Monolithic Carbide-Derived Carbon Films for Micro-Supercapacitors

Microbatteries with dimensions of tens to hundreds of micrometers that are produced by common microfabrication techniques are poised to provide integration of power sources onto electronic devices, but they still suffer from poor cycle lifetime, as well as power and temperature range of operation issues that are alleviated with the use of supercapacitors. There have been a few reports on thin-film and other micro-supercapacitors, but they are either too thin to provide sufficient energy or the technology is not scalable. By etching supercapacitor electrodes into conductive titanium carbide substrates, we demonstrate that monolithic carbon films lead to a volumetric capacity exceeding that of micro- and macroscale supercapacitors reported thus far, by a factor of 2. This study also provides the framework for integration of high-performance micro-supercapacitors onto a variety of devices

Microelectrode study of pore size, ion size, and solvent effects on the charge/discharge behavior of microporous carbons for electrical double-layer capacitors

The capacitive behavior of TiC-derived carbon powders in two different electrolytes, NEt4BF4 in acetonitrile AN and NEt4BF4 in propylene carbonate PC, was studied using the cavity microelectrode CME technique. Comparisons of the cyclic voltammograms recorded at 10–1000 mV/s enabled correlation between adsorbed ion sizes and pore sizes, which is important for understanding the electrochemical capacitive behavior of carbon electrodes for electrical double-layer capacitor applications. The CME technique also allows a fast selection of carbon electrodes with matching pore sizes different sizes are needed for the negative and positive electrodes for the respective electrolyte system. Comparison of electrochemical capacitive behavior of the same salt, NEt4BF4, in different solvents, PC and AN, has shown that different pore sizes are required for different solvents, because only partial desolvation of ions occurs during the double-layer charging. Squeezing partially solvated ions into subnanometer pores, which are close to the desolvated ion size, may lead to distortion of the shape of cyclic voltammograms

Monolithic Carbide-Derived Carbon Films for Micro-Supercapacitors

Microbatteries with dimensions of tens to hundreds of micrometers that are produced by common microfabrication techniques are poised to provide integration of power sources onto electronic devices, but they still suffer from poor cycle lifetime, as well as power and temperature range of operation issues that are alleviated with the use of supercapacitors. There have been a few reports on thin-film and other micro-supercapacitors, but they are either too thin to provide sufficient energy or the technology is not scalable. By etching supercapacitor electrodes into conductive titanium carbide substrates, we demonstrate that monolithic carbon films lead to a volumetric capacity exceeding that of micro- and macroscale supercapacitors reported thus far, by a factor of 2. This study also provides the framework for integration of high-performance micro-supercapacitors onto a variety of devices

Anomalous Increase in Carbon Capacitance at Pore Sizes Less Than 1 Nanometer

Carbon supercapacitors, which are energy storage devices that use ion adsorption on the surface of highly porous materials to store charge, have numerous advantages over other power-source technologies, but could realize further gains if their electrodes were properly optimized. Studying the effect of the pore size on capacitance could potentially improve performance by maximizing the electrode surface area accessible to electrolyte ions, but until recently, no studies had addressed the lower size limit of accessible pores. Using carbide-derived carbon, we generated pores with average sizes from 0.6 to 2.25 nanometer and studied double-layer capacitance in an organic electrolyte. The results challenge the long-held axiom that pores smaller than the size of solvated electrolyte ions are incapable of contributing to charge storage

Solvent effect on the ion adsorption from ionic liquid electrolyte into sub-nanometer carbon pores

This paper presents the results from the investigation of the influence of ion size on the capacitance behaviour of TiC-derived carbon (CDC) powders in the ethyl-methylimmidazolium-bis(trifluoromethane-sulfonyl)imide ionic liquid (EMI, TFSI) used as neat electrolyte at 60°C or as salt dissolved in acetonitrile and tested at room temperature. These studies were carried out with the assembly of conventional 3-electrode electrochemical cells as well as using the Cavity-MicroElectrode (CME) technique. The issues regarding the extents of desolvation of the electrolyte ions when adsorbed in the pores of the CDCs under applied potential were studied, the CME technique was found to be particularly efficient in the deduction of the effective ion size under solvated conditions

Charge storage mechanism in nanoporous carbons and its consequence for electrical double layer capacitors

