Electrochemical Characterization of Single Layer Graphene/Electrolyte Interface: Effect of Solvent on the Interfacial Capacitance.

The development of the basic understanding of the charge storage mechanisms in electrodes for energy storage applications needs deep characterization of the electrode/electrolyte interface. In this work, we studied the charge of the double layer capacitance at single layer graphene (SLG) electrode used as a model material, in neat (EMIm-TFSI) and solvated (with acetonitrile) ionic liquid electrodes. The combination of electrochemical impedance spectroscopy and gravimetric electrochemical quartz crystal microbalance (EQCM) measurements evidence that the presence of solvent drastically increases the charge carrier density at the SLG/ionic liquid interface. The capacitance is thus governed not only by the electronic properties of the graphene, but also by the specific organization of the electrolyte side at the SLG surface originating from the strong interactions existing between the EMIm+ cations and SLG surface. EQCM measurements also show that the carbon structure, with the presence of sp2 carbons, affects the charge storage mechanism by favoring counter-ion adsorption on SLG electrode versus ion exchange mechanism in amorphous porous carbons.

Charge Storage Mechanisms of Single-Layer Graphene in Ionic Liquid.

Graphene-based carbon materials are promising candidates for electrical double-layer (EDL) capacitors, and there is considerable interest in understanding the structure and properties of the graphene/electrolyte interface. Here, electrochemical impedance spectroscopy (EIS) and electrochemical quartz crystal microbalance (EQCM) are used to characterize the ion fluxes and adsorption on single-layer graphene in neat ionic liquid (EMI-TFSI) electrolyte. It is found that a positively charged ion-species desorption and ion reorganization dominate the double-layer charging during positive and negative polarizations, respectively, leading to the increase in EDL capacitance with applied potential.

Diameter-Sensitive Breakdown of Single-Walled Carbon Nanotubes upon KOH Activation.

While potassium hydroxide (KOH) activation has been used to create pores in carbon nanotubes (CNTs) for improved energy-storage performance, the KOH activation mechanism of CNTs has been rarely investigated. In this work, the reaction between single-walled CNTs (SWCNTs) and KOH is studied in situ by thermogravimetric analysis coupled to infrared (IR) spectroscopy and gas chromatography/mass spectrometry (MS). The IR and MS results clearly demonstrate the sequential evolution of CO, hydrocarbons, CO2 , and H2 O in the activation process. By using the radial breathing mode of Raman spectroscopy, a diameter-sensitive selectivity is observed in the reaction between SWCNTs and KOH, leading to a preferential distribution of SWCNTs with diameters larger than 1 nm after activation at 900 °C and a preferential removal of SWCNTs with diameters below 1 nm upon activation.

Designing ionic channels in novel carbons for electrochemical energy storage.

Tremendous efforts have been dedicated to developing high-performance energy storage devices based on the micro- or nano-manipulation of novel carbon electrodes, as certain nanocarbons are perceived to have advantages such as high specific surface areas, superior electric conductivities, excellent mechanical properties and so on. In typical electrochemical electrodes, ions are intercalated/deintercalated into/from the bulk (for batteries) or adsorbed/desorbed on/from the surface (for electrochemical capacitors). Fast ionic transport, significantly determined by ionic channels in active electrodes or supporting materials, is a prerequisite for the efficient energy storage with carbons. In this report, we summarize recent design strategies for ionic channels in novel carbons and give comments on the promising features based on those carbons towards tailorable ionic channels.

A Sponge-Driven Elastic Interface for Lithium Metal Anodes.

