Supercapacitor performances of rich nitrogen-doped mesoporous graphene fabricated by a facile template-free copyrolysis process

Rich nitrogen-doped mesoporous graphene (NDMG) with a large specific surface area of 496.8 m² g^?1 and high electrical conductivity of 327.2 S cm^?1, and suitable pore size was synthesized by a facile co-thermal annealing of pre-prepared phenolic polymer and dicyandiamide. The NDMG has a high nitrogen content (7.9 wt%) and can act as promising electroactive materials for two-electrode symmetric supercapacitors. The NDMG cells displayed a high specific capacitance of ca. 316 F g^?1 at 0.5 A g^?1, which is much higher than that of the pristine graphene devices (ca. 123 F g^?1). Moreover, compared with the capacitance drop rate of pristine graphene devices (8.9 %), the specific capacitance of NDMG cells was decreased by only 3.2 % after 2000 cycles, exhibiting a good cycling performance and reversibility. In addition, the specific capacitance of the NDMG cells can reach 251 F g^?1 at 5.0 A g^?1, revealing an excellent rate capability and implying the ability to deliver a high energy density at a high power density. The good electrochemical performances of NDMG can be attributed to its high surface area, suitable mesopore size, and high electrical conductivity.     

Fabrication of functionalized nitrogen-doped graphene for supercapacitor electrodes

A unique and convenient one-step hydrothermal process for synthesizing functionalized nitrogen-doped graphene (FGN) via ethylenediamine, hydroquinone, and graphene oxide (GO) is described. The graphene sheets of FGN provide a large surface area for hydroquinone molecules to be anchored on, which can greatly enhance the contribution of pseudocapacitance. X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Raman spectroscopy, and electrochemical workstation are used to characterize the materials. The nitrogen content exhibited in FGN can be up to 9.83 at.%, and the as-produced graphene material shows an impressive specific capacitance of 364.6 F g^?1 at a scan rate of 10 mV s^?1, almost triple that of the graphene (GN)-based one (127.5 F g^?1). Furthermore, the FGN electrodes show excellent electrochemical cycle stability with 94.4 % of its initial capacitance retained after 500 charge/discharge cycles at the current density of 3 A g^?1.     

N-doped graphene/Bi nanocomposite with excellent electrochemical properties for lithium–ion batteries

N-doped graphene/Bi nanocomposite was prepared via a two-step method, combining the gas/liquid interface reaction with the rapid heat treatment method. The as-prepared sample was characterized by X-ray diffraction (XRD), field-emission scanning electron microscope (FESEM), X-ray photoelectron spectroscopy (XPS), and elemental analyzer. The XRD, FESEM, XPS, and elemental analysis results confirm the successful synthesis of N-doped graphene/Bi nanocomposite. As a result, the prepared N-doped graphene/Bi nanocomposite as an anode material for lithium-ion batteries delivers excellent electrochemical performance. A high lithium storage capacity of about 522 mAh g^?1 in the voltage range of 0.01–3.5 V is obtained. After 50 cycles at different current densities from 50 to 1000 mA g^?1, the specific capacity can still remain 386 mAh g^?1. Even at the high current density of 1000 mA g^?1, the N-doped graphene/Bi nanocomposite can still deliver a specific capacity of 218 mAh g^?1. The excellent electrochemical performance of the N-doped graphene/Bi nanocomposite is supposed to benefit from the high electronic conductivity of nitrogen-doped graphene and the synergistic effect of bismuth nanoparticles and nitrogen-doped graphene.     

Effect of pyrolytic polyacrylonitrile on electrochemical performance of Si/graphite composite anode for lithium-ion batteries

The silicon/graphite (Si/G) composite was prepared using pyrolytic polyacrylonitrile (PAN) as carbon precursor, which is a nitrogen-doped carbon that provides efficient pathway for electron transfer. The combination of flake graphite and pyrolytic carbon layer accommodates the large volume expansion of Si during discharge-charge process. The Si/G composite was synthesized via cost-effective liquid solidification followed by carbonization process. The effect of PAN content on electrochemical performance of composites was investigated. The composite containing 40 wt% PAN exhibits a relatively better rate capability and cycle performance than others. It exhibits initial reversible specific capacity of 793.6 mAh g^?1 at a current density of 100 mA g^?1. High capacity of 661 mAh g^?1 can be reached after 50 cycles at current density of 500 mA g^?1.     

