Inkjet printing of single-walled carbon nanotube/RuO<Subscript>2</Subscript> nanowire supercapacitors on cloth fabrics and flexible substrates

Single-walled carbon nanotube (SWNT) thin film electrodes have been printed on flexible substrates and cloth fabrics by using SWNT inks and an off-the-shelf inkjet printer, with features of controlled pattern geometry (0.4–6 cm²), location, controllable thickness (20–200 nm), and tunable electrical conductivity. The as-printed SWNT films were then sandwiched together with a piece of printable polymer electrolyte to form flexible and wearable supercapacitors, which displayed good capacitive behavior even after 1,000 charge/discharge cycles. Furthermore, a simple and efficient route to produce ruthenium oxide (RuO₂) nanowire/SWNT hybrid films has been developed, and it was found that the knee frequency of the hybrid thin film electrodes can reach 1,500 Hz, which is much higher than the knee frequency of the bare SWNT electrodes (˜158 Hz). In addition, with the integration of RuO₂ nanowires, the performance of the printed SWNT supercapacitor was significantly improved in terms of its specific capacitance of 138 F/g, power density of 96 kW/kg, and energy density of 18.8 Wh/kg. The results indicate the potential of printable energy storage devices and their significant promise for application in wearable energy storage devices.      

Fabrication of a low defect density graphene-nickel hydroxide nanosheet hybrid with enhanced electrochemical performance

The development of efficient energy storage devices with high capacity and excellent stability is a demanding necessary to satisfy future societal and environmental needs. A hybrid material composed of low defect density graphene-supported Ni(OH)₂ sheets has been fabricated via a soft chemistry route and investigated as an advanced electrochemical pseudocapacitor material. The low defect density graphene effectively prevents the restacking of Ni(OH)₂ nanosheets as well as boosting the conductivity of the hybrid electrodes, giving a dramatic rise in capacity performance of the overall system. Moreover, graphene simultaneously acts as both nucleation center and template for the in situ growth of smooth and large scale Ni(OH)₂ nanosheets. By virtue of the unique two-dimensional nanostructure of graphene, the as-obtained Ni(OH)₂ sheets are closely protected by graphene, effectively suppressing their microstructural degradation during the charge and discharge processes, enabling an enhancement in cycling capability. Electrochemical measurements demonstrated that the specific capacitance of the as-obtained composite is high as 1162.7 F/g at a scan rate of 5 mV/s and 1087.9 F/g at a current density of 1.5 A/g. In addition, there was no marked decrease in capacitance at a current density of 10·A/g after 2000 cycles, suggesting excellent long-term cycling stability.      

One-step strategy to graphene/Ni(OH)2 composite hydrogels as advanced three-dimensional supercapacitor electrode materials

Graphene-based three-dimensional (3D) macroscopic materials have recently attracted increasing interest by virtue of their exciting potential in electrochemical energy conversion and storage. Here we report a facile one-step strategy to prepare mechanically strong and electrically conductive graphene/Ni(OH)₂ composite hydrogels with an interconnected porous network. The composite hydrogels were directly used as 3D supercapacitor electrode materials without adding any other binder or conductive additives. An optimized composite hydrogel containing ～82 wt.% Ni(OH)₂ exhibited a specific capacitance of ～1,247 F/g at a scan rate of 5 mV/s and ～785 F/g at 40 mV/s (～63% capacitance retention) with excellent cycling stability. The capacity of the 3D hydrogels greatly surpasses that of a physical mixture of graphene sheets and Ni(OH)₂ nanoplates (～309 F/g at 40 mV/s). The same strategy was also applied to fabricate graphene-carbon nanotube/Ni(OH)₂ ternary composite hydrogels with further improved specific capacitances (～1,352 F/g at 5 mV/s) and rate capability (～66% capacitance retention at 40 mV/s). Both composite hydrogels obtained here can deliver high energy densities (～43 and ～47 Wh/kg, respectively) and power densities (～8 and ～9 kW/kg, respectively), making them attractive electrode materials for supercapacitor applications. This study opens a new pathway to the design and fabrication of functional 3D graphene composite materials, and can significantly impact broad areas including energy storage and beyond.      

