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    High-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.
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    Anodically 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.
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    Surfactant stabilization of vanadium iron oxide derived from Prussian blue analog for lithium-ion battery electrodes
    (Cambridge : Royal Society of Chemistry, 2023) Bornamehr, Behnoosh; El Gaidi, Hiba; Arnold, Stefanie; Pameté, Emmanuel; Presser, Volker
    Due to their high energy density, Li-ion batteries have become indispensable for energy storage in many technical devices. Prussian blue and its analogs are a versatile family of materials. Apart from their direct use as an alkali-ion battery electrode, they are a promising source for templating other compounds due to the presence of carbon, nitrogen, and metallic elements in their structure, ease of synthesis, and high tunability. In this study, homogeneous iron vanadate derivatization from iron vanadium Prussian blue was successfully carried out using an energy efficient infrared furnace utilizing CO2 gas. Iron-vanadate is an inherently unstable electrode material if cycled at low potentials vs. Li/Li+. Several parameters were optimized to achieve a stable electrochemical performance of this derivative, and the effect of surfactants, such as tannic acid, sodium dodecylbenzene sulfonate, and polyvinylpyrrolidone were shown with their role in the morphology and electrochemical performance. While stabilizing the performance, we demonstrate that the type and order of addition of these surfactants are fundamental for a successful coating formation, otherwise they can hinder the formation of PBA, which has not been reported previously. Step-by-step, we illustrate how to prepare self-standing electrodes for Li-ion battery cells without using an organic solvent or a fluorine-containing binder while stabilizing the electrochemical performance. A 400 mA h g−1 capacity at the specific current of 250 mA g−1 was achieved after 150 cycles while maintaining a Coulombic efficiency of 99.2% over an extended potential range of 0.01–3.50 V vs. Li/Li+.