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1.
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.  相似文献   

2.
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.  相似文献   

3.
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.  相似文献   

4.
A novel three‐electrode electrolyte supercapacitor (electric double‐layer capacitor [EDLC]) architecture in which a symmetrical interdigital “working” two‐electrode micro‐supercapacitor array (W‐Cap) is paired with a third “gate” electrode that reversibly depletes/injects electrolyte ions into the system controlling the “working” capacity effectively is described. All three electrodes are based on precursor‐derived nanoporous carbons with well‐defined specific surface area (735 m2 g?1). The interdigitated architecture of the W‐Cap is precisely manufactured using 3D printing. The W‐Cap operating with a proton conducting PVA/H2SO4‐hydrogel electrolyte and high capacitance (6.9 mF cm?2) can be repeatedly switched “on” and “off”. By applying a low DC bias potential (?0.5 V) at the gate electrode, the AC electroadsorption in the coupled interdigital nanoporous carbon electrodes of the W‐Cap is effectively suppressed leading to a stark capacity drop by two orders of magnitude from an “on” to an “off” state. The switchable micro‐supercapacitor is the first of its kind. This general concept is suitable for implementing a broad range of nanoporous materials and advanced electrolytes expanding its functions and applications in future. The integration of intelligent functions into EDLC devices has extensive implications for diverse areas such as capacitive energy management, microelectronics, iontronics, and neuromodulation.  相似文献   

5.
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.  相似文献   

6.
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.  相似文献   

7.
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 (Careal) values up to 1.324 mF cm?2 (5.296 mF cm?2 for a single electrode), corresponding to an outstanding volumetric capacitance (Cvol) 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.  相似文献   

8.
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.  相似文献   

9.
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.  相似文献   

10.
Micro‐supercapacitors (MSCs), albeit powerful, are unable to broaden their potential applications primarily because they are not as flexible and morphable as electronics. To address this problem, a universal strategy to fabricate substrate‐free, ultrathin, shapeless planar‐MSCs with high‐performance tenability under serious deformation is put forward. These represent a new class of “all‐inside‐one” film supercapacitors, achieved by encapsulating two‐dimensional interdigital microelectrodes within chemically cross‐linked polyvinyl‐alcohol‐based hydrogel electrolyte containing graphene oxide (GO). GO nanosheets significantly improve ionic conductivity, enhance the capacitance, and boost robustness of hydrogel electrolyte. Consequently, the entire MSC, while being only 37 µm thick, can be crumpled and its shape can self‐adjust through fluid channel ten times smaller than its original size without any damage, demonstrating shapelessness. Using MXene as active material, high single‐cell areal capacitance of 40.8 mF cm?2 is achieved from microelectrodes as thin as 5 µm. Furthermore, to demonstrate wide applicability of this protocol, screen‐printed graphene‐based highly integrated MSCs connecting nine cells in series are fabricated to stably output a high voltage of 7.2 V while crumpling them from 0.11 to 0.01 cm?3, manifesting superior performance uniformity. This protocol allows the coexistence of high performance with incredible flexibility that may greatly diversify MSCs' applications.  相似文献   

11.
Iron oxides are promising to be utilized in rechargeable alkaline battery with high capacity upon complete redox reaction (Fe3+ Fe0). However, their practical application has been hampered by the poor structural stability during cycling, presenting a challenge that is particularly huge when binder‐free electrode is employed. This paper proposes a “carbon shell‐protection” solution and reports on a ferroferric oxide–carbon (Fe3O4–C) binder‐free nanorod array anode exhibiting much improved cyclic stability (from only hundreds of times to >5000 times), excellent rate performance, and a high capacity of ≈7776.36 C cm?3 (≈0.4278 C cm?2; 247.5 mAh g?1, 71.4% of the theoretical value) in alkaline electrolyte. Furthermore, by pairing with a capacitive carbon nanotubes (CNTs) film cathode, a unique flexible solid‐state rechargeable alkaline battery‐supercapacitor hybrid device (≈360 μm thickness) is assembled. It delivers high energy and power densities (1.56 mWh cm?3; 0.48 W cm?3/≈4.8 s charging), surpassing many recently reported flexible supercapacitors. The highest energy density value even approaches that of Li thin‐film batteries and is about several times that of the commercial 5.5 V/100 mF supercapacitor. In particular, the hybrid device still maintains good electrochemical attributes in cases of substantially bending, high mechanical pressure, and elevated temperature (up to 80 °C), demonstrating high environmental suitability.  相似文献   

12.
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.  相似文献   

13.
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.  相似文献   

14.
Developing advanced three‐dimensional (3D) structural supercapacitors with both high capacity and good mechanical strength remains challenging. Herein, a novel road is reported for fabricating 3D structural strengthening supercapacitors with adjustable capacitance based on urchin‐like Cu(OH)2 lattice electrodes by bridging 3D printing technology with a facile electroless plating and electro‐oxidation method. As revealed by the results, the 3D‐printed octet‐truss lattice electrode features a high volumetric capacitance of 8.46 F cm?3 at 5 mA cm?3 and superior retention capacity of 68% at 1 A cm?3. The assembled symmetric supercapacitor with a 70.2% capacitance retention after 5000 cycles possesses a 12.8 Wh kg?1 energy density at a power density of 2110.2 W kg?1. Additionally, the resulting 3D structural strengthening electrodes can achieve both high compressive strength and toughness of 30 MPa and 264.7 kJ m?3, respectively, demonstrating high mechanical strength and excellent antideformation capacity. With the proposed strategy, the electrochemical and mechanical properties of these novel 3D structural strengthened supercapacitors can be easily tuned by a simple spatial framework design, fulfilling the increasing demand of highly customized power sources in the space‐constrained microelectronics and astronautic electronics industries.  相似文献   