Facile growth of homogeneous Ni(OH)<Subscript>2</Subscript> coating on carbon nanosheets for high-performance asymmetric supercapacitor applications

The growth of a Ni(OH)₂ coating on conductive carbon substrates is an efficient way to address issues related to their poor conductivity in electrochemical capacitor applications. However, the direct growth of nickel hydroxide coatings on a carbon substrate is challenging, because the surfaces of these systems are not compatible and a preoxidation treatment of the conductive carbon substrate is usually required. Herein, we present a facile preoxidation-free approach to fabricate a uniform Ni(OH)₂ coating on carbon nanosheets (CNs) by an ion-exchange reaction to achieve the in situ transformation of a MgO/C composite to a Ni(OH)₂/C one. The obtained Ni(OH)₂/CNs hybrids possess nanosheet morphology, a large surface area (278 m²/g), and homogeneous elemental distributions. When employed as supercapacitors in a three-electrode configuration, the Ni(OH)₂/CNs hybrid achieves a large capacitance of 2,218 F/g at a current density of 1.0 A/g. Moreover, asymmetric supercapacitors fabricated with the Ni(OH)₂/CNs hybrid exhibit superior supercapacitive performances, with a large capacity of 198 F/g, and high energy density of 56.7 Wh/kg at a power density of 4.0 kW/kg. They show excellent cycling stability with 93% capacity retention after 10,000 cycles, making the Ni(OH)₂/CNs hybrid a promising candidate for practical applications in supercapacitor devices.

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Different growth behaviors of ambient pressure chemical vapor deposition graphene on Ni(111) and Ni films: A scanning tunneling microscopy study

Graphene growth on the same metal substrate with different crystal morphologies, such as single crystalline and polycrystalline, may involve different mechanisms. We deal with this issue by preparing graphene on single crystal Ni(111) and on ∼300 nm thick Ni films on SiO₂ using an ambient pressure chemical vapor deposition (APCVD) method, and analyze the different growth behaviors for different growth parameters by atomically-resolved scanning tunneling microscopy (STM) and complementary macroscopic analysis methods. Interestingly, we obtained monolayer graphene on Ni(111), and multilayer graphene on Ni films under the same growth conditions. Based on the experimental results, it is proposed that the graphene growth on Ni(111) is strongly templated by the Ni(111) lattice due to the strong Ni-C interactions, leading to monolayer graphene growth. Multilayer graphene flakes formed on polycrystalline Ni films are usually stacked with deviations from the Bernal stacking type and show small rotations among the carbon layers. Considering the different substrate features, the inevitable grain boundaries on polycrystalline Ni films are considered to serve as the growth fronts for bilayer and even multilayer graphene.      

Hierarchical ferric-cobalt-nickel ternary oxide nanowire arrays supported on graphene fibers as high-performance electrodes for flexible asymmetric supercapacitors

Fiber-based supercapacitors (FSCs) are new members of the energy storage family. They present excellent flexibility and have promising applications in lightweight, flexible, and wearable devices. One of the existing challenges of FSCs is enhancing their energy density while retaining the flexibility. We developed a facile and cost-effective method to fabricate a highly capacitive positive electrode based on hierarchical ferric-cobalt-nickel ternary oxide nanowire arrays/graphene fibers and a negative electrode based on polyaniline-derived carbon nanorods/graphene fibers. The elegant microstructures and excellent electrochemical performances of both electrodes enabled us to construct a highperformance flexible asymmetric graphene fiber-based supercapacitor device with an operating voltage of 1.4 V, a specific capacitance up to 61.58 mF·cm^–2, and an energy density reaching 16.76 μW·h·cm^–2. Moreover, the optimal device presents an outstanding cycling stability with 87.5% initial capacitance retention after 8,000 cycles, and an excellent flexibility with a capacitance retention of 90.9% after 4,000 cycles of repetitive bending.

