Solid‐State Hybrid Fibrous Supercapacitors Produced by Dead‐End Tube Membrane Ultrafiltration

The development of flexible supercapacitors with high volumetric performance is critically important for portable electronics applications, which are severely volume limited. Here, dead‐end tube membrane (DETM) ultrafiltration is used to produce densely compacted carbon‐nanotube/graphene fibrous films as solid‐state supercapacitor electrodes. DETM is widely used in the water purification industry, but to date its use has not been explored for making supercapacitor electrode materials. Compared with vacuum‐assisted filtration, dead‐end filtration of the mixture through a porous membrane is carried out under much higher pressure, and thus the solvent can be gotten rid of much faster, with less energy consumption and in an environmentally friendly manner. More importantly, phase separation of the solid constituents in the mixture, due to concentration increase, can be suppressed in DETM. Therefore, highly uniform and densely compacted supercapacitor electrodes can be obtained with very high volumetric energy and power density. The volumetric energy density in this work (≈2.7 mWh cm^‐3) is at a higher level than all the all‐solid‐state fibrous supercapacitors reported to date. This can be attributed to the DETM process used, which produces a densely compacted network structure without compromising the availability of electrochemically active surface area.     

A Low‐Cost,Self‐Standing NiCo2O4@CNT/CNT Multilayer Electrode for Flexible Asymmetric Solid‐State Supercapacitors

The demand for a new generation of flexible, portable, and high‐capacity power sources increases rapidly with the development of advanced wearable electronic devices. Here we report a simple process for large‐scale fabrication of self‐standing composite film electrodes composed of NiCo₂O₄@carbon nanotube (CNT) for supercapacitors. Among all composite electrodes prepared, the one fired in air displays the best electrochemical behavior, achieving a specific capacitance of 1,590 F g^?1 at 0.5 A g^?1 while maintaining excellent stability. The NiCo₂O₄@CNT/CNT film electrodes are fabricated via stacking NiCo₂O₄@CNT and CNT alternately through vacuum filtration. Lightweight, flexible, and self‐standing film electrodes (≈24.3 µm thick) exhibit high volumetric capacitance of 873 F cm^?3 (with an areal mass of 2.5 mg cm^?2) at 0.5 A g^?1. An all‐solid‐state asymmetric supercapacitor consists of a composite film electrode and a treated carbon cloth electrode has not only high energy density (≈27.6 Wh kg^?1) at 0.55 kW kg^?1 (including the weight of the two electrodes) but also excellent cycling stability (retaining ≈95% of the initial capacitance after 5000 cycles), demonstrating the potential for practical application in wearable devices.     

Advanced Asymmetric Supercapacitors Based on Ni(OH)2/Graphene and Porous Graphene Electrodes with High Energy Density

Hierarchical flowerlike nickel hydroxide decorated on graphene sheets has been prepared by a facile and cost‐effective microwave‐assisted method. In order to achieve high energy and power densities, a high‐voltage asymmetric supercapacitor is successfully fabricated using Ni(OH)₂/graphene and porous graphene as the positive and negative electrodes, respectively. Because of their unique structure, both of these materials exhibit excellent electrochemical performances. The optimized asymmetric supercapacitor could be cycled reversibly in the high‐voltage region of 0–1.6 V and displays intriguing performances with a maximum specific capacitance of 218.4 F g^?1 and high energy density of 77.8 Wh kg^?1. Furthermore, the Ni(OH)₂/graphene//porous graphene supercapacitor device exhibits an excellent long cycle life along with 94.3% specific capacitance retained after 3000 cycles. These fascinating performances can be attributed to the high capacitance and the positive synergistic effects of the two electrodes. The impressive results presented here may pave the way for promising applications in high energy density storage systems.     

