In-situ synthesis and characterization of electrically conductive polypyrrole/graphene nanocomposites

Polypyrrole (PPy)/graphene (GR) nanocomposites were successfully prepared via in-situ polymerization of graphite oxide (GO) and pyrrole monomer followed by chemical reduction using hydrazine monohydrate. The large surface area and high aspect ratio of the in-situ generated graphene played an important role in justifying the noticeable improvements in electrical conductivity of the prepared composites via chemical reduction. X-ray photoelectron spectroscopy (XPS) analysis revealed the removal of oxygen functionality from the GO surface after reduction and the bonding structure of the reduced composites were further determined from FTIR and Raman spectroscopic analysis. For PPy/GR composite, intensity ratio between D band and G band was high (∼1.17), indicating an increased number of c-sp² domains that were formed during the reduction process. A reasonable improvement in thermal stability of the reduced composite was also observed. Transmission electron microscopy (TEM) observations indicated the dispersion of the graphene nanosheets within the PPy matrix.     

Potentiostatically deposited polypyrrole/graphene decorated nano-manganese oxide ternary film for supercapacitors

A simple method based on potentiostatic polymerization was developed for the preparation of ternary manganese oxide-based nanocomposite films. The ternary nanocomposites, which were characterized using x-ray diffraction spectroscopy and x-ray photoelectron spectroscopy, showed that the manganese oxide within the film consisted of MnO₂ and Mn₂O₃. Electrochemical measurements showed that the ternary nanocomposite electrode exhibited high specific capacitance (up to 320.6 F/g), which was attributed to the morphology of a polypyrrole/graphene/manganese-oxide (PPy/GR/MnO_x) ternary nanocomposite. The experimental approach maximized the pseudocapacitive contribution from redox-active manganese oxide (MnO_x) and polypyrrole (PPy), as well as the electrochemical double layer capacitive (EDLC) characteristic from graphene (GR) sheets. Long cyclic measurements indicated that the specific capacitance of the ternary nanocomposite film could retain 93% of its initial value over 1000 charge/discharge cycles, in the potential range of −0.2 to 0.7 V versus silver/silver chloride electrode (Ag/AgCl).     

Effect of 2D MoS2 and Graphene interfaces with CoSb3 nanoparticles in enhancing thermoelectric properties of 2D MoS2-CoSb3 and Graphene-CoSb3 nanocomposites

The approach of incorporating a secondary phase in the bulk thermoelectric (TE) material has proved to be beneficial for enhancing the thermoelectric performance. We have investigated the effect of the presence of two-dimensional (2D) materials (MoS₂ or graphene) on the structural, electrical, and thermoelectric properties of CoSb₃ nanocomposite, in which CoSb₃ nanoparticles of sizes 20–50?nm are uniformly anchored on the surface of 2D-sheets of MoS₂ or graphene. The presence of 2D nanosheets enhances TE power factor and figure of merit (ZT). Inclusion of graphene in CoSb₃ causes large enhancement in power factor as a result of significantly high electrical conductivity and appreciable Seebeck coefficient. 2D graphene seems to work by providing extra carrier conduction channels along with a low interfacial potential barrier for charge transport. Homogeneously dispersed 2D-sheets of MoS₂ in CoSb₃ seem to cause interfacial modulation of charge carrier effective mass assisted by relatively larger interfacial barrier to result in significantly larger Seebeck coefficient and highly suppressed phonon conductivity, much more than graphene. The ZT value in both nanocomposites gets significantly enhanced in the entire studied temperature range of 300–700?K, the gain increasing with temperature over the CoSb₃. Whereas CoSb₃/graphene nanocomposites exhibit unusually high ZT at higher temperatures (550–700?K), the CoSb₃/2D-MoS₂ nanocomposites exhibit better performance (over graphene) in near room temperature range. The present study provides a possible strategy to enhance the conversion efficiency of various TE materials and has significant potential for waste heat recovery applications in various temperature ranges.     