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Highly bonded <Emphasis Type="Italic">T</Emphasis>-Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>/rGO nanohybrids for 4 V quasi-solid state asymmetric supercapacitors with improved electrochemical performance

T-Nb₂O₅/reduced graphene oxide nanohybrids were fabricated via the hydrothermal attachment of Nb₂O₅ nanowires to dispersed graphene oxide nanosheets followed by a high-temperature phase transformation. Electrochemical measurements showed that the nanohybrid anodes possessed enhanced reversible capacity and superior cycling stability compared to those of a pristine T-Nb₂O₅ nanowire electrode. Owing to the strong bonds between graphene nanosheets and T-Nb₂O₅ nanowires, the nanohybrids achieved an initial capacity of 227 mAh·g^?1. Additionally, non-aqueous asymmetric supercapacitors (ASCs) were fabricated with the synthesized nanohybrids as the anode and activated carbon as the cathode. The 3 V Li-ion ASC with a LiPF₆-based organic electrolyte achieved an energy density of 45.1 Wh·kg^?1 at 715.2 W·kg^?1. The working potential could be further enhanced to 4 V when a polymer ionogel separator (PVDF-HFP/LiTFSI/EMIMBF₄) and formulated ionic liquid electrolyte were employed. Such a quasi-solid state ASC could operate at 60 °C and delivered a maximum energy density of 70 Wh·kg^?1 at 1 kW·kg^?1.

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Massless and massive particle-in-a-box states in single- and bi-layer graphene

Electron transport through short, phase-coherent metal-graphene-metal devices occurs via resonant transmission through particle-in-a-box-like states defined by the atomically-sharp metal leads. We study the spectrum of particle-in-a-box states for single- and bi-layer graphene, corresponding to massless and massive two-dimensional (2-D) fermions. The density of states D as a function of particle number n shows the expected relationships D(n) ∼ n ^1/2 for massless 2-D fermions (electrons in single-layer graphene) and D(n) ∼ constant for massive 2-D fermions (electrons in bi-layer graphene). The single parameters of the massless and massive dispersion relations are found, namely Fermi velocity υ _F = 1.1 × 10⁶ m/s and effective mass m* = 0.032 m _e, where m _e is the electron mass, in excellent agreement with theoretical expectations.      

Rational design of novel ultra-small amorphous Fe2O3 nanodots/graphene heterostructures for all-solid-state asymmetric supercapacitors

Constructing graphene-based heterostructures with large interfacial area is an efficient approach to enhance the electrochemical performance of supercapacitors but remains great challenges in their synthesis.Herein,a novel ultra-small amorphous Fe₂O₃nanodots/graphene heterostructure(a-Fe₂O₃NDs/RGO)aerogel was facilely synthesized via excessive metal-ion-induced self-assembly and subsequent calcination route using Prussian blue/graphene oxide(PB/GO)composite aerogel as precursors.The deliberately designed a-Fe₂O₃NDs/RGO heterostructure offers a highly interconnected porous conductive network,large heterostructure interfacial area,and plenty of accessible active sites,greatly facilitating the electron transfer,electrolyte diffusion,and pseudocapacitive reactions.The obtained a-Fe₂O₃NDs/RGO aerogel could be used as flexible free-standing electrodes after mechanical compression,which exhibited a significantly enhanced specific capacitance of 347.4 F·g^-1at 1 A·g^-1,extraordinary rate capability of 184 F·g^-1at 10 A·g^-1,and decent cycling stability.With the as-prepared a-Fe₂O₃NDs/RGO as negative electrodes and the Co₃O₄NDs/RGO as positive electrodes,an all-solid-state asymmetric supercapacitor(a-Fe₂O₃NDs/RGO//Co₃O₄NDs/RGO asymmetric supercapacitor(ASC))was assembled,which delivered a high specific capacitance of 69.1 F·g^-1at 1 A·g^-1and an impressive energy density of 21.6 W·h·k·g^-1at 750 W·k·g^-1,as well as good cycling stability with a capacity retention of 94.3%after 5,000 cycles.This work provides a promising avenue to design high-performance graphene-based composite electrodes and profound inspiration for developing advanced flexible energy-storage devices.     

