In situ synthesis of crosslinked-polyaniline nano-pillar arrays/reduced graphene oxide nanocomposites for supercapacitors

Crosslinked-polyaniline (CPA) nano-pillar arrays adsorbed on the surface of reduced graphene oxide (RGO) sheets were synthesized by in situ solution polymerization through two steps of reduction. The electrochemical analyses demonstrated that the befittingly reduced CPA/RGO composite exhibited high performance as electrode materials for supercapacitors. The CPA/RGO composite showed very high specific capacitance of 1532 F g^?1 at a scan rate of 10 mV s^?1 or 694 F g^?1 at a current density of 2 A g^?1 in 1 M H₂SO₄ electrolyte, as well as great energy density of 61.4 W h kg^?1 at a current density of 2 A g^?1. The electrode material also had decent power density of 4 kW kg^?1 at a current density of 10 A g^?1, and good cycling stability of 92.5 % capacitance retained after 500 cycles of cyclic voltammetry at 500 mV s^?1. The neat microstructures and super electrochemical properties suggest the potential use of the composites in supercapacitors.     

The preparation of LaSr<Subscript>3</Subscript>Fe<Subscript>3</Subscript>O<Subscript>10 − <Emphasis Type="Italic">δ</Emphasis></Subscript> and its electrochemical performance

LaSr₃Fe₃O_10 ? δ powders were synthesized by hydrothermal method and characterized by XRD and SEM. The XRD patterns showed that the sample calcined at 1000 °C was single phase and the sample calcined at 900 °C had tiny amount of LaSrFeO₄ phase. The single-phase LaSr₃Fe₃O_10 ? δ powders were used to prepare test electrode. The capacitive behaviors of LaSr₃Fe₃O_10 ? δ electrode were analyzed by cyclic voltammetry, galvanostatic charge-discharge techniques, and electrochemical impedance spectroscopy. The electrochemical results showed a capacity as high as 470 F g^?1 at a scan rate of 1 mV s^?1 and 380 F g^?1 at a charge-discharge current density of 0.1 A g^?1 in 6 M KOH solution. The electrode showed good cyclic stability since its capacitive retention is 87.1% after 1000 charge-discharge cycles. The electrochemical performances suggest that LaSr₃Fe₃O_10 ? δ could be a potential candidate as a capacitive electrode material.     

Thiourea aldehyde resin-based carbon/graphene composites for high-performance supercapacitors

Thiourea aldehyde resin-based heteroatom doping carbon and graphene composites (RHDC/GN) were prepared by an in situ polymerization and carbonization. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images showed that thiourea aldehyde resin deposited on lamellar GO flakes during the polymerization and RHDC/GN composites had a hierarchical structure. The specific capacitance of the RHDC/GN composites was high up to 355 F g^?1, much higher than that of the pure thiourea aldehyde resin-based heteroatom doping carbon (RHDC) with specific capacitance of 135 F g^?1 at a current density of 1.0 A g^?1 in 6-M KOH electrolyte. And the hetroatoms in RHDC/GN composites increase the specific capacitance, and GN enhances the conductivity of the electrodes which is beneficial to improving electrochemical cycling stability of the electrode significantly. The specific capacitance retains 90.97% after 5000 charge-discharge processes at 10 A g^?1, which provides potential as supercapacitors.     

Hierarchical nanocomposites of polyaniline scales coated on graphene oxide sheets for enhanced supercapacitors

The homogeneous polyaniline–graphene oxide (PANI-GO) nanocomposites were facilely assembled with a redox system in which cumene hydroperoxide (CHP) and iron dichloride (FeCl₂) acted as oxidant and reductant, respectively. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images showed that PANI scales coated uniformly on the surface of GO sheets owing to the synergistic effect between the PANI and GO. The obtained PANI-GO nanocomposites exhibited improved electrochemical performance as an electrode material for supercapacitors compared with the pure PANI. The specific capacitance of the PANI-GO nanocomposites was high up to 308.3 F g^?1, much higher than that of the pure PANI with specific capacitance of 150 F g^?1 at a current density of 1 A g^?1 in 2 M H₂SO₄ electrolyte. The Raman and XPS results illustrated that enhanced electrochemical performance might be attributed to the π-π conjugation between the PANI and GO sheets.     

