Ti3C2Tx-foam as free-standing electrode for supercapacitor with improved electrochemical performance

To prevent restacking of the Ti₃C₂T_x layers, the Ti₃C₂T_x-foam has been successfully synthesized through thermal treatment of Ti₃C₂T_x-film with the hydrazine monohydrate. The interconnected porous structure of Ti₃C₂T_x-foam could effectively reduce the restacking of the Ti₃C₂T_x sheets and shorten the diffusion path of ions and accelerate the intercalation/de-intercalation of ions. The Ti₃C₂T_x-foam-80 used as free-standing electrode achieves a high areal capacitance of 271.2 mF/cm² (122.7?F/g) at a scan rate of 5?mV/s in 1?M KOH electrolyte. It also exhibited a high capability rate of 65.5% from 5?mV/s to 100?mV/s and good cycle life with 88.7% retention of its initial after 10,000 cycles at a scan rate of 50?mV/s.     

Liquid-phase synthesized mesoporous electrochemical supercapacitors of nickel hydroxide

Electrochemical supercapacitive (ES) properties of liquid-phase synthesized mesoporous (pore size distribution centered ∼12 nm) and of 120 m²/g surface area nickel hydroxide film electrodes onto tin-doped indium oxide substrate are discussed. The amounts of inner and outer charges are calculated to investigate the contribution of mesoporous structure on charge storage where relatively higher contribution of inner charge infers good ion diffusion into matrix of nickel hydroxide. Effect of different electrolytes, electrolyte concentrations, deposit mass and scan rates on the current-voltage profile in terms of the shape and enclosed area is investigated. Specific capacitance of ∼85 F/g at a constant current density of 0.03 A/g is obtained from the discharge curve.     

Facile synthesis and strongly microstructure-dependent electrochemical properties of graphene/manganese dioxide composites for supercapacitors

Graphene has attracted much attention since it was firstly stripped from graphite by two physicists in 2004, and the supercapacitor based on graphene has obtained wide attention and much investment as well. For practical applications of graphene-based supercapacitors, however, there are still many challenges to solve, for instance, to simplify the technological process, to lower the fabrication cost, and to improve the electrochemical performance. In this work, graphene/MnO₂ composites are prepared by a microwave sintering method, and we report here a relatively simple method for the supercapacitor packaging, i.e., dipping Ni-foam into a graphene/MnO₂ composite solution directly for a period of time to coat the active material on a current collector. It is found that the microwave reaction time has a significant effect on the microstructure of graphene/MnO₂ composites, and consequently, the electrochemical properties of the supercapacitors based on graphene/MnO₂ composites are strongly microstructure dependent. An appropriately longer microwave reaction time, namely, 15 min, facilitates a very dense and homogeneous microstructure of the graphene/MnO₂ composites, and thus, excellent electrochemical performance is achieved in the supercapacitor device, including a high specific capacitance of 296 F/g and a high capacitance retention of 93% after 3,000 times of charging/discharging cycles.

PACS

81.05.ue; 78.67.Sc; 88.80.fh     

石墨烯/硅负极材料的制备及其电化学性能的研究

通过将亚微米硅与石墨烯进行原位还原复合(SG1)和机械混合(SG2)这2种方式制备了不同的石墨烯/硅复合锂离子电池负极材料。SEM结果显示,2种复合物中硅颗粒都被石墨烯片层所包夹,且分散均匀;充放电测试表明,这2种复合方式均使复合电极的首次容量损失大大减小,循环稳定性得到很大提高,其首次放电比容量分别为2 070.5mAh/g和1 534.2mAh/g,循环12次后均保持在1 000mAh/g以上;通过EIS阻抗谱对硅复合电极的导电性以及电极结构的初步研究,发现复合电极本身导电性以及材料的电接触性远优于纯硅,电极结构也相对稳定。     

Mechanochemical preparation of polydiphenylamine and its electrochemical performance in hybrid supercapacitors

A simple mechanochemical route for the synthesis of high quality inorganic anion doped polydiphenylamines (PDPAs) is reported in this article. Elemental analysis performed for the PDPAs indicated the presence of dopant anions in the polymeric chain. PDPA prepared in the presence of 96 wt% H₂SO₄ (PDPA–H₂SO₄) was found to be better doped than the other polymeric salts. Spectroscopic profiles of the polymers showed that the PDPAs were in a doped conducting state. The X-ray diffraction (XRD) pattern of the as-prepared polymeric powders revealed the presence of more crystalline phases in PDPA–H₂SO₄. Field emission scanning electron microscopic (FESEM) images highlighted the formation of inorganic anion doped PDPA particles with different sizes (80–100 nm). Electrochemical studies performed for the polymeric particles depicted the redox behavior and good electrochemical activity of PDPA salts. Thermogravimetric analysis (TGA)/differential thermal analysis (DTA) proved that all the PDPA salts were thermally stable up to 300 °C. The electrochemical performance of PDPA–H₂SO₄ in hybrid supercapacitors was evaluated due to its superior physicochemical properties. The maximum specific capacitance of the hybrid supercapacitor constructed out of PDPA–H₂SO₄ powder was found to be 108 F g⁻¹.     