Microwave-assisted one-pot synthesis of SnC2O4/graphene composite anode material for lithium-ion batteries

Currently, SnC₂O₄ is considered as one of the most promising anode materials for high-energy lithium-ion batteries (LIBs) because its charge capacity is higher than that of metal oxides. Herein, a facile microwave-assisted solvothermal method was employed to obtain SnC₂O₄/GO composites within only 30?min, which is time-efficient. The amount of SnC₂O₄ was increased to 95.3?wt% to improve the capacity of the composite. Pure SnC₂O₄ with a high specific surface area of 19.6?m² g^?1 without any other tin compound was used for fabrication. The SnC₂O₄/GO composite exhibited excellent electrochemical performance, with reversible discharge/charge capacity of 657/659?mA?h?g^?1 after 100 cycles at 0.2?A?g^?1. Furthermore, at high current densities of 1.0 and 2.0?A?g^?1, the SnC₂O₄/GO composite anode exhibited high reversible discharge/charge capacities of 553/552 and 418/414?mA?h?g^?1, respectively, after 200 cycles at room temperature. These improvements were likely obtained because SnC₂O₄ was well composited with graphene, which not only offered rapid electron transfer but also released the tension produced by the volumetric effect during repeated lithiation/delithiation. Cyclic voltammetry (CV) was also performed to further study the electrochemical reactions of SnC₂O₄/GO. The facile microwave-assisted solvothermal method used herein is considered as a highly efficient method to fabricate metal oxalate/graphene composites for use as anode materials in LIBs.     

Grain growth kinetics in microwave sintered graphene platelets reinforced ZrO2/Al2O3 composites

The grain growth kinetics and mechanical properties of graphene platelets(GPLs) reinforced ZrO₂/Al₂O₃(ZTA) composites prepared by microwave sintering were investigated. The calculated grain growth kinetics exponent n indicated that the GPLs could accelerate the process of the Al₂O₃ columnar crystal growth. And the grain growth activation energy of the Al₂O₃ columnar crystal indicated that the grain growth activation energy of the GPLs doped ZTA composites is much higher than those of pure Al₂O₃ and ZTA in microwave sintering. The optimal mechanical properties were achieved with 0.4?vol% GPLs, whose relative density, Vickers hardness and fracture toughness were 98.76%, 18.10?GPa and 8.86?MPa?m^1/2, respectively. The toughening mechanisms were crack deflection, bridging, branching and pull-out of GPLs. The results suggested that GPLs-doped are good for the Al₂O₃ columnar crystal growth in the ZTA ceramic and have a potentially improvement for the fracture toughness of the ceramics.     

H2 sorption in HCl-treated polyaniline and polypyrrole

Hydrogen sorption in conducting polymers was investigated in order to determine their potential as hydrogen storage media. The conducting polymers, polyaniline and polypyrrole, were treated with an acid, which resulted in an exceptionally high hydrogen sorption, 6 and 8 wt% at room temperature and under 9.3 MPa. Both the molecular effect and electrical effects by the conducting polymers appear to play an important role in hydrogen sorption. This paper presents the preliminary results of hydrogen sorption in a conducting polymer along with its characterization by XRD, scanning electron microscopy, TGA, and conductivity measurement using a four-probe method. A possible mechanism for the extraordinarily high hydrogen storage is suggested.     

High reversible capacity of SnO2/graphene nanocomposite as an anode material for lithium-ion batteries

A gas–liquid interfacial synthesis approach has been developed to prepare SnO₂/graphene nanocomposite. The as-prepared nanocomposite was characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, and Brunauer–Emmett–Teller measurements. Field emission scanning electron microscopy and transmission electron microscopy observation revealed the homogeneous distribution of SnO₂ nanoparticles (2–6 nm in size) on graphene matrix. The electrochemical performances were evaluated by using coin-type cells versus metallic lithium. The SnO₂/graphene nanocomposite prepared by the gas–liquid interface reaction exhibits a high reversible specific capacity of 1304 mAh g⁻¹ at a current density of 100 mA g⁻¹ and excellent rate capability, even at a high current density of 1000 mA g⁻¹, the reversible capacity was still as high as 748 mAh g⁻¹. The electrochemical test results show that the SnO₂/graphene nanocomposite prepared by the gas–liquid interfacial synthesis approach is a promising anode material for lithium-ion batteries.     

