Showing papers by "Rodney S. Ruoff published in 2016"

Two-Dimensional Materials for Beyond-Lithium-Ion Batteries

Abstract: Lithium-ion batteries (LIBs) have dominated the portable electronics industry and solid-state electrochemical research and development for the past two decades. In light of possible concerns over the cost and future availability of lithium, sodium-ion batteries (SIBs) and other new technologies have emerged as candidates for large-scale stationary energy storage. Research in these technologies has increased dramatically with a focus on the development of new materials for both the positive and negative electrodes that can enhance the cycling stability, rate capability, and energy density. Two-dimensional (2D) materials are showing promise for many energy-related applications and particularly for energy storage, because of the efficient ion transport between the layers and the large surface areas available for improved ion adsorption and faster surface redox reactions. Recent research highlights on the use of 2D materials in these future ‘beyond-lithium-ion’ battery systems are reviewed, and strategies to address challenges are discussed as well as their prospects.

Interaction of black phosphorus with oxygen and water

Abstract: Black phosphorus (BP) has attracted significant interest as a monolayer or few-layer material with extraordinary electrical and optoelectronic properties. Chemical reactions with different ambient species, notably oxygen and water, are important as they govern key properties such as stability in air, electronic structure and charge transport, wetting by aqueous solutions, and so on. Here, we report experiments combined with ab initio calculations that address the effects of oxygen and water in contact with BP. Our results show that the reaction with oxygen is primarily responsible for changing properties of BP. Oxidation involving the dissociative chemisorption of O2 causes the decomposition of BP and continuously lowers the conductance of BP field-effect transistors (FETs). In contrast, BP is stable in contact with deaerated (i.e., O2 depleted) water and the carrier mobility in BP FETs gated by H2O increases significantly due to efficient dielectric screening of scattering centers by the high-k dielectri...

Synthesis of Graphene Films on Copper Foils by Chemical Vapor Deposition.

Abstract: Over the past decade, graphene has advanced rapidly as one of the most promising materials changing human life. Development of production-worthy synthetic methodologies for the preparation of various types of graphene forms the basis for its investigation and applications. Graphene can be used in the forms of either microflake powders or large-area thin films. Graphene powders are prepared by the exfoliation of graphite or the reduction of graphene oxide, while graphene films are prepared predominantly by chemical vapor deposition (CVD) on a variety of substrates. Both metal and dielectric substrates have been explored; while dielectric substrates are preferred over any other substrate, much higher quality graphene large-area films have been grown on metal substrates such as Cu. The focus here is on the progress of graphene synthesis on Cu foils by CVD, including various CVD techniques, graphene growth mechanisms and kinetics, strategies for synthesizing large-area graphene single crystals, graphene transfer techniques, and, finally, challenges and prospects are discussed.

Oxygen-activated growth and bandgap tunability of large single-crystal bilayer graphene

Abstract: Large, bilayer graphene single crystals can be grown by oxygen-activated chemical vapour deposition. Bernal (AB)-stacked bilayer graphene (BLG) is a semiconductor whose bandgap can be tuned by a transverse electric field, making it a unique material for a number of electronic and photonic devices1,2,3. A scalable approach to synthesize high-quality BLG is therefore critical, which requires minimal crystalline defects in both graphene layers4,5 and maximal area of Bernal stacking, which is necessary for bandgap tunability6. Here we demonstrate that in an oxygen-activated chemical vapour deposition (CVD) process, half-millimetre size, Bernal-stacked BLG single crystals can be synthesized on Cu. Besides the traditional ‘surface-limited’ growth mechanism for SLG (1st layer), we discovered new microscopic steps governing the growth of the 2nd graphene layer below the 1st layer as the diffusion of carbon atoms through the Cu bulk after complete dehydrogenation of hydrocarbon molecules on the Cu surface, which does not occur in the absence of oxygen. Moreover, we found that the efficient diffusion of the carbon atoms present at the interface between Cu and the 1st graphene layer further facilitates growth of large domains of the 2nd layer. The CVD BLG has superior electrical quality, with a device on/off ratio greater than 104, and a tunable bandgap up to ∼100 meV at a displacement field of 0.9 V nm−1.