On the growth mechanism of nickel and cobalt nanowires and comparison of their magnetic properties

Magnetic nanowires (NWs) are ideal materials for the fabrication of various multifunctional nanostructures which can be manipulated by an external magnetic field. Highly crystalline and textured nanowires of nickel (Ni NWs) and cobalt (Co NWs) with high aspect ratio (∼330) and high coercivity have been synthesized by electrodeposition using nickel sulphate hexahydrate (NiSO₄·6H₂O) and cobalt sulphate heptahydrate (CoSO₄·7H₂O) respectively on nanoporous alumina membranes. They exhibit a preferential growth along 〈110〉. A general mobility assisted growth mechanism for the formation of Ni and Co NWs is proposed. The role of the hydration layer on the resulting one-dimensional geometry in the case of potentiostatic electrodeposition is verified. A very high interwire interaction resulting from magnetostatic dipolar interactions between the nanowires is observed. An unusual low-temperature magnetisation switching for field parallel to the wire axis is evident from the peculiar high field M(T) curve.      

Binder-free activated carbon/carbon nanotube paper electrodes for use in supercapacitors

Novel inexpensive, light, flexible, and even rollup or wearable devices are required for multi-functional portable electronics and developing new versatile and flexible electrode materials as alternatives to the materials used in contemporary batteries and supercapacitors is a key challenge. Here, binder-free activated carbon (AC)/carbon nanotube (CNT) paper electrodes for use in advanced supercapacitors have been fabricated based on low-cost, industrial-grade aligned CNTs. By a two-step shearing strategy, aligned CNTs were dispersed into individual long CNTs, and then 90 wt%–99 wt% of AC powder was incorporated into the CNT pulp and the AC/CNT paper electrode was fabricated by deposition on a filter. The specific capacity, rate performance, and power density of the AC/CNT paper electrode were better than the corresponding values for an AC/acetylene black electrode. The capacity reached a maximum value of 267.6 F/g with a CNT loading of 5 wt%, and the energy density and power density were 22.5 W·h/kg and 7.3 kW/kg at a high current density of 20 A/g. The AC/CNT paper electrode also showed a good cycle performance, with 97.5% of the original capacity retained after 5000 cycles at a scan rate of 200 mV/s. This method affords not only a promising paper-like nanocomposite for use in low-cost and flexible supercapacitors, but also a general way of fabricating multi-functional paper-like CNT-based nanocomposites for use in devices such as flexible lithium ion batteries and solar cells.      

Sequential assembly of metal-free phthalocyanine on few-layer epitaxial graphene mediated by thickness-dependent surface potential

Due to strong interactions between epitaxial graphene and SiC(0001) substrates, the overlayer charge density induced by the interface charging effect is much more attenuated than that of exfoliated graphene on SiO₂. We report herein a quantitive detection of the charge properties of few-layer graphene by surface potential measurements using electrostatic force microscopy (EFM). A minor difference in surface potential is observed to mediate a sequential assembly of metal-free phthalocyanine (H₂Pc) on monolayer, bilayer and trilayer graphenes, as demonstrated by scanning tunneling microscopy (STM). In order to understand this, we further executed density functional theory (DFT) calculations which showed higher adsorption energies for Pc on thinner graphenes. In this case, we attribute the unique growth behavior of Pc to its variable adsorption energies on few-layer graphene, and in turn the layer charge variations from the viewpoint of energy minimizations. This work is expected to provide fundamental data useful for related nanodevice fabrications.      

Heterogeneous lamellar-edged Fe-Ni(OH)2/Ni3S2 nanoarray for efficient and stable seawater oxidation

Development of efficient non-precious catalysts for seawater electrolysis is of great significance but challenging due to the sluggish kinetics of oxygen evolution reaction(OER)and the impairment of chlorine electrochemistry at anode.Herein,we report a heterostructure of Ni₃S₂nanoarray with secondary Fe-Ni(OH)₂lamellar edges that exposes abundant active sites towards seawater oxidation.The resultant Fe-Ni(OH)₂/Ni₃S₂nanoarray works directly as a free-standing anodic electrode in alkaline artificial seawater.It only requires an overpotential of 269 mV to afford a current density of 10 mA·cm^-2and the Tafel slope is as low as 46 m V·dec^-1.The 27-hour chronopotentiometry operated at high current density of 100 mA·cm^-2shows negligible deterioration,suggesting good stability of the Fe-Ni(OH)₂/Ni₃S₂@NF electrode.Faraday efficiency for oxygen evolution is up to?95%,revealing decent selectivity of the catalyst in saline water.Such desirable catalytic performance could be benefitted from the introduction of Fe activator and the heterostructure that offers massive active and selective sites.The density functional theory(DFT)calculations indicate that the OER has lower theoretical overpotential than Cl₂ evolution reaction in Fe sites,which is contrary to that of Ni sites.The experimental and theoretical study provides a strong support for the rational design of high-performance Fe-based electrodes for industrial seawater electrolysis.     

