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.     

High Areal Capacitance of N‐Doped Graphene Synthesized by Arc Discharge

The lack of cost effective, industrial‐scale production methods hinders the widespread applications of graphene materials. In spite of its applicability in the mass production of graphene flakes, arc discharge has not received considerable attention because of its inability to control the synthesis and heteroatom doping. In this study, a facile approach is proposed for improving doping efficiency in N‐doped graphene synthesis through arc discharge by utilizing anodic carbon fillers. Compared to the N‐doped graphene (1–1.5% N) synthesized via the arc process according to previous literature, the resulting graphene flakes show a remarkably increased doping level (≈3.5% N) with noticeable graphitic N enrichment, which is rarely achieved by the conventional process, while simultaneously retaining high turbostratic crystallinity. The electrolyte ion storage of synthesized materials is examined in which synthesized N‐doped graphene material exhibits a remarkable area normalized capacitance of 63 µF cm^?2. The surprisingly high areal capacitance, which is superior to that of most carbon materials, is attributed to the synergistic effect of extrinsic pseudocapacitance, high crystallinity, and abundance of exposed graphene edges. These results highlight the great potentials of N‐doped graphene flakes produced by arc discharge in graphene‐based supercapacitors, along with well‐studied active exfoliated graphene and reduced graphene oxide.     

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.     

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).     

Sputtered Titanium Carbide Thick Film for High Areal Energy on Chip Carbon‐Based Micro‐Supercapacitors

The areal energy density of on‐chip micro‐supercapacitors should be improved in order to obtain autonomous smart miniaturized sensors. To reach this goal, high surface capacitance electrode (>100 mF cm^?2) has to be produced while keeping low the footprint area. For carbide‐derived carbon (CDC) micro‐supercapacitors, the properties of the metal carbide precursor have to be fine‐tuned to fabricate thick electrodes. The ad‐atoms diffusion process and atomic peening effect occurring during the titanium carbide sputtering process are shown to be the key parameters to produce low stress, highly conductive, and thick TiC films. The sputtered TiC at 10^?3 mbar exhibits a high stress level, limiting the thickness of the TiC‐CDC electrode to 1.5 µm with an areal capacitance that is less than 55 mF cm^?2 in aqueous electrolyte. The pressure increase up to 10^?2 mbar induces a clear reduction of the stress level while the layer thickness increases without any degradation of the TiC electronic conductivity. The volumetric capacitance of the TiC‐CDC electrodes is equal to 350 F cm^?3 regardless of the level of pressure. High values of areal capacitance (>100 mF cm^?2) are achieved, whereas the TiC layer is relatively thick, which paves the way toward high‐performance micro‐supercapacitors.     

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.     

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.     

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.     

Prolifera‐Green‐Tide as Sustainable Source for Carbonaceous Aerogels with Hierarchical Pore to Achieve Multiple Energy Storage

The increasing demand for efficient energy storage and conversion devices has aroused great interest in designing advanced materials with high specific surface areas, multiple holes, and good conductivity. Here, we report a new method for fabricating a hierarchical porous carbonaceous aerogel (HPCA) from renewable seaweed aerogel. The HPCA possesses high specific surface area of 2200 m² g^?1 and multilevel micro/meso/macropore structures. These important features make HPCA exhibit a reversible lithium storage capacity of 827.1 mAh g^?1 at the current density of 0.1 A g^?1, which is the highest capacity for all the previously reported nonheteroatom‐doped carbon nanomaterials. It also shows high specific capacitance and excellent rate performance for electric double layer capacitors (260.6 F g^?1 at 1 A g^?1 and 190.0 F g^?1 at 50 A g^?1), and long cycle life with 91.7% capacitance retention after 10 000 cycles at 10 A g^?1. The HPCA also can be used as support to assemble Co₃O₄ nanowires (Co₃O₄@HPCA) for constructing a high performance pseudocapacitor with the maximum specific capacitance of 1167.6 F g^?1 at the current density of 1 A g^?1. The present work highlights the first example in using prolifera‐green‐tide as a sustainable source for developing advanced carbon porous aerogels to achieve multiple energy storage.     

