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.     

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.     

Dandelion-like mesoporous Co<Subscript>3</Subscript>O<Subscript>4</Subscript> as anode materials for lithium ion batteries

A dandelion-like mesoporous Co₃O₄ was fabricated and employed as anode materials of lithium ion batteries (LIBs). The architecture and electrochemical performance of dandelion-like mesoporous Co₃O₄ were investigated through structure characterization and galvanostatic charge/discharge test. The as-prepared dandelion-like mesoporous Co₃O₄ consisted of well-distributed nanoneedles (about 40 nm in width and about 5 μm in length) with rich micropores. Electrochemical experiments illustrated that the as-prepared dandelion-like mesoporous Co₃O₄ as anode materials of LIBs exhibited high reversible specific capacity of 1430.0 mA h g^?1 and 1013.4 mA h g^?1 at the current density of 0.2 A g^?1 for the first and 100th cycle, respectively. The outstanding lithium storage properties of the as-prepared dandelion-like mesoporous Co₃O₄ might be attributed to its dandelion-like mesoporous nanostructure together with an open space between adjacent nanoneedle networks promoting the intercalation/deintercalation of lithium ions and the charge transfer on the electrode. The enhanced capacity as well as its high-rate capability made the as-prepared dandelion-like mesoporous Co₃O₄ to be a good candidate as a high-performance anode material for LIBs.     

A novel synthesis of size-controllable mesoporous NiMoO<Subscript>4</Subscript> nanospheres for supercapacitor applications

A novel hydrothermal emulsion method is proposed to synthesize mesoporous NiMoO₄ nanosphere electrode material. The size of sphere-shaped NiMoO₄ nanostructure is controlled by the mass ratio of water and oil phases. Nickel acetate tetrahydrate and ammonium heptamolybdate were used as nickel and molybdate precursors, respectively. The resultant mesoporous NiMoO₄ nanospheres were characterized by X-ray diffraction, N₂ adsorption and desorption, scanning electron microscopy, and transmission electron microscopy. The electrochemical performances were evaluated by cyclic voltammetry (CV), cyclic chronopotentiometry (CP), and electrochemical impedance spectroscopy (EIS) in 6 M KOH solution. The typical mesoporous NiMoO₄ nanospheres exhibit the large specific surface area of 113 m² g^?1 and high specific capacitance of 1443 F g^?1 at 1 A g^?1, an outstanding cyclic stability with a capacitance retention of 90 % after 3000 cycles of charge-discharge at a current density of 10 A g^?1, and a low resistance.     

An investigation into the influence of zinc precursor on the microstructural,photoluminescence, and gas-sensing properties of ZnO nanoparticles

Carbon/silica-nanostructured microfibers were synthesized via electrospinning method using phenol-formaldehyde resin and tetraethyl orthosilicate as carbon and silica precursor with triblock copolymer Pluronic P123 as soft template. The prepared samples show uniform microfiber structure with ~1 μm in diameter and dozens of microns in length. Additionally, the mesopores in the material is about 2–6 nm. When the silica component was removed by HF, the porous carbon microfibers (PCMFs) were obtained. In addition, after the carbon/silica composites were calcined in air, the porous silica microfibers (PSiMFs) were obtained, revealing the converse porous nanostructure as PCMFs. It is a simple way to prepare PCMFs and PSiMFs with silica and carbon as the template to each other. Additionally, PCMFs possess an ultrahigh specific surface area (2,092 m² g^?1) and large pore volume. The electrochemical performance of the prepared PCMF material was investigated in 6.0 M KOH electrolyte. The PCMF electrode exhibits a high specific capacitance (252 F g^?1 at 0.5 A g^?1). Then, superior cycling stability (97 % retention after 4,000 cycles) mainly is due to its unique nanostructure.     

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.     

