Publications by Year: 2015

2015
Bozym, D. J. ; Uralcan, B. ; Limmer, D. T. ; Pope, M. A. ; Szamreta, N. J. ; Debenedetti, P. G. ; Aksay, I. A. Anomalous Capacitance Maximum of the Glassy Carbon-Ionic Liquid Interface through Dilution with Organic Solvents. J. Phys. Chem. Lett. 2015, 6 2644-2648.Abstract

We use electrochemical impedance spectroscopy to measure the effect of diluting a hydrophobic room temperature ionic liquid with miscible organic solvents on the differential capacitance of the glassy carbon − electrolyte interface. We show that the minimum differential capacitance increases with dilution and reaches a maximum value at ionic liquid contents near 5 − 10 mol% (i.e., ∼ 1 M). We provide evidence that mixtures with 1,2-dichloroethane, a low- dielectric constant solvent, yield the largest gains in capacitance near the open circuit potential when compared against two traditional solvents, acetonitrile and propylene carbonate. To provide a fundamental basis for these observations, we use a coarse-grained model to relate structural variations at the double layer to the occurrence of the maximum. Our results reveal the potential for the enhancement of double-layer capacitance through dilution.

Crain, J. M. ; Lettow, J. S. ; Aksay, I. A. ; Prud'homme, R. K. ; Korkut, S. Coatings Containing Functionalized Graphene Sheets and Articles Coated Therewith, 2015.Abstract
Coatings are provided containing functionalized graphene sheets and at least one binder. In one embodiment, the coatings are electrically conductive.
Zhang, C. ; Dabbs, D. M. ; Liu, L. - M. ; Aksay, I. A. ; Car, R. ; Selloni, A. Combined Effects of Functional Groups, Lattice Defects, and Edges in the Infrared Spectra of Graphene Oxide. J. Phys. Chem. C 2015, 119, 18167-18176.Abstract

Infrared spectroscopy in combination with density functional theory calculations has been widely used to characterize the structure of graphene oxide and its reduced forms. Yet, the synergistic effects of different functional groups, lattice defects, and edges on the vibrational spectra are not well understood. Here, we report first-principles calculations of the infrared spectra of graphene oxide performed on realistic, thermally equilibrated, structural models that incorporate lattice vacancies and edges along with various oxygen-containing functional groups. Models including adsorbed water are examined as well. Our results show that lattice vacancies lead to important blue and red shifts in the OH stretching and bending bands, respectively, whereas the presence of adsorbed water leaves these shifts largely unaffected. We also find unique infrared features for edge carboxyls resulting from interactions with both nearby functional groups and the graphene lattice. Comparison of the computed vibrational properties to our experiments clarifies the origin of several observed features and provides evidence that defects and edges are essential for characterizing and interpreting the infrared spectrum of graphene oxide.

Pope, M. A. ; Aksay, I. A. Four-Fold Increase in the Intrinsic Capacitance of Graphene through Functionalization and Lattice Disorder. J. Phys. Chem. C 2015, 119, 20369-20378.Abstract

Graphene has been heralded as a promising electrode material for high energy and power density electrochemical supercapacitors. This is in spite of recent work confirming the low double-layer capacitance (CDL) of the graphene/electrolyte interface limited by graphene’s low quantum capacitance (CQ), an effect known for the basal plane of graphite for over four decades. Consistent with this limit, much of the supercapacitor research implies the use of pristine graphene but, in contrast, uses a functionalized and defective graphene formed through the reduction of graphene oxide, without clarifying why reduced graphene oxide is needed to achieve high capacitance. Herein, we show that an optimal level of functionalization and lattice disorder in reduced graphene oxide yields a 4-fold increase in CDL over that of pristine graphene, suggesting graphene-based materials can indeed be tailored to engineer electrodes with significantly higher gravimetric capacitance limits exceeding 450 F/g than what has been achieved (∼ 274 F/g) thus far, even in nonaqueous electrolytes capable of high voltage operation.

Li, Y. ; Alain-Rizzo, V. ; Galmiche, L. ; Audebert, P. ; Miomandre, F. ; Louarn, G. ; Bozlar, M. ; Pope, M. A. ; Dabbs, D. M. ; Aksay, I. A. Functionalization of Graphene Oxide by Tetrazine Derivatives: A Versatile Approach toward Covalent Bridges between Graphene Sheets. Chem. Mater. 2015, 27, 4298-4310.Abstract

We have covalently grafted tetrazine derivatives to graphene oxide through nucleophilic substitution. Since the tetrazine unit is electroactive and nitrogen-rich, with a reduction potential sensitive to the type of substituent and degree of substitution, we used electrochemistry and X-ray photoelectron spectroscopy to demonstrate clear evidence for grafting through covalent bonding. Chemical modification was supported by Fourier transform infrared spectroscopy and thermal analysis. Tetrazines grafted onto graphene oxide displayed different mass losses compared to unmodified graphene and were more stable than the molecular precursors. Finally, a bridging tetrazine derivative was grafted between sheets of graphene oxide to demonstrate that the separation distance between sheets can be maintained while designing new graphene-based materials, including chemically bound, redox structures.