Three-dimensional nitrogen-doped graphene/sulfur composite for lithium-sulfur battery

A three-dimensional nitrogen-doped graphene/sulfur composite (NGS3) was synthesized by a simple hydrothermal method using urea as the nitrogen source and subsequent thermal treatment. The structure and electrochemical performance of the prepared nitrogen-doped graphene/sulfur composite (NGS3) were confirmed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), Energy dispersive spectroscopy mapping (EDS), and galvanostatic charge/discharge measurements. SEM and EDS mapping show that NGS3 exhibits a porous structure with uniform distribution of sulfur. Compared with the graphene/sulfur composite (NGS1), NGS3 delivers an outstanding rate capability with 1501, 1278, 1136, and 1024 mAh g^?1 at 200, 400, 800, and 1000 mA g^?1, respectively, and the cycle stability of NGS3 is also wonderful, a reversible discharge capacity of 1330 mAh g^?1 is obtained after 80 cycles under the current rate of 200 mA g^?1. The wonderful electrochemical performance could be attributed to the special three-dimensional conductive structure with the help of nitrogen atom.     

Hollow polypyrrole nanosphere embedded in nitrogen-doped graphene layers to obtain a three-dimensional nanostructure as electrode material for electrochemical supercapacitor

A novel approach was developed to prepare hollow polypyrrole (PPy) nanospheres and nitrogen-doped graphene/hollow PPy nanospheres (NG/H-PPy) composites. In this process, uniform poly (methyl methacrylate-butyl methacrylate-methacrylic acid) (PMMA-PBMA-PMAA) latex microspheres as sacrificial templates were synthesized by using an emulsion polymerization method. Then, hollow PPy nanospheres were obtained on the surface of PMMA-PBMA-PMAA microspheres by in situ chemical oxidative polymerization. Finally, H-PPy was embedded in NG layers successfully through a simple approach. The nanobeads have been characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectra, and Fourier transform infrared spectra (FTIR). Different electrochemical methods including cyclic voltammetry (CV), galvanostatic charge–discharge (GCD), and electrochemical impedance spectroscopy (EIS) have been applied to study the electrochemical properties. The specific capacitance of NG/H-PPy composites based on the three-electrode system is as high as 575 F g^?1 at a current density of 1 A g^?1 and enhanced stability about 90.1 % after 500 cycles, indicating that the composite has an impressive capacitance and excellent cycling performance.     

Promising nitrogen-doped porous nanosheets carbon derived from pomegranate husk as advanced electrode materials for supercapacitors

Nitrogen-doped porous activated carbons (N-PHACs) have been successfully synthesized using pomegranate husk as carbon precursor via ZnCl₂-activation carbonization and subsequent urea-assisted hydrothermal nitrogen-doping method. The obtained N-PHACs possesses abundant mesoporous structure, high specific surface area (up to 1754.8 m² g^?1), pore volume (1.05 cm³ g^?1), and nitrogen-doping content (4.51 wt%). Besides, the N-PHACs-based material showed a high specific capacitance of 254 F g^?1 at a current density of 0.5 A g^?1 and excellent rate performance (73% capacitance retention ratio even at 20 A g^?1) in 2 M KOH aqueous electrolyte, which is attributed to the contribution of double-layer capacitance and pseudocapacitance. The assembled N-PHACs-based symmetric capacitor with a wide operating voltage range of 0–1.8 V exhibits a maximum energy density of 15.3 Wh kg^?1 at a power density of 225 W kg^?1 and superior cycle stability (only 6% loss after 5000 cycles) in 0.5 M Na₂SO₄ aqueous electrolyte. These exciting results suggest that the novel N-doping porous carbon material prepared by a green and low-cost design strategy has a potential application as high-performance electrode materials for supercapacitors.     

Construction of 3D polypyrrole/CoS/graphene composite electrode with enhanced pseudocapacitive performance

Herein, 3D graphene/nickel foam (GE/NF) composite matrix was successfully fabricated by using NF as template through a self-catalytic thermal chemical vapor deposition process. By using the prepared GE/NF as substrate, CoS nanosheets were deposited via a facial one-step electrochemical deposition method. Owing to the advantage of GE in boosting the electrical contact between the electroactive host material and current collector, the as-prepared 3D CoS/GE/NF electrode demonstrated a superior capacitance value of 2308 F g^?1 at 1 A g^?1 and a high rate capability of 70.49% at 20 A g^?1. After depositing the polypyrrole (PPY) film on 3D CoS/GE/NF electrode, the electrochemical performance of CoS was further greatly improved and delivered an extremely high capacitance value of 3450 F g^?1 at 1 A g^?1, with good rate capability (62.61% at 20 A g^?1) and improved cycling stability. The enhanced electrochemical performance of PPY/CoS/GE/NF electrode is closely related to the advantage of PPY film in increasing the electrical conductivity and reinforcing the integrity of electrode.     

