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- ItemReview: Carbon onions for electrochemical energy storage(Cambridge : Royal Society of Chemistry, 2016) Zeiger, Marco; Jäckel, Nicolas; Mochalin, Vadym N.; Presser, VolkerCarbon 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.
- ItemHigh-defect hydrophilic carbon cuboids anchored with Co/CoO nanoparticles as highly efficient and ultra-stable lithium-ion battery anodes(Cambridge : Royal Society of Chemistry, 2016) Sun, Xiaolei; Hao, Guang-Ping; Lu, Xueyi; Xi, Lixia; Liu, Bo; Si, Wenping; Ma, Chuansheng; Liu, Qiming; Zhang, Qiang; Kaskel, Stefan; Schmidt, Oliver G.We propose an effective strategy to engineer a unique kind of porous carbon cuboid with tightly anchored cobalt/cobalt oxide nanoparticles (PCC–CoOx) that exhibit outstanding electrochemical performance for many key aspects of lithium-ion battery electrodes. The host carbon cuboid features an ultra-polar surface reflected by its high hydrophilicity and rich surface defects due to high heteroatom doping (N-/O-doping both higher than 10 atom%) as well as hierarchical pore systems. We loaded the porous carbon cuboid with cobalt/cobalt oxide nanoparticles through an impregnation process followed by calcination treatment. The resulting PCC–CoOx anode exhibits superior rate capability (195 mA h g−1 at 20 A g−1) and excellent cycling stability (580 mA h g−1 after 2000 cycles at 1 A g−1 with only 0.0067% capacity loss per cycle). Impressively, even after an ultra-long cycle life exceeding 10 000 cycles at 5 A g−1, the battery can recover to 1050 mA h g−1 at 0.1 A g−1, perhaps the best performance demonstrated so far for lithium storage in cobalt oxide-based electrodes. This study provides a new perspective to engineer long-life, high-power metal oxide-based electrodes for lithium-ion batteries through controlling the surface chemistry of carbon host materials.
- ItemElectrochemically deposited nanocrystalline InSb thin films and their electrical properties(Cambridge : Royal Society of Chemistry, 2016) Hnida, K.E.; Bäßler, S.; Mech, J.; Szaciłowski, K.; Socha, R.P.; Gajewska, M.; Nielsch, K.; Przybylski, M.; Sulka, G.D.We present an electrochemical route to prepare nanocrystalline InSb thin films that can be transferred to an industrial scale. The morphology, composition, and crystallinity of the prepared uniform and compact thin films with a surface area of around 1 cm2 were investigated. The essential electrical characteristics such as conductivity, Seebeck coefficient, the type, concentration and mobility of charge carriers have been examined and compared with InSb nanowires obtained in the same system for electrochemical deposition (fixed pulse sequence, temperature, electrolyte composition, and system geometry). Moreover, obtained thin films show much higher band gap energy (0.53 eV) compared to the bulk material (0.17 eV) and InSb nanowires (0.195 eV).
- ItemAnodically fabricated TiO2–SnO2 nanotubes and their application in lithium ion batteries(Cambridge : Royal Society of Chemistry, 2016) Madian, M.; Klose, M.; Jaumann, T.; Gebert, A.; Oswald, S.; Ismail, N.; Eychmüller, A.; Eckerta, J.; Giebeler, L.Developing novel electrode materials is a substantial issue to improve the performance of lithium ion batteries. In the present study, single phase Ti–Sn alloys with different Sn contents of 1 to 10 at% were used to fabricate Ti–Sn–O nanotubes via a straight-forward anodic oxidation step in an ethylene glycolbased solution containing NH4F. Various characterization tools such as SEM, EDXS, TEM, XPS and Raman spectroscopy were used to characterize the grown nanotube films. Our results reveal the successful formation of mixed TiO2/SnO2 nanotubes in the applied voltage range of 10–40 V. The as-formed nanotubes are amorphous and their dimensions are precisely controlled by tuning the formation voltage which turns Ti–Sn–O nanotubes into highly attractive materials for various applications. As an example, the Ti–Sn–O nanotubes offer promising properties as anode materials in lithium ion batteries. The electrochemical performance of the grown nanotubes was evaluated against a Li/Li+ electrode at a current density of 504 mA cm2. The results demonstrate that TiO2/SnO2 nanotubes prepared at 40 V on a TiSn1 alloy substrate display an average 1.4 fold increase in areal capacity with excellent cycling stability over more than 400 cycles compared to the pure TiO2 nanotubes fabricated and tested under identical conditions. This electrode was tested at current densities of 50, 100, 252, 504 and 1008 mA cm2 exhibiting average capacities of 780, 660, 490, and 405 mA cm2 (i.e. 410, 345, 305 and 212 mA h g1), respectively. The remarkably improved electrochemical performance is attributed to enhanced lithium ion diffusion which originates from the presence of SnO2 nanotubes and the high surface area of the mixed oxide tubes. The TiO2/SnO2 electrodes retain their original tubular structure after electrochemical cycling with only slight changes in their morphology.