Covalently Connected Carbon Nanostructures for Current Collectors in Both the Cathode and Anode of Li-S Batteries.

Abstract: A 3D current collector made of covalently connected carbon nanostructures is presented, which can significantly improve battery performance when used as the cathode and/or anode. A Li-S cell assembled using these current collectors, with the cathode loaded with elemental sulfur and the anode loaded with lithium metal, delivers a high-rate capacity of 860 mA h g-1 at 12 C.

The Origin of Improved Electrical Double-Layer Capacitance by Inclusion of Topological Defects and Dopants in Graphene for Supercapacitors

Abstract: Low-energy density has long been the major limitation to the application of supercapacitors. Introducing topological defects and dopants in carbon-based electrodes in a supercapacitor improves the performance by maximizing the gravimetric capacitance per mass of the electrode. However, the main mechanisms governing this capacitance improvement are still unclear. We fabricated planar electrodes from CVD-derived single-layer graphene with deliberately introduced topological defects and nitrogen dopants in controlled concentrations and of known configurations, to estimate the influence of these defects on the electrical double-layer (EDL) capacitance. Our experimental study and theoretical calculations show that the increase in EDL capacitance due to either the topological defects or the nitrogen dopants has the same origin, yet these two factors improve the EDL capacitance in different ways. Our work provides a better understanding of the correlation between the atomic-scale structure and the EDL capacitance and presents a new strategy for the development of experimental and theoretical models for understanding the EDL capacitance of carbon electrodes.

Synthesis of aligned symmetrical multifaceted monolayer hexagonal boron nitride single crystals on resolidified copper

Abstract: Atomically smooth hexagonal boron nitride (h-BN) films are considered as a nearly ideal dielectric interface for two-dimensional (2D) heterostructure devices. Reported mono- to few-layer 2D h-BN films, however, are mostly small grain-sized, polycrystalline and randomly oriented. Here we report the growth of centimetre-sized atomically thin h-BN films composed of aligned domains on resolidified Cu. The films consist of monolayer single crystalline triangular and hexagonal domains with size of up to ∼10 μm. The domains converge to symmetrical multifaceted shapes such as "butterfly" and "6-apex-star" and exhibit ∼75% grain alignment for over millimetre distances as verified through transmission electron microscopy. Scanning electron microscopy images reveal that these domains are aligned for over centimetre distances. Defect lines are generated along the grain boundaries of mirroring h-BN domains due to the two different polarities (BN and NB) and edges with the same termination. The observed triangular domains with truncated edges and alternatively hexagonal domains are in accordance with Wulff shapes that have minimum edge energy. This work provides an extensive study on the aligned growth of h-BN single crystals over large distances and highlights the obstacles that are needed to be overcome for a 2D material with a binary configuration.

Two‐Dimensional Materials for Beyond‐Lithium‐Ion Batteries

Abstract: Lithium-ion batteries (LIBs) have dominated the portable electronics industry and solid-state electrochemical research and development for the past two decades. In light of possible concerns over the cost and future availability of lithium, sodium-ion batteries (SIBs) and other new technologies have emerged as candidates for large-scale stationary energy storage. Research in these technologies has increased dramatically with a focus on the development of new materials for both the positive and negative electrodes that can enhance the cycling stability, rate capability, and energy density. Two-dimensional (2D) materials are showing promise for many energy-related applications and particularly for energy storage, because of the efficient ion transport between the layers and the large surface areas available for improved ion adsorption and faster surface redox reactions. Recent research highlights on the use of 2D materials in these future ‘beyond-lithium-ion’ battery systems are reviewed, and strategies to address challenges are discussed as well as their prospects.

Laser-induced phase separation of silicon carbide.

