Synthesis of conductive PPy/graphene/rare-earth ions composites and its application in the electrode materials

PPy/graphene/rare-earth ions composites were prepared by in-situ polymerization. The structure and morphology of the composites are characterized by transmission electron microscope and scanning electron microscope, the results revealed that the graphene nanosheets were distributed homogeneously within the PPy matrix. Cyclic voltammetry was used to study the electrochemical properties of composites in K₃Fe(CN)₆ (pH 7.4) at a scan rate of 10 mV s^?1 with a applied voltage range of ?0.2 to 0.6 V, indicating that composite has excellent cycling performance. These results demonstrate the viability of the use of this composites as electrode material for the capacitors.     

Three-dimensional heterostructured MnO2/graphene/carbon nanotube composite on Ni foam for binder-free supercapacitor electrode

In this article, three-dimensional (3D) heterostructured of MnO₂/graphene/carbon nanotube (CNT) composites were synthesized by electrochemical deposition (ELD)-electrophoretic deposition (EPD) and subsequently chemical vapour deposition (CVD) methods. MnO₂/graphene/CNT composites were directly used as binder-free electrodes to investigate the electrochemical performance. To design a novel electrode material with high specific area and excellent electrochemical property, the Ni foam was chosen as the substrate, which could provide a 3D skeleton extremely enhancing the specific surface area and limiting the huge volume change of the active materials. The experimental results indicated that the specific capacitance of MnO₂/graphene/CNT composite was up to 377.1 F g^?1 at the scan speed of 200 mV s^?1 with a measured energy density of 75.4 Wh kg^?1. The 3D hybrid structures also exhibited superior long cycling life with close to 90% specific capacitance retained after 500 cycles.     

“Cubism” on the Nanoscale: From Squaric Acid to Porous Carbon Cubes

3D cube‐shaped composites and carbon microparticles with hierarchically porous structure are prepared by a facile template‐free synthesis route. Via the coordination of zinc acetate dihydrate and squaric acid, porous 3D cubic crystalline particles of zinc squarate can be obtained. These are easily transformed into the respective zinc oxide carbon composites under preservation of the macromorphology by heat treatment. Washing of the composite materials results in hierarchically porous carbons with high surface areas (1295 m² g^–1) and large pore volumes (1.5 cm³ g^?1) under full retention of the cube‐like architecture of the initial crystals. The materials are shown to be promising electrode materials for supercapacitor applications with a specific capacitance of 133 F g^?1 in H₂SO₄ at a scan rate of 5 mV s^?1, while 67% of this specific capacitance is retained, when increasing the scan rate to 200 mV s^?1.     

Super-capacitive performance depending on different crystal structures of MnO2 in graphene/MnO2 composites for supercapacitors

In the present study, we synthesize nanoneedle structures of MnO₂/graphene nanocomposites (N-RGO/MnO₂) and birnessite-type MnO₂/graphene nanocomposites (B-RGO/MnO₂). The morphologies and microstructures of as-prepared composites are characterized by X-ray diffractometry, field-emission scanning electron microscopy, X-ray photoelectron spectroscopy, and thermogravimetric analysis. Our characterizations indicate that nanoneedle structures of MnO₂ and birnessite-type MnO₂ are successfully formed on graphene surfaces. Capacitive properties of the N-RGO/MnO₂ and B-RGO/MnO₂ electrodes are measured using cyclic voltammetry, galvanostatic charge/discharge tests, and electrochemical impedance spectroscopy in a three-electrode experimental setup using a 1 M Na₂SO₄ aqueous solution as the electrolyte. The N-RGO/MnO₂ electrode displays a specific capacitance as high as 327.5 F g^?1 at 10 mV s^?1, which is higher than that of a B-RGO/MnO₂ electrode (248.5 F g^?1). It is believed that the nanoneedle structure of MnO₂ shows excellent electrochemical properties than birnessite-type MnO₂ for the electrode materials for supercapacitors.     

Graphene/MnO2 hybrid nanosheets as high performance electrode materials for supercapacitors

Graphene/MnO₂ hybrid nanosheets were prepared by incorporating graphene and MnO₂ nanosheets in ethylene glycol. Scanning electron microscopy and transmission electron microscopy analyses confirmed nanosheet morphology of the hybrid materials. Graphene/MnO₂ hybrid nanosheets with different ratios were investigated as electrode materials for supercapacitors by cyclic voltammetry (CV) and galvanostatic charge–discharge in 1 M Na₂SO₄ electrolyte. We found that the graphene/MnO₂ hybrid nanosheets with a weight ratio of 1:4 (graphene:MnO₂) delivered the highest specific capacitance of 320 F g⁻¹. Graphene/MnO₂ hybrid nanosheets also exhibited good capacitance retention on 2000 cycles.     