Hierarchical Ni–Co Hydroxide Petals on Mechanically Robust Graphene Petal Foam for High‐Energy Asymmetric Supercapacitors

A hierarchical structure consisting of Ni–Co hydroxide nanopetals (NCHPs) grown on a thin free‐standing graphene petal foam (GPF) has been designed and fabricated by a two‐step process for pseudocapacitive electrode applications. The mechanical behavior of GPFs has been, for the first time to our knowledge, quantitatively measured from in situ scanning electron microscope characterization of the petal foams during in‐plane compression and bending processes. The Young's modulus of a typical GPF is 3.42 GPa, indicating its outstanding mechanical robustness as a nanotemplate. The GPF/NCHP electrodes exhibit volumetric capacitances as high as 765 F cm^?3, equivalent to an areal capacitance of 15.3 F cm^?2 and high rate capability. To assess practical functionality, two‐terminal asymmetric solid‐state supercapacitors with 3D GPF/NCHPs as positive electrodes are fabricated and shown to exhibit outstanding energy and power densities, with maximum average energy density of ≈10 mWh cm^?3 and maximum power density of ≈3 W cm^?3, high rate capability (a capacitance retention of ≈60% at 100 mA cm^?2), and excellent long‐term cyclic stability (full capacitance retention over 15 000 cycles).     

Micro‐Supercapacitors Based on Interdigital Electrodes of Reduced Graphene Oxide and Carbon Nanotube Composites with Ultrahigh Power Handling Performance

A novel method for fabricating micro‐patterned interdigitated electrodes based on reduced graphene oxide (rGO) and carbon nanotube (CNT) composites for ultra‐high power handling micro‐supercapacitor application is reported. The binder‐free microelectrodes were developed by combining electrostatic spray deposition (ESD) and photolithography lift‐off methods. Without typically used thermal or chemical reduction, GO sheets are readily reduced to rGO during the ESD deposition. Electrochemical measurements show that the in‐plane interdigital design of the microelectrodes is effective in increasing accessibility of electrolyte ions in‐between stacked rGO sheets through an electro‐activation process. Addition of CNTs results in reduced restacking of rGO sheets and improved energy and power density. Cyclic voltammetry (CV) measurements show that the specific capacitance of the micro‐supercapacitor based on rGO–CNT composites is 6.1 mF cm^?2 at 0.01 V s^?1. At a very high scan rate of 50 V s^?1, a specific capacitance of 2.8 mF cm^?2 (stack capacitance of 3.1 F cm^?3) is recorded, which is an unprecedented performance for supercapacitors. The addition of CNT, electrolyte‐accessible and binder‐free microelectrodes, as well as an interdigitated in‐plane design result in a high‐frequency response of the micro‐supercapacitors with resistive‐capacitive time constants as low as 4.8 ms. These characteristics suggest that interdigitated rGO–CNT composite electrodes are promising for on‐chip energy storage application with high power demands.     

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.     

Flexible MXene/Graphene Films for Ultrafast Supercapacitors with Outstanding Volumetric Capacitance

A strategy to prepare flexible and conductive MXene/graphene (reduced graphene oxide, rGO) supercapacitor electrodes by using electrostatic self‐assembly between positively charged rGO modified with poly(diallyldimethylammonium chloride) and negatively charged titanium carbide MXene nanosheets is presented. After electrostatic assembly, rGO nanosheets are inserted in‐between MXene layers. As a result, the self‐restacking of MXene nanosheets is effectively prevented, leading to a considerably increased interlayer spacing. Accelerated diffusion of electrolyte ions enables more electroactive sites to become accessible. The freestanding MXene/rGO‐5 wt% electrode displays a volumetric capacitance of 1040 F cm^?3 at a scan rate of 2 mV s^?1 , an impressive rate capability with 61% capacitance retention at 1 V s^?1 and long cycle life. Moreover, the fabricated binder‐free symmetric supercapacitor shows an ultrahigh volumetric energy density of 32.6 Wh L^?1, which is among the highest values reported for carbon and MXene based materials in aqueous electrolytes. This work provides fundamental insight into the effect of interlayer spacing on the electrochemical performance of 2D hybrid materials and sheds light on the design of next‐generation flexible, portable and highly integrated supercapacitors with high volumetric and rate performances.     

