Electrochemical energy storage performance of heterostructured SnO2@MnO2 nanoflakes

In this work, we report synthesis of SnO₂@MnO₂ nanoflakes grown on nickel foam through a facile two-step hydrothermal route. The as-obtained products are characterized by series of techniques such as scanning electron microscopy (SEM), X-ray diffraction spectroscopy (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The as-obtained SnO₂@MnO₂ nanoflakes are directly used as supercapacitor electrode materials. The results show that the electrode possesses a high discharge areal capacitance of 1231.6 mF cm⁻² at 1 mA cm⁻² and benign cycling stability with 67.2% of initial areal capacitance retention when the current density is 10 mA cm⁻² after 6000 cycles. Moreover, the heterostructured electrode shows 41.1% retention of the initial capacitance when the current densities change from 1 to 10 mA cm⁻², which reveals good rate capability. SnO₂@MnO₂ nanoflakes products which possess excellent electrochemical properties might be used as potential electrode materials for supercapacitor applications.     

Kilohertz ultrafast electrochemical supercapacitors based on perpendicularly-oriented graphene grown inside of nickel foam

Ultrafast electrochemical supercapacitors (EC) that can work at or above kilohertz (kHz) frequency, 3–4 orders higher than traditional EC, call for a structure with extremely low equivalent serial resistance (ESR) and a reasonably large surface area. Three-dimensional perpendicularly-oriented graphene (POG) network, grown inside of Ni foam (NF) by microwave plasma chemical vapor deposition, is reported as electrode to fabricate such ultrafast EC. The folded POG inside NF provides a large surface area, while the straight-forward and wide-open porous structure of POG ensures fast ion migration. In conjunction with the intrinsic high electronic conductivity of graphene and Ni, POG/NF electrode based ultrafast EC was demonstrated with a specific cell capacitance of 0.32 mF/cm² at 1 kHz, a relaxation time constant of 0.248 ms, and an ESR of 70 mΩ. A charge–discharge rate as high as 500 V/s was also measured, at which the cyclic voltammogram maintained a rectangular shape, corresponding to a single electrode capacitance of 0.83 mF/cm².     

Photoresist-derived porous carbon for on-chip micro-supercapacitors

Photoresist, which is frequently used in existing microelectronics processing, can be pyrolyzed to form a conductive carbon film. We demonstrate that a pyrolysis technique of SPR-220 photoresist, consisting of heating in Ar ambient to 900 °C followed by further annealing in an H₂/Ar mixture, results in a high surface area porous carbon, applicable to supercapacitor electrode fabrication. Electrochemical testing of the pyrolyzed photoresist film yields a specific areal capacitance of 1.5–3.5 mF/cm² and a specific volumetric capacitance of 15–35 F/cm³. These results are obtained on the as-pyrolyzed films, without additional activation or deposition of electroactive species. The cycling stability of the films is shown to be robust over 10,000 cycles. This photoresist pyrolysis process could be readily integrated into microelectromechanical systems or microelectronics technology for on-chip energy storage.     

Cathode materials based on carbon nanotubes for high-energy-density lithium–sulfur batteries

The rational integration of conductive nanocarbon scaffolds and insulative sulfur is an efficient method to build composite cathodes for high-energy-density lithium–sulfur batteries. The full demonstration of the high-energy-density electrodes is a key issue towards full utilization of sulfur in a lithium–sulfur cell. Herein, carbon nanotubes (CNTs) that possess robust mechanical properties, excellent electrical conductivities, and hierarchical porous structures were employed to fabricate carbon/sulfur composite cathode. A family of electrodes with areal sulfur loading densities ranging from 0.32 to 4.77 mg cm⁻² were fabricated to reveal the relationship between sulfur loading density and their electrochemical behavior. At a low sulfur loading amount of 0.32 mg cm⁻², a high sulfur utilization of 77% can be achieved for the initial discharge capacity of 1288 mAh g_S⁻¹, while the specific capacity based on the whole electrode was quite low as 84 mAh g_{C/S+binder+Al}⁻¹ at 0.2 C. Moderate increase in the areal sulfur loading to 2.02 mg cm⁻² greatly improved the initial discharge capacity based on the whole electrode (280 mAh g_{C/S+binder+Al}⁻¹) without the sacrifice of sulfur utilization. When sulfur loading amount further increased to 3.77 mg cm⁻², a high initial areal discharge capacity of 3.21 mAh cm⁻² (864 mAh g_S⁻¹) was achieved on the composite cathode.     