Hydrothermal synthesis of carbon- and reduced graphene oxide-supported CoMoO4 nanorods for supercapacitor

Hybrid CoMoO₄ nanorods with carbon (C) and graphene oxide (rGO) are successfully synthesized via one-step hydrothermal process. Hybrid α-CoMoO₄ nanorods have shown excellent electrochemical performances compared to pristine CoMoO₄ in alkaline electrolyte. Specifically, CoMoO₄/C nanorod exhibits a maximum specific capacitance of 451.6 F g^?1 at the current density of 1 A g^?1, whereas CoMoO₄/rGO shows high specific capacitance of 336.1 F g^?1 at the same current density. Both the hybrid nanorods show good rate capability even at high current density of 20 A g^?1 and long-term cyclic stability. The observed electrochemical features of the hybrid CoMoO₄ nanostructure could be attributed to the presence of highly conductive carbonaceous material on unique one-dimensional nanorod microstructure which enhances the electrical conductivity of the nanorods thereby allowing faster electrolyte ion diffusion during the redox process.     

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.     

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.     

Mesoporous MnCo2O4 spinel oxide nanostructure synthesized by solvothermal technique for supercapacitor

A manganese cobaltite spinel oxide was synthesized successfully via d-glucose-assisted solvothermal process. The structure and morphology of the sample heat treated at 300 and 400 °C for 6 h has been studied with X-ray diffraction, scanning electron microscope, and transmission electron microscope. Cyclic voltammograms at different scan rate have demonstrated that an excellent capacitance feature of MnCo₂O₄ spinel oxide electrode. Pseudotype-capacitive behavior of the sample was further corroborated by the charge–discharge measurements at various current densities. The estimated specific capacitance of spinel oxides with two calcination temperature was found to be 189 and 346 F g^?1 at a constant current density of 1 A g^?1. Observed specific capacitance and excellent cyclic stability of MnCo₂O₄ spinel oxide has ascribed to their high surface area and mesoporous microstructure. This facilitates to easy electrolyte ion intercalation and deintercalation at electrode/electrolyte interface. In this study, we suggest that the MnCo₂O₄ spinel nanostructure with high surface area and desired cation distribution could be a promising electrode material for next-generation high-performance supercapacitor.     

Hydrothermal synthesis of pure LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> from nanostructured MnO<Subscript>2</Subscript> precursors for aqueous hybrid supercapacitors

Pure LiMn₂O₄ samples with high crystallinity (LMO-1# and LMO-2#) were successfully synthesized by a facile hydrothermal method using δ-MnO₂ nanoflowers and α-MnO₂ nanowires as the precursors. The as-prepared samples were analyzed by XRD, SEM, and Brunauer-Emmett-Teller (BET), and their capacitive properties were investigated by cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge/discharge test. Two LiMn₂O₄ samples showed good capacitive behavior in aqueous hybrid supercapacitors. AC//LMO-1# and AC//LMO-2# delivered the initial specific capacitance of 45.4 and 40.7 F g^?1 in 1 M Li₂SO₄ electrolyte at a current density of 200 mA g^?1 in the potential range of 0～1.5 V, respectively. After 1000 cycles, the capacitance retention was 97.6% for AC//LMO-1# and 93.7% for AC//LMO-2#. Obviously, LMO-1# from δ-MnO₂ nanoflowers exhibited higher specific capacitance and better cycling performance than LMO-2#, so LMO-1# was more suitable as the positive electrode material in hybrid supercapacitors.     

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.     

Microspherical ZnO synthesized from a metal-organic precursor for supercapacitors

In this paper, ZnO microspheres, which are composed of irregular nanoparticles, have been synthesized successfully from a metal-organic precursor. The average diameter is about 3.5 μm and the specific surface area is 7.53 m² g^?1. Measured by electrochemical tests as electrode materials for supercapacitors, the ZnO powders show high specific capacitances (1017.5 Fg^?1 at 5 Ag^?1 and 562.5 Fg^?1 at 50 Ag^?1, respectively) and excellent cycling stability (the specific capacitance was kept at 631.2 Fg^?1 and 89.2 % retention after 3000 cycles at 18 Ag^?1). These results show that the microspherical ZnO could be a potential electrode material for supercapacitors.     

Preparation and electrochemical performance of spherical MnOx with high capacitance

A promising electrode material, MnO_x, was prepared by chemical precipitation method using MnSO₄?·?H₂O as manganese source and (NH₄)₂CO₃ as precipitant. The as-prepared manganese oxide was characterized by field emission scanning electron microscopy (FESEM), transmission electron microscope (TEM), and X-ray diffraction (XRD), respectively. The effects of reaction temperature and calcination temperature on the electrochemical properties of the electrode materials were investigated. The results show that MnO_x with a spherical morphology exhibits an excellent performance in the energy storage field. Under the optimal experimental conditions, the specific capacitance of pure MnO_x reaches up to 592 F g^?2 in the alkaline media when the current density is 5 mA cm^?2 over the potential window from ?0.3 to +0.4 V. The combination resistance and transfer resistance of MnO_x are 0.86 and 0.08 Ω, respectively. These findings make MnO_x a promising electrode material for electrochemical capacitors.     

