Gram-scale bottom-up flash graphene synthesis

Abstract

Most bulk-scale graphene is produced by a top-down approach, exfoliating graphite, which often requires large amounts of solvent with high-energy mixing, shearing, sonication or electrochemical treatment1,2,3. Although chemical oxidation of graphite to graphene oxide promotes exfoliation, it requires harsh oxidants and leaves the graphene with a defective perforated structure after the subsequent reduction step3,4. Bottom-up synthesis of high-quality graphene is often restricted to ultrasmall amounts if performed by chemical vapour deposition or advanced synthetic organic methods, or it provides a defect-ridden structure if carried out in bulk solution4,5,6. Here we show that flash Joule heating of inexpensive carbon sources—such as coal, petroleum coke, biochar, carbon black, discarded food, rubber tyres and mixed plastic waste—can afford gram-scale quantities of graphene in less than one second. The product, named flash graphene (FG) after the process used to produce it, shows turbostratic arrangement (that is, little order) between the stacked graphene layers. FG synthesis uses no furnace and no solvents or reactive gases. Yields depend on the carbon content of the source; when using a high-carbon source, such as carbon black, anthracitic coal or calcined coke, yields can range from 80 to 90 per cent with carbon purity greater than 99 per cent. No purification steps are necessary. Raman spectroscopy analysis shows a low-intensity or absent D band for FG, indicating that FG has among the lowest defect concentrations reported so far for graphene, and confirms the turbostratic stacking of FG, which is clearly distinguished from turbostratic graphite. The disordered orientation of FG layers facilitates its rapid exfoliation upon mixing during composite formation. The electric energy cost for FG synthesis is only about 7.2 kilojoules per gram, which could render FG suitable for use in bulk composites of plastic, metals, plywood, concrete and other building materials.

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Fig. 1: FG synthesized from various carbon sources.
Fig. 2: FJH critical parameters.
Fig. 3: Molecular dynamics simulations.
Fig. 4: Scaling up and applications of CB-FG.

Data availability

The datasets generated and/or analysed during the current study are available from the corresponding author on reasonable request.

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Acknowledgements

We thank G. A. Lopez Silva for preparing the schematic of the FJH process, J. Li for preparing the olive oil soot, Oxbow Calcining International LLC for donating the calcined coke, Ergon Asphalt and Emulsions, Inc. for donating the rubber-tyre-derived carbon black, and Neroval LLC for donating the biochar. K.V.B. and B.I.Y. thank the National Science Foundation (NSF) for support (CBET-1605848) and B. Sastri of the US Department of Energy for discussions. R.S. thanks the partial support of NSF-DMR 1709051. J.M.T. thanks the US Air Force Office of Scientific Research (FA9550-19-1-0296) for support.

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Authors

Contributions

D.X.L. discovered the FJH conversion of carbon materials to graphene, designed and built the FJH apparatus, designed and built the spectrometer for temperature determination, acquired most of the data, and wrote most of the manuscript. K.V.B. conducted the mechanistic theory calculations under the guidance of B.I.Y. W.A.A. and P.A.A. fabricated some FG samples, and blended and tested the polymer blends. M.G.S. obtained the SEM images and wrote parts of Supplementary Information, especially regarding FG morphology. C.K. assisted with the design of the FG apparatus and the spectrometer, and wrote parts of Supplementary Information regarding turbostratic graphene. R.V.S. obtained most of the TEM images and all of the selected-area electron diffraction data. W.C. and H.G. obtained some of the TEM images. M.R. built and tested the lithium-ion capacitor. C.K. and V.M. assisted D.X.L. in the design and safety features of the FJH system. E.A.M. performed the thermogravimetric analysis. Z.W. obtained the surface area. M.B. obtained the cement and polymer composite data under the guidance of R.S. All aspects of the research were overseen by J.M.T., who co-wrote some sections of the manuscript.

Corresponding authors

Correspondence to Rouzbeh Shahsavari or Boris I. Yakobson or James M. Tour.

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Competing interests

The FG synthesis process is the intellectual property of Rice University. J.M.T., D.X.L. and V.M. will be stockholders in Universal Matter Ltd, a company licensing the FG intellectual property of Rice University and scaling up this process. At the time of the writing and submission of this manuscript, the license to Universal Matter has not been consummated. C-Crete Technologies owns intellectual property on the strengthening of graphene–cement/concrete composites. V.M. is now employed by Universal Matter. D.X.L. and J.M.T. will remain full time with Rice University, whereas D.X.L. might be employed by Universal Matter in two years. All conflicts of interest for J.M.T. and D.X.L. are managed through regular disclosure to the Rice University Office of Sponsored Programs and Research Compliance.

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Supplementary Information

This file contains Supplementary Text and Data, Supplementary Figures 1–21 and Supplementary Tables 1–3.

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Luong, D.X., Bets, K.V., Algozeeb, W.A. et al. Gram-scale bottom-up flash graphene synthesis. Nature 577, 647–651 (2020). https://doi.org/10.1038/s41586-020-1938-0

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