Hierarchical Composite Electrodes of Nickel Oxide Nanoflake 3D Graphene for High‐Performance Pseudocapacitors

NiO nanoflakes are created with a simple hydrothermal method on 3D (three‐dimensional) graphene scaffolds grown on Ni foams by microwave plasma enhanced chemical vapor deposition (MPCVD). Such as‐grown NiO‐3D graphene hierarchical composites are then applied as monolithic electrodes for a pseudo‐supercapacitor application without needing binders or metal‐based current collectors. Electrochemical measurements impart that the hierarchical NiO‐3D graphene composite delivers a high specific capacitance of ≈1829 F g^?1 at a current density of 3 A g^?1 (the theoretical capacitance of NiO is 2584 F g^?1). Furthermore, a full‐cell is realized with an energy density of 138 Wh kg^?1 at a power density of 5.25 kW kg^?1, which is much superior to commercial ones as well as reported devices in asymmetric capacitors of NiO. More attractively, this asymmetric supercapacitor exhibits capacitance retention of 85% after 5000 cycles relative to the initial value of the 1^st cycle.     

A highly flexible solid-state supercapacitor based on the carbon nanotube doped graphene oxide/polypyrrole composites with superior electrochemical performances

Flexible electrodes of ternary composites, in which highly conductive carbon nanotube films (CNFs) are coated with carbon nanotube-doped graphene oxide/polypyrrole (CNT-GO/PPy), have been fabricated via facile electrochemical synthesis. Long and short CNTs are separately doped into the composites (lCNT-GO/PPy and sCNT-GO/PPy) and their electrochemical performances are compared. Electrochemical measurements indicate that the doping of CNTs in the composites significantly improves the electrochemical behaviors of the GO/PPy electrodes. Notably, the lCNT-GO/PPy electrodes show superior electrochemical properties with respect to the sCNT-GO/PPy electrodes, which is related to the introduction of abundant CNTs in the former electrodes and their special microstructures. Two symmetric electrodes with the lCNT-GO/PPy composites coated on CNFs are assembled to fabricate a solid-state supercapacitor device, which features lightweight, ultrathinness, and high flexibility. The device achieves a high areal and volumetric specific capacitance of 70.0 mF cm⁻² at 10 mV s⁻¹ and 6.3 F cm⁻³ at 0.043 A cm⁻³, respectively. It also shows superior rate performance and cycle stability, with a capacitance retention rate of 87.7% for 10,000 cycles. The supercapacitor device fabricated is promising for the use in lightweight and flexible integrated electronics.     

Boosting the Electrical Double‐Layer Capacitance of Graphene by Self‐Doped Defects through Ball‐Milling

Improving the capacitance of carbon materials for supercapacitors without sacrificing their rate performance, especially volumetric capacitance at high mass loadings, is a big challenge because of the limited assessable surface area and sluggish electrochemical kinetics of the pseudocapacitive reactions. Here, it is demonstrated that “self‐doping” defects in carbon materials can contribute to additional capacitance with an electrical double‐layer behavior, thus promoting a significant increase in the specific capacitance. As an exemplification, a novel defect‐enriched graphene block with a low specific surface area of 29.7 m² g^?1 and high packing density of 0.917 g cm^?3 performs high gravimetric, volumetric, and areal capacitances of 235 F g^?1, 215 F cm^?3, and 3.95 F cm^?2 (mass loading of 22 mg cm^?2) at 1 A g^?1, respectively, as well as outstanding rate performance. The resulting specific areal capacitance reaches an ultrahigh value of 7.91 F m^?2 including a “self‐doping” defect contribution of 4.81 F m^?2, which is dramatically higher than the theoretical capacitance of graphene (0.21 F m^?2) and most of the reported carbon‐based materials. Therefore, the defect engineering route broadens the avenue to further improve the capacitive performance of carbon materials, especially for compact energy storage under limited surface areas.     