Advanced LiTi<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C anode by incorporation of carbon nanotubes for aqueous lithium-ion batteries

Inferior rate capability is a big challenge for LiTi₂(PO₄)₃ anode for aqueous lithium-ion batteries. Herein, to address such issue, we synthesized a high-performance LiTi₂(PO₄)₃/carbon/carbon nanotube (LTP/C/CNT) composite by virtue of high-quality carbon coating and incorporation of good conductive network. The as-prepared LTP/C/CNT composite exhibits excellent rate performance with discharge capacity of 80.1 and 59.1 mAh g^?1 at 10 C and 20 C (based on the mass of anode, 1 C = 150 mA g^?1), much larger than that of the LTP/C composite (53.4 mAh g^?1 at 10 C, and 31.7 mAh g^?1 at 20 C). LTP/C/CNT also demonstrates outstanding cycling stability with capacity retention of 83.3 % after 1000 cycles at 5 C, superior to LTP/C without incorporation of CNTs (60.1 %). As verified, the excellent electrochemical performance of the LTP/C/CNT composite is attributed to the enhanced electrical conductivity, rapid charge transfer, and Li-ion diffusion because of the incorporation of CNTs.     

Fabrication of Ni-Co binary oxide/reduced graphene oxide composite with high capacitance and cyclicity as efficient electrode for supercapacitors

Nickel-cobalt binary oxide/reduced graphene oxide (G-NCO) composite with high capacitance is synthesized via a mild method for electrochemical capacitors. G-NCO takes advantages of reduced graphene oxide (RGO) and nickel-cobalt binary oxide. As an appropriate matrix, RGO is beneficial to form homogeneous structure and improve the electron transport ability. The binary oxide owns more active sites than those of nickel oxide and cobalt oxide to promote the redox reaction. Attributed to the well crystallinity, homogeneous structure, increased active sites, and improved charge transfer property, the G-NCO composite exhibits highly enhanced electrochemical performance compared with G-NiO and G-Co₃O₄ composites. The specific capacitance of the G-NCO composite is about 1750 F g^?1 at 1 A g^?1 together with capacitance retention of 79 % (900/1138 F g^?1) over 10,000 cycles at 4 A g^?1. To research its practical application, an asymmetric supercapacitor with G-NCO as positive electrode and activated carbon as negative electrode was fabricated. The asymmetric device exhibits a prominent energy density of 37.7 Wh kg^?1 at a power density of 800 W kg^?1. The modified G-NCO composite shows great potential for high-capacity energy storage.     

Synthesis and characterization of nitrogen-doped graphene hollow spheres as electrode material for supercapacitors

Recently, the rapid development of graphene industry in the world, especially in China, provides more opportunities for the further extension of the application field of graphene-based materials. Graphene has also been considered as a promising candidate for use in supercapacitors. Here, nitrogen-doped graphene hollow spheres (NGHS) have been successfully synthesized by using industrialized and pre-processed graphene oxide (GO) as raw material, SiO₂ spheres as hard templates, and urea as reducing-doping agents. The results demonstrate that the content and pretreatment of GO sheets have important effect on the uniform spherical morphologies of the obtained samples. Industrialized GO and low-cost urea are used to prepare graphene hollow spheres, which can be a promising route to achieve mass production of NGHS. The obtained NGHS have a cavity of about 270 nm, specific surface area of 402.9 m² g^?1, ultrathin porous shells of 2.8 nm, and nitrogen content of 6.9 at.%. As electrode material for supercapacitors, the NGHS exhibit a specific capacitance of 159 F g^?1 at a current density of 1 A g^?1 in 6 M KOH aqueous electrolyte. Moreover, the NGHS exhibit superior cycling stability with 99.24% capacitive retention after 5000 charge/discharge cycles at a current density of 5 A g^?1.     

New insight on nanostructure assembling of high-performance electrode materials: synthesis of surface-modified hexagonal β-Ni(OH)<Subscript>2</Subscript> nanosheets as an example

Hexagonal β-Ni(OH)₂ nanosheets with thickness of ～12 nm were synthesized by a hydrothermal method at 150 °C using nickel chloride as nickel source and morpholine as alkaline. Electrodes for application in pseudocapacitor were assembled through a traditional technique: pressing a mixture of β-Ni(OH)₂ nanosheets and acetylene black onto nickel foam. Due to the hexagonal shape of rigid β-Ni(OH)₂ nanosheet and the mediation of surface-modified glycerol during electrochemical charge–discharge cycles, a nanostructure of electrode material with facile interior pathway for the transfer of electrolyte was formed. As a result, the as-formed electrodes presented high specific capacitance of 1,917 F g^?1 at current density of 1.6 A g^?1 in 3 mol L^?1 KOH solution. At high charge and discharge current density of 31.3 A g^?1, the electrodes still remained a high specific capacitance of 1,289 F g^?1. The interesting results obtained from this investigation may provide a new insight for the synthesis of electrode materials with high electrochemical performance.     

