Source: http://mrc.org.ua/news-from-mrc/273-carbon-onions-synthesis-and-electrochemical-applications
Timestamp: 2019-04-25 11:57:06+00:00

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Carbon onions represent one of the least studied carbon nanomaterials, and are seeing a large increase in attention for energy storage applications.
Beginning with fullerenes, moving to carbon nanotubes, and most recently to graphene, carbon nanomaterials are widely studied and used in a range of applications including electronics, tribology, and energy storage. However, two kinds of carbon nanoparticles, nanodiamond1 and carbon onions, 2 which were discovered before fullerenes and nanotubes, stayed for a long time in the shadow of more popular and better investigated nanocarbons. However, both have become increasingly studied in recent years. Carbon onions consist of spherical closed carbon shells and owe their name to the concentric layered structure resembling that of an onion. Carbon onions are sometimes called carbon nano-onions (CNOs) or onion-like carbon (OLC). Those names cover all kinds of concentric shells, from nested fullerenes to small (<100 nm) polyhedral nanostructures. This review is dedicated to those materials. We first discuss the structure of carbon onions and provide an overview of their synthesis methods. Also, electrochemical applications of carbon onions are reviewed with an emphasis on supercapacitor electrodes.
Although OLC has been synthesized by many different methods in the last 30 years, large scale production (gram quantities) of OLC was first realized in 1994 by Vladimir Kuznetsov and co- workers, who used vacuum annealing of a nanodiamond precursor. 5,6 Similar to vacuum annealing, other groups have also utilized annealing in inert gases to transform nanodiamond, which is currently produced in ton quantities, 1 to OLC. 7 This is one of the methods that has a potential for industrial applications, as the onion yield is close to 100% and the manufacturing volume is only limited by the size of the furnace, and can be scaled accordingly. This material rarely has ideal spherical carbon onions, but can be produced in large quantities and finds practical applications. The transition of nanodiamond to a carbon onion can be seen in a molecular dynamics (MD) simulation (Fig. 1a-c). A 2-nm particle of nanodiamond (Fig. 1a) was annealed at 1400 °C (Fig. 1b) causing the outer layers of the nanodiamond to convert to graphitic carbon; however the annealing was not at high enough temperature to convert the entire particle. At higher temperatures (Fig. 1c), the entire particle is converted to an OLC particle. 8 At the highest annealing temperatures, the OLC particle begins to polygonize (Fig. 1d) as the structure becomes more ordered. The particle size of OLC produced via nanodiamond annealing is dependent on the nanodiamond precursor, which is generally about 5 nm in diameter, 1 producing onions in the 5-10 nm size range.
Recently, OLC and carbon nanotubes (CNTs) were used to store energy from -50 to 100 °C—a wider temperature range than any porous activated carbons can deliver with organic or aqueous electrolytes. The exohedral carbons were combined with a eutectic mixture of ionic liquids, which remains liquid at temperatures down to -80 °C. The arrangement of ions around the respective electrode materials can be seen in Fig. 5a and 5b. Both, carbon onions and nanotubes were found to operate efficiently at temperatures as low as -50 °C and as high as +100 °C. Conventional EDLC electrolytes utilize propylene carbonate (PC) as the solvent and begin to see a decrease in performance below 0 °C (Fig. 5c). Activated carbon was used in the same eutectic mixture of ionic liquids and failed at temperatures of -20 °C, even at slow charge- discharge rates. 36 This shows that adsorption of ions on the exohedral surfaces of onions (Fig. 5a) minimizes ion transport limitations allowing either very fast charge-discharge rates (Fig. 4a) or use of electrolytes with low mobility (Fig. 5c).
Carbon onions represent one of the least studied carbon nanomaterials, and are seeing a large increase in attention for energy storage applications. Because of their unique 0-D structure, small (<10 nm) diameter, high electrical conductivity, and relatively easy dispersion, compared to 1-D nanotubes and 2-D graphene, OLC has been shown to be ideal as a conductive additive to battery and supercapacitor electrodes, or as active material for supercapacitor electrodes for high-power applications and for low temperature devices using ionic liquid electrolytes.
This work was supported as part of the Fluid Interface Reactions, Structures and Transport (FIRST) Center, an Energy Frontiers Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences. The authors are thankful to Dr. Vadym Mochalin (Drexel University) for Fig. 4b.
John K. McDonough received his BS in Physics in 2009 from Lycoming College. Presently, he is a PhD candidate at Drexel University, Philadelphia, in the Department of Materials Science and Engineering, studying under the guidance of Yury Gogotsi. His research focuses on carbon nanomaterials for electrical energy storage, specifically on onion-like carbon for electrochemical capacitors. McDonough serves as the President of the MRS Chapter at Drexel and is also highly involved in the ECS and ASM Chapters.
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