Abstract: Understanding the phase separation mechanism of solid-state binary compounds induced by laser–material interaction is a challenge because of the complexity of the compound materials and short processing times. Here we present xenon chloride excimer laser-induced melt-mediated phase separation and surface reconstruction of single-crystal silicon carbide and study this process by high-resolution transmission electron microscopy and a time-resolved reflectance method. A single-pulse laser irradiation triggers melting of the silicon carbide surface, resulting in a phase separation into a disordered carbon layer with partially graphitic domains (∼2.5 nm) and polycrystalline silicon (∼5 nm). Additional pulse irradiations cause sublimation of only the separated silicon element and subsequent transformation of the disordered carbon layer into multilayer graphene. The results demonstrate viability of synthesizing ultra-thin nanomaterials by the decomposition of a binary system. Laser beam-induced processing is industrially relevant but often challenging to study in terms of underlying phase transformations. Here authors characterize formation of thin, phase-separated carbon and silicon layers on a silicon carbide substrate by laser-induced melting and solidification.

Support-Free Transfer of Ultrasmooth Graphene Films Facilitated by Self-Assembled Monolayers for Electronic Devices and Patterns

Abstract: We explored a support-free method for transferring large area graphene films grown by chemical vapor deposition to various fluoric self-assembled monolayer (F-SAM) modified substrates including SiO2/Si wafers, polyethylene terephthalate films, and glass. This method yields clean, ultrasmooth, and high-quality graphene films for promising applications such as transparent, conductive, and flexible films due to the absence of residues and limited structural defects such as cracks. The F-SAM introduced in the transfer process can also lead to graphene transistors with enhanced field-effect mobility (up to 10,663 cm2/Vs) and resistance modulation (up to 12×) on a standard silicon dioxide dielectric. Clean graphene patterns can be realized by transfer of graphene onto only the F-SAM modified surfaces.

Graphene Coatings as Barrier Layers to Prevent the Water-Induced Corrosion of Silicate Glass

Abstract: Corrosion-protective coatings for silicate glass based on the transfer of one or two layers of graphene grown on copper by chemical vapor deposition have been demonstrated. The effectiveness of graphene to act as a glass corrosion inhibitor was evaluated by water immersion testing. After 120 days of immersion in water, bare glass samples had a significant increase in surface roughness and defects, which resulted in a marked reduction in fracture strength. In contrast, the single- and double-layer graphene-coated glasses experienced negligible changes in both fracture strength and surface roughness. The anticorrosion mechanism was also studied.

Molecule-Induced Conformational Change in Boron Nitride Nanosheets with Enhanced Surface Adsorption

Abstract: Surface interaction is extremely important to both fundamental research and practical application. Physisorption can induce shape and structural distortion (i.e., conformational changes) in macromolecular and biomolecular adsorbates, but such phenomena have rarely been observed on adsorbents. Here, it is demonstrated theoretically and experimentally that atomically thin boron nitride (BN) nanosheets as an adsorbent experience conformational changes upon surface adsorption of molecules, increasing adsorption energy and efficiency. The study not only provides new perspectives on the strong adsorption capability of BN nanosheets and many other two-dimensional (2D) nanomaterials but also opens up possibilities for many novel applications. For example, it is demonstrated that BN nanosheets with the same surface area as bulk hexagonal BN particles are more effective in purification and sensing.

Molecule-Induced Conformational Change in Boron Nitride Nanosheets with Enhanced Surface Adsorption

Abstract: Surface interaction is extremely important to both fundamental research and practical application. Physisorption can induce shape and structural distortion (i.e. conformational changes) in macromolecular and biomolecular adsorbates, but such phenomenon has rarely been observed on adsorbents. Here, we demonstrate theoretically and experimentally that atomically thin boron nitride (BN) nanosheets as an adsorbent experience conformational changes upon surface adsorption of molecules, increasing adsorption energy and efficiency. The study not only provides new perspectives on the strong adsorption capability of BN nanosheets and many other two-dimensional nanomaterials but also opens up possibilities for many novel applications. For example, we demonstrate that BN nanosheets with the same surface area as bulk hBN particles are more effective in purification and sensing.