Electrochemical capacitors, also known as supercapacitors, are energy storage devices that fill the gap between batteries and dielectric capacitors. Thanks to their unique features, they have a key role to play in energy storage and harvesting, acting as a complement to or even a replacement of batteries which has already been achieved in various applications. One of the challenges in the supercapacitor area is to increase their energy density. Some recent discoveries regarding ion adsorption in microporous carbon exhibiting pores in the nanometre range can help in designing the next generation of high-energy-density supercapacitors

Defect-engineered graphene for bulk supercapacitors with high energy and power densities

The development of high-energy and high-power density supercapacitors (SCs) is critical for enabling next-generation energy storage applications. Nanocarbons are excellent SC electrode materials due to their economic viability, high-surface area, and high stability. Although nanocarbons have high theoretical surface area and hence high double layer capacitance, the net amount of energy stored in nanocarbon-SCs is much below theoretical limits due to two inherent bottlenecks: i) their low quantum capacitance and ii) limited ion-accessible surface area. Here, we demonstrate that defects in graphene could be effectively used to mitigate these bottlenecks by drastically increasing the quantum capacitance and opening new channels to facilitate ion diffusion in otherwise closed interlayer spaces. Our results support the emergence of a new energy paradigm in SCs with 250% enhancement in double layer capacitance beyond the theoretical limit. Furthermore, we demonstrate prototype defect engineered bulk SC devices with energy densities 500% higher than state-of-the-art commercial SCs without compromising the power density.Comment: 15 pages, 5 figures, and 8 supplemental figure

Potential-Induced Electronic Structure Changes in Supercapacitor Electrodes Observed by In Operando Soft X-Ray Spectroscopy

[[abstract]]The dynamic physiochemical response of a functioning graphene-based aerogel supercapacitor is monitored in operando by soft X-ray spectroscopy and interpreted through ab initio atomistic simulations. Unanticipated changes in the electronic structure of the electrode as a function of applied voltage bias indicate structural modifications across multiple length scales via independent pseudocapacitive and electric double layer charge storage channels.[[notice]]補正完畢[[journaltype]]國外[[incitationindex]]SCI[[ispeerreviewed]]Y[[booktype]]電子版[[countrycodes]]US

Ultrahigh Surface Area Three-Dimensional Porous Graphitic Carbon from Conjugated Polymeric Molecular Framework

Porous graphitic carbon is essential for many applications such as energy storage devices, catalysts, and sorbents. However, current graphitic carbons are limited by low conductivity, low surface area, and ineffective pore structure. Here we report a scalable synthesis of porous graphitic carbons using a conjugated polymeric molecular framework as precursor. The multivalent cross-linker and rigid conjugated framework help to maintain micro- and mesoporous structures, while promoting graphitization during carbonization and chemical activation. The above unique design results in a class of highly graphitic carbons at temperature as low as 800 ??C with record-high surface area (4073 m2 g-1), large pore volume (2.26 cm-3), and hierarchical pore architecture. Such carbons simultaneously exhibit electrical conductivity >3 times more than activated carbons, very high electrochemical activity at high mass loading, and high stability, as demonstrated by supercapacitors and lithium-sulfur batteries with excellent performance. Moreover, the synthesis can be readily tuned to make a broad range of graphitic carbons with desired structures and compositions for many applications.clos

Screening Methodology for the Efficient Pairing of Ionic Liquids and Carbonaceous Electrodes Applied to Electric Energy Storage

A model is presented that correlates the measured electric capacitance with the energy that comprises the desolvation, dissociation and adsorption energy of an ionic liquid into carbonaceous electrode (represented by single-wall carbon nanotubes). An original methodology is presented that allows for the calculation of the adsorption energy of ions in a host system that does not necessarily compensate the total charge of the adsorbed ions, leaving an overall net charge. To obtain overall negative (favorable) energies, adsorption energies need to overcome the energy cost for desolvation of the ion pair and its dissociation into individual ions. Smaller ions, such as BF4 −, generally show larger dissociation energies than anions such as PF6 − or TFSI−. Adsorption energies gradually increase with decreasing pore size of the CNT and show a maximum when the pore size is slightly greater than the dimensions of the adsorbed ion and the attractive van der Waals forces dominate the interaction. At smaller pore diameters, the adsorption energy sharply declines and becomes repulsive as a result of geometry deformations of the ion. Only for those diameters where the adsorption reaches maximum values is the adsorption energy sufficiently negative to balance the positive dissociation and desolvation energies. We present for each ion (and ionic liquid) what the most adequate electrode pore size should be for maximum capacitance