Author
Noel Díez
Other affiliations: Wrocław University of Technology
Bio: Noel Díez is an academic researcher from Spanish National Research Council. The author has contributed to research in topics: Supercapacitor & Carbonization. The author has an hindex of 21, co-authored 44 publications receiving 1350 citations. Previous affiliations of Noel Díez include Wrocław University of Technology.
Papers
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Heidelberg University1, Trinity College, Dublin2, University of Cambridge3, Autonomous University of Madrid4, Université Paris-Saclay5, Spanish National Research Council6, University of Zaragoza7, University of Nottingham8, RWTH Aachen University9, Kessler Foundation10, Istituto Italiano di Tecnologia11, University of Grenoble12, Georgia Institute of Technology13, Dresden University of Technology14, Polytechnic University of Turin15, University of Zurich16, Bielefeld University17, University of Strasbourg18, Technical University of Denmark19, Swiss Federal Laboratories for Materials Science and Technology20, Ikerbasque21, University of Erlangen-Nuremberg22, Technische Universität München23, Bundeswehr University Munich24, University of Bern25, University of Patras26, Foundation for Research & Technology – Hellas27, Center for Theoretical Studies, University of Miami28, École Polytechnique Fédérale de Lausanne29, University of Ulm30, University of Eastern Finland31, Aristotle University of Thessaloniki32, University of Manchester33, Polish Academy of Sciences34, Aalto University35, University of Castilla–La Mancha36, ShanghaiTech University37, University of Exeter38, Chalmers University of Technology39, Warsaw University of Technology40, University of Trieste41, University of Trento42, Queen Mary University of London43, Instituto Politécnico Nacional44, University of the Basque Country45, Chemnitz University of Technology46, Charles University in Prague47, University of Jena48, University of Texas at Dallas49
TL;DR: In this article, the authors present an overview of the main techniques for production and processing of graphene and related materials (GRMs), as well as the key characterization procedures, adopting a 'hands-on' approach, providing practical details and procedures as derived from literature and from the authors' experience, in order to enable the reader to reproduce the results.
Abstract: © 2020 The Author(s). We present an overview of the main techniques for production and processing of graphene and related materials (GRMs), as well as the key characterization procedures. We adopt a 'hands-on' approach, providing practical details and procedures as derived from literature as well as from the authors' experience, in order to enable the reader to reproduce the results. Section I is devoted to 'bottom up' approaches, whereby individual constituents are pieced together into more complex structures. We consider graphene nanoribbons (GNRs) produced either by solution processing or by on-surface synthesis in ultra high vacuum (UHV), as well carbon nanomembranes (CNM). Production of a variety of GNRs with tailored band gaps and edge shapes is now possible. CNMs can be tuned in terms of porosity, crystallinity and electronic behaviour. Section II covers 'top down' techniques. These rely on breaking down of a layered precursor, in the graphene case usually natural crystals like graphite or artificially synthesized materials, such as highly oriented pyrolythic graphite, monolayers or few layers (FL) flakes. The main focus of this section is on various exfoliation techniques in a liquid media, either intercalation or liquid phase exfoliation (LPE). The choice of precursor, exfoliation method, medium as well as the control of parameters such as time or temperature are crucial. A definite choice of parameters and conditions yields a particular material with specific properties that makes it more suitable for a targeted application. We cover protocols for the graphitic precursors to graphene oxide (GO). This is an important material for a range of applications in biomedicine, energy storage, nanocomposites, etc. Hummers' and modified Hummers' methods are used to make GO that subsequently can be reduced to obtain reduced graphene oxide (RGO) with a variety of strategies. GO flakes are also employed to prepare three-dimensional (3d) low density structures, such as sponges, foams, hydro- or aerogels. The assembly of flakes into 3d structures can provide improved mechanical properties. Aerogels with a highly open structure, with interconnected hierarchical pores, can enhance the accessibility to the whole surface area, as relevant for a number of applications, such as energy storage. The main recipes to yield graphite intercalation compounds (GICs) are also discussed. GICs are suitable precursors for covalent functionalization of graphene, but can also be used for the synthesis of uncharged graphene in solution. Degradation of the molecules intercalated in GICs can be triggered by high temperature treatment or microwave irradiation, creating a gas pressure surge in graphite and exfoliation. Electrochemical exfoliation by applying a voltage in an electrolyte to a graphite electrode can be tuned by varying precursors, electrolytes and potential. Graphite electrodes can be either negatively or positively intercalated to obtain GICs that are subsequently exfoliated. We also discuss the materials that can be amenable to exfoliation, by employing a theoretical