3D Graphene Frameworks/Co3O4 Composites Electrode for High‐Performance Supercapacitor and Enzymeless Glucose Detection

3D graphene frameworks/Co₃O₄ composites are produced by the thermal explosion method, in which the generation of Co₃O₄ nanoparticles, reduction of graphene oxide, and creation of 3D frameworks are simultaneously completed. The process prevents the agglomeration of Co₃O₄ particles effectively, resulting in monodispersed Co₃O₄ nanoparticles scattered on the 3D graphene frameworks evenly. The prepared 3D graphene frameworks/Co₃O₄ composites used as electrodes for supercapacitor display a definite improvement on electrochemical performance with high specific capacitance (≈1765 F g^?1 at a current density of 1 A g^?1), good rate performance (≈1266 F g^?1 at a current density of 20 A g^?1), and excellent stability (≈93% maintenance of specific capacitance at a constant current density of 10 A g^?1 after 5000 cycles). In addition, the composites are also employed as nonenzymatic sensors for the electrochemical detection of glucose, which exhibit high sensitivity (122.16 µA mM ^?1 cm^?2) and noteworthy lower detection limit (157 × 10^?9 M , S/N = 3). Therefore, the authors expect that the 3D graphene frameworks/Co₃O₄ composites described here would possess potential applications as the electrode materials in supercapacitors and nonenzymatic detection of glucose.     

The effect of Ag loading on supercapacitor performance of graphene based nanocomposites

In the present study, we prepared reduced graphene oxide (rGO) decorated with Ag nanoparticles by a one pot, simultaneous reduction method. The effect of AgNO₃ amount on the chemical, morphological and electrochemical properties of binary rGO-Ag nanocomposite for supercapacitor application was investigated. The chemical and morphological characterization of prepared rGO-Ag nanocomposites was realized with field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), ultraviolet-visible spectroscopy (UV-Vis), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). For supercapacitor application, electrochemical performance of the nanocomposites was investigated with cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS) techniques. As a result of their excellent conductivity and spacer role which prevent aggregation of rGO nanosheets and maintain the electroactive surface area, Ag nanoparticles significantly enhance the electrochemical performance of the nanocomposite. The rGO-Ag nanoparticle nanocomposite exhibited a maximum specific capacitance of 34.2?mF?cm^?2 at 0.6?A?cm^?2 current density. The nanocomposite electrode also has excellent rate capability and cycle life. The capacitance retention of rGO-Ag electrode is 98% after 1000 charge-discharge cycle. The results showed that rGO-Ag nanocomposite is a building block for ternary or other multicomponent nanocomposites.     

An Electrosynthesized 3D Porous Molybdenum Sulfide/Graphene Film with Enhanced Electrochemical Performance for Lithium Storage

Molybdenum sulfide/graphene composites are promising anode materials for lithium‐ion batteries (LIBs). In this work, MoS_x/graphene composite film with an ideal 3D porous structure is developed via a facile and straightforward electrochemical route. The MoS_x nanoparticles are uniformly anchored on the graphene nanosheets that are randomly arranged, resulting in MoS_x/graphene composites with well‐developed porous structure. Benefiting from such structure and the synergistic effect from two components, this material shows a high specific capacity over 1200 mA h g^?1, an excellent rate performance, and superior cycling stability. The dominating pseudocapacitive behavior in Li storage contributes to the outstanding rate capacity. Importantly, this kind of novel material can be easily produced as 3D microelectrodes for microscaled LIBs that are highly demanded for autonomous microelectronic systems.     

Chemical adsorption of NiO nanostructures on nickel foam-graphene for supercapacitor applications

Few-layer graphene was synthesized on a nickel foam template by chemical vapor deposition. The resulting three-dimensional (3D) graphene was loaded with nickel oxide nanostructures using the successive ionic layer adsorption and reaction technique. The composites were characterized and investigated as electrode material for supercapacitors. Raman spectroscopy measurements on the sample revealed that the 3D graphene consisted of mostly few layers, while X-ray diffractometry and scanning electron microscopy revealed the presence of nickel oxide. The electrochemical properties were investigated using cyclic voltammetry, electrochemical impedance spectroscopy, and potentiostatic charge–discharge in aqueous KOH electrolyte. The novelty of this study is the use of the 3D porous cell structure of the nickel foam which allows for the growth of highly conductive graphene and subsequently provides support for uniform adsorption of the NiO onto the graphene. The NF-G/NiO electrode material showed excellent properties as a pseudocapacitive device with a high-specific capacitance value of 783 F g^?1 at a scan rate of 2 mV s^?1. The device also exhibited excellent cycle stability, with 84 % retention of the initial capacitance after 1000 cycles. The results demonstrate that composites made using 3D graphene are versatile and show considerable promise as electrode materials for supercapacitor applications.     