Improvement of cycle performance of lithium ion cell LiMn2O4/LixV2O5 with aqueous solution electrolyte by polypyrrole coating on anode

The reasons of capacity fading during cycling process of LiMn₂O₄/Li_xV₂O₅ lithium ion cell with 5 M LiNO₃ aqueous solution as electrolyte were investigated. XRD and ICP results showed that the properties of the anode have more impact on the cycle life of the cell. In an attempt to improve the cycle performance of the as-assembled cell, coating with an ionic conductive polypyrrole (PPy) on the surface of the anode was proposed via in situ polymerization method. Cycling tests revealed that the stability of the lithium ion cell with surface coated anode has been greatly improved. Moreover, the capability of the cell with coated anode was also enhanced compared with the cell with bare anode.     

Performance evaluation of CNT/polypyrrole/MnO2 composite electrodes for electrochemical capacitors

A ternary composite of CNT/polypyrrole/hydrous MnO₂ is prepared by in situ chemical method and its electrochemical performance is evaluated by using cyclic voltammetry (CV), impedance measurement and constant-current charge/discharge cycling techniques. For comparative purpose, binary composites such as CNT/hydrous MnO₂ and polypyrrole/hydrous MnO₂ are prepared and also investigated for their physical and electrochemical performances. The specific capacitance (SC) values of the ternary composite, CNT/hydrous MnO₂ and polypyrrole/hydrous MnO₂ binary composites estimated by CV technique in 1.0 M Na₂SO₄ electrolyte are 281, 150 and 35 F g⁻¹ at 20 mV s⁻¹ and 209, 75 and 7 F g⁻¹ at 200 mV s⁻¹, respectively. The electrochemical stability of ternary composite electrode is investigated by switching the electrode back and forth for 10,000 times between 0.1 and 0.9 V versus Ag/AgCl at 100 mV s⁻¹. The electrode exhibits good cycling stability, retaining up to 88% of its initial charge at 10,000th cycle. A full cell assembled with the ternary composite electrodes shows a SC value of 149 F g⁻¹ at a current loading of 1.0 mA cm⁻² during initial cycling, which decreased drastically to a value of 35 F g⁻¹ at 2000th cycle. Analytical techniques such as scanning electron microscopy (SEM), X-ray diffraction spectroscopy (XRD), Brunauer-Emmet-Teller (BET) surface area measurement and inductively coupled plasma-atomic emission spectrometry (ICP-AES) are also used to characterize the composite materials.     

Solvothermal synthesis of SnO2/graphene nanocomposites for supercapacitor application

A facile solvent-based synthesis route based on the oxidation–reduction reaction between graphene oxide (GO) and SnCl₂·2H₂O has been developed to synthesize SnO₂/graphene (SnO₂/G) nanocomposites. The reduction of GO and the in situ formation of SnO₂ nanoparticles were achieved in one step. Characterization by X-ray diffraction (XRD), ultraviolet-visible (UV–vis) absorption spectroscopy, Raman spectroscopy, and field emission scanning electron microscopy (FESEM) confirmed the feasibility of using the solvothermally treated reaction system to simultaneously reduce GO and form SnO₂ nanoparticles with an average particle size of 10 nm. The electrochemical performance of SnO₂/graphene showed an excellent specific capacitance of 363.3 F/g, which was five-fold higher than that of the as-synthesized graphene (68.4 F/g). The contributing factors were the synergistic effects of the excellent conductivity of graphene and the nanosized SnO₂ particles.     

Electrochemical characteristics of porous TiO2 encapsulated silicon anode

TiO₂ coated silicon, which was prepared by the modified sol–gel method, was employed as the anode material for lithium secondary batteries and the relationship between the diffusivity and electrochemical characteristics was investigated. The results showed that the physical properties of the samples, such as their diffusivity and pore size distribution, enhanced the cycling efficiency of the TiO₂ coated silicon, probably due to the reduction of the side reactions, which may be closely related to the pore size distribution of the TiO₂ coating layer. The pore size of the coating layer plays an important role in retarding the lithium ion diffusion. In the experimental range studied herein, higher capacity retention was exhibited for the TiO₂ coated silicon prepared at pH 10.7.     