Cathodic electrodeposition of MnOx films for electrochemical supercapacitors

Cathodic electrosynthesis has been utilized for the fabrication of MnO_x films. The use of polyethylenimine (PEI) as an additive enabled the formation of adherent films, which exhibited enhanced resistance to cracking during drying. The polymer content in the deposits can be varied by the variation of the polymer concentration in the solutions. The mechanism of PEI deposition was proposed which is based on the use of PEI-Mn²⁺ complexes. The deposition yield has been studied at different deposition durations. X-ray diffraction analysis showed the crystallization of Mn₃O₄ phase at 300 °C and Mn₂O₃ at 500 °C. The electrochemical performance of the MnO_x films sintered at different temperatures was studied by cyclic voltammetry (CV), chronopotentiometry and impedance spectroscopy in Na₂SO₄ solutions. The films showed excellent pseudocapacitive behavior. The specific capacitance (SC) of 425 F/g in a potential window of 0-0.9 V was obtained from the CV data at a scan rate of 10 mV/s. The SC calculated from the chronopotentiometry data is about 445 F/g. The SC decreased by ∼20% after 1000 cycles. SEM investigations revealed changes in the film morphology during cycling. Obtained results indicate that the proposed method can be used for the fabrication of electrodes for electrochemical supercapacitors.     

Improving the electrochemical performance of polyaniline electrode for supercapacitor by chemical oxidative copolymerization with p-phenylenediamine

A series of poly(aniline-co-p-phenylenediamine) (P(ANI-co-PPDA)) copolymers were synthesized via the chemical oxidative polymerization of aniline with p-phenylenediamine (PPDA) as the comonomer. The structure and morphology of the P(ANI-co-PPDA) copolymers prepared with different feeding ratio of PPDA under different polymerizing temperature were compared with the two homopolymers polyaniline (PANI) and poly(p-phenylenediamine) (PPPDA). It is interesting to find that the electrical conductivity, specific capacitance and cycling stability of the P(ANI-co-PPDA) copolymer electrode materials were obviously improved with certain feeding ratio of PPDA, compared with those two homopolymers.     

NiO-based composite electrode with RuO2 for electrochemical capacitors

NiO/RuO₂ composite materials were prepared for use in electrochemical capacitors (ECs) by co-precipitation method followed by heat treatment. X-ray diffraction (XRD) spectra indicated that no new structural materials were formed and ruthenium oxide particles were coated by NiO particles. RuO₂ partly introduced into NiO-based electrode had improved its electrochemical performance and capacitive properties by using electrochemical measurements. A maximum specific capacitance of 210 F/g was obtained for NiO-based composite electrode with 10 wt.% RuO₂ in the voltage range from −0.4 to 0.5 V in 1 mol/l KOH solution. By comparison of effect of modified modes on the specific capacitance, chemically modified composite electrodes had more stable cycling properties than those of physically modified electrodes. After 200 cycles, specific capacitance of NiO-based chemical composite electrode with 5 wt.% RuO₂ kept 95% above, while that of physical electrode was only 79% of initial specific capacitance.     

Copper substituted nickel ferrite nanoparticles anchored onto the graphene sheets as electrode materials for supercapacitors fabrication