Efficient synthesis of graphene nanoribbons sonochemically cut from graphene sheets

We report a facile approach to synthesize narrow and long graphene nanoribbons (GNRs) by sonochemically cutting chemically derived graphene sheets (GSs). The yield of GNRs can reach ∼5 wt% of the starting GSs. The resulting GNRs are several micrometers in length, with ∼75% being single-layer, and ∼40% being narrower than 20 nm in width. A chemical tailoring mechanism involving oxygen-unzipping of GSs under sonochemical conditions is proposed on the basis of experimental observations and previously reported theoretical calculations; it is suggested that the formation and distribution of line faults on graphite oxide and GSs play crucial roles in the formation of GNRs. These results open up the possibilities of the large-scale synthesis and various technological applications of GNRs.      

Carbon quantum dot-induced self-assembly of ultrathin Ni(OH)<Subscript>2</Subscript> nanosheets: A facile method for fabricating three-dimensional porous hierarchical composite micro-nanostructures with excellent supercapacitor performance

Significant efforts have been directed towards the preparation and application of porous hierarchically structured materials owing to their large surface area, rich active sites, and enhanced mass transport and diffusion. In this study, a simple and cost-effective method for the carbon quantum dot (CQD)-induced assembly of two-dimensional ultrathin Ni(OH)₂ nanosheets into a three-dimensional (3D) porous hierarchical structure was developed. The electrostatic forces between the CQDs and cations drove the self-assembly of the 3D CQDs/Ni(OH)₂ hierarchical structures. As a new type of structure-directing agent, the CQDs played dual roles in tuning the morphology of the products and improving the supercapacitor performance. The multilevel CQDs/Ni(OH)₂ micro-nanostructures had a large specific surface area and rich porosity. Owing to their unique structures and the conductivity of the CQDs, an optimized asymmetric supercapacitor using the CQDs/Ni(OH)₂ exhibited a maximum specific capacity of 161.3 F·g^–1 and a high energy density of 57.4 Wh·kg^–1. This study introduces a potential method for the fabrication of many other 3D hierarchical structures with great potential for applications in various fields.

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Hierarchical Co<Subscript>3</Subscript>O<Subscript>4</Subscript>@Ni-Co-O supercapacitor electrodes with ultrahigh specific capacitance per area

High specific capacitance per area is a critical requirement for a practical supercapacitor electrode, and needs a combination of high mass-loading of the electrochemically active material per area, and high utilization efficiency of this material. However, pursuing high mass-loading on conventional electrodes usually leads to an increase in “dead” material which is not accessible to the electrolyte in the supercapacitor, and thus prevents high utilization efficiencies of the material being realized. Here we show that this antagonism can be overcome by incorporating the electrochemically active material in a mesoporous hierarchical architecture. Fabrication of ternary ordered hierarchical Co₃O₄@Ni-Co-O nanosheet-nanorod arrays—involving the growth of densely aligned slim Ni-Co-O nanorods (diameter <20 nm) on Co₃O₄ microsheets which had been previously loaded on macroporous nickel foam—gives a material with excellent electrochemical performance as a supercapacitor electrode. At a current density of 5 mA/cm², the electrodes have both high mass loading per area (12 mg/cm²) and high efficiency of 2098 F/g, giving specific capacitances per area as high as ～25 F/cm². When the current density was increased from 5 to 30 mA/cm², 72% of the specific capacitance was retained and, furthermore, no significant decrease in capacitance was observed over 1000 charge/discharge cycles. The combination of these merits makes the composite material an excellent candidate for practical application as a supercapacitor electrode and, more generally, highlights the increased efficacies of materials which can result from fabricating mesoporous hierarchical structures at the nanoscale.