Nitrogen‐Enriched Nonporous Carbon Electrodes with Extraordinary Supercapacitance

Nitrogen‐enriched nonporous carbon materials derived from melamine–mica composites are subjected to ammonia treatment to further increase the nitrogen content. For samples preoxidized prior to the ammonia treatment, the nitrogen content is doubled and is mainly incorporated in pyrrol‐like groups. The materials are tested as electrodes for supercapacitors, and in acidic or basic electrolytes, the gravimetric capacitance of treated samples is three times higher than that of untreated samples. This represents a tenfold increase of the capacitance per surface area (3300 µF cm^?2) in basic electrolyte. Due to the small volume of the carbon materials, high volumetric capacitances are achieved in various electrolytic systems: 280 F cm^?3 in KOH, 152 F cm^?3 in H₂SO₄, and 92 F cm^?3 in tetraethylammonium tetrafluoroborate/propylene carbonate.     

Polypyrrole‐Derived Activated Carbons for High‐Performance Electrical Double‐Layer Capacitors with Ionic Liquid Electrolyte

As electrical energy storage and delivery devices, carbon‐based electrical double‐layer capacitors (EDLCs) have attracted much attention for advancing the energy‐efficient economy. Conventional methods for activated carbon (AC) synthesis offer limited control of their surface area and porosity, which results in a typical specific capacitance of 70–120 F g^?1 in commercial EDLCs based on organic electrolytes and ionic liquids (ILs). Additionally, typical ACs produced from natural precursors suffer from the significant variation of their properties, which is detrimental for EDLC use in automotive applications. A novel method for AC synthesis for EDLCs is proposed. This method is based on direct activation of synthetic polymers. The proposed procedure allowed us to produce ACs with ultrahigh specific surface area of up to 3432 m² g^?1 and volume of 0.5–4 nm pores up to 2.39 cm³ g^?1. The application of the produced carbons in EDLCs based on IL electrolyte showed specific capacitance approaching 300 F g^?1, which is unprecedented for carbon materials, and 5–8% performance improvement after 10 000 charge–discharge cycles at the very high current density of 10 A g^?1. The remarkable characteristics of the produced materials and the capability of the fabricated EDLCs to operate safely in a wide electrochemical window at elevated temperatures, suggest that the proposed synthesis route offers excellent potential for large‐scale material production for EDLC use in electric vehicles and industrial applications.     

Large‐Area Flexible Core–Shell Graphene/Porous Carbon Woven Fabric Films for Fiber Supercapacitor Electrodes

New porous materials are of great importance in many technological applications. Here, the direct synthesis of multi‐layer graphene and porous carbon woven composite films by chemical vapor deposition on Ni gauze templates is reported. The composite films integrate the dual advantages of graphene and porous carbon, having not only the excellent electrical properties and flexibility of graphene but also the porous characteristics of amorphous carbon. The multi‐layer graphene/porous carbon woven fabric film creates a new platform for a variety of applications, such as fiber supercapacitors. The designed composite film has a capacitance of 20 μF/cm², which is close to the theoretical value and a device areal capacitance of 44 mF/cm².     

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.     