Nickel ferrites with high theoretical capacitance value as compared to the other metal oxides have been applied as electrode material for energy storage devices i.e. batteries and supercapacitors. High tendency towards aggregation and less specific surface area make the metal oxides poor candidate for electrochemical applications. Therefore, the improvements in the electrochemical properties of nickel ferrites (NiFe₂O₄) are required. Here, we report the synthesis of graphene nano-sheets decorated with spherical copper substituted nickel ferrite nanoparticles for supercapacitors electrode fabrication. The copper substituted and unsubstituted NiFe₂O₄ nanoparticles were prepared via wet chemical co-precipitation route. Reduced graphene oxide (rGO) was prepared via well-known Hummer's method. After structural characterization of both ferrite (Ni_1-xCu_xFe₂O₄) nanoparticles and rGO, the ferrite particles were decorated onto the graphene sheets to obtain Ni_1-xCu_xFe₂O₄@rGO nanocomposites. The confirmation of preparation of these nanocomposites was confirmed by scanning electron microscopy (SEM). The electrochemical measurements of nanoparticles and their nanocomposites (Ni_0.9Cu_0.1Fe₂O₄@rGO) confirmed that the nanocomposites due to highly conductive nature and relatively high surface area showed better capacitive behavior as compared to bare nanoparticles. This enhanced electrochemical energy storage properties of nanocomposites were attributed to the graphene and also supported by electrical (I-V) measurements. The cyclic stability experiments results showed ~65% capacitance retention after 1000 cycles. However this retention was enhanced from 65% to 75% for the copper substituted nanoparticles (Ni_0.9Cu_0.1Fe₂O₄) and 65–85% for graphene based composites. All this data suggest that these nanoparticles and their composites can be utilized for supercapacitors electrodes fabrication.     

Preparation of polyaniline nanowire arrayed electrodes for electrochemical supercapacitors

Polyaniline (PANI) nanowire arrayed electrodes were successfully synthesized by means of anodic deposition technique using the membrane-template synthesis route. The desired three-dimensional architecture of PANI nanowire arrayed electrodes was characterized with field emission scanning electron microscope (FESEM) and X-ray diffraction (XRD) techniques. It was found that the co-deposition nanowires were regular size and continuous with an average diameter of about 30 nm, and the nanowires have an amorphous nature. The electrochemical characterization was performed in 2 M H₂SO₄ aqueous solution. The capacitance of the PANI nanowire arrayed electrode at a charge–discharge current density of 5 Ag⁻¹ is 1142 Fg⁻¹. The nanowire arrayed electrodes showed an excellent capacitive ability for the facility of electrolyte penetration, the ease of proton exchange/diffusion and the metallic conductivity of PANI nanowire arrayed electrodes.     

Porous NiO/Ag composite film for electrochemical capacitor application

A highly porous NiO/Ag composite film is prepared by the combination of chemical bath deposition and silver mirror reaction. The as-prepared NiO/Ag composite film has an interconnecting reticular morphology made up of NiO flakes with highly dispersed Ag nanoparticles of about 6 nm. The pseudocapacitive behavior of the NiO/Ag composite film is investigated by cyclic voltammograms (CV) and galvanostatic charge–discharge tests in 1 M KOH. The NiO/Ag composite film exhibits weaker polarization, higher specific capacitance and better cycling performance as compared to the unmodified porous NiO film. The specific capacitance of the porous NiO/Ag composite film is 330 F g⁻¹ at 2 A g⁻¹ and 281 F g⁻¹ at 40 A g⁻¹, respectively, much higher than that of the unmodified porous NiO film (261 F g⁻¹ at 2 A g⁻¹ and 191 F g⁻¹ at 40 A g⁻¹). The enhancement of pseudocapacitive properties is due to highly dispersed Ag nanoparticles in the composite film, which improves the electric conductivity of the film electrode.     

Morphology-controlled porous Bi0.9La0.1FeO3 microspheres for applications in supercapacitors

Morphology-controlled porous Bi_0.9La_0.1FeO₃ (BLFO) microspheres with high specific surface area and pore volume have been synthesized by a novel one-step etching approach, in which BLFO particles were used as precursors, hydrazine and methyl mercaptoacetate function as reducing and complexation agent respectively. As the etching time goes in order from 30 to 90 min, different morphologies of porous BLFO microspheres can be obtained, such as dandelion, corolla, and acanthosphere-like architectures respectively, which corresponds to different surface area and pore volume of porous BLFO microspheres. Particularly, porous BLFO microspheres etched for 60 min has the largest specific surface area of 75.09 m² g^-1 m²g, much larger than 1.44 m² g^-1m², that of unetched BLFO particles. The enhanced surface area and pore volume brings about a great number of active sites that boost the intercalation and de-intercalation of electrolyte ions, and compared with unetched BLFO particles, porous BLFO microspheres exhibit the good conductivity and ion diffusion behavior, which are both conducive to excellent performance as supercapacitors. The largest specific capacitance of 561.48 F g^-1 Fg^?1 at a scan rate of 2 mV s^-1mV/s can be obtained when the etching time is 60 min, and it exhibits a good capacitance retention of 85.76% after 1500 cycles with the current density of 5 A g^-1A/g, much superior to 75.66%, that of BLFO particles. This research may offer a facile method to fabricate stable, flexible and high performance energy storage devices.     