Scalable Production of Graphene Inks via Wet‐Jet Milling Exfoliation for Screen‐Printed Micro‐Supercapacitors

The miniaturization of energy storage units is pivotal for the development of next‐generation portable electronic devices. Micro‐supercapacitors (MSCs) hold great potential to work as on‐chip micro‐power sources and energy storage units complementing batteries and energy harvester systems. Scalable production of supercapacitor materials with cost‐effective and high‐throughput processing methods is crucial for the widespread application of MSCs. Here, wet‐jet milling exfoliation of graphite is reported to scale up the production of graphene as a supercapacitor material. The formulation of aqueous/alcohol‐based graphene inks allows metal‐free, flexible MSCs to be screen‐printed. These MSCs exhibit areal capacitance (C_areal) values up to 1.324 mF cm^?2 (5.296 mF cm^?2 for a single electrode), corresponding to an outstanding volumetric capacitance (C_vol) of 0.490 F cm^?3 (1.961 F cm^?3 for a single electrode). The screen‐printed MSCs can operate up to a power density above 20 mW cm^?2 at an energy density of 0.064 µWh cm^?2. The devices exhibit excellent cycling stability over charge–discharge cycling (10 000 cycles), bending cycling (100 cycles at a bending radius of 1 cm) and folding (up to angles of 180°). Moreover, ethylene vinyl acetate‐encapsulated MSCs retain their electrochemical properties after a home‐laundry cycle, providing waterproof and washable properties for prospective application in wearable electronics.     

High Electroactive Material Loading on a Carbon Nanotube@3D Graphene Aerogel for High‐Performance Flexible All‐Solid‐State Asymmetric Supercapacitors

Freestanding carbon‐based hybrids, specifically carbon nanotube@3D graphene (CNTs@3DG) hybrid, are of great interest in electrochemical energy storage. However, the large holes (about 400 µm) in the commonly used 3D graphene foams (3DGF) constitute as high as 90% of the electrode volume, resulting in a very low loading of electroactive materials that is electrically connected to the carbon, which makes it difficult for flexible supercapacitors to achieve high gravimetric and volumetric energy density. Here, a hierarchically porous carbon hybrid is fabricated by growing 1D CNTs on 3D graphene aerogel (CNTs@3DGA) using a facile one‐step chemical vapor deposition process. In this architecture, the 3DGA with ample interconnected micrometer‐sized pores (about 5 µm) dramatically enhances mass loading of electroactive materials comparing with 3DGF. An optimized all‐solid‐state asymmetric supercapacitor (AASC) based on MnO₂@CNTs@3DGA and Ppy@CNTs@3DGA electrodes exhibits high volumetric energy density of 3.85 mW h cm^?3 and superior long‐term cycle stability with 84.6% retention after 20 000 cycles, which are among the best reported for AASCs with both electrodes made of pseudocapacitive electroactive materials.     

Phthalocyanine‐Based 2D Conjugated Metal‐Organic Framework Nanosheets for High‐Performance Micro‐Supercapacitors

2D conjugated metal‐organic frameworks (2D c‐MOFs) are emerging as a novel class of conductive redox‐active materials for electrochemical energy storage. However, developing 2D c‐MOFs as flexible thin‐film electrodes have been largely limited, due to the lack of capability of solution‐processing and integration into nanodevices arising from the rigid powder samples by solvothermal synthesis. Here, the synthesis of phthalocyanine‐based 2D c‐MOF (Ni₂[CuPc(NH)₈]) nanosheets through ball milling mechanical exfoliation method are reported. The nanosheets feature with average lateral size of ≈160 nm and mean thickness of ≈7 nm (≈10 layers), and exhibit high crystallinity and chemical stability as well as a p‐type semiconducting behavior with mobility of ≈1.5 cm² V^?1 s^?1 at room temperature. Benefiting from the ultrathin feature, the nanosheets allow high utilization of active sites and facile solution‐processability. Thus, micro‐supercapacitor (MSC) devices are fabricated mixing Ni₂[CuPc(NH)₈] nanosheets with exfoliated graphene, which display outstanding cycling stability and a high areal capacitance up to 18.9 mF cm^?2; the performance surpasses most of the reported conducting polymers‐based and 2D materials‐based MSCs.     