Enhanced electrochemical performance of hybrid composite microstructure of CuCo2O4 microflowers-NiO nanosheets on 3D Ni foam as positive electrode for stable hybrid supercapacitors

Self-assembled composite porous structures comprising CuCo₂O₄ microflowers and NiO hexagonal nanosheets were synthesized on a conducting 3D Ni foam surface [CCO/NO] using a simple hydrothermal method. This unique composite assembly was further characterized and electrochemically evaluated as a binder-free positive electrode for hybrid supercapacitor application. The study showed that the CCO/NO exhibited a maximum areal capacitance of 1444 mF cm^?2, significantly higher than the parent CuCo₂O₄ and NiO electrodes, with remarkable stability of 88.5% for 10,000 galvanostatic charge-discharge cycles. Key features for the enhanced electrochemical performance of CCO/NO can be related to a lowered diffusion resistance because the hybrid nanocomposite porous assembly generates short diffusion paths for electrolyte ions and more active sites for reversible faradaic transition for charge storage. The hybrid supercapacitor was assembled using activated carbon as a negative electrode and CCO/NO as a positive electrode in alkaline electrolyte, performed at an improved potential of 1.6 V. Device showed a maximum areal capacitance of 122 mF cm^?2, a maximum areal energy density of 43 μWh cm^?2, and a maximum areal power density of 5.1 mW cm^?2. This hybrid supercapacitor showed remarkable cyclic stability up to 98% for 10,000 cycles. This study encourages the development of low-cost, high-performance, durable electrode designs using hybrid composite for next-generation energy storage systems.     

Carbon nanotube capacitors arrays using high-k dielectrics

The electrical characteristics and fabrication process of nanocapacitor arrays using metal-high-k dielectric-carbon nanotube-metal layers (MICntM) were studied. MWCNTs arrays were fabricated using an electron beam lithography based lift-off process for catalyst definition and the high-k dielectric layer, hafnium oxide (HfO₂), was deposited using rf magnetron sputtering. The MICntM structures show high capacitance and the compatibility with high-k dielectric material and its deposition processes. MICntM capacitors arrays with sputtered HfO₂ show specific capacitance of 0.62 μF/cm². The leakage current density at 1 V is less than 5 μA/cm². The high aspect ratio of MWCNTs increases the effective electrode area and HfO₂ allows higher permittivity, hence, higher capacitance structures are realized.     

A combined salt–hard templating approach for synthesis of multi-modal porous carbons used for probing the simultaneous effects of porosity and electrode engineering on EDLC performance

A new approach, based on a combination of salt and hard templating for producing multi-modal porous carbons is demonstrated. The hard template, silica nanoparticles, generate mesopores (∼22 nm), and in some cases borderline-macropores (∼64 nm), resulting in high pore volume (∼3.9 cm³/g) while the salt template, zinc chloride, generates borderline-mesopores (∼2 nm), thus imparting high surface area (∼2100 m²/g). The versatility of the proposed synthesis technique is demonstrated using: (i) dual salt templates with hard template resulting in magnetic, nanostructured-clay embedded (∼27% clay content), high surface area (∼1527 m²/g) bimodal carbons (∼2 and 70 nm pores), (ii) multiple hard templates with salt template resulting in tri-modal carbons (∼2, 12 and 28 nm pores), (iii) low temperature (450 °C) synthesis of bimodal carbons afforded by the presence of hygroscopic salt template, (iv) easy coupling with physical activation approaches. A selected set of thus synthesized carbons were used to evaluate, for the first time, the simultaneous effects of carbon porosity and pressure applied during electrode fabrication on EDLC performance. Electrode pressing was found to be more favorable for carbons containing hard-templated mesopores (∼87% capacitance retention at current density of 40 A/g) as compared to those without (∼54% capacitance retention).     