Ultrasonic-assisted synthesis of magnetite/carbon nanocomposite for electrochemical supercapacitor

Iron oxides are considered as the promising pseudocapacitive materials for high-performance supercapacitors due to their high theoretical specific capacitance, low cost, environmental benignity, and natural abundance. In this work, we study capacitive behavior of different magnetite (Fe₃O₄) nanoparticles/carbon black (CB) composites ratios. These composites are synthesized by the coprecipitation method in the presence of ultrasonic waves. The structural and morphological characteristics of the magnetite/CB composites are investigated by X-ray diffraction and scanning electron microscopy, respectively. The electrochemical performance of magnetite/CB composite electrodes is tested by cyclic voltammetry and galvanostatic charge/discharge in a Na₂SO₄ electrolyte. The results indicate that the magnetite/CB electrodes show typical pseudo-capacitive behavior in Na₂SO₄ solution. Moreover, in comparison to the pure Fe₃O₄ (37 F g^?1) and carbon black (23 F g^?1), the as-prepared 45 % magnetite/CB nanocomposite electrode shows a higher specific capacitance (300 F g^?1). Additionally, the supercapacitor device of the magnetite/CB nanocomposite exhibits excellent long cycle life along with 98.5 % specific capacitance retained after 10,000 cycle tests.     

Design of high-performance core-shell hollow carbon nanofiber@nickel-cobalt double hydroxide composites for supercapacitive energy storage

The supercapacitive performances of supercapacitor mainly depend on the physical nanostructure and micro-morphology of electrode materials. Here, we demonstrated the design, synthesis and electrochemical performances of core-shell hollow carbon nanofiber@nickel-cobalt-layered double hydroxide (HCNF@ Ni_0.67Co_0.33-LDH) nanocomposites with an optimized Ni/Co molar ratio of 2:1. The HCNF was used as superiorly conductive core to sustain the nanoporous silky Ni_0.67Co_0.33-LDH shell, which can efficiently provide fast transport pathways for electrons and electrolyte ions. The outstanding specific capacitance of 2486 F g^?1 at 1 A g^?1 based on galvanostatic charge-discharge curves were acquired for the highly electroactive HCNF@Ni_0.67Co_0.33-LDH. Furthermore, the HCNF@Ni_0.67Co_0.33-LDH electrode delivered a distinguished rate capability with a specific capacitance of 1890 F g^?1 even at 15 A g^?1. Notably, an asymmetric supercapacitor with HCNF@Ni_0.67Co_0.33-LDH as cathode and HCNF as anode was devised, which presented a prominent specific capacitance of 228 F g^?1, good energy density of 62.1 Wh kg^?1, and impressive cycling stability (90.6% capacitance retention after 10,000 cycles).     

Effect of solvents on the morphology of NiCo<Subscript>2</Subscript>O<Subscript>4</Subscript>/graphene nanostructures for electrochemical pseudocapacitor application

The large internal surface areas and outstanding electrical and mechanical properties of graphene have prompted to blend graphene with NiCo₂O₄ to fabricate nanostructured NiCo₂O₄/graphene composites for supercapacitor applications. The use of graphene as blending with NiCo₂O₄ enhances the specific capacitance and rate capability and improves the cyclic performance when compared to the pristine NiCo₂O₄ material. Here, we synthesized two different nanostructured morphologies of NiCo₂O₄ on graphene sheets by solvothermal method. It has been suggested that the morphologies of oxides are greatly influenced by dielectric constant, thermal conductivity, and viscosity of solvents employed during the synthesis. In order to test this concept, we have synthesized nanostructured NiCo₂O₄ on graphene sheets by facile solvothermal method using N-methyl pyrrolidone and N,N-dimethylformamide solvents with water. We find that mixture of N-methyl pyrrolidone and water solvent favored the formation of nanonet-like NiCo₂O₄/graphene (NiCoO-net) whereas mixture of N,N-dimethylformamide and water solvent produced microsphere-like NiCo₂O₄/graphene (NiCoO-sphere). Electrochemical pseudocapacitance behavior of the two NiCo₂O₄/graphene electrode materials was studied by cyclic voltammetry, chronopotentiometry, and electrochemical impedance spectroscopy techniques. The supercapacitance measurements on NiCoO-net and NiCoO-sphere electrodes showed specific capacitance values of 1060 and 855 F g^?1, respectively, at the current density of 1.5 A g^?1. The capacitance retention of NiCoO-net electrode is 93 % while that of NiCoO-sphere electrode is 77 % after long-term 5000 charge-discharge cycles at high current density of 10 A g^?1.     

