in spite of the use of aqueous electrolyte, revealing a high energy density of 42.6 Wh kg^?1 at a power density of 276 W kg^?1 and a maximum specific capacitance of 307 F g^?1, consequently giving rise to an excellent Ragone plot. In addition, the GrMnO₂//GrMoO₃ supercapacitor exhibits improved capacitance with cycling up to 1000 cycles, which is explained by the development of micropore structures during the repetition of ion transfer. This strategy for the choice of metal oxides provides a promising route for next‐generation supercapacitors with high energy and high power densities.     

Flexible and Wire‐Shaped Micro‐Supercapacitor Based on Ni(OH)2‐Nanowire and Ordered Mesoporous Carbon Electrodes

Portable and multifunctional electronic devices are developing in the trend of being small, flexible, roll‐up, and even wearable, which asks us to develop flexible and micro‐sized energy conversion/storage devices. Here, the high performance of a flexible, wire‐shaped, and solid‐state micro‐supercapacitor, which is prepared by twisting a Ni(OH)2‐nanowire fiber‐electrode and an ordered mesoporous carbon fiber‐electrode together with a polymer electrolyte, is demonstrated. This micro‐supercapacitor displays a high specific capacitance of 6.67 mF cm^–1 (or 35.67 mF cm^–2) and a high specific energy density of 0.01 mWh cm^–2 (or 2.16 mWh cm^–3), which are about 10–100 times higher than previous reports. Furthermore, its capacitance retention is 70% over 10 000 cycles, indicating perfect cyclic ability. Two wire‐shaped micro‐supercapacitors (0.6 mm in diameter, ≈3 cm in length) in series can successfully operate a red light‐emitting‐diode, indicating promising practical application. Furthermore, synchrotron radiation X‐ray computed microtomo­graphy technology is employed to investigate inner structure of the micro‐device, confirming its solid‐state characteristic. This micro‐supercapacitor may bring new design opportunities of device configuration for energy‐storage devices in the future wearable electronic area.     

Facile Synthesis of Hematite Quantum‐Dot/Functionalized Graphene‐Sheet Composites as Advanced Anode Materials for Asymmetric Supercapacitors

For building high‐energy density asymmetric supercapacitors, developing anode materials with large specific capacitance remains a great challenge. Although Fe₂O₃ has been considered as a promising anode material for asymmetric supercapacitors, the specific capacitance of the Fe₂O₃‐based anodes is still low and cannot match that of cathodes in the full cells. In this work, a composite material with well dispersed Fe₂O₃ quantum dots (QDs, ≈2 nm) decorated on functionalized graphene‐sheets (FGS) is prepared by a facile and scalable method. The Fe₂O₃ QDs/FGS composites exhibit a large specific capacitance up to 347 F g^?1 in 1 m Na₂SO₄ between –1 and 0 V versus Ag/AgCl. An asymmetric supercapacitor operating at 2 V is fabricated using Fe₂O₃/FGS as anode and MnO₂/FGS as cathode in 1 m Na₂SO₄ aqueous electrolyte. The Fe₂O₃/FGS//MnO₂/FGS asymmetric supercapacitor shows a high energy density of 50.7 Wh kg^?1 at a power density of 100 W kg^?1 as well as excellent cycling stability and power capability. The facile synthesis method and superior supercapacitive performance of the Fe₂O₃ QDs/FGS composites make them promising as anode materials for high‐performance asymmetric supercapacitors.