Hierarchical Co3O4@ZnWO4 core/shell nanostructures on nickel foam: Synthesis and electrochemical performance for supercapacitors

To improve the electrochemical properties of Co₃O₄ for supercapacitors application, a hierarchical Co₃O₄@ZnWO₄ core/shell nanowire arrays (NWAs) material is designed and synthesized successfully via a facile two-step hydrothermal method followed by the heat treatment. Co₃O₄@ZnWO₄ NWAs exhibits excellent electrochemical performances with areal capacitance of 4.1 F cm⁻² (1020.1 F g⁻¹) at a current density of 2 mA cm⁻² and extremely good cycling stability (99.7% of the initial capacitance remained even after 3000 cycles). Compared with pure Co₃O₄ electrodes, the results prove that this unique hierarchical hybrid nanostructure and reasonable assembling of two electrochemical pseudocapacitor materials are more advantageous to enhance the electrochemical performance. Considering these remarkable capacitive behaviors, the hierarchical Co₃O₄@ZnWO₄ core/shell NWAs nanostructure electrode can be revealed promising for high-performance supercapacitors.     

Porous carbon thin films for electrochemical capacitors

Activation effects on carbon films, derived from commercial aromatic polyimide films (Kapton, DuPont), in CO₂ atmosphere at 1203 K on capacitance properties were studied. Two thicknesses of polyimide films were used: 7 and 25 μm. Pore formation during the activation process progresses in two steps due to the existence of a denser surface layer and a more porous core material. In the first step micropores are opening in the dense surface region of the material with average pore diameter smaller than 1 nm. During the second step, mesopores start opening, while micropore volume remains constant with the average micropore diameter of over 1 nm, producing bimodal texture. The first step finishes after 30 min for the thinner samples while for the thicker samples it finishes after 60 min of activation. As a consequence of such textural changes during activation, the thicker sample has a maximum areal capacitance of 0.35 F/cm². The thinner sample activated for 30 min has a maximum volumetric capacitance of 220 F/cm³ and achieves a maximum gravimetric capacitance of 240 F/g when the texture becomes bimodal after 240 min of activation. These results confirm that activation of carbonized Kapton films gives promising electrode materials for supercapacitors.     

Vertically aligned epitaxial graphene nanowalls with dominated nitrogen doping for superior supercapacitors

For graphene-based electrode materials, N doping is one of the leading approaches for enhancing the performance of supercapacitors. However, such an outstanding performance is suppressed by the agglomeration of graphene and unspecified N incorporation. Here, we demonstrate a direct growth of vertically epitaxial graphene nanowalls (GNWs) on flexible carbon cloths (CCs) via microwave plasma-enhanced chemical vapor deposition, whereby predominantly N doping was sequentially achieved by introducing in situ NH₃ plasma, to form N-doped GNWs (NGNWs). The vertically aligned three-dimensional (3D) architecture of epitaxial NGNWs and their unique selectivity to the specific N dopants make such electrodes an ideal platform, not only for enhancing the capacitive performance but also for studying the role of the CN bonding configuration in its performance. Remarkably, NGNW supercapacitors exhibit an excellent specific capacitance of 991.6 F/g (estimation based on the actively contributing component) and an apparent area-normalized capacitance of 1488.9 mF/cm², at a specific current of 14.8 A/g. This approach allows us to achieve an energy density of 275.4 Wh/kg at a power density of 14.8 kW/kg (specific current of 14.8 A/g), and a power density of 74.1 kW/kg at an energy density of 232.6 Wh/kg (specific current of 74.1 A/g) in 1 M H₂SO₄.     

Composites of MnO2 nanocrystals and partially graphitized hierarchically porous carbon spheres with improved rate capability for high-performance supercapacitors

Manganese dioxide/carbon nanocomposites with partially graphitized hierarchical porous structure have been designed and synthesized. A high specific capacitance of 412 F g⁻¹ and excellent rate capability of these composites can be achieved owing to the interconnected meso- and micro-porous structure and the graphitic pore walls facilitating the ion diffusion and electron transportation, respectively, which is highly demanded for high-performance supercapacitor electrodes materials. Even at a high scan rate of 100 mV s⁻¹, a specific capacitance of 251 F g⁻¹ can be obtained, corresponding to 61% capacitance retention. Moreover, a long cycling stability with initial capacitance retention of ∼88% is obtained after over 4000 cycles at a current density of 1.0 A g⁻¹. This work presents an efficient electrode materials design and a novel composite which holds great promise in high-performance supercapacitor applications.     