Reed straw derived active carbon/graphene hybrids as sustainable high-performance electrodes for advanced supercapacitors

Reed straw-derived active carbon@graphene (AC@GR) hybrids were prepared by one-step carbonization/activation process using a mixture of reed straw and graphene oxide (GO) as raw materials and ZnCl₂ as activation agent. The as-prepared hybrids exhibit high specific surface area in a range of 1971–2497 m² g^?1, abundant porosity, as well as excellent energy storage capability. The symmetric C//C supercapacitor using the hybrid obtained at 700 °C as electrodes demonstrates superior cycling durability, ca. 90 % retention after 6000 cycles at 2 A g^?1, and a high energy density of 6.12 Wh kg^?1 at a power density of up to 4660 W kg^?1 in 6 M KOH aqueous electrolyte. The excellent capacitive performance is attributed to the synergistic effect of AC and GR.     

Electrochemical exfoliation and in situ carboxylic functionalization of graphite in non-fluoro ionic liquid for supercapacitor application

Simultaneous electrochemical generation and functionalization of nano-sized graphite from graphite had been carried out in a non-fluoroanion-based ionic liquid, namely, triethylmethylammonium methylsulfate (TEMAMS) containing water and acetonitrile (AN) in different weight ratios. The oxygen-based functional groups attached with the exfoliated material had been identified using Fourier transform infrared spectroscopy (FTIR), and morphological changes were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). A symmetrical supercapacitor was fabricated using the exfoliated nano-sized graphite, and the influence of surface functionalities on its performance was investigated using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and galvanostatic charge–discharge cycles (CC). The highest specific capacitance (C _sp) value of 140 F g^?1 at 0.25 A g^?1 was obtained in 1.0 M H₂SO₄, followed by aqueous TEMAMS (125 F g^?1), TEMAMS/acetonitrile (115 F g^?1), and TEMAMS (106 F g^?1) at 0.10 A g^?1.     

Synthesis of micro- and mesoporous carbon spheres for supercapacitor electrode

Micro- and mesoporous carbon spheres (MMCSs) are synthesized by the polymerization of colloidal silica-entrapped resorcinol/formaldehyde in the presence of ammonia as catalyst, followed by carbonization, sodium hydroxide (NaOH) etching to remove silica template, and potassium hydroxide (KOH) activation. The morphology and microstructure are characterized by scanning electron microscopy, transmission electron microscopy, and nitrogen adsorption–desorption. The results show that a typical sample (denoted as MMCS-3) unites the characteristics of regular spherical shape (uniform diameters of 500 nm), high specific surface area (1,620 m² g^?1), large pore volume (1.037 cm³ g^?1), and combined micropores and mesopores (11.0 nm), which endows MMCS-3 good electrochemical performance. MMCS-3 as supercapacitor electrode shows a specific capacitance of 314 F g^?1 under a current density of 0.5 A g^?1 and low internal resistance of 0.2 Ω in 6 M KOH aqueous solution. The electrochemical capacitance still retains 198 F g^?1 at a high current density of 10 A g^?1. After 500 cycle numbers of galvanostatic charge/discharge at 0.5 A g^?1, MMCS-3 electrode still remains the specific capacitance of 301 F g^?1 with the retention of 96 %. This study highlights the potential of well-designed MMCSs as electrodes for widespread supercapacitor applications.     