The lithium (Li) metal is one promising anode for next generation high-energy-density batteries, but the large stress fluctuation and the nonuniform Li deposition upon cycling result in a highly unstable interface of the Li anode. Herein, a simple yet facile engineering of the elastic interface on the Li metal anodes is designed by inserting a melamine sponge between Li and the separator. Driven by the good elasticity of the sponge, the modified Li anode maintains a Coulombic efficiency of 98.8% for 60 cycles and is cyclable at 10 mA cm-2 for 250 cycles, both with a high capacity of 10 mA h cm-2. We demonstrate that the sponge can be used to replace the conventional polypropylene as a porous yet elastic separator, showing superior cycling and rate performance as well. In addition to the efficiency of the elastic interface on the cycling stability, which is further confirmed by an in situ compression-electrochemistry measurement, the porous structure and polar groups of the sponge demonstrate an ability of regulating the transport of Li ions, leading to a uniform deposition of Li and the suppression of Li dendrites in cycling.

Incorporating Flexibility into Stiffness: Self-Grown Carbon Nanotubes in Melamine Sponges Enable A Lithium-Metal-Anode Capacity of 15 mA h cm-2 Cyclable at 15 mA cm-2.

Although with an extremely high theoretical capacity (3860 mA h g-1 ), the lithium (Li) metal anodes reported so far typically possess capacities of ≤5 mA h cm-2 and cyclable at currents of ≤5 mA cm-2 . In this work, a hierarchal carbon scaffold is designed with the self-growth of carbon nanotubes (CNTs) in nickel-decorated melamine sponges via thermal annealing. It is found that the nitrogen-doped carbon obtained from the melamine sponge, coupled with CNTs, provides an overall strong yet internally flexible host which enables an areal capacity of up to 15 mA h cm-2 cyclable at a charging/discharging current of 15 mA cm-2 as Li metal anodes. Characterizations show that the highly conductive yet uniformly distributed CNTs effectively suppress the local current density, leading to more uniform Li nucleation in Li plating. The flexible CNTs in the stiff scaffold enhance the tolerance to the stress caused by the intrinsic volume variation in Li plating/striping, resulting in the stable cycling performance at high currents. This study provides a potentially scalable and cost-effective strategy for preparation of high-performance Li-metal anodes.

In Operando Probing of Lithium-Ion Storage on Single-Layer Graphene.

Despite high-surface area carbons, e.g., graphene-based materials, being investigated as anodes for lithium (Li)-ion batteries, the fundamental mechanism of Li-ion storage on such carbons is insufficiently understood. In this work, the evolution of the electrode/electrolyte interface is probed on a single-layer graphene (SLG) film by performing Raman spectroscopy and Fourier transform infrared spectroscopy when the SLG film is electrochemically cycled as the anode in a half cell. The utilization of SLG eliminates the inevitable intercalation of Li ions in graphite or few-layer graphene, which may have complicated the discussion in previous work. Combining the in situ studies with ex situ observations and ab initio simulations, the formation of solid electrolyte interphase and the structural evolution of SLG are discussed when the SLG is biased in an electrolyte. This study provides new insights into the understanding of Li-ion storage on SLG and suggests how high-surface-area carbons could play proper roles in anodes for Li-ion batteries.

Tailoring the Structure of Carbon Nanomaterials toward High-End Energy Applications.

Carbon nanomaterials are perceived to be ideally suited candidates for high-end energy applications, owing to their unparalleled advantages including superior electric and thermal conductivity, excellent mechanical properties, and high specific surface areas. It has been demonstrated through several research contributions that the electrochemical performance of carbon nanomaterials significantly depends upon their versatile electronic structures and microstructures. These can be precisely tailored by rational defect engineering, heteroatom doping, heterostructure coupling, and pore fabrication, which largely affect the intrinsic nature of active sites and facilitate the ion/electron transfer. Herein, the recent progress in tailoring carbon nanostructures toward high-end electrocatalysis and supercapacitor applications is summarized, with an emphasis on synthesis strategies, advanced characterizations, and specific elucidation of structure-performance relationship. The challenges and opportunities for the rational design and detection of variously tailored carbon nanomaterials that can further improve the fundamental understanding and practical applications in the field of energy storage and conversion are also discussed.