Solvothermal synthesis of mesoporous NiCo2O4 spinel oxide nanostructure for high-performance electrochemical capacitor electrode

NiCo₂O₄ nanostructure was successfully synthesized via a d-glucose-assisted solvothermal process. Spinel-type cubic phase and mesoporous microstructure of the sample for different calcination temperatures were confirmed by X-ray diffraction and transmission electron microscopy. Typical pseudocapacitance feature of the NiCo₂O₄ treated at different temperatures was then evaluated in aqueous 6 M KOH electrolyte solution. Electrochemical measurements showed that the spinel nickel cobaltite nanostructure heated at 300 °C exhibits maximum specific capacitances of 524 F g^?1 at 0.5 A g^?1 and 419 F g^?1 at 10 A g^?1 with excellent cycle stability and only ~9 % of capacitance loss after 2,500 cycles. This demonstrates the potential application of the material for supercapacitors. The attractive pseudocapacitive performance of NiCo₂O₄ is mainly attributed to the redox contribution of the Ni and Co metal species, high surface area, and their desired mesoporous nanostructure.     

Experimental studies on high-performance supercapacitor based on nanogel polymer electrolyte with treated activated charcoal

Electrochemical capacitors, based on the double-layer capacitance of high specific surface area carbon materials, are attracting major fundamental and technological interest as highly reversible, electrical-charge storage and delivery devices, capable of being operated at high power densities. In the present paper, studies have been carried out on nanocomposite gel polymer electrolyte comprising poly(vinylidene fluoride-co-hexafluoropropylene)-propylene carbonate-magnesium perchlorate-nanofumed silica with a view to use them as electrolyte in electrochemical double-layer capacitors (EDLCs) based on chemically treated activated charcoal as electrodes. The optimized composition of nanogel polymer electrolyte exhibits high room-temperature ionic conductivity of 5.4?×?10^?3 S cm^?1 with good mechanical and dimensional stability which is suitable for their application as electrolyte in EDLCs. Detailed chemical and microstructural characterization of chemically treated and untreated activated charcoal was conducted using scanning electron microscopy and Brunauer–Emmett–Teller (BET). BET studies reveal that the effective surface area of treated activated charcoal powder (1,515 m² g^?1) increases by more than double-fold compared with untreated one (721 m² g^?1). Performance characteristics of EDLCs have been tested using cyclic voltammetry, impedance spectroscopy, prolonged cyclic test, and charge–discharge techniques. Analysis shows that the treated activated charcoal electrodes have almost five times more capacitance values as compared with the untreated one. The maximum capacitance of 324 mF cm^?2, equivalent to single electrode specific capacitance of 216 F?g^?1 was achieved. It corresponds to an energy density of 20 Wh kg^?1 and a power density of 2.2 kW kg^?1.     

Superior electrochemical performance of carbon cloth electrode-based supercapacitors through surface activation and nitrogen doping

A simple and low-cost strategy is developed to fabricate three-dimensional (3D) nitrogen-doped carbon cloth electrode through surface activation and nitrogen-doping process. The process can exfoliate the smooth surfaces of micro carbon fibers into nanostructures together with the doping of nitrogen-containing species. The as-fabricated carbon cloth electrode shows excellent areal capacitances of 882.36 and 706.68 mF cm^?2 at the current density of 1 and 60 mA cm^?2, respectively, exhibiting good rate performance. It also exhibits outstanding cycling stability with 98.7 % retention of its initial capacitance after 30,000 continuous charging/discharging tests. When the electrodes were assembled and tested as a symmetric supercapacitor, it also demonstrates superior electrochemical performance. It is believed that the 3D carbon structures with enlarged surface area, improved conductivity and electrode/electrolyte wettability, and enhanced pseudocapacitance by doping of nitrogen lead to the vast improvement of electrochemical performance.     