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。     

Efficient construction of a CoCO3/graphene composite anode material for lithium-ion batteries by stirring solvothermal reaction

Transition-metal carbonates have recently been investigated as anode materials for lithium-ion batteries because of their relatively high capacity compared with that of the corresponding transition-metal oxides. In this work, a facile stirring solvothermal reaction is used to prepare a CoCO₃/graphene composite without the use of an additional organic chelating agent. The as-prepared CoCO₃/graphene composite exhibits a smaller cubic particle size of 1–2 µm and a larger specific surface area than the composite obtained by a traditional solvothermal reaction. The composite prepared with stirring delivers a highly reversible capacity of 602 mAh g^?1 after 100 cycles. Even at a high current density of 2.0 A g^?1, the composite maintains charge–discharge capacities of 605/598 mAh g^?1. The composites contained the same amount of graphene, indicating that the improved electrochemical properties are attained independently of the amount of the graphene. In addition, the results of cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS)experiments also reveal that the CoCO₃/graphene composite electrode materials synthesised via a stirring solvothermal reaction exhibit substantially enhanced kinetics. The stirring solvo/hydrothermal reaction develops in this work is considered a promising candidate for efficiently preparing carbonate/graphene composites with better electrochemical properties for practical applications, without the use of an extra chelating agent.     

Nb2O5 nanospheres/surface-modified graphene composites as superior anode materials in lithium ion batteries

Uniform Nb₂O₅ nanospheres/surface-modified graphene (SMG) composites for anode materials in lithium ion batteries were synthesized by hydrothermal method. The microstructure and morphology of composites were investigated by X-ray diffraction, scanning electron microscopy and transmission electron microscope techniques. The experimental results showed that Nb₂O₅ nanospheres were tightly and uniformly grown on the surface of SMG nanosheets. Nb₂O₅ nanospheres/SMG composites exhibited an impressive reversible capacity of 404.6 mA h g⁻¹ at the current density of 40 mA g⁻¹ after 100 cycles, and an excellent rate capacity of 345.5 mA h g⁻¹ at the current density of 400 mA g⁻¹.     

One-step hydrothermal synthesis and enhanced microwave absorption properties of Ni0.5Co0.5Fe2O4/graphene composites in low frequency band

Ni_0.5Co_0.5Fe₂O₄/graphene composites were synthesized successfully via one-step hydrothermal method. The crystal structure, morphology and corresponding elemental distribution, electromagnetic parameters and microwave absorption performances of the as-prepared composites were measured by XRD, SEM, TEM and VNA, respectively. The results indicated that the microwave absorbing performance can be obviously enhanced through the addition of graphene in a suitable range, the magnetic loss plays a dominant contribution for the microwave absorption of composites. The maximum reflection loss of ?30.92?dB at 0.84?GHz with a ?10?dB bandwidth over the frequency range of 0.58–1.19?GHz is obtained when the composite contains 12?wt% graphene and the thickness of sample is 4?mm. This investigation presents a simple method to prepare Ni_0.5Co_0.5Fe₂O₄/graphene composites with excellent microwave absorption performance in the low frequency band of 0.1–3?GHz.     

Evidence of redox interactions between polypyrrole and Fe3O4 in polypyrrole-Fe3O4 composite films

The electrical properties of conducting polymers make them useful materials in a wide number of technological applications. In the last decade, an important effect on the properties of the conducting polymer when iron oxides particles are incorporated into the conductive matrix was shown. In the present study, films of polypyrrole were synthesized in the presence of magnetite particles. The effect of the magnetite particles on the structure of the polymer matrix was determined using Raman spectroscopy. Mass variations at different concentrations of Fe₃O₄ incorporated into the conducting matrix were also measured by means of quartz crystal microbalance. Additionally, the changes in the resistance of the films were evaluated over time by electrochemical impedance spectroscopy in solid state. These results show that the magnetite incorporation decreases polymeric film resistance and Raman experiments have evidenced that the incorporation of magnetite into polymeric matrix not only stabilizes the polaronic form of the polypyrrole, but also preserves the polymer from further oxidation.     