Facile synthesis of poly(Safranine T)/Reduced graphene oxide nanocomposite for supercapacitors with wide potential window in aqueous neutral electrolyte

A facile method is introduced for incorporating reduced graphene oxide (rGO) into poly(safranine T) (PST) films. First, ST-functionalized GO (ST/GO) was obtained via the absorption of ST on GO in pH 7.0 phosphate buffer solution. Then rGO/PST composite was synthesized by the electropolymerization of ST and the subsequent electrochemical reduction of GO. The as-prepared PST/rGO composite films are characterized using scanning electron microscope, X-ray diffraction, and Fourier transform–infrared spectroscopy. PST/rGO composites possess a microporous structure, which creates enormous amount of pores, and therefore provides larger interfaces for charge carrier. The properties of electrochemical capacitance for PST/rGO composites have also been investigated with cyclic voltammetry (CV) and galvanostatic charge–discharge measurements. The experimental results manifest that the PST/rGO composite showed high capacitance (293.2 F g^?1) at 20-mV s^?1 CV scan and an excellent cycling stability (8.3% drop after 1000 cycles) in 0.1 M Na₂SO₄ electrolyte.     

Vertically Oriented Graphene Nanoribbon Fibers for High‐Volumetric Energy Density All‐Solid‐State Asymmetric Supercapacitors

Graphene fiber based micro‐supercapacitors (GF micro‐SCs) have attracted great attention for their potential applications in portable and wearable electronics. However, due to strong π–π stacking of nanosheets for graphene fibers, the limited ion accessible surface area and slow ion diffusion rate leads to low specific capacitance and poor rate performance. Here, the authors report a strategy for the synthesis of a vertically oriented graphene nanoribbon fiber with highly exposed surface area through confined‐hydrothermal treatment of interconnected graphene oxide nanoribbons and consequent laser irradiation process. As a result, the as‐obtained fiber shows high length specific capacitance of 3.2 mF cm^?1 and volumetric capacitance of 234.8 F cm^?3 at 2 mV s^?1, as well as excellent rate capability and outstanding cycling performance (96% capacitance retention after 10 000 cycles). Moreover, an all‐solid‐state asymmetric supercapacitor based on graphene nanoribbon fiber as negative electrode and MnO₂ coated graphene ribbon fiber as positive electrode, shows high volumetric capacitance and energy density of 12.8 F cm^?3 and 5.7 mWh cm^?3 (normalized to the device volume), respectively, much higher than those of previously reported GF micro‐SCs, as well as a long cycle life with 88% of capacitance retention after 10 000 cycles.     

The influence of Graphene quality on performance of a Si/Graphene nanocomposite anode

Si/Graphene nanoparticles represent attractive alternative anode materials for Lithium-ion batteries. Graphene nanosheets with different properties, including surface area, defect distance, and charge-transfer resistance, were fabricated and characterised in Si/Graphene nanocomposites formed by static-electric self-assembly then by an in-situ reduction process. Graphene nanosheets that exhibited the highest surface area, the shortest defect distance, and the lowest charge-transfer resistance demonstrated the best overall electrochemical performance, with a high initial discharge capacity of 2692?mAh?g^?1, good cycling performance of 1135?mAh?g^?1, at the 200th cycle at the current rate of 0.5?C. This work shows the preferable graphene quality for Si/Graphene nanocomposite anode and provides insights into the design of graphene nanocomposite electrodes, regardless of the graphene synthesis method.     