data-mining approach. The exfoliation of LMs usually results in a heterogeneous dispersion of flakes with different lateral size and thickness. This is a critical bottleneck for applications, and hinders the full exploitation of GRMs produced by solution processing. The establishment of procedures to control the morphological properties of exfoliated GRMs, which also need to be industrially scalable, is one of the key needs. Section III deals with the processing of flakes. (Ultra)centrifugation techniques have thus far been the most investigated to sort GRMs following ultrasonication, shear mixing, ball milling, microfluidization, and wet-jet milling. It allows sorting by size and thickness. Inks formulated from GRM dispersions can be printed using a number of processes, from inkjet to screen printing. Each technique has specific rheological requirements, as well as geometrical constraints. The solvent choice is critical, not only for the GRM stability, but also in terms of optimizing printing on different substrates, such as glass, Si, plastic, paper, etc, all with different surface energies. Chemical modifications of such substrates is also a key step. Sections IV-VII are devoted to the growth of GRMs on various substrates and their processing after growth to place them on the surface of choice for specific applications. The substrate for graphene growth is a key determinant of the nature and quality of the resultant film. The lattice mismatch between graphene and substrate influences the resulting crystallinity. Growth on insulators, such as SiO2, typically results in films with small crystallites, whereas growth on the close-packed surfaces of metals yields highly crystalline films. Section IV outlines the growth of graphene on SiC substrates. This satisfies the requirements for electronic applications, with well-defined graphene-substrate interface, low trapped impurities and no need for transfer. It also allows graphene structures and devices to be measured directly on the growth substrate. The flatness of the substrate results in graphene with minimal strain and ripples on large areas, allowing spectroscopies and surface science to be performed. We also discuss the surface engineering by intercalation of the resulting graphene, its integration with Si-wafers and the production of nanostructures with the desired shape, with no need for patterning. Section V deals with chemical vapour deposition (CVD) onto various transition metals and on insulators. Growth on Ni results in graphitized polycrystalline films. While the thickness of these films can be optimized by controlling the deposition parameters, such as the type of hydrocarbon precursor and temperature, it is difficult to attain single layer graphene (SLG) across large areas, owing to the simultaneous nucleation/growth and solution/precipitation mechanisms. The differing characteristics of polycrystalline Ni films facilitate the growth of graphitic layers at different rates, resulting in regions with differing numbers of graphitic layers. High-quality films can be grown on Cu. Cu is available in a variety of shapes and forms, such as foils, bulks, foams, thin films on other materials and powders, making it attractive for industrial production of large area graphene films. The push to use CVD graphene in applications has also triggered a research line for the direct growth on insulators. The quality of the resulting films is lower than possible to date on metals, but enough, in terms of transmittance and resistivity, for many applications as described in section V. Transfer technologies are the focus of section VI. CVD synthesis of graphene on metals and bottom up molecular approaches require SLG to be transferred to the final target substrates. To have technological impact, the advances in production of high-quality large-area CVD graphene must be commensurate with those on transfer and placement on the final substrates. This is a prerequisite for most applications, such as touch panels, anticorrosion coatings, transparent electrodes and gas sensors etc. New strategies have improved the transferred graphene quality, making CVD graphene a feasible option for CMOS foundries. Methods based on complete etching of the metal substrate in suitable etchants, typically iron chloride, ammonium persulfate, or hydrogen chloride although reliable, are time- and resourceconsuming, with damage to graphene and production of metal and etchant residues. Electrochemical delamination in a low-concentration aqueous solution is an alternative. In this case metallic substrates can be reused. Dry transfer is less detrimental for the SLG quality, enabling a deterministic transfer. There is a large range of layered materials (LMs) beyond graphite. Only few of them have been already exfoliated and fully characterized. Section VII deals with the growth of some of these materials. Amongst them, h-BN, transition metal tri- and di-chalcogenides are of paramount importance. The growth of h-BN is at present considered essential for the development of graphene in (opto) electronic applications, as h-BN is ideal as capping layer or substrate. The interesting optical and electronic properties of TMDs also require the development of scalable methods for their production. Large scale growth using chemical/physical vapour deposition or thermal assisted conversion has been thus far limited to a small set, such as h-BN or some TMDs. Heterostructures could also be directly grown.