- ItemSelf-assembly of endohedral metallofullerenes: A decisive role of cooling gas and metal-carbon bonding(Cambridge : Royal Society of Chemistry, 2016) Deng, Qingming; Heine, Thomas; Irle, Stephan; Popov, Alexey A.The endohedral metallofullerene (EMF) self-assembly process in Sc/carbon vapor in the presence and absence of an inert cooling gas (helium) is systematically investigated using quantum chemical molecular dynamics simulations. It is revealed that the presence of He atoms accelerates the formation of pentagons and hexagons and reduces the size of the self-assembled carbon cages in comparison with analogous He-free simulations. As a result, the Sc/C/He system simulations produce a larger number of successful trajectories (i.e. leading to Sc-EMFs) with more realistic cage-size distribution than simulations of the Sc/C system. The main Sc encapsulation mechanism involves nucleation of several hexagons and pentagons with Sc atoms already at the early stages of carbon vapor condensation. In such proto-cages, both Sc–C σ-bonds and coordination bonds between Sc atoms and the π-system of the carbon network are present. Sc atoms are thus rather labile and can move along the carbon network, but the overall bonding is sufficiently strong to prevent dissociation even at temperatures around 2000 kelvin. Further growth of the fullerene cage results in the encapsulation of one or two Sc atoms within the fullerene. In agreement with experimental studies, an extension of the simulations to Fe and Ti as the metal component showed that Fe-EMFs are not formed at all, whereas Ti is prone to form Ti-EMFs with small cage sizes, including Ti@C28-Td and Ti@C30-C2v(3).
- ItemTunable charge transfer properties in metal-phthalocyanine heterojunctions(Cambridge : Royal Society of Chemistry, 2016) Siles, P.F.; Hahn, T.; Salvan, G.; Knupfer, M.; Zhu, F.; Zahn, D.R.T.; Schmidt, O.G.Organic materials such as phthalocyanine-based systems present a great potential for organic device applications due to the possibility of integrating films of different organic materials to create organic heterostructures which combine the electrical capabilities of each material. This opens the possibility to precisely engineer and tune new electrical properties. In particular, similar transition metal phthalocyanines demonstrate hybridization and charge transfer properties which could lead to interesting physical phenomena. Although, when considering device dimensions, a better understanding and control of the tuning of the transport properties still remain in the focus of research. Here, by employing conductive atomic force microscopy techniques, we provide an insight about the nanoscale electrical properties and transport mechanisms of MnPc and fluorinated phthalocyanines such as F16CuPc and F16CoPc. We report a transition from typical diode-like transport mechanisms for pure MnPc thin films to space-charge-limited current transport regime (SCLC) for Pc-based heterostructures. The controlled addition of fluorinated phthalocyanine also provides highly uniform and symmetric-polarized transport characteristics with conductance enhancements up to two orders of magnitude depending on the polarization. We present a method to spatially map the mobility of the MnPc/F16CuPc structures with a nanoscale resolution and provide theoretical calculations to support our experimental findings. This well-controlled nanoscale tuning of the electrical properties for metal transition phthalocyanine junctions stands as key step for future phthalocyanine-based electronic devices, where the low dimension charge transfer, mediated by transition metal atoms could be intrinsically linked to a transfer of magnetic moment or spin.
- ItemInfluence 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, VolkerManganese 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.
- ItemCarbon 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, VolkerIn 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.
- ItemTransformation of epitaxial NiMnGa/InGaAs nanomembranes grown on GaAs substrates into freestanding microtubes(Cambridge : Royal Society of Chemistry, 2016) Müller, C.; Neckel, I.; Monecke, M.; Dzhagan, V.; Salvan, G.; Schulze, S.; Baunack, S.; Gemming, T.; Oswald, S.; Engemaiere, V.; Mosca, D.H.We report the fabrication of Ni2.7Mn0.9Ga0.4/InGaAs bilayers on GaAs (001)/InGaAs substrates by molecular beam epitaxy. To form freestanding microtubes the bilayers have been released from the substrate by strain engineering. Microtubes with up to three windings have been successfully realized by tailoring the size and strain of the bilayer. The structure and magnetic properties of both, the initial films and the rolled-up microtubes, are investigated by electron microscopy, X-ray techniques and magnetization measurements. A tetragonal lattice with c/a = 2.03 (film) and c/a = 2.01 (tube) is identified for the Ni2.7Mn0.9Ga0.4 alloy. Furthermore, a significant influence of the cylindrical geometry and strain relaxation induced by roll-up on the magnetic properties of the tube is found.
- ItemCarbon 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, VolkerA 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.