15.
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.  相似文献   

16.
2D soft nanomaterials are an emerging research field due to their versatile chemical structures, easily tunable properties, and broad application potential. In this study, a benzene‐bridged polypyrrole film with a large area, up to a few square centimeters, is synthesized through an interfacial polymerization approach. As‐prepared semiconductive films exhibit a bandgap of ≈2 eV and a carrier mobility of ≈1.5 cm2 V?1 s?1, inferred from time‐resolved terahertz spectroscopy. The samples are employed to fabricate in‐plane micro‐supercapacitors (MSCs) by laser scribing and exhibit an ultrahigh areal capacitance of 0.95 mF cm?2, using 1‐ethyl‐3‐methylimidazolium tetrafluoroborate ([EMIM][BF4]) as an electrolyte. Importantly, the maximum energy and power densities of the developed MSCs reach values up to 50.7 mWh cm?3 and 9.6 kW cm?3, respectively; the performance surpassing most of the 2D material‐based MSCs is reported to date.  相似文献   

17.
The rapid development of miniature electronics has accelerated the demand for simplified and scalable production of micro‐supercapacitors (MSCs); however, the preparation of active materials, patterning microelectrodes, and subsequent modular integration of the reported MSCs are normally separated and are involved in multiple complex steps. Herein, a one‐step, cost‐effective strategy for fast and scalable fabrication of patterned laser‐induced graphene (LIG) for all‐solid‐state planar integrated MSCs (LIG‐MSCs) with various form factors of designable shape, exceptional flexibility, performance uniformity, superior modularization, and high‐temperature stability is demonstrated. Notably, using the conductive and porous LIG patterns composed of randomly stacked graphene nanosheets simultaneously acting as both microelectrodes and interconnects, the resulting LIG‐MSCs represent typical electrical double capacitive behavior, having an impressive areal capacitance of 0.62 mF cm?2 and long‐term stability without capacitance degeneration after 10 000 cycles. Furthermore, LIG‐MSCs display exceptional mechanical flexibility and adjustable voltage and capacitance output through arbitrary arrangement of cells connected in series and in parallel, indicative of exceptional performance customization. Moreover, all‐solid‐state LIG‐MSCs working at ionogel electrolyte exhibit highly stable performance even at high temperature of 100 °C, with 90% capacitance retention over 3000 cycles, suggestive of outstanding reliability. Therefore, the LIG‐MSCs offer tremendous opportunities for miniature power source‐integrated microelectronics.  相似文献   

18.
A novel method is described for fabricating an all‐solid‐state flexible micro‐supercapacitor. The microelectrodes of the supercapacitor are prepared by in situ electrodeposition of polyaniline (PANI) nanorods on the surface of reduced graphene oxide (rGO) patterns that are fabricated by micromolding in capillaries. The morphologies of PANI nanorods could be controlled by the concentration of aniline and the growth time in the electrodeposition process. The micro‐supercapacitor possesses electrochemical capacitance as high as 970 F g?1 at a discharge current density of 2.5 A g?1, as well as good stability, retaining 90% of its initial capacitance after 1700 consecutive cycles for the synergistic effect of these new rGO/PANI nanostructures. The results show that the method could represent a route for translating the interesting fundamental properties of rGO and conducting polymers into technologically viable energy devices. Furthermore, this study might further guide the preparation of functional graphene‐based materials.  相似文献   

19.
Fiber‐shaped micro‐supercapacitors (micro‐SCs) have attracted enormous interest in wearable electronics due to high flexibility and weavability. However, they usually present a low energy density because of inhomogeneity and less pores. Here, we demonstrate a microfluidic‐directed strategy to synthesize homogeneous nitrogen‐doped porous graphene fibers. The porous fibers‐based micro‐SCs utilize solid‐state phosphoric acid/polyvinyl alcohol (H3PO4/PVA) and 1‐ethyl‐3‐methylimidazolium tetrafluoroborate/poly(vinylidenefluoride‐co‐hexafluoropropylene) (EMIBF4/PVDF‐HFP) electrolytes, which show significant improvements in electrochemical performances. Ultralarge capacitance (1132 mF cm?2), high cycling‐stability, and long‐term bending‐durability are achieved based on H3PO4/PVA. Additionally, high energy densities of 95.7–46.9 µWh cm?2 at power densities of 1.5–15 W cm?2 are obtained in EMIBF4/PVDF‐HFP. The key to higher performances stems from microfluidic‐controlled fibers with a uniformly porous network, large specific surface area (388.6 m2 g?1), optimal pyridinic nitrogen (2.44%), and high electric conductivity (30785 S m?1) for faster ion diffusion and flooding accommodation. By taking advantage of these remarkable merits, this study integrates micro‐SCs into flexible and fabric substrates to power audio–visual electronics. The main aim is to clarify the important role of microfluidic techniques toward the architecture of electrodes and promote development of wearable electronics.  相似文献   

20.
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.  相似文献   

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