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Now showing 1 - 7 of 7
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    Review: Carbon onions for electrochemical energy storage
    (Cambridge : Royal Society of Chemistry, 2016) Zeiger, Marco; Jäckel, Nicolas; Mochalin, Vadym N.; Presser, Volker
    Carbon onions are a relatively new member of the carbon nanomaterials family. They consist of multiple concentric fullerene-like carbon shells which are highly defective and disordered. Due to their small size of typically below 10 nm, the large external surface area, and high conductivity they are used for supercapacitor applications. As electrode materials, carbon onions provide fast charge/discharge rates resulting in high specific power but present comparatively low specific energy. They improve the performance of activated carbon electrodes as conductive additives and show suitable properties as substrates for redox-active materials. This review provides a critical discussion of the electrochemical properties of different types of carbon onions as electrode materials. It also compares the general advantages and disadvantages of different carbon onion synthesis methods. The physical and chemical properties of carbon onions, in particular nanodiamond-derived carbon onions, are described with emphasis on those parameters especially important for electrochemical energy storage systems, including the structure, conductivity, and porosity. Although the primary focus of current research is on electrode materials for supercapacitors, the use of carbon onions as conductive additives and for redox-active species is also discussed.
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    Emulsion soft templating of carbide-derived carbon nanospheres with controllable porosity for capacitive electrochemical energy storage
    (Cambridge : Royal Society of Chemistry, 2015) Oschatz, Martin; Zeiger, Marco; Jaeckel, Nicolas; Strubel, Patrick; Borchardt, Lars; Reinhold, Romy; Nickel, Winfried; Eckert, Jürgen; Presser, Volker; Kaskel, Stefan
    A new approach to produce carbide-derived carbon nanospheres of 20-200 nm in diameter based on a novel soft-templating technique is presented. Platinum catalysis is used for the cross-linking of liquid (allylhydrido)polycarbosilane polymer chains with para-divinylbenzene within oil-in-water miniemulsions. Quantitative implementation of the pre-ceramic polymer can be achieved allowing precise control over the resulting materials. After pyrolysis and high-temperature chlorine treatment, resulting particles offer ideal spherical shape, very high specific surface area (up to 2347 m^2/g^-1), and large micro/mesopore volume (up to 1.67 cm^3/g^-1). The internal pore structure of the nanospheres is controllable by the composition of the oil phase within the miniemulsions. The materials are highly suitable for electrochemical double-layer capacitors with high specific capacitances in aqueous 1 M Na2SO4 solution (110 F/g^-1) and organic 1 M tetraethylammonium tetrafluoroborate in acetonitrile (130 F/g^-1).
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    A high-rate aqueous symmetric pseudocapacitor based on highly graphitized onion-like carbon/ barnessite-type manganese oxide nanohybrids
    (Cambridge : Royal Society of Chemistry, 2015) Makgopa, Katlego; Ejikeme, Paul M.; Jafta, Charl J.; Raju, Kumar; Zeiger, Marco; Presser, Volker; Ozoemena, Kenneth I.
    We present a study on the pseudocapacitive properties of birnessite-type MnO2 grafted on highly graphitized onion-like carbon (OLC/MnO2). In a three-electrode setup, we evaluated two different substrates, namely a platinum disc and nickel foam. The OLC/MnO2 nanohybrid exhibited a large specific capacitance (Csp) of 295 and 323 F g−1 (at 1 A g−1) for the Pt disc and Ni foam, respectively. In addition, the Ni foam substrate exhibited much higher rate capability (power density) than the Pt disc. A symmetrical two-electrode device, fabricated with the Ni foam, showed a large Csp of 254 F g−1, a specific energy density of 5.6 W h kg−1, and a high power density of 74.8 kW kg−1. These values have been the highest for onion-based electrodes so far. The device showed excellent capacity retention when subjected to voltage-holding (floating) experiments for 50 h. In addition, the device showed a very short time constant (τ = 40 ms). This high rate handling ability of the OLC/MnO2 nanohybrid, compared to literature reports, promises new opportunities for the development of aqueous-based pseudocapacitors.
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    Enhanced capacitance of nitrogen-doped hierarchically porous carbide-derived carbon in matched ionic liquids
    (Cambridge : Royal Society of Chemistry, 2015) Ewert, Julia K.; Weingarth, Daniel; Denner, Christine; Friedrich, Martin; Zeiger, Marco; Schreiber, Anna; Jäckel, Nicolas; Presser, Volker; Kempe, Rhett
    Supercapacitors combine efficient electrical energy storage and performance stability based on fast electrosorption of electrolyte ions at charged interfaces. They are a central element of existing and emerging energy concepts. A better understanding of capacitance enhancement options is essential to exploit the full potential of supercapacitors. Here, we report a novel hierarchically structured N-doped carbon material and a significant capacitance enhancement for a specific ionic liquid. Our studies indicate that matching of the electrode material and the ionic liquid specifically leads to a constant normalized resistance of the electrode material (voltage window up to ±1 V vs. carbon) and a significant enhancement of the specific capacitance. Such effects are not seen for standard organic electrolytes, non-matched ionic liquids, or non-N-doped carbons. A higher N-doping of the electrode material improves the symmetric full cell capacitance of the match and considerably increases its long-term stability at +3 V cell voltage. This novel observance of enhanced specific capacitance for N-doped carbons with matched ionic liquid may enable a new platform for developing supercapacitors with enhanced energy storage capacity.