High-performance asymmetric supercapacitors based on reduced graphene oxide/polyaniline composite electrodes with sandwich-like structure

The sandwich-like structure of reduced graphene oxide/polyaniline(RGO/PANI) hybrid electrode was prepared by electrochemical deposition. Both the voltage windows and electrolytes for electrochemical deposition of PANI and RGO were optimized. In the composites, PANI nanofibers were anchored on the surface of the RGO sheets, which avoids the re-stacking of neighboring sheets. The RGO/PANI composite electrode shows a high specific capacitance of 466 F/g at 2 m A/cm~2 than that of previously reported RGO/PANI composites. Asymmetric flexible supercapacitors applying RGO/PANI as positive electrode and carbon fiber cloth as negative electrode can be cycled reversibly in the high-voltage region of 0–1.6 V and displays intriguing performance with a maximum specific capacitance of 35.5 m F cm~(-2). Also, it delivers a high energy density of 45.5 m W h cm~(-2) at power density of 1250 m W cm~(-2). Furthermore, the asymmetric device exhibits an excellent long cycle life with 97.6% initial capacitance retention after 5000 cycles.Such composite electrode has a great potential for applications in flexible electronics, roll-up display,and wearable devices.     

Polyaniline Derived N‐Doped Carbon‐Coated Cobalt Phosphide Nanoparticles Deposited on N‐Doped Graphene as an Efficient Electrocatalyst for Hydrogen Evolution Reaction

The development of highly efficient and durable non‐noble metal electrocatalysts for the hydrogen evolution reaction (HER) is significant for clean and renewable energy research. This work reports the synthesis of N‐doped graphene nanosheets supported N‐doped carbon coated cobalt phosphide (CoP) nanoparticles via a pyrolysis and a subsequent phosphating process by using polyaniline. The obtained electrocatalyst exhibits excellent electrochemical activity for HER with a small overpotential of ?135 mV at 10 mA cm^?2 and a low Tafel slope of 59.3 mV dec^?1 in 0.5 m H₂SO₄. Additionally, the encapsulation of N‐doped carbon shell prevents CoP nanoparticles from corrosion, exhibiting good stability after 14 h operation. Moreover, the as‐prepared electrocatalyst also shows outstanding activity and stability in basic and neutral electrolytes.     

Facile preparation and electrochemical characterization of graphene/ZnO nanocomposite for supercapacitor applications

Graphene/ZnO nanocomposites were successfully synthesized by microwave-assisted method. The structure, morphology, optical and composition of the obtained samples were characterized using XRD, FT-IR, laser Raman, UV–Vis spectroscopy and XPS analysis. XRD analysis confirmed the presence of graphene/ZnO nanocomposite. FE-SEM image reveals that the homogenous distribution of ZnO nanoparticles on the graphene nanosheets. The electrochemical properties of the graphene/ZnO electrodes were analyzed by cyclic voltammetry and impedance spectroscopy. The results confirmed that the incorporation of ZnO nanoparticles enhanced the capacitive performance of graphene electrode. Graphene/ZnO nanocomposite electrode showed higher capacitance value of 109 F g⁻¹ at a scan rate of 5 mV s⁻¹ in 1 M KCl solution as compared to the graphene electrodes. These results demonstrated the importance and great potential of graphene based composites in the development of high-performance energy-storage systems.     

In Situ Formation of Hierarchical Bismuth Nanodots/Graphene Nanoarchitectures for Ultrahigh‐Rate and Durable Potassium‐Ion Storage

Metallic bismuth (Bi) has been widely explored as remarkable anode material in alkali‐ion batteries due to its high gravimetric/volumetric capacity. However, the huge volume expansion up to ≈406% from Bi to full potassiation phase K₃Bi, inducing the slow kinetics and poor cycling stability, hinders its implementation in potassium‐ion batteries (PIBs). Here, facile strategy is developed to synthesize hierarchical bismuth nanodots/graphene (BiND/G) composites with ultrahigh‐rate and durable potassium ion storage derived from an in situ spontaneous reduction of sodium bismuthate/graphene composites. The in situ formed ultrafine BiND (≈3 nm) confined in graphene layers can not only effectively accommodate the volume change during the alloying/dealloying process but can also provide high‐speed channels for ionic transport to the highly active BiND. The BiND/G electrode provides a superior rate capability of 200 mA h g^?1 at 10 A g^?1 and an impressive reversible capacity of 213 mA h g^?1 at 5 A g^?1 after 500 cycles with almost no capacity decay. An operando synchrotron radiation‐based X‐ray diffraction reveals distinctively sharp multiphase transitions, suggesting its underlying operation mechanisms and superiority in potassium ion storage application.     