Facile fabrication of mesoporous manganese oxides as advanced electrode materials for supercapacitors

Mesoporous manganese oxides (MnO₂) were synthesized via a facile chemical deposition strategy. Three kinds of basic precipitants including sodium carbonate (Na₂CO₃), sodium bicarbonate (NaHCO₃), and sodium hydroxide (NaOH) were employed to adjust the microstructures and surface morphologies of MnO₂ materials. The obtained MnO₂ materials display different microstructures. Great differences are observed in their specific surface area and porosity properties. The microstructures and surface morphologies characteristics of MnO₂ materials largely determine their pseudocapacitive behavior for supercapacitors. The MnO₂ prepared with Na₂CO₃ precipitant exhibits the optimal microstructures and surface morphologies compared with the other two samples, contributing to their best electrochemical performances for supercapacitors when conducted either in the single electrode tests or in the capacitor measurements. The optimal MnO₂ electrode exhibits a high specific capacitance (173 F g^–1 at 0.25 A g^?1), high-rate capability (123 F g^?1 at 4 A g^?1), and excellent cyclic stability (no capacitance loss after 5,000 cycles at 1 A g^?1). The optimal activated carbon//MnO₂ hybrid capacitor exhibits a wide working voltage (1.8 V), high-power and high-energy densities (1,734 W kg^?1 and 20.9 Wh kg^?1), and excellent cycling behavior (93.8 % capacitance retention after 10,000 cycles at 1 A g^?1), indicating the promising applications of the easily fabricated mesoporous MnO₂ for supercapacitors.     

Pyridine-containing metal-organic frameworks as precursor for nitrogen-doped porous carbons with high-performance capacitive behavior

A novel pyridine-containing metal-organic framework (MOF, [Zn(bpdc)DMA]·DMF, bpdc = 2,2′-bipyridine-5,5′-dicarboxylate) was directly carbonized at different temperature to produce nitrogen-doped porous carbons (NPCs). The as-prepared porous carbons, NPC800 (obtained at 800 °C) and NPC1000 (obtained at 1000 °C), were characterized by scanning electron microscopy, X-ray powder diffraction, N₂ sorption isotherms, and X-ray photoelectron spectroscopy (XPS). The results from elemental analysis and XPS confirmed that the pyridine groups in MOF served as nitrogen sources to produce NPCs, and NPC800 possessed the higher nitrogen content than NPC1000. N₂ sorption data demonstrated that NPC800 exhibited the larger specific surface area and pore volume than NPC1000. The capacitive properties of NPC800 and NPC1000 were investigated in KOH aqueous electrolyte by cyclic voltammetry and galvanostatic charge–discharge curves. NPC800 showed the higher specific capacitance (226.6 F g^?1 at 1 A g^?1) than NPC1000 and retained 178.0 F g^?1 even at a high current density up to 10 A g^?1. It was found that the donation of N species to capacitance was more than the role of porosity in view of their synergetic effect.     

Capacity of graphene anode in ionic liquid electrolyte

The graphene anode was investigated in an ionic liquid electrolyte (0.7 M lithium bis(trifluoromethanesulfonyl)imide (LiNTf₂)) in room temperature ionic liquid (N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (MPPyrNTf₂)). SEM and TEM images suggested that the electrochemical intercalation/deintercalation process in the ionic liquid electrolyte without vinylene carbonate (VC) leads to small changes on the surface of graphene particles. However, a similar process in the presence of VC results in the formation of a coating (SEI—solid electrolyte interface) on the graphene surface. During charging/discharging tests, the graphene electrode working together with the 0.7 M LiNTf₂ in MPPyrNTf₂ electrolyte lost its capacity, during cycling and stabilizes at ca. 200 mAh g^?1 after 20 cycles. The addition of VC to the electrolyte (0.7 M LiNTf₂ in MPPyrNTf₂?+?10 wt.% VC) considerably increases the anode capacity. Electrodes were tested at different current regimes: ranging between 50 and 1,000 mA g^?1. The capacity of the anode, working at a low current regime of 50 mA g^?1, was ca. 1,250 mAh g^?1, while the current of 500 mA g^?1 resulted in capacity of 350 mAh g^?1. Coulombic efficiency was stable and close to 95 % during ca. 250 cycles. The exchange current density, obtained from impedance spectroscopy, was 1.3?×?10^?7 A cm^?2 (at 298 K). The effect of the anode capacity decrease with increasing current rate was interpreted as the result of kinetic limits of the electrode operation.     