Seedless growth of zinc oxide flower-shaped structures on multilayer graphene by electrochemical deposition

A seedless growth of zinc oxide (ZnO) structures on multilayer (ML) graphene by electrochemical deposition without any pre-deposited ZnO seed layer or metal catalyst was studied. A high density of a mixture of vertically aligned/non-aligned ZnO rods and flower-shaped structures was obtained. ML graphene seems to generate the formation of flower-shaped structures due to the stacking boundaries. The nucleation of ZnO seems to be promoted at the stacking edges of ML graphene with the increase of applied current density, resulting in the formation of flower-shaped structures. The diameters of the rods/flower-shaped structures also increase with the applied current density. ZnO rods/flower-shaped structures with high aspect ratio over 5.0 and good crystallinity were obtained at the applied current densities of −0.5 and −1.0 mA/cm². The growth mechanism was proposed. The growth involves the formation of ZnO nucleation below 80°C and the enhancement of the growth of vertically non-aligned rods and flower-shaped structures at 80°C. Such ZnO/graphene hybrid structure provides several potential applications in sensing devices.     

Synthesis and electrochemical properties of graphene oxide/nanosulfur/polypyrrole ternary nanocomposite hydrogel for supercapacitors

A method for synthesizing Graphene oxide (GO)/nano‐sulfur/polypyrrole (PPy) ternary nanocomposite hydrogel is depicted. The higher surface area of GO, PPy porous structure and their excellent conductivity are utilized, and the GO hydrogel can be made easily. The products are characterized by field‐emission scanning electron microscopy (FESEM), X‐ray diffraction (XRD), Fourier transform infrared (FTIR) spectra, and electrochemical workstation. The results demonstrated that GO/nano‐S/PPy ternary nanocomposite hydrogel is successfully synthesized. The electrochemical properties are investigated by cyclic voltammetry, galvanostatic charge/discharge measurements, and cycling life in a three‐electrode system in 1M Li₂SO₄ electrolyte solution. The GO/nano‐S/PPy ternary nanocomposite hydrogel exhibit a high specific capacitance of 892.5 F g^?1 at scan rates of 5 mV s^?1 and the capacitance retain about 81.2% (594.8 F g^?1) of initial capacitance (732.5 F g^?1) after 500 cycles at a current density of 1 A g^?1. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40814.     

Synthesis and characterization of aerogel-like mesoporous nickel oxide for electrochemical supercapacitors

Highly porous NiO was prepared via a combination of sol-gel process with supercritical drying method in this paper. The as-synthesized NiO samples exhibit 80–90% porosity and high surface area, ie, 180.5–325.6 m²g⁻¹. Cyclic voltammetric and chronopotentiometric measurements indicated the aerogel-like NiO in 1 mol.L⁻¹ KOH solution to behave capacitive well due to its uniform mesoporous microstructure. It was also observed that post-heating temperature plays a critical role in the mesoporous nature of the aerogel-like materials. An optimal heating temperature of 300^∘C was found to favor the formation of mesopores, which account for the large specific capacitance of as high as 125 F.g⁻¹. The average specific capacitance of the aerogel-like NiO was observed to be about 75–125 F.g⁻¹ between a potential window of 0–0.35 V vs. SCE.     

Synthesis and characterization of aerogel-like mesoporous nickel oxide for electrochemical supercapacitors

Highly porous NiO was prepared via a combination of sol-gel process with supercritical drying method in this paper. The as-synthesized NiO samples exhibit 80–90% porosity and high surface area, ie, 180.5–325.6 m²g^?1. Cyclic voltammetric and chronopotentiometric measurements indicated the aerogel-like NiO in 1 mol.L^?1 KOH solution to behave capacitive well due to its uniform mesoporous microstructure. It was also observed that post-heating temperature plays a critical role in the mesoporous nature of the aerogel-like materials. An optimal heating temperature of 300^°C was found to favor the formation of mesopores, which account for the large specific capacitance of as high as 125 F.g^?1. The average specific capacitance of the aerogel-like NiO was observed to be about 75–125 F.g^?1 between a potential window of 0–0.35 V vs. SCE.     