A high-performance three-dimensional micro supercapacitor based on ripple-like ruthenium oxide–carbon nanotube composite films

A micro-supercapacitor with a three-dimensional configuration has been fabricated using an inductively coupled plasma etching technique. A ruthenium oxide–carbon nanotube (CNT) composite with a ripple-like morphology is successfully synthesized using a cathodic deposition technique while using silica-based three-dimensional microstructures as a template. The desired network of carbon nanotubes in the composite facilitates electrolyte penetration and proton exchange/diffusion. A single three dimensional microelectrode is studied using cyclic voltammetry, and a specific capacitance of 272 mF·cm⁻² is observed at 5 mV s⁻¹ in a neutral Na₂SO₄ solution. The accelerated cycle life is tested at 80 mV s⁻¹, and a satisfactory cyclability is observed. When placed on a chip, the symmetric cell exhibits good supercapacitor properties, the specific capacitance up to 37.23 mF cm⁻² and specific power density up to 19.04 mW cm⁻² were obtained at 50 mA cm⁻².     

Insight into high areal capacitances of low apparent surface area carbons derived from nitrogen-rich polymers

The energy storage mechanism of N-doped carbons with low apparent specific surface areas (Brunauer–Emmett–Teller specific surface area determined by N₂ adsorption) has puzzled the researchers in the supercapacitor field in recent years. In order to explore this scientific problem, such carbon materials were prepared through pyrolysis of N-rich polymers such as melamine formaldehyde resin and polyaniline. Although these carbons possess low apparent specific surface areas of no more than 60 m² g⁻¹, their areal capacitance could reach up to an abnormally high value of 252 μF cm⁻². The results of systematical materials characterizations and electrochemical measurements show that these carbons contain numerous ultramicropores which could not be detected by the adsorbate of N₂ but are accessible to CO₂ and electrolyte ions. These ultramicropores play dominant roles in the charge storage process for these low apparent surface area carbons, leading to an energy storage mechanism of electric double layer capacitance. The contribution of pseudocapacitance to the total capacitance is calculated to be less than 15%. This finding challenges the widely accepted viewpoint that the high capacitance of N-doped carbon is mainly attributed to the pseudocapacitance generated from the faradic reactions between nitrogen functionalities and electrolyte.     

Preparation of on chip,flexible supercapacitor with high performance based on electrophoretic deposition of reduced graphene oxide/polypyrrole composites

A new concept is introduced to fabricate flexible, on-chip supercapacitors by electrophoretically depositing highly dispersed reduced graphene oxide/polypyrrole on interdigital-like electrodes. By the unique method, the deposited films could construct on the substrate facilely and uniformly. The prepared all-solid-state device demonstrates high volumetric capacitance (about 147.9 F cm⁻³), high energy density (13.15 mWh cm⁻³ at a power density of 1300 mW cm⁻³) and excellent cycling stability (approximately 71.7% of the initial capacitance retained after 5000 cycles). Compared with other supercapacitor, the device demonstrated here is lightweight, flexible and inexpensive.     

Functionalized three-dimensional graphene networks for high performance supercapacitors

Three-dimensional (3D) thermal reduced graphene network (TRGN) deposition on Ni foam without any conductive agents and polymer binders was successfully synthesized by dipping Ni foam into graphene oxide (GO) suspension and subsequent thermal reduction process. The direct and close contact between thermal reduced graphene and Ni foam is beneficial to the enhanced conductivity of the electrode, as well as the improvement of ion diffusion/transport into the electrode. Additionally, low-temperature reduction of GO possesses a large amount of stable oxygen-containing groups that can provide high pseudocapacitance. As a result, the TRGN electrode delivers a high specific capacitance of 442.8 F g⁻¹ at 2 mV s⁻¹ in 6 mol L⁻¹ KOH. Moreover, symmetric supercapacitor based on TRGN exhibits a maximum energy density of 30.4 Wh kg⁻¹ based on the total mass of the two electrodes in 1 mol L⁻¹ Na₂SO₄ electrolyte, as well as excellent cycling stability with 118% of its initial capacitance after 5000 cycles.     

Fabrication of hollow N-doped carbon supported ultrathin NiO nanosheets for high-performance supercapacitor

The polydopamine-assisted hierarchical composites of ultrathin NiO nanosheets uniformly coating on the surface of hollow nitrogen-doped carbon spheres (HNCS-NiO) were successfully fabricated via a facile synthesis method. The hierarchical HNCS-NiO composites as electrode materials for supercapacitors exhibit high capacitance of 550.4 F g^− 1 (880.6 mF cm^− 2) at the current density of 0.5 A g^− 1 (0.8 mA cm^− 2), and present a good rate capability. The composites display excellent improved electrochemical properties not only because their hierarchical hollow nanostructures can provide enough space to buffer the volume expansion during the reversible intercalation/deintercalation processes, but also because their larger specific surface areas can provide adequate active sites for the redox electrochemical reaction.     

