This paper presents a review of the research progress in the carbon–metal oxide composites for supercapacitor electrodes. In the past decade, various carbon–metal oxide composite electrodes have been developed by integrating metal oxides into different carbon nanostructures including zero-dimensional carbon nanoparticles, one-dimensional nanostructures (carbon nanotubes and carbon nanofibers), two-dimensional nanosheets (graphene and reduced graphene oxides) as well as three-dimensional porous carbon nano-architectures. This paper has described the constituent, the structure and the properties of the carbon–metal oxide composites. An emphasis is placed on the synergistic effects of the composite on the performance of supercapacitors in terms of specific capacitance, energy density, power density, rate capability and cyclic stability. This paper has also discussed the physico-chemical processes such as charge transport, ion diffusion and redox reactions involved in supercapacitors.

Nanostructured carbon–metal oxide composite electrodes for supercapacitors: a review

In recent years, tremendous research effort has been aimed at increasing the energy density of supercapacitors without sacrificing high power capability so that they reach the levels achieved in batteries and at lowering fabrication costs For this purpose, two important problems have to be solved: first, it is critical to develop ways to design high performance electrode materials for supercapacitors; second, it is necessary to achieve controllably assembled supercapacitor types (such as symmetric capacitors including double-layer and pseudo-capacitors, asymmetric capacitors, and Li-ion capacitors) The explosive growth of research in this field makes this review timely Recent progress in the research and development of high performance electrode materials and high-energy supercapacitors is summarized Several key issues for improving the energy densities of supercapacitors and some mutual relationships among various effecting parameters are reviewed, and challenges and perspectives in this exciting field are also discussed This provides fundamental insight into supercapacitors and offers an important guideline for future design of advanced next-generation supercapacitors for industrial and consumer applications

Recent Advances in Design and Fabrication of Electrochemical Supercapacitors with High Energy Densities

Heteroatom doping can endow graphene with various new or improved electromagnetic, physicochemical, optical, and structural properties. This greatly extends the arsenal of graphene materials and their potential for a spectrum of applications. Considering the latest developments, we comprehensively and critically discuss the syntheses, properties and emerging applications of the growing family of heteroatom-doped graphene materials. The advantages, disadvantages, and preferential doping features of current synthesis approaches are compared, aiming to provide clues for developing new and controllable synthetic routes. We emphasize the distinct properties resulting from various dopants, different doping levels and configurations, and synergistic effects from co-dopants, hoping to assist a better understanding of doped graphene materials. The mechanisms underlying their advantageous uses for energy storage, energy conversion, sensing, and gas storage are highlighted, aiming to stimulate more competent applications.

/pdf/heteroatom-doped-graphene-materials-syntheses-properties-and-2gkc1nc0vf.pdf

Heteroatom-doped graphene materials: syntheses, properties and applications

A lightweight, flexible, and highly efficient energy management strategy is needed for flexible energy-storage devices to meet a rapidly growing demand. Graphene-based flexible supercapacitors are one of the most promising candidates because of their intriguing features. In this report, we describe the use of freestanding, lightweight (0.75 mg/cm2), ultrathin (<200 μm), highly conductive (55 S/cm), and flexible three-dimensional (3D) graphene networks, loaded with MnO2 by electrodeposition, as the electrodes of a flexible supercapacitor. It was found that the 3D graphene networks showed an ideal supporter for active materials and permitted a large MnO2 mass loading of 9.8 mg/cm2 (∼92.9% of the mass of the entire electrode), leading to a high area capacitance of 1.42 F/cm2 at a scan rate of 2 mV/s. With a view to practical applications, we have further optimized the MnO2 content with respect to the entire electrode and achieved a maximum specific capacitance of 130 F/g. In addition, we have also explored t...

Freestanding three-dimensional graphene/MnO2 composite networks as ultralight and flexible supercapacitor electrodes.

Carbon nanotubes and graphene are some of the most intensively explored carbon allotropes in materials science. This interest mainly resides in their unique properties with electrical conductivities as high as 104 S cm−1, thermal conductivities as high as 5000 W m−1 K and superior mechanical properties with elastic moduli on the order of 1 TPa for both of them. The possibility to translate the individual properties of these monodimensional (e.g. carbon nanotubes) and bidimensional (e.g. graphene) building units into two-dimensional free-standing thick and thin films has paved the way for using these allotropes in a number of applications (including photocatalysis, electrochemistry, electronics and optoelectronics, among others) as well as for the preparation of biological and chemical sensors. More recently and while recognizing the tremendous interest of these two-dimensional structures, researchers are noticing that the performance of certain devices can experience a significant enhancement by the use of three-dimensional architectures and/or aerogels because of the increase of active material per projected area. This is obviously the case as long as the nanometre-sized building units remain accessible so that the concept of hierarchical three-dimensional organization is critical to guarantee the mass transport and, as consequence, performance enhancement. Thus, this review aims to describe the different synthetic processes used for preparation of these three-dimensional architectures and/or aerogels containing either any or both allotropes, and the different fields of application in which the particular structure of these materials provided a significant enhancement in the efficacy as compared to their two-dimensional analogues or even opened the path to novel applications. The unprecedented compilation of information from both CNT- and graphene-based three-dimensional architectures and/or aerogels in a single revision is also of interest because it allows a straightforward comparison between the particular features provided by each allotrope.