Novel synthesis and characterization of ZnCo<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoflakes grown on nickel foam as efficient electrode materials for electrochemical supercapacitors

ZnCo₂O₄ nanoflakes were directly grown on Ni foam via a two-step facile strategy, involving cathodic electrolytic electrodeposition (ELD) method and followed by a thermal annealing treatment step. The results of physical characterizations exhibit that the mesoporous ZnCo₂O₄ nanoflakes have large electroactive surface areas (138.8 m² g^?1) and acceptable physical stability with the Ni foam, providing fast electron and ion transport sites. The ZnCo₂O₄ nanoflakes on Ni foam were directly used as integrated electrodes for supercapacitors and their electrochemical properties were measured in 2 M KOH aqueous solution. The ZnCo₂O₄ nanoflake electrode exhibits a high capacitance of 1781.7 F g^?1 at a current density of 5 A g^?1 and good rate capability (62% capacity retention at 50 A g^?1). Also, an excellent cycling ability at various current densities from 5 to 50 A g^?1 was obtained and 92% of the initial capacitance maintained after 4000 cycles. The results demonstrate that the proposed synthesis route is cost-effective and facile and can be developed for preparation of electrode materials in other electrochemical supercapacitors.     

Pulsed electrodeposition of mesoporous cobalt-doped manganese dioxide as supercapacitor electrode material

Cobalt-doped MnO₂, as electrode material for supercapacitor, was synthesized by pulse electrodeposition method. The morphology and structure of the products were characterized by X-ray diffraction (XRD) and field-emission scanning electron microscope (FE-SEM). The results show that the crystal structure of the products is γ-type, and the samples reveals a porous texture composed of manganese oxide nanosheets. Cyclic voltammetry (CV), electrochemical impedance spectrometry (EIS), and galvanostatic charge–discharge tests indicate that doping cobalt has great effect on the electrochemical performance of manganese dioxide material. A specific capacitance of 354 F g^?1 is obtained when the molar ratio of Mn to Co is 200:10. After 100 charge–discharge cycles in 6 M KOH solution, the specific capacitance stabilized at 333.6 F g^?1, exhibiting excellent capacitance retention ability.     

Synthesis of nanofiber-composed dandelion-like CoNiAl triple hydroxide as an electrode material for high-performance supercapacitor

In this work, CoNiAl triple hydroxide with nanofiber-composed dandelion-like morphology was synthesized on nickel foam by a hydrothermal route. This delicate nanostructure was initiated from the rolling up of hydroxide nanosheets. The hierarchical nanostructure and optimized molar ratio of Co, Ni, and Al guarantees the high electrochemical performance of obtained samples. The maximum specific capacitance of 2,791 F g^?1 for the as-prepared CoNiAl hydroxides was achieved at scan rate of 5 mV s^?1 in 3 M KOH aqueous solution. The capacitance of material still remained 85 % after 2,000 charge–discharge cycles. These results demonstrated that the as-prepared CoNiAl triple hydroxide can be applied as a high-performance electrode material for supercapacitor.     

Hierarchical porous ZnMn<Subscript>2</Subscript>O<Subscript>4</Subscript> synthesized by the sucrose-assisted combustion method for high-rate supercapacitors

A simple sucrose-assisted combustion and subsequent high-temperature calcination route have been employed to prepare hierarchical porous ZnMn₂O₄ nanostructure. When used as an electrode for supercapacitor, the ZnMn₂O₄ electrode displays a high specific capacitance of 411.75 F g^?1 at a current density of 1 A g^?1, remarkable capacitance retention rate of 64.28 % at current density of 32 A g^?1 compared with 1 A g^?1, as well as excellent cycle stability (reversible capacity retention of 88.32 % after 4000 cycles). The outstanding electrochemical performances are mainly attributed to its hierarchical porous architecture, which provides large reaction surface area, fast ion and electron transfer, and good structure stability. All these impressive results demonstrate that ZnMn₂O₄ shows promise for its application in supercapacitors.     

Li4Mn5O12 prepared using l-lysine as additive and its electrochemical performance

l-Lysine was employed as additive to prepare face-centered cubic spinel Li₄Mn₅O₁₂. During the process, l-lysine played important roles such as complexing agent as well as combusting agent and adjusting the pH values of solution. The physical characteristics of Li₄Mn₅O₁₂ were characterized by X-ray diffraction and scanning electron microscopy. The electrochemical capacitance performance of Li₄Mn₅O₁₂ electrode was characterized by cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy. These analyses indicated that Li₄Mn₅O₁₂ was able to deliver 168 F?g^?1 within the potential range of 0–1.4 V at a scan rate of 5 mV?s^?1 in 1 mol?L^?1 Li₂SO₄. Nine hundred cycles later, the capacitance faded to 165 F?g^?1 with cutting down by 0.003 F?g^?1 per cycling period and also can remain 98.2 % of original value, displaying a good cycling performance.