John K. McDonough

Carbon coated textiles for flexible energy storage

This paper describes a flexible and lightweight fabric supercapacitor electrode as a possible energy source in smart garments. We examined the electrochemical behavior of porous carbon materials impregnated into woven cotton and polyester fabrics using a traditional printmaking technique (screen printing). The porous structure of such fabrics makes them attractive for supercapacitor applications that need porous films for ion transfer between electrodes. We used cyclic voltammetry, galvanostatic cycling and electrochemical impedance spectroscopy to study the capacitive behaviour of carbon materials using nontoxic aqueous electrolytes including sodium sulfate and lithium sulfate. Electrodes coated with activated carbon (YP17) and tested at ∼0.25 A·g−1 achieved a high gravimetric and areal capacitance, an average of 85 F·g−1 on cotton lawn and polyester microfiber, both corresponding to ∼0.43 F·cm−2.

Effect of pore size on carbon dioxide sorption by carbide derived carbon

CO2 sorption at atmospheric and sub-atmospheric pressures is a key step towards carbon capture and sequestration (CCS) and materials capable of fast and efficient CO2 uptake are currently being studied extensively. Carbide-derived carbons (CDCs) show a very high sorption capacity for CO2 of up to 7.1 mol/kg at 0 °C and ambient pressure. This value is significantly higher than other carbon materials. Systematic experimental investigation of a large number of different CDCs derived from nano- and micrometer sized precursors with and without activation show a linear correlation between the CO2 uptake at a certain pressure and the pore volume. However, CO2 sorption is not limited by the total pore volume but only by pores smaller than a certain diameter. At 1 bar, pores smaller than 0.8 nm contribute the most to the CO2 uptake and at 0.1 bar pores smaller or equal to 0.5 nm are preferred. With lower total pressure, smaller pores contribute more to the measured amount of adsorbed CO2. The prediction of the CO2 uptake based on the pore volume for pores of a certain diameter is much more accurate than predictions based on the mean pore size or the specific surface area. This study provides guidelines for the design of materials with an improved ability to remove carbon dioxide from the environment at atmospheric and lower pressures.

Knitted and screen printed carbon-fiber supercapacitors for applications in wearable electronics

The field of energy textiles is growing but continues to face two main challenges: (1) flexible energy storage does not yet exist in a form that is directly comparable with everyday fabrics including their feel, drape and thickness, and (2) in order to produce an “energy textile” as part of a garment, it must be fabricated in a systematic manner allowing for multiple components of e-textiles to be integrated simultaneously. To help address these issues, we have developed textile supercapacitors based on knitted carbon fibers and activated carbon ink. We show capacitances as high as 0.51 F cm−2 per device at 10 mV s−1, which is directly comparable with those of standard activated carbon film electrodes tested under the same conditions. We also demonstrate the performance of the device when bent at 90°, 135°, 180° and when stretched. This is the first report on knitting as a fabrication technique for integrated energy storage devices.

Nanoscale Perturbations of Room Temperature Ionic Liquid Structure at Charged and Uncharged Interfaces

The nanoscale interactions of room temperature ionic liquids (RTILs) at uncharged (graphene) and charged (muscovite mica) solid surfaces were evaluated with high resolution X-ray interface scattering and fully atomistic molecular dynamics simulations. At uncharged graphene surfaces, the imidazolium-based RTIL ([bmim(+)][Tf(2)N(-)]) exhibits a mixed cation/anion layering with a strong interfacial densification of the first RTIL layer. The first layer density observed via experiment is larger than that predicted by simulation and the apparent discrepancy can be understood with the inclusion of, dominantly, image charge and π-stacking interactions between the RTIL and the graphene sheet. In contrast, the RTIL structure adjacent to the charged mica surface exhibits an alternating cation-anion layering extending 3.5 nm into the bulk fluid. The associated charge density profile demonstrates a pronounced charge overscreening (i.e., excess first-layer counterions with respect to the adjacent surface charge), highlighting the critical role of charge-induced nanoscale correlations of the RTIL. These observations confirm key aspects of a predicted electric double layer structure from an analytical Landau-Ginzburg-type continuum theory incorporating ion correlation effects, and provide a new baseline for understanding the fundamental nanoscale response of RTILs at charged interfaces.

Raman spectroscopy study of the nanodiamond-to-carbon onion transformation

Here, we present a comprehensive study analyzing early stages of the transformation of detonation nanodiamond (ND) powder to graphitic carbon onions via thermal annealing in argon atmosphere. Raman spectroscopy was employed to monitor this transformation, starting with the sp³-to-sp² conversion of the ND surface at the onset of the graphitization process. Additionally, transmission electron microscopy, x-ray diffraction, and thermogravimetric analysis were used to supplement the structural information obtained from Raman spectroscopy and allow for an accurate interpretation of the obtained Raman data. The effect of the annealing time on the transformation process was also studied to determine the kinetics of the conversion at low temperatures. The results presented in this study complement previous work on ND annealing and provide deeper insight into the nanodiamond-to-carbon onion conversion mechanism, in particular the time and size dependence. We present further evidence for the existence of a disordered sp² phase as an intermediate step in the transformation process.