Flexible Solid‐State Supercapacitor Based on Graphene‐based Hybrid Films

A flexible solid‐state asymmetric supercapacitor based on bendable film electrodes with 3D expressway‐like architecture of graphenes and “hard nano‐spacer” is fabricated via an extended filtration assisted method. In the designed structure of the positive electrode, graphene sheets are densely packed, and Ni(OH)₂ nanoplates are intercalated in between the densely stacked graphenes. The 3D expressway‐like electrodes exhibit superior supercapacitive performance including high gravimetric capacitance (≈573 F g^‐1), high volumetric capacitance (≈655 F cm^‐3), excellent rate capability, and superior cycling stability. In addition, another hybrid film of graphene and carbon nanotubes (CNT) is fabricated as the negative electrodes for the designed asymmetric device. In the obtained graphene@CNT films, CNTs served as the hard spacer to prevent restacking of graphene sheets but also as a conductive and robust network to facilitate the electrons collection/transport in order to fulfill the demand of high‐rate performance of the asymmetric supercapacitor. Based on these two hybrid electrode films, a solid‐state flexible asymmetric supercapacitor device is assembled, which is able to deliver competitive volumetric capacitance of 58.5 F cm^‐3 and good rate capacity. There is no obvious degradation of the supercapacitor performance when the device is in bending configuration, suggesting the excellent flexibility of the device.     

Ultra‐High Surface Area Nitrogen‐Doped Carbon Aerogels Derived From a Schiff‐Base Porous Organic Polymer Aerogel for CO2 Storage and Supercapacitors

Nitrogen‐doped carbon aerogels (NCAs) have received great attention for a wide range of applications, from thermal electronics to waste water purification, heavy metal or gas adsorption, energy storage, and catalyst supports. Herein NCAs are developed via the synthesis of a Schiff‐base porous organic polymer aerogel followed by pyrolysis. By controlling the pyrolysis temperature, the polymer aerogel can be simply converted into porous NCAs with a low bulk density (5 mg cm^?3), high surface area (2356 m² g^?1), and high bulk porosity (70%). The NCAs containing 1.8–5.3 wt% N atoms exhibit remarkable CO₂ uptake capacities (6.1 mmol g^?1 at 273 K and 1 bar, 33.1 mmol g^?1 at 323 K and 30 bar) and high ideal adsorption solution theory selectivity (47.8) at ambient pressure. Supercapacitors fabricated with NCAs display high specific capacitance (300 F g^?1 at 0.5 A g^?1), fast rate (charge to 221 F g^?1 within only 17 s), and high stability (retained >98% capacity after 5000 cycles). Asymmetric supercapacitors assembled with NCAs also show high energy density and power density with maximal values of 30.5 Wh kg^?1 and 7088 W kg^?1, respectively. The outstanding CO₂ uptake and energy storage abilities are attributed to the ultra‐high surface area, N‐doping, conductivity, and rigidity of NCA frameworks.     

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.     

Oxidation‐Resistant and Elastic Mesoporous Carbon with Single‐Layer Graphene Walls

An oxidation‐resistant and elastic mesoporous carbon, graphene mesosponge (GMS), is prepared. GMS has a sponge‐like mesoporous framework (mean pore size is 5.8 nm) consisting mostly of single‐layer graphene walls, which realizes a high electric conductivity and a large surface area (1940 m² g^?1). Moreover, the graphene‐based framework includes only a very small amount of edge sites, thereby achieving much higher stability against oxidation than conventional porous carbons such as carbon blacks and activated carbons. Thus, GMS can simultaneously possess seemingly incompatible properties; the advantages of graphitized carbon materials (high conductivity and high oxidation resistance) and porous carbons (large surface area). These unique features allow GMS to exhibit a sufficient capacitance (125 F g^?1), wide potential window (4 V), and good rate capability as an electrode material for electric double‐layer capacitors utilizing an organic electrolyte. Hence, GMS achieves a high energy density of 59.3 Wh kg^?1 (material mass base), which is more than twice that of commercial materials. Moreover, the continuous graphene framework makes GMS mechanically tough and extremely elastic, and its mean pore size (5.8 nm) can be reversibly compressed down to 0.7 nm by simply applying mechanical force. The sponge‐like elastic property enables an advanced force‐induced adsorption control.     

