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

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

Pore-size ion-size correlations for carbon supercapacitors

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. This could lead to fleet-wide improvements in economy, performance, lifetime and environmental impact of Hybrid Electric Vehicles (HEVs), as well as enable or advance many other applications. To determine correlations between ion-size and pore-size in carbon supercapacitors, we generated a well-characterized set of porous carbide-derived carbons (CDC) with average pore sizes from 0.6 to 2.25 nm and used them to probe the limits of understanding. Performing the first systematic study of the effect of pore size on capacitance showed that, in general, decreasing the pore size below the size of the solvated ion, or to precisely the size of the ionic liquid ion, allowed higher accumulation of charge. Using CDC with properly tuned porosity showed excellent performance in H2SO4, ~200 F/g, andperformance superior to all prior reported results in organic (CH3CH2)4NBF4 (TEABF4) electrolytes as well as 1-ethyl-3-methyl immidazolium bis-(trifluoromethanesulfonyl)imide (EMI-TFSI) ionic liquid, ~150 F/g. This work conclusively showed that precisely matching the pore size with the ion size is the key factor for maximizing capacitance. Understanding that pores significantly larger than the effective ion size do not have large contributions to energy storage, work on dense porous CDC films on conductive substrates showed ~100% larger volumetric capacitance than any previously reported. Depositing patterned films of carbide and electrical contacts could lead to microfabricated energy storage devices directly on a chip, or built up in layers for performances yet unrealized.Ph.D., Materials Science and Engineering -- Drexel University, 200

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

Titanium Carbide Derived Nanoporous Carbon for Energy-Related Applications

High surface area nanoporous carbon has been prepared by thermo-chemical etching of titanium carbide TiC in chlorine in the temperature range 200–1200 °C. Structural analysis showed that this carbide-derived carbon (CDC) was highly disordered at all synthesis temperatures. Higher temperature resulted in increasing ordering and formation of bent graphene sheets or thin graphitic ribbons. Soft X-ray absorption near-edge structure spectroscopy demonstrated that CDC consisted mostly of sp2 bonded carbon. Small-angle X-ray scattering and argon sorption measurements showed that the uniform carbon-carbon distance in cubic TiC resulted in the formation of small pores with a narrow size distribution at low synthesis temperatures; synthesis temperatures above 800 °C resulted in larger pores. CDC produced at 600–800 °C show great potential for energy-related applications. Hydrogen sorption experiments at −195.8 °C and atmospheric pressure showed a maximum gravimetric capacity of ∼ 330 cm3/g (3.0 wt.%). Methane sorption at 25 °C demonstrated a maximum capacity above 46 cm3/g (45 vol/vol or 3.1 wt.%) at atmospheric pressure. When tested as electrodes for supercapacitors with an organic electrolyte, the hydrogen-treated CDC showed specific capacitance up to 130 F/g with no degradation after 10 000 cycles

Double-layer capacitance of carbide derived carbons in sulfuric acid

Electrochemical and Solid-State Letters, 8(7): pp. A357-A360. Retrieved September 19, 2006 from http://nano.materials.drexel.edu/Papers/EDLC_CDC.pdf. DOI: http://dx.doi.org/10.1149/1.1921134Nanoporous carbons obtained by selective leaching of Ti and Al from Ti2AlC, as well as B from B4C, were investigated as electrode materials in electric double-layer capacitors. Cyclic voltammetry tests were conducted in 1 M H2SO4 from 0-250 mV on carbons synthesized at 600, 800, 1000, and 1200°C. Results show that the structure and pore sizes can be tailored and that the optimal synthesis temperature is 1000°C. Specific capacitances for Ti2AlC CDCs and B4C CDCs were 175 and 147 F/g, respectively, compared to multiwall carbon nanotubes and two types of activated carbon, measured herein to be 15, 52, and 125 F/g, respectively

In Situ NMR Spectroscopy of Supercapacitors: Insight into the Charge Storage Mechanism

Electrochemical capacitors, commonly known as supercapacitors, are important energy storage devices with high power capabilities and long cycle lives. Here we report the development and application of in situ nuclear magnetic resonance(NMR) methodologies to study changes at the electrode−electrolyte interface in working devices as they charge and discharge. For a supercapacitor comprising activated carbon electrodes and an organic electrolyte, NMR experiments carried out at different charge states allow quantification of the number of charge storing species and show that there are at least two distinct charge storage regimes. At cell voltages below 0.75 V, electrolyte anions are increasingly desorbed from the carbon micropores at the negative electrode, while at the positive electrode there is little change in the number of anions that are adsorbed as the voltage is increased. However, above a cell voltage of 0.75 V, dramatic increases in the amount of adsorbed anions in the positive electrode are observed while anions continue to be desorbed at the negative electrode. NMR experiments with simultaneous cyclic voltammetry show that supercapacitor charging causes marked changes to the local environments of charge storing species, with periodic changes of their chemical shift observed. NMR calculations on a model carbon fragment show that the addition and removal of electrons from a delocalized system should lead to considerable increases in the nucleus-independent chemical shift of nearby species, in agreement with our experimental observations

Relation between the Ion Size and Pore Size for an Electric Double-Layer Capacitor.

The research on electrochemical double layer capacitors (EDLC), also known as supercapacitors or ultracapacitors, is quickly expanding because their power delivery performance fills the gap between dielectric capacitors and traditional batteries. However, many fundamental questions, such as the relations between the pore size of carbon electrodes, ion size of the electrolyte, and the capacitance have not yet been fully answered. We show that the pore size leading to the maximum double-layer capacitance of a TiC-derived carbon electrode in a solvent-free ethyl-methylimmidazolium-bis(trifluoro-methane-sulfonyl)imide (EMI-TFSI) ionic liquid is roughly equal to the ion size (0.7 nm). The capacitance values of TiC−CDC produced at 500 °C are more than 160 F/g and 85 F/cm3 at 60 °C, while standard activated carbons with larger pores and a broader pore size distribution present capacitance values lower than 100 F/g and 50 F/cm3 in ionic liquids. A significant drop in capacitance has been observed in pores that were larger or smaller than the ion size by just an angstrom, suggesting that the pore size must be tuned with sub-angstrom accuracy when selecting a carbon/ion couple. This work suggests a general approach to EDLC design leading to the maximum energy density, which has been now proved for both solvated organic salts and solvent-free liquid electrolytes