330 citations
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TL;DR: In this article, a commercial graphite oxides with different oxygen contents and specifications were prepared by different versions of the Hummers method and by oxidation with sodium dichromate, and the results showed that even using the same oxidizing method, the chemical structure can be tailored by changing reaction conditions.
161 citations
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TL;DR: In this paper, a high-pressure assisted hydrothermal treatment is proposed as a facile, green and efficient route for the reduction of aqueous dispersions of graphene oxide.
Abstract: A high-pressure assisted hydrothermal treatment is proposed as a facile, green and efficient route for the reduction of aqueous dispersions of graphene oxide. Reactions were performed in an autoclave at mild temperature (180 °C) using only water and nitrogen or hydrogen gas. No further separation or purification of the reduced products was required. X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction and thermogravimetric analysis revealed that the application of high pressure significantly enhanced oxygen removal. The C/O atomic ratio of the graphene oxide sheets increased from 1.65 to 5.29 upon conventional hydrothermal treatment using autogenous pressure. Higher C/O ratios of 6.35 and 7.93 were obtained for graphene oxides that were reduced under high-pressure of nitrogen and hydrogen, respectively. Specifically, the use of high-pressure hydrogen improved the removal of oxygen double-bonded to carbon. The introduction of covalently bonded heteroatoms, which is commonly observed for the use of reductants such as hydrazine, was not detected. Furthermore, high-pressure reduction led to a better restoration of the sp2 conjugation than was obtained by conventional hydrothermal treatment, as determined by XPS and Raman spectroscopies. These findings illustrate the promise of high-pressure hydrothermal treatments for the eco-friendly mass production of reduced graphene oxide.
152 citations
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TL;DR: In this article, the authors used the FICYT Regional Project (GRUPIN14-102) and the Spanish MINECO-FEDER (CTQ2015-63552-R) to support their work.
111 citations
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TL;DR: In this article, high-surface area carbons are produced from wood sawdust and tannic acid by means of an environmentally friendly process based on the use of sodium thiosulfate as activating agent and an inert salt (KCl) that serves as a confinement medium for the activation reaction.
109 citations
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28,685 citations
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1,178 citations
01 Apr 2014
TL;DR: In this article, a mesoporous nitrogen-doped carbon (MPNC)-sulfur nanocomposite is reported as a novel cathode for advanced Li-S batteries.
Abstract: As one important component of sulfur cathodes, the carbon host plays a key role in the electrochemical performance of lithium-sulfur (Li-S) batteries. In this paper, a mesoporous nitrogen-doped carbon (MPNC)-sulfur nanocomposite is reported as a novel cathode for advanced Li-S batteries. The nitrogen doping in the MPNC material can effectively promote chemical adsorption between sulfur atoms and oxygen functional groups on the carbon, as verifi ed by X-ray absorption near edge structure spectroscopy, and the mechanism by which nitrogen enables the behavior is further revealed by density functional theory calculations. Based on the advantages of the porous structure and nitrogen doping, the MPNC-sulfur cathodes show excellent cycling stability (95% retention within 100 cycles) at a high current density of 0.7 mAh cm −2 with a high sulfur loading (4.2 mg S cm −2 ) and a sulfur content (70 wt%). A high areal capacity (≈3.3 mAh cm −2 ) is demonstrated by using the novel cathode, which is crucial for the practical application of Li-S batteries. It is believed that the important role of nitrogen doping promoted chemical adsorption can be extended for development of other high performance carbon-sulfur composite cathodes for Li-S batteries.
826 citations
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01 Jan 1991
TL;DR: Improvement in understanding has led in some cases to better management with improved outcome for the patient, whereas in other areas the way is now clear towards a better prospect for the future.
Abstract: The various contributions to this book record the remarkable progress that has been made in the understanding and management of pancreatic diseases over the last decade. The improvement in understanding has led in some cases to better management with improved outcome for the patient, whereas in other areas the way is now clear towards a better prospect for the future.
552 citations