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.     

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.     

A facile synthesis about amorphous CoS<Subscript>2</Subscript> combined with first principle analysis for supercapacitor materials

The structure and electrochemical properties of amorphous CoS₂ and crystalline CoS₂ have been studied with both experimental characterization and theoretical calculations. In the field of experimental characterization, a facile chemical precipitation method is used to synthesize amorphous and crystalline CoS₂ samples with calcining temperatures of 200 and 280 °C, respectively. Comparing with crystalline CoS₂, amorphous structure of CoS₂ manifests great electron conductivity, effective porous structure, and exhibit a high specific capacitance of 996.16 F g^?1 at current density of 0.5 A g^?1, excellent rate capability of 89.8% retention with the current density ranging from 0.5 to 5 A g^?1, and a great cycling stability of 97.6% retention after 10,000 cycles at 2 A g^?1 in 6 mol L^?1 KOH aqueous electrolyte. In the area of theoretical calculation, we used the first principle and obtained the band structure with band gap of 0.00369 eV and DOSs with high locality of D-orbital from 69.88689 electrons/eV main peak, in the CoS₂ amorphous. The result confirms that amorphous CoS₂ have higher conductivity than crystalline CoS₂ in theory. In addition, the as-assembled asymmetric supercapacitor of Co-S-200//AC also exhibits the maximum specific capacitance of 104 F g^?1 within a cell voltage from 0 to 1.5 V at current density of 0.5 A g^?1 and indicates a great cycling stability of 95.68% and excellent capacitance behavior. All results demonstrate a great potential of amorphous CoS₂ active material for supercapacitors.     

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 of δ-MnO<Subscript>2</Subscript> film on FTO glass with high electrochemical performance

δ-Manganese dioxide (MnO₂) has been proved to own the excellent electrochemical performances for a long time. But few of studies report the electrochemical performances of δ-MnO₂ film. Here, we synthesize δ-MnO₂ film on fluorine-doped tin oxide (FTO) glass via a simple redox reaction at the room temperature. The X-ray diffraction (XRD) and Raman spectroscopy are used to confirm the physical structure, whilst cyclic voltammetry and galvanostatic charge-discharge measurements are performed to investigate the electrochemical performances. Encouragingly, δ-MnO₂ film delivers a high specific capacitance (C _s) of 350.5 F g^?1 at 100 mV s^?1 and 275.0 F g^?1 at 5 A g^?1. The capacitance retention of δ-MnO₂ film can be up to 100 % after being charge/discharge at 2 A g^?1 with 1000 cycles. This research might further indicate that δ-MnO₂ film is a promising electrode material for supercapacitors.     

Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/functional exfoliation graphene on carbon paper nanocomposites for supercapacitor electrode

In this work, the commercial carbon paper was firstly peeled in K₂CO₃ solution and then was further treated in a KNO₃ solution to form functional exfoliation graphene (FEG) on the commercial carbon paper. The FEG/carbon paper was characterized by Raman spectra and scanning electron microscopy, confirming that some typical layered fold graphenes were successfully peeled off and stood on the carbon paper matrix. Then, Fe₃O₄ nanoparticles (NPs) were grown on the surface of FEG/carbon paper and the as-prepared Fe₃O₄ NPs/FEG/carbon paper was directly used as supercapacitor electrode. The specific capacitance of Fe₃O₄ NPs/FEG/carbon paper was about 316.07 F g^?1 at a current density of 1 A g^?1. Furthermore, the FEG/carbon papers were also functionalized by benzene carboxylic acid to form FFEG/carbon papers, and then the Fe₃O₄ NPs were grown on the surface of FFEG/carbon paper. The specific capacitance of Fe₃O₄ NPs/FFEG/carbon paper was 470 F g^?1 at a current density of 1 A g^?1, superior to some previous reported results. This work might provide a new strategy to prepare various nanostructures on FFEG/carbon papers for future applications.