Engineering graphene for high-performance supercapacitors: Enabling role of colloidal chemistry

The high electrical conductivity and high specific surface area of graphene are traditionally regarded as the most intriguing features for its promise as the electrode material for supercapacitors. In this perspective, we highlight that from the engineering point of view, the unique colloidal chemistry of chemically functionalized graphene is the key property that has made graphene stand out as a promising nanoscale building block for constructing unique nanoporous electrodes for capacitive energy storage, We present several examples to demonstrate bow the non-covalent colloidal forces between graphene sheets can be harnessed to engineer the nanostructure of graphene-based bulk electrodes for supercapacitors based on both the electrical double layer storage and the redox reaction or pseudo-capacitance mechanisms. The colloidal engineering strategy can be extended to enable other nanomaterials to achieve high energy storage performance.

Microwave-hydrothermal preparation of a graphene/hierarchy structure MnO_2 composite for a supercapacitor

Graphene/hierarchy structure manganese dioxide （GN/MnO2） composites were synthesized using a simple microwave-hydrothermal method. The properties of the prepared composites were analyzed using field emission scanning electron microscopy （FE-SEM）, X-ray diffraction （XRD）, transmission electron microscopy （TEM）, and X-ray photoelectron spectroscopy （XPS） measurements. The electrochemical performances of the composites were analyzed using cyclic voltammetry, electrochemical impedance spectrometry （EIS）, and chronopotentiometry. The results showed that GN/MnO2 （10 wt% graphene） displayed a specific capacitance of 244 F/g at a current density of 100 mA/g. An excellent cyclic stability was obtained with a capacity retention of approximately 94.3% after 500 cycles in a 1 mol/L Li2SO4 solution. The improved electrochemical performance is attributed to the hierarchy structure of the manganese dioxide, which can enlarge the interface between the active materials and the electrolyte. The prepa- ration route provides a new approach for hierarchy structure graphene composites; this work could be readily extended to the preparation of other graphene-based composites with different structures for use in energy storage devices.

Mesoporous tubular graphene electrode for high performance supercapacitor

We report the fabrication of mesoporous tubular graphene（MTG） by a chemical vapor deposition method using Mg O@Zn O core-shell structure as the template. The unique bi-directional ions transfer in unstack graphene layers and high mesopore ratio of MTGs allows capacitance reach 15 μF/cm^2 at 0.5 A/g, and11 μF/cm^2 at 10 A/g, which is closer to theoretical value（21μF/cm^2） than SWCNTs and DWCNTs at either low or high rate. Meanwhile, MTGs exhibited good structural stability, high surface area（701 m^2/g）, high conductivity（30 S/cm） and low oxygen ratio（0.7 atom%）, allowing excellent SC performance. The 4 V EDLC using MTGs and EMIMBF_4 electrolyte exhibited high energy density in wide range of high power density and excellent cycling stability, showing strong potential in EDLC and other electrochemical energy storage systems, in addition, showing significant factor of ion transfer distance for high performance SCs especially operating at high voltage using ionic liquid electrolyte.

Facile synthesis of nitrogen-doped graphene aerogels functionalized with chitosan for supercapacitors with excellent electrochemical performance

Three-dimensional porous nitrogen-doped graphene aerogels（NGAs） were synthesized by using graphene oxide（GO） and chitosan via a self-assembly process by a rapid method.The morphology and structure of the as-prepared aerogels were characterized.The results showed that NGAs possesed the hierarchical pores with the wide size distribution ranging from mesopores to macropores.The NGAs carbonized at different temperature all showed excellent electrochemical performance in 6 mol/L KOH electrolyte and the electrochemical performance of the NGA-900 was the best.When working as a supercapacitor electrode,NGA-900 exhibited a high specific capacitance（244.4 F/g at a current density of 0.2 A/g）,superior rate capability（51.0% capacity retention） and excellent cycling life（96.2% capacitance retained after 5000 cycles）.

Freestanding hierarchical porous carbon film derived from hybrid nanocellulose for high-power supercapacitors

Nanocellulose is a sustainable and eco-friendly nanomaterial derived from renewable biomass. In this study, we utilized the structural advantages of two types of nanocellulose and fabricated freestanding carbonized hybrid nanocellulose films as electrode materials for supercapacitors. The long cellulose nanofibrils （CNFs） formed a macroporous framework, and the short cellulose nanocrystals were assembled around the CNF framework and generated micro/mesopores. This two-level hierarchical porous structure was successfully preserved during carbonization because of a thin atomic layer deposited （ALD） A1203 conformal coating, which effectively prevented the aggregation of nanocellulose. These carbonized, partially graphitized nanocellulose fibers were interconnected, forming an integrated and highly conductive network with a large specific surface area of 1,244 m2·g-1. The two-level hierarchical porous structure facilitated fast ion transport in the film. When tested as an electrode material with a high mass loading of 4 mg·cm-2 for supercapacitors, the hierarchical porous carbon film derived from hybrid nanocellulose exhibited a specific capacitance of 170 F·g-1 and extraordinary performance at high current densities. Even at a very high current of 50 A-g-l, it retained 65% of its original specific capacitance, which makes it a promising electrode material for high-power applications.

Superelastic wire-shaped supercapacitor sustaining 850% tensile strain based on carbon nanotube@graphene fiber

Stretchable and flexible supercapacitors are highly desired due to their many potential applications in wearable devices. However, it is challenging to fabricate supercapacitors that can withstand large tensile strain while maintaining high performance. Herein, we report an ultra-stretchable wire-shaped supercapacitor based on carbon nanotube@graphene@MnO2 fibers wound around a superelastic core fiber. The supercapacitor can sustain tensile strain up to 850%, which is the highest value reported for this type of device to date, while maintaining stable electrochemical performance. The energy density of the supercapacitor is 3.37 mWh·cm^-3 at a power density of 54.0 mW·cm^-3. The results show that 82% of the specific capacitance is retained after 1,000 stretch-release cycles with strains of 700%, demonstrating the superior durability of the elastic supercapacitor and showcasing its potential application in ultra-stretchable flexible electronics.

Flexible asymmetric supercapacitor based on MnO_2 honeycomb structure

A flexible asymmetric supercapacitor with high energy density was constructed by using a flexible substrate of carbonized silk-fabrics decorated with carbon nanotube, electroplating MnO2 nanosheets and dip-coating activated carbon powders as the positive and the negative electrodes, respectively. By controlling the electroplating time, the MnO2 nanosheets can be self-assembled to honeycomb structure and showed excellent electrochemical performance in 1 mol/L Na2SO4 electrolyte with SC950-EP30 performing the best. It exhibited a high specific capacitance（1110.85 F/g at a current density of 1 A/g based on the mass of MnO2） and superior rate capability（77.44% capacity retention from 1 A/g to 10 A/g）.Thus, the optimal asymmetric device assembled with this material as positive electrode can deliver a maximum energy density of 43.84 Wh/kg and a maximum power density of 6.62 kW/kg.