Oxygen‐Deficient Bismuth Oxide/Graphene of Ultrahigh Capacitance as Advanced Flexible Anode for Asymmetric Supercapacitors

Oxygen‐deficient bismuth oxide (r‐Bi₂O₃)/graphene (GN) is designed, fabricated, and demonstrated via a facile solvothermal and subsequent solution reduction method. The ultrafine network bacterial cellulose (BC) as substrate for r‐Bi₂O₃/GN exhibits high flexibility, remarkable tensile strength (55.1 MPa), and large mass loading of 9.8 mg cm^?2. The flexible r‐Bi₂O₃/GN/BC anode delivers appreciable areal capacitance (6675 mF cm^?2 at 1 mA cm^?2) coupled with good rate capability (3750 mF cm^?2 at 50 mA cm^?2). In addition, oxygen vacancies have great influence on the capacitive performance of Bi₂O₃, delivering significantly improved capacitive values than the untreated Bi₂O₃ flexible electrode, and ultrahigh gravimetric capacitance of 1137 F g^?1 (based on the mass of r‐Bi₂O₃) can be obtained, achieving 83% of the theoretical value (1370 F g^?1). Flexible asymmetric supercapacitor is fabricated with r‐Bi₂O₃/GN/BC and Co₃O₄/GN/BC paper as the negative and positive electrodes, respectively. The operation voltage is expanded to 1.6 V, revealing a maximum areal energy density of 0.449 mWh cm^?2 (7.74 mWh cm^?3) and an areal power density of 40 mW cm^?2 (690 mW cm^?3). Therefore, this flexible anode with excellent electrochemical performance and high mechanical properties shows great potential in the field of flexible energy storage devices.     

Development of Graphene Oxide/Polyaniline Inks for High Performance Flexible Microsupercapacitors via Extrusion Printing

Extrusion printing of interdigitated electrodes for flexible microsupercapacitors (fMSCs) offers an attractive route to the fabrication of flexible devices where cost, scalability, and processability of ink formulations are critical. In this work, highly concentrated, viscous, and water‐dispersible inks are developed based on graphene oxide (GO)/polyaniline (PANi) composite for extrusion printing. The optimized GO/PANi‐based all‐solid‐state symmetric fMSCs obtained by extrusion printing interdigitated microelectrodes can deliver outstanding areal capacitance of 153.6 mF cm^?2 and volumetric capacitance of 19.2 F cm^?3 at 5 mV s^?1. It is shown that by fabricating asymmetric fMSCs using the GO/PANi as positive electrode and a graphene‐based negative electrode, the voltage window can be widened from 0.8 to 1.2 V and improvements can be achieved in energy density (from 3.36 to 4.83 mWh cm^?3), power density (from 9.82 to 25.3 W cm^?3), and cycling stability (from 75% to 100% capacitance retention over 5000 cycles) compared with the symmetric counterpart. The simple ink preparation and facile device fabrication protocols reported here make the scalable fabrication of extrusion printed fMSCs a promising technology.     

A Self‐Branched Lamination of Hierarchical Patronite Nanoarchitectures on Carbon Fiber Cloth as Novel Electrode for Ionic Liquid Electrolyte‐Based High Energy Density Supercapacitors

