Richard D. Piner

Graphene-based composite materials

Graphene sheets—one-atom-thick two-dimensional layers of sp2-bonded carbon—are predicted to have a range of unusual properties. Their thermal conductivity and mechanical stiffness may rival the remarkable in-plane values for graphite (∼3,000 W m-1 K-1 and 1,060 GPa, respectively); their fracture strength should be comparable to that of carbon nanotubes for similar types of defects; and recent studies have shown that individual graphene sheets have extraordinary electronic transport properties. One possible route to harnessing these properties for applications would be to incorporate graphene sheets in a composite material. The manufacturing of such composites requires not only that graphene sheets be produced on a sufficient scale but that they also be incorporated, and homogeneously distributed, into various matrices. Graphite, inexpensive and available in large quantity, unfortunately does not readily exfoliate to yield individual graphene sheets. Here we present a general approach for the preparation of graphene-polymer composites via complete exfoliation of graphite and molecular-level dispersion of individual, chemically modified graphene sheets within polymer hosts. A polystyrene–graphene composite formed by this route exhibits a percolation threshold of ∼0.1 volume per cent for room-temperature electrical conductivity, the lowest reported value for any carbon-based composite except for those involving carbon nanotubes; at only 1 volume per cent, this composite has a conductivity of ∼0.1 S m-1, sufficient for many electrical applications. Our bottom-up chemical approach of tuning the graphene sheet properties provides a path to a broad new class of graphene-based materials and their use in a variety of applications.

Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils

Growing Graphene The highest quality graphene samples, single-atom-thick layers of carbon, are suspended flakes exfoliated from graphite, but these samples are very small in size (square micrometers). For many electronics applications, larger areas are needed. Li et al. (p. 1312, published online 7 May) show that graphene grows in a self-limiting way on copper films as large-area sheets (one square centimeter) from methane through a chemical vapor deposition process. The films, which are mainly one layer in thickness, can be transferred to other substrates and have electron mobilities as high as 4300 square centimeters per volt second. Predominantly single-layer graphene films grow in a self-limited manner on copper and can be transferred to other substrates. Graphene has been attracting great interest because of its distinctive band structure and physical properties. Today, graphene is limited to small sizes because it is produced mostly by exfoliating graphite. We grew large-area graphene films of the order of centimeters on copper substrates by chemical vapor deposition using methane. The films are predominantly single-layer graphene, with a small percentage (less than 5%) of the area having few layers, and are continuous across copper surface steps and grain boundaries. The low solubility of carbon in copper appears to help make this growth process self-limiting. We also developed graphene film transfer processes to arbitrary substrates, and dual-gated field-effect transistors fabricated on silicon/silicon dioxide substrates showed electron mobilities as high as 4050 square centimeters per volt per second at room temperature.

Preparation and characterization of graphene oxide paper.

Free-standing paper-like or foil-like materials are an integral part of our technological society. Their uses include protective layers, chemical filters, components of electrical batteries or supercapacitors, adhesive layers, electronic or optoelectronic components, and molecular storage. Inorganic ‘paper-like’ materials based on nanoscale components such as exfoliated vermiculite or mica platelets have been intensively studied and commercialized as protective coatings, high-temperature binders, dielectric barriers and gas-impermeable membranes4,5. Carbon-based flexible graphite foils composed of stacked platelets of expanded graphite have long been used in packing and gasketing applications because of their chemical resistivity against most media, superior sealability over a wide temperature range, and impermeability to fluids. The discovery of carbon nanotubes brought about bucky paper, which displays excellent mechanical and electrical properties that make it potentially suitable for fuel cell and structural composite applications. Here we report the preparation and characterization of graphene oxide paper, a free-standing carbon-based membrane material made by flow-directed assembly of individual graphene oxide sheets. This new material outperforms many other paper-like materials in stiffness and strength. Its combination of macroscopic flexibility and stiffness is a result of a unique interlocking-tile arrangement of the nanoscale graphene oxide sheets.

Functionalized graphene sheets for polymer nanocomposites

Polymer-based composites were heralded in the 1960s as a new paradigm for materials. By dispersing strong, highly stiff fibres in a polymer matrix, high-performance lightweight composites could be developed and tailored to individual applications. Today we stand at a similar threshold in the realm of polymer nanocomposites with the promise of strong, durable, multifunctional materials with low nanofiller content. However, the cost of nanoparticles, their availability and the challenges that remain to achieve good dispersion pose significant obstacles to these goals. Here, we report the creation of polymer nanocomposites with functionalized graphene sheets, which overcome these obstacles and provide superb polymer-particle interactions. An unprecedented shift in glass transition temperature of over 40 degrees C is obtained for poly(acrylonitrile) at 1 wt% functionalized graphene sheet, and with only 0.05 wt% functionalized graphene sheet in poly(methyl methacrylate) there is an improvement of nearly 30 degrees C. Modulus, ultimate strength and thermal stability follow a similar trend, with values for functionalized graphene sheet- poly(methyl methacrylate) rivaling those for single-walled carbon nanotube-poly(methyl methacrylate) composites.