Understanding controls on interfacial wetting at epitaxial graphene: Experiment and Theory

The interaction of interfacial water with graphitic carbon at the atomic scale is studied as a function of the hydrophobicity of epitaxial graphene. High resolution x-ray reflectivity shows that the graphene-water contact angle is controlled by the average graphene thickness, due to the fraction of the film surface expressed as the epitaxial buffer layer whose contact angle (contact angle {Theta}{sub c} = 73{sup o}) is substantially smaller than that of multilayer graphene ({Theta}{sub c} = 93{sup o}). Classical and ab initio molecular dynamics simulations show that the reduced contact angle of the buffer layer is due to both its epitaxy with the SiC substrate and the presence of interfacial defects. This insight clarifies the relationship between interfacial water structure and hydrophobicity, in general, and suggests new routes to control interface properties of epitaxial graphene.

Interfacial ionic ‘liquids’: connecting static and dynamic structures

It is well known that room temperature ionic liquids (RTILs) often adopt a charge-separated layered structure, i.e. with alternating cation- and anion-rich layers, at electrified interfaces. However, the dynamic response of the layered structure to temporal variations in applied potential is not well understood. We used in situ, real-time x-ray reflectivity to study the potential-dependent electric double layer (EDL) structure of an imidazolium-based RTIL on charged epitaxial graphene during potential cycling as a function of temperature. The results suggest that the graphene-RTIL interfacial structure is bistable in which the EDL structure at any intermediate potential can be described by the combination of two extreme-potential structures whose proportions vary depending on the polarity and magnitude of the applied potential. This picture is supported by the EDL structures obtained by fully atomistic molecular dynamics simulations at various static potentials. The potential-driven transition between the two structures is characterized by an increasing width but with an approximately fixed hysteresis magnitude as a function of temperature. The results are consistent with the coexistence of distinct anion- and cation-adsorbed structures separated by an energy barrier (∼0.15 eV).

Effect of cation on diffusion coefficient of ionic liquids at onion-like carbon electrodes

While most supercapacitors are limited in their performance by the stability of the electrolyte, using neat ionic liquids (ILs) as the electrolyte can expand the voltage window and temperature range of operation. In this study, ILs with bis(trifluoromethylsulfonyl)imide (Tf2N) as the anion were investigated as the electrolyte in onion-like carbon-based electrochemical capacitors. To probe the influence of cations on the electrochemical performance of supercapacitors, three different cations were used: 1-ethyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium and 1,6-bis(3-methylimidazolium-1-yl). A series of electrochemical characterization tests was performed using cyclic voltammetry (CV), galvanostatic cycling and electrochemical impedance spectroscopy (EIS). Diffusion coefficients were measured using EIS and correlated with quasielastic neutron scattering and molecular dynamics simulation. These three techniques were used in parallel to confirm a consistent trend between the three ILs. It was found that the IL with the smaller sized cation had a larger diffusion coefficient, leading to a higher capacitance at faster charge-discharge rates. Furthermore, the IL electrolyte performance was correlated with increasing temperature, which limited the voltage stability window and led to the formation of a solid electrolyte interphase on the carbon electrode surface, evident in both the CV and EIS experiments.

Nanodiamond graphitization: a magnetic resonance study.

We report on the first nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) study of the high-temperature nanodiamond-to-onion transformation. (1)H, (13)C NMR and EPR spectra of the initial nanodiamond samples and those annealed at 600, 700, 800 and 1800 ° C were measured. For the samples annealed at 600 to 800 ° C, our NMR data reveal the early stages of the surface modification, as well as a progressive increase in sp(2) carbon content with increased annealing temperature. Such quantitative experimental data were recorded for the first time. These findings correlate with EPR data on the sensitivity of the dangling bond EPR line width to air content, progressing with rising annealing temperature, that evidences consequent graphitization of the external layers of the diamond core. The sample annealed at 1800 ° C shows complete conversion of nanodiamond particles into carbon onions.

Onion-like carbon and carbon nanotube film antennas

In this paper, radiating dipole antennas have been fabricated from rolled carbon films, which are typically used for supercapacitor electrodes. Return loss and radiation pattern measurements for onion-like carbon (OLC) and multi-walled carbon nanotubes (MWCNTs) antenna samples are presented and compared to a copper standard. The OLC antennas radiation pattern measurements show a peak gain of −1.48 dBi, just less than 3 dB of a copper dipole antenna. Compared to antennas made from MWCNT films, the OLC samples show better radiation performance despite a lower measured conductivity.