Hsieh, A. G. ; Punckt, C. ; Aksay, I. A. High-Rate Li+ Storage Capacity of Surfactant-Templated Graphene-TiO2 Nanocomposites. J. Electrochem. Soc. 2015, 162, A1566-A1573.Abstract
Graphene-TiO2 nanocomposites are a promising anode material for Li-ion batteries due to their good high-rate capacity, inherent safety, and mechanical and chemical robustness. However, despite a large number of scientific reports on the material, the mechanism of the enhanced high-rate Li+ storage capacity that results from the addition of graphene to TiO2 – typically attributed to improved electrical conductivity – is still not well understood. In this work, we focus on optimizing the processing of surfactant-templated graphene-TiO2 hybrid nanocomposites. Towards this end, we examine the influence of various processing parameters, in particular the surfactant-mediated colloidal dispersion of graphene, on the material properties and electrochemical performance of graphene-TiO2. We investigate the influence of electrode mass loading on Li+ storage capacity, focusing mainly on high-rate performance. Furthermore, we demonstrate an approach for estimating power loss during charge/discharge cycling, which offers a succinct method for characterizing the high-rate performance of Li-ion battery electrodes.
Liu, J. ; Aksay, I. A. ; Choi, D. W. ; Wang, D. H. ; Yang, Z. G. Nanocomposite of Graphene and Metal Oxide Materials, 2015.Abstract
Nanocomposite materials comprising a metal oxide bonded to at least one graphene material. The nanocomposite materials exhibit a specific capacity of at least twice that of the metal oxide material without the graphene at a charge/discharge rate greater than about 10 C.
Crain, J. M. ; Lettow, J. S. ; Aksay, I. A. ; Korkut, S. ; Chiang, K. S. ; Chen, C. H. ; Prud'homme, R. K. Printed Electronics, 2015.Abstract
Printed electronic device comprising a substrate onto at least one surface of which has been applied a layer of an electrically conductive ink comprising functionalized graphene sheets and at least one binder. A method of preparing printed electronic devices is further disclosed.
Aksay, I. A. ; Buyukdincer, B. ; Javaherian, N. ; Lettow, J. S. ; Pino, G. ; Redmond, K. ; Yildirim, I. Reinforced Polymeric Materials, 2015.Abstract
Polymeric article reinforced with a reinforcing component. The reinforcing component includes a composition made from at least one polymer and graphene sheets.
Liu, J. ; Aksay, I. A. ; Choi, D. W. ; Kou, R. ; Nie, Z. M. ; Wang, D. H. ; Yang, Z. G. Self-Assembled Multi-Layer Nanocomposite of Graphene and Metal Oxide Materials, 2015.Abstract
Nanocomposite materials having at least two layers, each layer consisting of one metal oxide bonded to at least one graphene layer were developed. The nanocomposite materials will typically have many alternating layers of metal oxides and graphene layers, bonded in a sandwich type construction and will be incorporated into an electrochemical or energy storage device.
Pope, M. A. ; Aksay, I. A. Structural Design of Cathodes for Li-S Batteries. Adv. Energy Mater. 2015, 5 1500124.Abstract

Battery technologies involving Li-S chemistries have been touted as one of the most promising next generation systems. The theoretical capacity of sulfur is nearly an order of magnitude higher than current Li-ion battery insertion cathodes and when coupled with a Li metal anode, Li-S batteries promise specific energies nearly five-fold higher. However, this assertion only holds if sulfur cathodes could be designed in the same manner as cathodes for Li-ion batteries. Here, the recent efforts to engineer high capacity, thick, sulfur-based cathodes are explored. Various works are compared in terms of capacity, areal mass loading, and fraction of conductive additive, which are the critical parameters dictating the potential for a device to achieve a specific energy higher than current Li-ion batteries (i.e., >200 Wh kg−1 ). While an inferior specific energy is projected in the majority of cases, several promising strategies have the potential to achieve >500 Wh kg−1 . The challenges associated with the limited cycle-life of these systems due to both the polysulfide shuttle phenomenon and the rapid degradation of the Li metal anode that is experienced at the current densities required to charge high specific energy batteries in a reasonable timeframe are also discussed.

Lee, Y. J. ; Huang, L. ; Wang, H. ; Sushko, M. L. ; Schwenzer, B. ; Aksay, I. A. ; Liu, J. Structural rearrangement and dispersion of functionalized graphene sheets in aqueous solutions. Colloids Interf. Sci. Comm. 2015, 8 1-5. Publisher's VersionAbstract

Surfactants are widely used for dispersing graphene and functionalized graphene sheets (FGS) in colloidal suspensions, but there have been few studies of the structure of the dispersed graphene–surfactant complexes in suspension and of their time evolution. Here, we combine experimental study of efficiencies of ionic surfactants/polymers in suspending FGS in water with characterization using atomic force microscopy, small angle neutron scattering, and molecular simulations to probe the detailed structures of FGSs. The small angle scattering technique provides quantitative measurement of structure of graphene sheets in the solution. This study suggests that in both ionic and nonionic surfactants, the dispersion tends to degrade over time through detachment of the surfactant molecules and structural rearrangements. Ionic surfactants with strong interfacial binding and large molecular weight increase the dispersing power by over an order of magnitude.