Transfer of Large-Area Graphene Films for High-Performance Transparent Conductive Electrodes

Graphene, a two-dimensional monolayer of sp(2)-bonded carbon atoms, has been attracting great interest due to its unique transport properties. One of the promising applications of graphene is as a transparent conductive electrode owing to its high optical transmittance and conductivity. In this paper, we report on an improved transfer process of large-area graphene grown on Cu foils by chemical vapor deposition. The transferred graphene films have high electrical conductivity and high optical transmittance that make them suitable for transparent conductive electrode applications. The improved transfer processes will also be of great value for the fabrication of electronic devices such as field effect transistor and bilayer pseudospin field effect transistor devices.

Stable aqueous dispersions of graphitic nanoplatelets via the reduction of exfoliated graphite oxide in the presence of poly(sodium 4-styrenesulfonate)

For the first time, stable aqueous dispersions of polymer-coated graphitic nanoplatelets can be prepared via an exfoliation/in-situ reduction of graphite oxide in the presence of poly(sodium 4-styrenesulfonate).

Synthesis and Solid-State NMR Structural Characterization of 13C-Labeled Graphite Oxide

The detailed chemical structure of graphite oxide (GO), a layered material prepared from graphite almost 150 years ago and a precursor to chemically modified graphenes, has not been previously resolved because of the pseudo-random chemical functionalization of each layer, as well as variations in exact composition. Carbon-13 (13C) solid-state nuclear magnetic resonance (SSNMR) spectra of GO for natural abundance 13C have poor signal-to-noise ratios. Approximately 100% 13C-labeled graphite was made and converted to 13C-labeled GO, and 13C SSNMR was used to reveal details of the chemical bonding network, including the chemical groups and their connections. Carbon-13–labeled graphite can be used to prepare chemically modified graphenes for 13C SSNMR analysis with enhanced sensitivity and for fundamental studies of 13C-labeled graphite and graphene.

Oxidation resistance of graphene-coated Cu and Cu/Ni alloy.

The ability to protect refined metals from reactive environments is vital to many industrial and academic applications. Current solutions, however, typically introduce several negative effects, including increased thickness and changes in the metal physical properties. In this paper, we demonstrate for the first time the ability of graphene films grown by chemical vapor deposition to protect the surface of the metallic growth substrates of Cu and Cu/Ni alloy from air oxidation. In particular, graphene prevents the formation of any oxide on the protected metal surfaces, thus allowing pure metal surfaces only one atom away from reactive environments. SEM, Raman spectroscopy, and XPS studies show that the metal surface is well protected from oxidation even after heating at 200 °C in air for up to 4 h. Our work further shows that graphene provides effective resistance against hydrogen peroxide. This protection method offers significant advantages and can be used on any metal that catalyzes graphene growth.

Tunable Electrical Conductivity of Individual Graphene Oxide Sheets Reduced at “Low” Temperatures

Step-by-step controllable thermal reduction of individual graphene oxide sheets, incorporated into multiterminal field effect devices, was carried out at low temperatures (125-240 degrees C) with simultaneous electrical measurements. Symmetric hysteresis-free ambipolar (electron- and hole-type) gate dependences were observed as soon as the first measurable resistance was reached. The conductivity of each of the fabricated devices depended on the level of reduction (was increased more than 10(6) times as reduction progressed), strength of the external electrical field, density of the transport current, and temperature.

Exfoliation of graphite oxide in propylene carbonate and thermal reduction of the resulting graphene oxide platelets

Graphite oxide was exfoliated and dispersed in propylene carbonate (PC) by bath sonication. Heating the graphene oxide suspensions at 150 degrees C significantly reduced the graphene oxide platelets; paper samples comprising such reduced graphene oxide platelets had an electrical conductivity of 5230 S/m. By adding tetraethylammonium tetrafluoroborate (TEA BF(4)) to the reduced graphene oxide/PC slurry and making a two-cell ultracapacitor, specific capacitance values of about 120 F/g were obtained.