Flexible All‐Solid‐State Supercapacitors of High Areal Capacitance Enabled by Porous Graphite Foams with Diverging Microtubes

The practical applications of wearable electronics rely on the successful development of flexible and integrable energy devices with small footprints. This work reports a completely new type of graphite foam made of strategically created superstructures with covalently attached diverging microtubes, and their applications as electrode supports for binder‐free and additive‐free flexible supercapacitors. Because of the enhanced volumetric surface areas compared to conventional graphite foams, a high loading of pseudocapacitive materials (Mn₃O₄, 3.91 mg cm^?2, 78 wt%) is achieved. The supercapacitors provide areal capacitances as high as 820 mF cm^?2 at 1 mV s^?1, while still maintaining high rate capability and 88% retention of capacitance after 3000 continuous charging and discharging cycles. When assembled as all‐solid‐state flexible symmetric supercapacitors, they offer one of the highest full‐cell capacitances (191 mF cm^?2) among similar manganese oxide/graphene foams, and retain 80% capacitance after 1000 mechanical cycles. The potential of such flexible supercapacitors is also manifested by directly powering electric nanomotors that can trace along letters “U” and T,” which is the first demonstration of flexible supercapacitors for wireless/portable nanomanipulation systems. This work could inspire a new paradigm in designing and creating 3D porous micro/nanosuperstructures for an array of self‐powered electronic and nanomechanical applications.     

Oxygen Clusters Distributed in Graphene with “Paddy Land” Structure: Ultrahigh Capacitance and Rate Performance for Supercapacitors

The introduction of surface functional groups onto graphene can provide additional pseudocapacitance for supercapacitors. However, the compensation for the loss of electrical conductivity arising from the disruption of the conjugated system remains a big challenge. Here, a novel strategy is reported for the design of oxygen clusters distributed in graphene with “paddy land” structure via a low‐temperature annealing process. Moreover, the distribution, content, and variety of oxygen groups and the conductivity of reduced graphene oxide (RGO) can be easily adjusted by annealing temperature and time. First‐principles calculations demonstrate that “paddy land” structure exhibits conjugated carbon network, ultralow HOMO–LUMO gap, and long span of atomic charge values, which are beneficial for the enhanced pseudocapacitance and rate performance. As a result, the functionalized graphene (GO‐160‐8D) exhibits high specific capacitance of 436 F g^?1 at 0.5 A g^?1, exceeding the values of previously reported RGO materials, as well as excellent rate performance (261 F g^?1 at 50 A g^?1) and cycling stability (94% of capacitance retention after 10 000 cycles). The findings may open a door for finely controlling the location and density of functionalities on graphene for applications in energy storage and conversion fields via a green and energy‐efficient process.     

A Flexible 3D Multifunctional MgO‐Decorated Carbon Foam@CNTs Hybrid as Self‐Supported Cathode for High‐Performance Lithium‐Sulfur Batteries

One of the critical challenges to develop advanced lithium‐sulfur (Li‐S) batteries lies in exploring a high efficient stable sulfur cathode with robust conductive framework and high sulfur loading. Herein, a 3D flexible multifunctional hybrid is rationally constructed consisting of nitrogen‐doped carbon foam@CNTs decorated with ultrafine MgO nanoparticles for the use as advanced current collector. The dense carbon nanotubes uniformly wrapped on the carbon foam skeletons enhance the flexibility and build an interconnected conductive network for rapid ionic/electronic transport. In particular, a synergistic action of MgO nanoparticles and in situ N‐doping significantly suppresses the shuttling effect via enhanced chemisorption of lithium polysulfides. Owing to these merits, the as‐built electrode with an ultrahigh sulfur loading of 14.4 mg cm^?2 manifests a high initial areal capacity of 10.4 mAh cm^?2, still retains 8.8 mAh cm^?2 (612 mAh g^?1 in gravimetric capacity) over 50 cycles. The best cycling performance is achieved upon 800 cycles with an extremely low decay rate of 0.06% at 2 C. Furthermore, a flexible soft‐packaged Li‐S battery is readily assembled, which highlights stable electrochemical characteristics under bending and even folding. This cathode structural design may open up a potential avenue for practical application of high‐sulfur‐loading Li‐S batteries toward flexible energy‐storage devices.