Fast Gelation of Ti3C2Tx MXene Initiated by Metal Ions

Gelation is an effective way to realize the self‐assembly of nanomaterials into different macrostructures, and in a typical use, the gelation of graphene oxide (GO) produces various graphene‐based carbon materials with different applications. However, the gelation of MXenes, another important type of 2D materials that have different surface chemistry from GO, is difficult to achieve. Here, the first gelation of MXenes in an aqueous dispersion that is initiated by divalent metal ions is reported, where the strong interaction between these ions and ? OH groups on the MXene surface plays a key role. Typically, Fe²⁺ ions are introduced in the MXene dispersion which destroys the electrostatic repulsion force between the MXene nanosheets in the dispersion and acts as linkers to bond the nanosheets together, forming a 3D MXene network. The obtained hydrogel effectively avoids the restacking of the MXene nanosheets and greatly improves their surface utilization, resulting in a high rate performance when used as a supercapacitor electrode (≈226 F g^?1 at 1 V s^?1). It is believed that the gelation of MXenes indicates a new way to build various tunable MXene‐based structures and develop different applications.     

Incorporating Nitrogen‐Doped Graphene Quantum Dots and Ni3S2 Nanosheets: A Synergistic Electrocatalyst with Highly Enhanced Activity for Overall Water Splitting

A noble‐metal‐free electrocatalyst is fabricated via in situ formation of nanocomposite of nitrogen‐doped graphene quantum dots (NGQDs) and Ni₃S₂ nanosheets on the Ni foam (Ni₃S₂‐NGQDs/NF). The resultant Ni₃S₂‐NGQDs/NF can serve as an active, binder‐free, and self‐supported catalytic electrode for direct water splitting, which delivers a current density of 10 mA cm^?2 at an overpotential of 216 mV for oxygen evolution reaction and 218 mV for hydrogen evolution reaction in alkaline media. This bifunctional electrocatalyst enables the construction of an alkali electrolyzer with a low cell voltage of 1.58 V versus reversible hydrogen electrode (RHE) at 10 mA cm^?2. The experimental results and theoretical calculations demonstrate that the synergistic effects of the constructed active interfaces are the key factor for excellent performance. The nanocomposite of NGQDs and Ni₃S₂ nanosheets can be promising water splitting electrocatalyst for large‐scale hydrogen generation or other energy storage and conversion applications.     

Preparation of graphene nanosheets/SnO2 composites by pre-reduction followed by in-situ reduction and their electrochemical performances

The Graphene nanosheets/SnO₂ composites were synthesized using stannous chloride to restore the semi-reduction graphene oxide (SRGO) under a simple hydrothermal reduction procedure. First graphene oxide was pre-reduced by glucose for a certain time to get SRGO, which keeps the good water-solubility of graphite oxide (GO) and has a good conductivity like graphene nanosheets. The higher electrostatic attraction between SRGO and Sn²⁺ makes SnO₂ nanoparticles tightly anchor on the graphene sheets in the hydrothermal reduction process. The formation mechanism of the composite was investigated by SEM, TEM, XRD, AFM and Raman. Moreover, the electrochemical behaviors of the Graphene nanosheets/SnO₂ nanocomposites were studied by cyclic voltammogram, electrical impedance spectroscopy (EIS) and chronopotentiometry. Results showed that the Graphene nanosheets/SnO₂ composites have excellent supercapacitor performances: the specific capacitance reached 368 F g⁻¹ at a current density of 5 mA cm⁻², and the energy density was much improved to 184 Wh kg⁻¹ with a power density of 16 kW kg⁻¹, and capacity retention was more than 95% after cycling 500 cycles with a constant current density of 50 mA cm⁻². The experimental results and the thorough analysis described in this work not only provide a potential electrode material for supercapacitors but also give us a new way to solve the reunification of the graphene sheets.     

CuS nanoplatelets arrays grown on graphene nanosheets as advanced electrode materials for supercapacitor applications

CuS nanoplatelets arrays grown on graphene nanosheets are successfully synthesized via a facile low-temperature solvothermal reaction with graphene oxide (GO), CH₃CSNH₂ and Cu(CH₃COO)₂·H₂O as the reactants. CH₃CSNH₂ plays an important role in being the reducing agent for GO and the sulfur source of CuS. Supercapacitive performance of the graphene/CuS nanocomposite as active electrode materials has been evaluated by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy measurements. The results indicate that graphene/CuS electrode delivers a high capacitance of 497.8 F g^–1 at a current density of 0.2 A g^–1, which outperforms bare CuS electrode. This excellent performance is ascribed to the short diffusion path and large surface area of the unique hierarchical nanostructure with nanoflakes building blocks for bulk accessibility of faradaic reaction.