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Nitrogen-rich carbon spheres made by a continuous spraying process for high-performance supercapacitors

Supercapacitors have high power densities, high efficiencies, and long cycling lifetimes; however, to enable their wider use, their energy densities must be significantly improved. The design and synthesis of improved carbon materials with better capacitance, rate performance, and cycling stability has emerged as the main theme of supercapacitor research. Herein, we report a facile synthetic method to prepare nitrogen-rich carbon particles based on a continuous aerosol-spraying process. The method yields particles that have high surface areas, a uniform microporous structure, and are highly N-doped, resulting in a synergism that enables the construction of supercapacitors with high energy and power density for use in both aqueous and commercial organic electrolytes. Furthermore, we have used density functional theory calculations to show that the improved performance is due to the enhanced wettability and ion adsorption interactions at the carbon/electrolyte interface that result from nitrogen doping. These findings provide new insights into the role of heteroatom doping in the capacitance enhancement of carbon materials; in addition, our method offers an efficient route for large-scale production of doped carbon.

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A general synthetic strategy to monolayer graphene

The emergence and establishment of new techniques for material fabrication are of fundamental importance in the development of materials science. Thus, we herein report a general synthetic strategy for the preparation of monolayer graphene. This novel synthetic method is based on the direct solid-state pyrolytic conversion of a sodium carboxylate, such as sodium gluconate or sodium citrate, into monolayer graphene in the presence of Na₂CO₃. In addition, gram-scale quantities of the graphene product can be readily prepared in several minutes. Analysis using Raman spectroscopy and atomic force microscopy clearly demonstrates that the pyrolytic graphene is composed of a monolayer with an average thickness of ～0.50 nm. Thus, the present pyrolytic conversion can overcome the issue of the low monolayer contents (i.e., 1 wt.%–12 wt.%) obtained using exfoliation methods in addition to the low yields of chemical vapor deposition methods. We expect that this novel technique may be suitable for application in the preparation of monolayer graphene materials for batteries, supercapacitors, catalysts, and sensors.

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A lamellar ceria structure with encapsulated platinum nanoparticles

A novel lamellar feather-like CeO₂ structure has been fabricated by using a triblock copolymer as the structure-directing agent. This material was characterized in detail by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and BET surface area measurements. Compared with conventional spherical shaped ceria prepared by ammonia gelation, the ceria feathers have superior ability to support nanosized platinum particles due to their special structure. The “skeletons” of ceria feathers can serve as an ideal host matrix to anchor the platinum particles. Furthermore, the inter-crossing pattern of the “skeletons” also acts as a partition to separate platinum particles, allowing the Pt nanoparticles (average diameter ∼6 nm) to be highly dispersed in the structure. The Pt/feather-like CeO₂ catalyst exhibits high activity in the water gas shift reaction.      

A facile preparation of graphene/reduced graphene oxide/Ni(OH)2 two dimension nanocomposites for high performance supercapacitors

A Ni(OH)₂ composite with good electrochemical performances was prepared by a facile method. Ni(OH)₂ was homogeneously grown on the hydrophilic graphene/graphene oxide (G/GO) nanosheets, which can be prepared in large scale in my lab. Then G/GO/Ni(OH)₂ was reduced by L-Ascorbic acid to obtain G/RGO/Ni(OH)₂. Caused by the synergy effects among the components, the G/RGO/Ni(OH)₂ electrode showed good electrochemical properties. The G/RGO/Ni(OH)₂ electrode possessed a specific capacitance as high as 1510 F g⁻¹ at 2 A g⁻¹ and even 890 F g⁻¹ at 40 A g⁻¹. An asymmetric supercapacitor device consisting of G/RGO/Ni(OH)₂ and reduced graphene oxide (RGO) was installed and displayed a high energy density of 44.9 W h kg⁻¹ at the power energy density of 400.1 W kg⁻¹. It was verified that the G/GO nanosheets are ideal supporting material in supercapacitor.