First-Principles Study of the Role of O2 and H2O in the Decoupling of Graphene on Cu(111)

Abstract: The structural and electronic properties of graphene coated on a Cu(111) surface can be strongly influenced by the arrangement of adsorbates at the graphene edges. Oxygen and water intercalation at the graphene edges could lead to oxidation and hydrolysis at the graphene/Cu(111) interface, eventually causing decoupling of graphene from the Cu substrate. However, the reaction pathways for oxygen or water (or both) intercalation at the graphene edges are not well understood at the molecular level. Using ab initio density functional theory calculations, we observed a strong hybridization of π orbitals at a zigzag edge of a graphene nanoribbon (GNR) on a bare Cu(111) surface, whereas such hybridization was absent for the corresponding armchair edge under otherwise identical conditions. These results indicate that the edge type influences the oxidation chemistry beneath the GNR. Moreover, we demonstrate that the presence of oxygen species, as well as GNR, facilitates the propagation of H2O. The following decou...

Birch-Type Hydrogenation of Few-Layer Graphenes: Products and Mechanistic Implications

Abstract: Few-layer graphenes, supported on Si with a superficial oxide layer, were subjected to a Birch-type reduction using Li and H2O as the electron and proton donors, respectively. The extent of hydrogenation for bilayer graphene was estimated at 1.6–24.1% according to Raman and X-ray photoelectron spectroscopic data. While single-layer graphene reacts uniformly, few-layer graphenes were hydrogenated inward from the edges and/or defects. The role of these reactive sites was reflected in the inertness of pristine few-layer graphenes whose edges were sealed. Hydrogenation of labeled bilayer (12C/13C) and trilayer (12C/13C/12C) graphenes afforded products whose sheets were hydrogenated to the same extent, implicating passage of reagents between the graphene layers and equal decoration of each graphene face. The reduction of few-layer graphenes introduces strain, allows tuning of optical transmission and fluorescence, and opens synthetic routes to long sought-after films containing sp3-hybridized carbon.

Graphene Films: Synthesis of Graphene Films on Copper Foils by Chemical Vapor Deposition (Adv. Mater. 29/2016).

Abstract: Synthesis of graphene films on copper foils is discussed by X. Li, L. Colombo, and R. S. Ruoff on page 6247. Graphene can grow on metal substrates by chemical vapor deposition of hydrocarbons. Hydrocarbons crack on a metal surface, nucleate, grow, and finally merge to form a continuous graphene film. Copper is one of the best candidates for graphene growth due to the advantages of good control over the graphene thickness, the growth of high-quality graphene, and the ease for graphene transfer, and has been widely used for production of large-area graphene films in both academia and industry.

Conversion of Langmuir-Blodgett monolayers and bilayers of poly (amic acid) through polyimide to graphene

Abstract: Various solid carbon sources, particularly poly(methyl methacrylate), have been used as precursors to graphene. The corresponding growth process generally involves the decomposition of the solids to hydrocarbon gases followed by their adsorption on metallic substrates (e.g., Cu). We report a different approach that uses a thermally-resistant polyimide (PI) as a carbon precursor. Langmuir–Blodgett films of poly(amic acid) (PAA) were transferred to copper foils and then converted to graphene via a PI intermediate. The Cu foil substrate was also discovered to facilitate the orientation of aromatic moieties upon carbonization process of the PI. As approximately 50% of the initial quantity of the PAA was found to remain at 1000 °C, thermally-stable polymers may reduce the quantity of starting material required to prepare high quality films of graphene. Graphene grown using this method featured a relatively large domain size and an absence of adventitious adlayers.

Effects of thermally-induced changes of Cu grains on domain structure and electrical performance of CVD-grown graphene

Abstract: During the chemical vapor deposition (CVD) growth of graphene on Cu foils, evaporation of Cu and changes in the dimensions of Cu grains in directions both parallel and perpendicular to the foils are induced by thermal effects. Such changes in the Cu foil could subsequently change the shape and distribution of individual graphene domains grown on the foil surface, and thus influence the domain structure and electrical properties of the resulting graphene films. Here, a slower cooling rate is used after the CVD process, and the graphene films are found to have an improved electrical performance, which is considered to be associated with the Cu surface evaporation and grain structure changes in the Cu substrate.

Ultracapacitor with a novel doped carbon

Abstract: Doped activated microwave expanded graphite oxide materials and doped monolayer graphene materials, and methods of making these materials. The materials exhibit increased capacitance relative to undoped activated microwave expanded graphite oxide and monolayer graphene. The materials are suitable for use in, for example, ultracapacitors.