Diamond-coated silicon wires for supercapacitor applications in ionic liquids

For a long time sp² carbon has been the dominating material for supercapacitor applications. In this paper a new concept of using boron-doped diamond for supercapacitors is proposed. Diamond surface enlargement is realized via bottom-up template-growth. In this method, silicon nanowire electrodes are coated with a thin (~ 100 nm) layer of nanocrystalline diamond (NCD) by microwave enhanced chemical vapor deposition (MWCVD). The quality of overgrowth is characterized by high resolution scanning electron microscopy which reveals a homogeneous coverage of diamond on Si nanowire surface. To enhance the potential window to 4 V, a room temperature ionic liquid is used as electrolyte. The dilution of the ionic liquid is investigated in terms of conductivity and specific capacitance. The capacitance as measured via cyclic voltammetry reaches 105 μF/cm². An energy density of 84 μJ/cm² and a high power density of 0.94 mW/cm² are obtained in combination with good stability of over 10,000 charging/discharging cycles.     

Facile synthesis of CuO mesocrystal/MWCNT composites as anode materials for high areal capacity lithium ion batteries

CuO mesocrystal entangled with multi-wall carbon nanotube (MWCNT) composites are synthesized through a facile scalable precipitation and a followed oriented aggregation process. When evaluated as anode materials for lithium ion batteries, the CuO-MWCNT composites exhibit high areal capacity and good cycling stability (1.11 mA h cm⁻² after 400 cycles at the current density of 0.39 mA cm⁻²). The excellent electrochemical performance can be ascribed to the synergy effect of the unique structure of defect-rich CuO mesocrystals and the flexible conductive MWCNTs. The assembled architecture of CuO mesocrystals can favor the Li-ion transport and accommodate the volume change effectively, as well as possess the structural and chemical stability of bulk materials, while the entangled MWCNTs can maintain the structural and electrical integrity of the electrode during the cycles.     

Scaleable ultra-thin and high power density graphene electrochemical capacitor electrodes manufactured by aqueous exfoliation and spray deposition

Graphene electrodes of high power density were manufactured by a surfactant-water based exfoliation method followed by a scaleable spray-deposition process. Cyclic voltammetry and galvanostatic charge–discharge experiments revealed a combination of electric double layer and pseudocapacitive behavior that, unlike the many graphene-oxide derived electrodes, was maintained to unusually high scan rates of 10,000 mV s⁻¹, reaching a maximum capacitance of 543 μF cm⁻² and with a capacitive retention of 57% at 10,000 mV s⁻¹. The performance of graphene electrodes was contrasted with carboxylated single walled carbon nanotubes that showed a sharp decrease in capacitance above 200 mV s⁻¹. Electrochemical impedance spectroscopy analysis showed a fast capacitor response of 17.4 ms for as manufactured electrodes which was further improved to 2.3 ms for surfactant-free 40 nm thick electrodes. A maximum energy density of 75.4 nW h cm⁻² gradually decreased as power density increased up to 2.6 mW cm⁻². Graphene electrodes showed 100% capacitance retention for 5000 cycles at the high power scan rate of 10,000 mV s⁻¹.     

Preparation and characterization of manganese oxide/CNT composites as supercapacitive materials

Manganese oxide was synthesized and dispersed on carbon nanotube (CNT) matrix by thermally decomposing manganese nitrates. CNTs used in this paper were grown directly on graphite disk by chemical vapor deposition technique. The capacitive behavior of manganese oxide/CNT composites was investigated by cyclic voltammetry and galvanostatic charge–discharge method in 1 M Na₂SO₄ aqueous solutions. When the loading mass of MnO₂ is 36.9 μg cm^− 2, the specific capacitance of manganese oxide/CNT composite (based on MnO₂) at the charge–discharge current density of 1 mA cm^− 2 equals 568 F g^− 1. Additionally, excellent charge–discharge cycle stability (ca. 88% value of specific capacitance remained after 2500 charge–discharge cycles) and power characteristics of the manganese oxide/CNT composite electrode can be observed. The effect of loading mass of MnO₂ on specific capacitance of the electrode has also been investigated.