Electrochemical reduction of graphene oxide and its electrochemical capacitive performance

A convenient method for the production of graphene is developed using the electrochemical reduction of graphite oxide (GO) in solution without assembling it onto the electrode. The samples were examined by X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy. The results show that the number of oxygen functional groups can be significantly decreased. The electrochemical capacitance of the prepared graphene after 8 h of reduction is 158.5 F g^?1 at 0.5 A g^?1, much higher than that of GO and carbon nanotubes. The mechanism for this reaction is also proposed in this paper.     

Fabrication of vesicular polyaniline using hard templates and composites with graphene for supercapacitor

Vesicular polyaniline (VPANI) has been fabricated for the first time via a facile two-step method, which uses high-quality multilamellar vesicular SiO₂ as hard templates. The graphene-wrapped VPANI (VPANI@RGO) composites were prepared by self-assembling graphene oxide onto VPANI and subsequently conducting the hydrothermal reduction process. The morphological characterization of the composites confirms the uniform wrapping of the graphene sheets on the VPANI. The structural characterization of the composites reveals a strong π–π electron and hydrogen bond interaction in the composites. The VPANI@RGO composites exhibit an excellent supercapacitor performance with an enhanced specific capacitance (573 F g^?1) and a good cycling stability, which maintains its capacity of up to 85.7 % over 1000 cycles at 1 A g^?1.     

Effect of crystallite size on the intercalation pseudocapacitance of lithium nickel vanadate in aqueous electrolyte

This work describes lithium nickel vanadate (LiNiVO₄) as a pseudocapacitor electrode material for the first time. The micro and nano-sized LiNiVO₄ are synthesized via mechanochemical reaction and hydrothermal reaction followed by calcination, respectively. The phase purity, surface morphology and microstructure of the LiNiVO₄ synthesized by both methods are analysed by X-ray diffraction and scanning electron microscopy techniques. The lithium ion intercalation-extraction behaviour of the LiNiVO₄ electrode material is investigated in 1 M LiOH electrolyte solution. The results demonstrate an improved capacitive performance for nano-sized LiNiVO₄ electrode synthesized via hydrothermal reaction due to the collective effect of small size and additional redox sites. The nanocrystalline LiNiVO₄ electrode exhibits a high specific capacitance of 456.56 F g^?1 at a current density of 0.5 A g^?1. The cycle stability test reveals exceptional capacitance retention of 99.60% even after 1000 cycles owing to the unique structural feature which permit intercalation mechanism. These findings demonstrate the significance of lithium transition metal vanadate-based electrode material in the development of lithium ion intercalation pseudocapacitors.     

Porous carbon synthesized by direct carbonization of potassium biphthalate for high-performance supercapacitors

Porous carbons have been synthesized by a direct carbonization of potassium biphthalate without an activation process. The experimental results demonstrate that the carbonization temperature plays a crucial role in determining the surface area and pore structure as well as the correlative capacitive performance. The carbon-700/800/900 samples display surface areas of 672, 1,023, and 1,380 m² g^?1 and total pore volumes of 0.38, 0.56, and 0.78 cm³ g^?1, respectively. The specific capacitances of the carbon-700/800/900 samples are 300.4, 272.3, and 243.4 F g^?1, respectively, at a current density of 0.5 A g^?1. More importantly, the carbon-900 sample possesses the highest capacitance retention (~98.4 %) even undergoing charge–discharge 10,000 times. The potassium biphthalate used as a carbon source is inexpensive and commercially available, making it promising for the large-scale production of porous carbons as an excellent electrode material for supercapacitors.     