Electrocatalytic activity of electrodeposited composite films of polypyrrole and CoFe2O4 nanoparticles towards oxygen reduction reaction

Electrochemical behaviour of sandwich-type composite electrodes of polypyrrole (PPy) and CoFe₂O₄ nanoparticles (Ox) were investigated in an aqueous solution of 0.5 M K₂SO₄ and 5mM KOH at 25 °C using electrochemical impedance (EI), cyclic voltammetry (CV) and Tafel polarization techniques. EI and CV studies indicated that the incorporation of oxide nanoparticles influenced the charge transfer and transport behaviours of the polymer matrix greatly. The bulk electrical resistances of pure polymer (4.5 ± 1.7 Ω) as well as composite (2.7 ± 0.8 Ω) electrodes were practically constant in the potential region, +0.1 to −0.7 V. The latter electrode showed a good electrocatalytic activity towards the oxygen reduction reaction (ORR).     

The role of graphene and europium on TiO2 performance for photocatalytic hydrogen evolution

Highly efficient Eu-TiO₂/graphene composites were synthesized by a two-step method such as sol-gel and hydrothermal process. The synthesized photocatalysts were characterized by XRD, TEM, XPS, UV–vis diffuse reflectance spectroscopy and photoluminescence (PL) spectroscopy. The results confirmed that anatase Eu-TiO₂ nanoparticles with average 10 nm sizes were successfully deposited on two-dimensional graphene sheets. The UV–visible spectroscopy showed a red shift in the absorption edge of TiO₂ due to Eu doping and graphene incorporation. Moreover, effective charge separation in Eu-TiO₂/graphene composites was confirmed by PL emission spectroscopy compared to TiO₂/graphene, Eu-TiO₂ and pure TiO₂. The photocatalytic activity for H₂ evolution over prepared composites was studied under visible light irradiation (λ ≥ 400 nm). The results demonstrate that photocatalytic performance of the photocatalysts for hydrogen production increases with increasing doping concentration of Eu upto 2 at%. However, further increase in doping content above this optimum level has decreased the performance of photocatalyst. The enhanced photocatalytic performance for H₂ evolution is attributed to extended visible light absorption, suppressed recombination of electron-hole pairs due to synergistic effects of Eu and graphene.     

Rapid microwave-assisted synthesis of graphene nanosheet/Co3O4 composite for supercapacitors

Graphene nanosheet (GNS)/Co₃O₄ composite has been rapidly synthesized by microwave-assisted method. Field emission scanning electron microscopy and transmission electron microscopy observation reveals the homogeneous distribution of Co₃O₄ nanoparticles (3-5 nm in size) on graphene sheets. Electrochemical properties are characterized by cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy. A maximum specific capacitance of 243.2 F g⁻¹ has been obtained at a scan rate of 10 mV s⁻¹ in 6 M KOH aqueous solution for GNS/Co₃O₄ composite. Furthermore, the composite exhibits excellent long cycle life along with ∼95.6% specific capacitance retained after 2000 cycle tests.     

Mesoporous polyaniline or polypyrrole/anatase TiO2 nanocomposite as anode materials for lithium-ion batteries

A functional composite as anode materials for lithium-ion batteries, which contains highly dispersed TiO₂ nanocrystals in polyaniline matrix and well-defined mesopores, is fabricated by employing a novel one-step approach. The as-prepared mesoporous polyaniline/anatase TiO₂ nanocomposite has a high specific surface area of 224 m² g⁻¹ and a predominant pore size of 3.6 nm. The electrochemical performance of the as-prepared composite as anode material is investigated by cyclic voltammograms and galvanostatic method. The results demonstrate that the polyaniline/anatase nanocomposite provides larger initial discharge capacity of 233 mAh g⁻¹ and good cycle stability at the high current density of 2000 mA g⁻¹. After 70th cycles, the discharge capacity is maintained at 140 mAh g⁻¹. The excellent electrochemical performance of the polyaniline/TiO₂ nanocomposite is mainly attributed to its special structure. Furthermore, it is accessible to extend the novel strategy to other polymer/TiO₂ composites, and the mesoporous polypyrrole/anatase TiO₂ is also successfully fabricated.