Three dimensional macroporous architectures and aerogels built of carbon nanotubes and/or graphene: synthesis and applications

Using a simple hydrothermal procedure, cobalt oxide (Co3O4) nanowires were in situ synthesized on three-dimensional (3D) graphene foam grown by chemical vapor deposition. The structure and morphology of the resulting 3D graphene/Co3O4 composites were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and Raman spectroscopy. The 3D graphene/Co3O4 composite was used as the monolithic free-standing electrode for supercapacitor application and for enzymeless electrochemical detection of glucose. We demonstrate that it is capable of delivering high specific capacitance of ∼1100 F g–1 at a current density of 10 A g–1 with excellent cycling stability, and it can detect glucose with a ultrahigh sensitivity of 3.39 mA mM–1 cm–2 and a remarkable lower detection limit of <25 nM (S/N = 8.5).

3D Graphene–Cobalt Oxide Electrode for High-Performance Supercapacitor and Enzymeless Glucose Detection

A selective phosphorescent biothiols probe is synthesized based on Ir(III) complex 1, which has 2,2'-biquinoline as the N^N ligand for realizing the satisfied two-photon absorption cross-section and two-functionalized 2-phenylpyridine ligands with an α,β-unsaturated ketone moiety as the thiol reaction site. The one- and two-photon optical properties of 1 are investigated through UV-vis absorption spectrum and photoluminescence spectrum. This Ir(III) complex can act as an excellent one- and two-photon excited "OFF-ON" phosphorescent probe for biothiols based on the 1,4-addition of biothiol to α,β-unsaturated ketones. Moreover, one- and two-photon-induced luminescent imagings of biothiols in living cells are also realized. Furthermore, the experiments of time-resolved photoluminescence technique and fluorescence lifetime imaging microscopy demonstrate that 1 is able to detect biothiols in the presence of strong background fluorescence. In addition, probe 1 is adsorbed into the shell of mesoporous silica nanoparticles with core-shell structure to form a nanoprobe, which can realize the ratiometric detection of biothiols in absolute water solution and living cells based on two phosphorescent signals.

Rational design of phosphorescent chemodosimeter for reaction-based one- and two-photon and time-resolved luminescent imaging of biothiols in living cells.

A series of hyper-branched cationic conjugated polyelectrolytes containing different contents of phosphorescent Ir(III) complex has been designed and synthesized successfully. Their photophysical properties in both aqueous solution and solid film are investigated and their morphologies in aqueous solution are observed by TEM. Nanoparticles with the size of 80–100 nm have been formed in aqueous solution through the self-assembly of polymers. An energy transfer process from host polyfluorene to guest Ir(III) complex exists and becomes more efficient in the solid films. Importantly, this series of hyper-branched polymers can be applied as light-up heparin probes with good selectivity, high sensitivity, and naked-eye detection through electrostatic interaction between polymers and heparin. Quantification for heparin in aqueous solution can be realized in the range of 0–44 μM in the buffer solution. Detection limit can reach as low as 50 nM. More meaningfully, time-resolved photoluminescence technique is utili...

Hyper-branched phosphorescent conjugated polyelectrolytes for time-resolved heparin sensing.

A phosphorescent CO2 gas probe based on an iridium(III) complex with 2-phenylimidazo-[4,5-f][1,10]phenanthroline ligand has been developed. Its phosphorescence is quenched by the addition of CH3COO−. The quenched phosphorescence can be recovered by bubbling CO2 into the detecting solution. This phosphorescent CO2 probe exhibits higher photostability and reduced photobleaching than some of the reported organic fluorescent probes. A time-resolved photoluminescence experiment was performed for CO2 gas detection, which could effectively remove the background fluorescence and improve the sensitivity and signal-to-noise ratio of the sensor in complicated media.

Hang Xu

Papers

3D Graphene–Cobalt Oxide Electrode for High-Performance Supercapacitor and Enzymeless Glucose Detection

Rational design of phosphorescent chemodosimeter for reaction-based one- and two-photon and time-resolved luminescent imaging of biothiols in living cells.

Hyper-branched phosphorescent conjugated polyelectrolytes for time-resolved heparin sensing.

A charged iridophosphor for time-resolved luminescent CO2 gas identification