Hybrid nanonet/nanoflake NiCo2O4 electrodes with an ultrahigh surface area for supercapacitors

An integrated electrode consisting of hybrid nanonet/nanoflake NiCo₂O₄ grown on stainless steel mesh substrates exhibits a high specific capacitance while maintaining high-rate capability and good cycling stability. The specific capacitance reaches a maximum of 911 F g^?1 at a current density of 10 A g^?1, which can still retain 864 F g^?1 (94.8 % retention) after 10,000 cycles. These much-improved electrochemical performances are attributed to the unique architecture of NiCo₂O₄ electrode. The interconnected nanonet NiCo₂O₄ with an ultrahigh surface area significantly facilitates the rapid ion/electron transport and guarantees good mechanical adhesion, while the ultrathin nanoflakes further extend the active sites for fast redox reactions for efficient energy storage. Figure

Hybrid nanonet/nanoflake NiCo₂O₄ grown on stainless steel mesh exhibits superior capacitive performance and long-life stability as an integrated electrode for high-performance supercapacitors.     

A tunable hierarchical porous carbon from starch pretreated by calcium acetate for high performance supercapacitors

Hierarchical porous carbons (HPCs) with abundant mesopores have been prepared by a facile route from the starch that was pretreated by calcium acetate. The scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and N₂ adsorption–desorption tests show that hierarchical porous carbons with bimodal mesopores have been obtained. Moreover, the pore sizes are tunable by simply adjusting the reactants ratio and carbonization temperature. The as-synthesized hierarchical porous carbon materials (HPCs-2-800) possesses the highest Brunauer-Emmett-Teller (BET)-specific surface area of 464 m² g^?1 and mesoporous volume of 0.663 cm³ g^?1 at the carbonization temperature of 800 °C and starch to calcium acetate mass ratio of 2. Electrochemical measurements also display that the HPCs-2-800 electrodes have a high reversible capacity of 244 F g^?1 at the current density of 0.1 A g^?1 and 182 F g^?1 at the current density of 10 A g^?1. When the current density is elevated from 0.1 to 10 A g^?1, the high capacitance retention of 74.6 % reveals a good rate performance. Long charge–discharge cycling measurements disclose good stabilities over 25,000 cycles at different current densities of 1–10 A g^?1 (5000 cycles at each current density) for HPCs-2-800 electrode. The cycling results indicate a high capacitance retention of 99.6 % over 5000 charge–discharge cycles even at the current density of 10 A g^?1. The excellent supercapacitive performances imply that HPCs-2-800 is a promising candidate for supercapacitors.     

Effect of carbonaceous support between graphite oxide and reduced graphene oxide with anchored Co<Subscript>3</Subscript>O<Subscript>4</Subscript> microspheres as electrode-active materials in a solid-state electrochemical capacitor

Hydrothermally synthesized Co₃O₄ microspheres were anchored to graphite oxide (GO) and thermally reduced graphene oxide (rGO) composites at different cobalt weight percentages (1, 10, and 100 wt%). The composite materials served as the active materials in bulk electrodes for two-electrode cell electrochemical capacitors (ECCs). GO/Co₃O₄–1 exhibited a high energy density of 35 W kg^?1 with a specific capacitance (C _sp) of 196 F g^?1 at a maximum charge density of 1 A g^?1. rGO/Co₃O₄-100 presented high specific power output values of up to 23.41 kW h kg^?1 with linear energy density behavior for the charge densities applied between 0.03 and 1 A g^?1. The composite materials showed Coulombic efficiencies of 96 and 93 % for GO/Co₃O₄–1 and rGO/Co₃O₄–100 respectively. The enhancement of capacitive performance is attributed to the oxygenated groups in the GO ECC and the specific area in the rGO ECC. These results offer an interesting insight into the type of carbonaceous support used for graphene derivative electrode materials in ECCs together with Co₃O₄ loading to improve capacitance performance in terms of specific energy density and specific power.

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