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    Influence of carbon substrate on the electrochemical performance of carbon/manganese oxide hybrids in aqueous and organic electrolytes
    (Cambridge : Royal Society of Chemistry, 2016) Zeiger, Marco; Fleischmann, Simon; Krüner, Benjamin; Tolosa, Aura; Bechtel, Stephan; Baltes, Mathias; Schreiber, Anna; Moroni, Riko; Vierrath, Severin; Thiele, Simon; Presser, Volker
    Manganese oxide presents very promising electrochemical properties as an electrode material in supercapacitors, but there remain important open questions to guide further development of the complex manganese oxide/carbon/electrolyte system. Our work addresses specifically the influence of carbon ordering and the difference between outer and inner porosity of carbon particles for the application in aqueous 1 M Na2SO4 and 1 M LiClO4 in acetonitrile. Birnessite-type manganese oxide was hydrothermally hybridized on two kinds of carbon onions with only outer surface area and different electrical conductivity, and conventional activated carbon with a high inner porosity. Carbon onions with a high degree of carbon ordering, high conductivity, and high outer surface area were identified as the most promising material, yielding 179 F g−1. Pore blocking in activated carbon yields unfavorable electrochemical performances. The highest specific energy of 16.4 W h kg−1 was measured for a symmetric full-cell arrangement of manganese oxide coated high temperature carbon onions in the organic electrolyte. High stability during 10 000 cycles was achieved for asymmetric full-cells, which proved as a facile way to enhance the electrochemical performance stability.
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    Carbon onion–sulfur hybrid cathodes for lithium–sulfur batteries
    (Cambridge : Royal Society of Chemistry, 2017) Choudhury, Soumyadip; Zeiger, Marco; Massuti-Ballester, Pau; Fleischmann, Simon; Formanek, Petr; Borchardt, Lars; Presser, Volker
    In this study, we explore carbon onions (diameter below 10 nm), for the first time, as a substrate material for lithium sulfur cathodes. We introduce several scalable synthesis routes to fabricate carbon onion–sulfur hybrids by adopting in situ and melt diffusion strategies with sulfur fractions up to 68 mass%. The conducting skeleton of agglomerated carbon onions proved to be responsible for keeping active sulfur always in close vicinity to the conducting matrix. Therefore, the hybrids are found to be efficient cathodes for Li–S batteries, yielding 97–98% Coulombic efficiency over 150 cycles with a slow fading of the specific capacity (ca. 660 mA h g−1 after 150 cycles) in long term cycle test and rate capability experiments.
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    Carbon onion / sulfur hybrid cathodes via inverse vulcanization for lithium sulfur batteries
    (Cambridge : Royal Society of Chemistry, 2017) Choudhury, Soumyadip; Srimuk, Pattarachai; Raju, Kumar; Tolosa, Aura; Fleischmann, Simon; Zeiger, Marco; Ozoemena, Kenneth I.; Borchardt, Lars; Presser, Volker
    A sulfur–1,3-diisopropenylbenzene copolymer was synthesized by ring-opening radical polymerization and hybridized with carbon onions at different loading levels. The carbon onion mixing was assisted by shear in a two-roll mill to capitalize on the softened state of the copolymer. The sulfur copolymer and the hybrids were thoroughly characterized in structure and chemical composition, and finally tested by electrochemical benchmarking. An enhancement of specific capacity was observed over 140 cycles at higher content of carbon onions in the hybrid electrodes. The copolymer hybrids demonstrate a maximum initial specific capacity of 1150 mA h gsulfur−1 (850 mA h gelectrode−1) and a low decay of capacity to reach 790 mA h gsulfur−1 (585 mA h gelectrode−1) after 140 charge/discharge cycles. All carbon onion/sulfur copolymer hybrid electrodes yielded high chemical stability, stable electrochemical performance superior to conventional melt-infiltrated reference samples having similar sulfur and carbon onion content. The amount of carbon onions embedded in the sulfur copolymer has a strong influence on the specific capacity, as they effectively stabilize the sulfur copolymer and sterically hinder the recombination of sulfur species to the S8 configuration.