The developments of rationally designed binder‐free metal chalcogenides decorated flexible electrodes are of paramount importance for advanced energy storage devices. Herein, binder‐free patronite (VS₄) flower‐like nanostructures are facilely fabricated on a carbon cloth (CC) using a facile hydrothermal method for high‐performance supercapacitors. The growth density and morphology of VS₄ nanostructures on CC are also controlled by varying the concentrations of vanadium and sulfur sources along with the complexing agent in the growth solution. The optimal electrode with an appropriate growth concentration (VS₄‐CC@VS‐3) demonstrates a considerable pseudocapacitance performance in the ionic liquid (IL) electrolyte (1‐ethyl‐3‐methylimidazolium trifluoromethanesulfonate), with a high operating potential of 2 V. Utilizing VS₄‐CC@VS‐3 as both positive and negative electrodes, the IL‐based symmetric supercapacitor is assembled, which demonstrates a high areal capacitance of 536 mF cm^?2 (206 F g^?1) and excellent cycling durability (93%) with superior energy and power densities of 74.4 µWh cm^?2 (28.6 Wh kg^?1) and 10154 µW cm^?2 (9340 W kg^?1), respectively. As for the high energy storage performance, the device stably energizes various portable electronic applications for a long time, which make the fabricated composite material open up news for the fabrication of fabrics supported binder‐free chalcogenides for high‐performance energy storage devices.     

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.     

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.     

Ultrafast Self‐Assembly of Graphene Oxide‐Induced Monolithic NiCo–Carbonate Hydroxide Nanowire Architectures with a Superior Volumetric Capacitance for Supercapacitors

The monolithic electrodes with high volumetric capacitance demonstrate a great potential in practical industrial applications for supercapacitors. Herein, a novel strategy for ultrafast self‐assembly of graphene oxides (GO)‐induced monolithic NiCo–carbonate hydroxide (NiCo–CH) nanowire composite films (G–CH) is reported. The oxygen‐containing functional groups on the GO surface help effectively to induce formation of the monodisperse NiCo–CH nanowires. Such a nanowire‐shaped structure further functions as a scaffold and/or support, leading to 25 s of ultrafast self‐assembly for G–CH composite films and a relatively loose and open channel that contributes to fast electrolyte transport. The as‐obtained monolithic G–CH architectures show an excellent supercapacitor performance as binder‐ and conductive agent‐free electrode, evidenced by a superior volumetric capacitance of 2936 F cm^?3 and good electrochemical stability. Combining highly conductive carbon nanotubes (CNTs) into the monolithic composite films can further create well‐interconnected conductive networks within the electrode matrix, thus to improve the reaction kinetics and rate capability. The present strategy that can modulate the growth of the high‐electroactive pseudocapacitive hydroxides and achieve an ultrafast self‐assembly of monolithic composites may pave a promising new way for development of high‐performance supercapacitors and shed a new light on the configuration of carbon‐based electrode materials in energy storage and conversion devices.     

3D Micro‐Extrusion of Graphene‐based Active Electrodes: Towards High‐Rate AC Line Filtering Performance Electrochemical Capacitors

A facile one‐step printing process by 3D micro‐extrusion affording binder‐free thermally reduced graphene oxide (TRGO) based electrochemical capacitors (ECs) that display high‐rate performance is presented. Key intermediates are binder‐free TRGO dispersion printing inks with concentrations up to 15 g L^?1. This versatile printing technique enables easy fabrication of EC electrodes, useful in both aqueous and non‐aqueous electrolyte systems. The as‐prepared TRGO material with high specific surface area (SSA) of 593 m² g^?1 and good electrical conductivity of ≈16 S cm^?1 exhibits impressive charge storage performances. At 100 and 120 Hz, ECs fabricated with TRGO show time constants of 2.5 ms and 2.3 ms respectively. Very high capacitance values are derived at both frequencies ranging from 3.55 mF cm^?2 to 1.76 mF cm^?2. Additionally, these TRGO electrodes can be charged and discharged at very high voltage scan rates up to 15 V s^?1 yielding 4 F cm^?3 with 50% capacitance retention. Electrochemical performance of TRGO electrodes in electrolyte containing tetraethyl ammonium tetrafluoroborate and acetonitrile (TEABF4‐ACN) yields high energy density of 4.43 mWh cm^?3 and power density up to 42.74 kW cm^?3, which is very promising for AC line filtering application and could potentially substitute state of the art electrolytic capacitor technology.