Morphological and structural studies of nanoporous nickel oxide films fabricated by anodic electrochemical deposition techniques

Porous nickel oxide films are directly deposited onto conducting indium tin oxide coated glass substrates by cyclic voltammetric (CV), galvanostatic, and potentiostatic strategies in a plating bath of sodium acetate, nickel sulfate, and sodium sulfate. By tuning the deposition parameters, it is possible to prepare nickel oxide films with various morphologies and structures. Film formation relies on the oxidation of dissolved Ni²⁺ to Ni³⁺, which further reacts with the available hydroxide ions from a slightly alkaline electrolyte to form insoluble nickel oxide/hydroxide deposits on the substrate. A compact film with particularly small pores is obtained by CV deposition in a potential range of 0.7-1.1 V. A galvanostatically deposited film is structurally denser near the surface of the substrate, and becomes less dense further away from the surface. Interestingly, a potentiostatically deposited film has pores distributed uniformly throughout the entire film. Therefore, for obtaining a uniform film with suitable pore size for electrolyte penetration, potentiostatic deposition technique is suggested. In addition, except for CV deposition, the deposited films resemble closely to cubic NiO when the annealing temperature exceeds 200 °C.     

Synthesis and plasma treatment of nitrogen-doped graphene fibers for high-performance supercapacitors

Graphene fiber-based supercapacitor has aroused great interest as a flexible power source in future wearable electronics. However, the low electrochemical performance of graphene fibers (GFs) usually causes the serious limitation of use in practical applications due to the material stacking, hydrophobicity and fabrication process complexity. In this work, a facile and effective plasma-assisted strategy is put forward to increase specific surface area, tune hierarchically porous structure and promote wettability of nitrogen-doped graphene fibers (NGFs), resulting in the improvement of electrochemical performance. The supercapacitor assembled from plasma-treated NGFs shows superior capacitance (878 mF/cm² at 0.1 mA/cm² current density) and high energy density (19.5 μW h/cm² at 40 mW/cm² power density), which is 23.7% and 131.4% higher than that of NGFs and GFs, respectively. Additionally, the fiber-based supercapacitor based on plasma-treated NGFs exhibits high rate capability of 59.8% and excellent cyclic performance (95.8% retention over 10,000 cycles). These plasma-treated NGFs can be promising candidates for high-performance and flexible power sources in future wearable electronics.     

Electrochemical deposition of zinc oxide on a thin nickel buffer layer on silicon substrates

Electrochemical deposition of ZnO from aqueous nitrate solutions on nickel and platinum electrodes was investigated using the voltammetry technique to determine the optimal regimes in both potentiostatic and galvanostatic modes for acquiring polycrystalline ZnO films. Scanning electron microscopy, X-ray diffractometry, and X-ray microanalysis of the formed ZnO films are presented, showing a polycrystalline structure of the ZnO films with a preferable orientation in the (0 0 0 2) direction and an exact stoichiometric composition. The deposited ZnO films demonstrate a strong visible yellow-greenish photoluminescence at room temperature with a maximum at 600 nm that can be referred to crystal lattice oxygen defects. The maximum of the photoluminescence excitation spectrum at 370 nm corresponds to the band gap of ZnO (3.3–3.35 eV) confirming that band-to-band excitation mechanism takes place.     

Synthesis of zinc oxide nanostructures on graphene/glass substrate by electrochemical deposition: effects of current density and temperature

The electrochemical growth of zinc oxide (ZnO) nanostructures on graphene on glass using zinc nitrate hexahydrate was studied. The effects of current densities and temperatures on the morphological, structural, and optical properties of the ZnO structures were studied. Vertically aligned nanorods were obtained at a low temperature of 75°C, and the diameters increased with current density. Growth temperature seems to have a strong effect in generating well-defined hexagonal-shape nanorods with a smooth top edge surface. A film-like structure was observed for high current densities above -1.0 mA/cm² and temperatures above 80°C due to the coalescence between the neighboring nanorods with large diameter. The nanorods grown at a temperature of 75°C with a low current density of -0.1 mA/cm² exhibited the highest density of 1.45 × 10⁹ cm^-2. X-ray diffraction measurements revealed that the grown ZnO crystallites were highly oriented along the c-axis. The intensity ratio of the ultraviolet (UV) region emission to the visible region emission, I_UV/I_VIS, showed a decrement with the current densities for all grown samples. The samples grown at the current density below -0.5 mA/cm² showed high I_UV/I_VIS values closer to or higher than 1.0, suggesting their fewer structural defects. For all the ZnO/graphene structures, the high transmittance up to 65% was obtained at the light wavelength of 550 nm. Structural and optical properties of the grown ZnO structures seem to be effectively controlled by the current density rather than the growth temperature. ZnO nanorod/graphene hybrid structure on glass is expected to be a promising structure for solar cell which is a conceivable candidate to address the global need for an inexpensive alternative energy source.