Enhanced physical properties of γ-Al2O3-rGO hybrids prepared by solvothermal and hot-press processing.

In this study, a solvothermal method was employed for the first time to fabricate hybrids composed of cross-linked γ-Al2O3 nanorods and reduced graphite oxide (rGO) platelets. After calcination and hot-press processing, monoliths of Al2O3-rGO hybrids were obtained with improved physical properties. It was found that the oxygen-containing groups on graphene oxide were beneficial for the adsorption of aluminum isopropoxide, leading to a uniform dispersion of rGO with Al2O3, which was obtained by hydrolysis of aluminum isopropoxide during the solvothermal reaction. The hybrid, which was subsequently calcinated for 3 h showed electrical conductivity of 6.7 × 101 S m-1 together with 90% higher mechanical tensile strength and 80% higher thermal conductivity as compared to the bare Al2O3. In addition, the dielectric constant of the hybrid was 12 times higher than that of the bare Al2O3. In this study, the highest values of electrical conductivity (8.2 × 101 S m-1), thermal conductivity (2.53 W m-1 K-1), dielectric constant (104) and Young's modulus (3.7 GPa) were obtained for the alumina-rGO hybrid calcinated for 1 h. XRD characterization showed that an increase in calcination temperature and further hot-press processing at 900 °C led to enhanced crystallinity in the γ-Al2O3 nanorods in the hybrid, resulting in enhanced physical properties in the hybrids.

Direct Laser Writing of Graphene Made from Chemical Vapor Deposition for Flexible, Integratable Micro-Supercapacitors with Ultrahigh Power Output.

High-performance yet flexible micro-supercapacitors (MSCs) hold great promise as miniaturized power sources for increasing demand of integrated electronic devices. Herein, this study demonstrates a scalable fabrication of multilayered graphene-based MSCs (MG-MSCs), by direct laser writing (DLW) of stacked graphene films made from industry-scale chemical vapor deposition (CVD). Combining the dry transfer of multilayered CVD graphene films, DLW allows a highly efficient fabrication of large-areal MSCs with exceptional flexibility, diverse planar geometry, and capability of customer-designed integration. The MG-MSCs exhibit simultaneously ultrahigh energy density of 23 mWh cm-3 and power density of 1860 W cm-3 in an ionogel electrolyte. Notably, such MG-MSCs demonstrate an outstanding flexible alternating current line-filtering performance in poly(vinyl alcohol) (PVA)/H2 SO4 hydrogel electrolyte, indicated by a phase angle of -76.2° at 120 Hz and a resistance-capacitance constant of 0.54 ms, due to the efficient ion transport coupled with the excellent electric conductance of the planar MG microelectrodes. MG-polyaniline (MG-PANI) hybrid MSCs fabricated by DLW of MG-PANI hybrid films show an optimized capacitance of 3.8 mF cm-2 in PVA/H2 SO4 hydrogel electrolyte; an integrated device comprising MG-MSCs line filtering, MG-PANI MSCs, and pressure/gas sensors is demonstrated.

Assembling carbon quantum dots to a layered carbon for high-density supercapacitor electrodes.

It is found that carbon quantum dots (CQDs) self-assemble to a layer structure at ice crystals-water interface with freeze- drying. Such layers interconnect with each other, forming a free-standing CQD assembly, which has an interlayer distance of about 0.366 nm, due to the existence of curved carbon rings other than hexagons in the assembly. CQDs are fabricated by rupturing C60 by KOH activation with a production yield of ~15 wt.%. The CQDs obtained have an average height of 1.14 nm and an average lateral size of 7.48 nm, and are highly soluble in water. By packaging annealed CQD assembly to high density (1.23 g cm(-3)) electrodes in supercapacitors, a high volumetric capacitance of 157.4 F cm(-3) and a high areal capacitance of 0.66 F cm(-2) (normalized to the loading area of electrodes) are demonstrated in 6 M KOH aqueous electrolyte with a good rate capability.