Weakly coordinating anions (WCAs) with the difluorophosphato ligand (O2PF2) were the target of this study. Initial experiments were conducted towards the preparation of homoleptic aluminates of the well-studied [Al(OR)4](-)-type. The preparation of the initial target structure Li[Al(O2PF2)4] failed due to the remaining Lewis acidic character of the central aluminum atom.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
March 2015
Lithium-sulfur batteries are amongst the most promising candidates to satisfy emerging energy-storage demands. Suppression of the polysulfide shuttle while maintaining high sulfur content is the main challenge that faces their practical development. Here, we report that 2D early-transition-metal carbide conductive MXene phases-reported to be impressive supercapacitor materials-also perform as excellent sulfur battery hosts owing to their inherently high underlying metallic conductivity and self-functionalized surfaces.
View Article and Find Full Text PDFThe lithium-sulfur battery is receiving intense interest because its theoretical energy density exceeds that of lithium-ion batteries at much lower cost, but practical applications are still hindered by capacity decay caused by the polysulfide shuttle. Here we report a strategy to entrap polysulfides in the cathode that relies on a chemical process, whereby a host--manganese dioxide nanosheets serve as the prototype--reacts with initially formed lithium polysulfides to form surface-bound intermediates. These function as a redox shuttle to catenate and bind 'higher' polysulfides, and convert them on reduction to insoluble lithium sulfide via disproportionation.
View Article and Find Full Text PDFA versatile, cost-effective electrochemical analysis strategy is described that determines the specific S(n)(2-) adsorptivity of materials, and allows prediction of the long-term performance of sulphur composite electrodes in Li-S cells. Measurement of nine different materials with varying surface area, and hydrophobicity using this protocol determined optimum properties for capacity stabilization.
View Article and Find Full Text PDFA new Li salt with views to success in electrolytes is synthesized in excellent yields from lithium borohydride with excess 2,2,2-trifluorethanol (HOTfe) in toluene and at least two equivalents of 1,2-dimethoxyethane (DME). The salt Li[B(OTfe)4 ] is obtained in multigram scale without impurities, as long as DME is present during the reaction. It is characterized by heteronuclear magnetic resonance and vibrational spectroscopy (IR and Raman), has high thermal stability (Tdecomposition >271 °C, DSC) and shows long-term stability in water.
View Article and Find Full Text PDFNonaqueous Li-O2 batteries are an intensively studied future energy storage technology because of their high theoretical energy density. However, a number of barriers prevent a practical application, and one of the major challenges is the reduction of the high charge overpotential: Whereas lithium peroxide (Li2O2) is formed during discharge at around 2.7 V (vs Li(+)/Li), its electrochemical decomposition during the charge process requires potentials up to 4.
View Article and Find Full Text PDFThe effect of fluorinated ethylene carbonate (FEC) as a cosolvent in alkyl carbonates/LiPF6 on the cycling performance of high-voltage (5 V) cathodes for Li-ion batteries was investigated using electrochemical tools, X-ray photoelectron spectroscopy (XPS), and high-resolution scanning electron microscopy (HRSEM). An excellent cycling stability of LiCoPO4/Li, LiNi0.5Mn1.
View Article and Find Full Text PDFACS Appl Mater Interfaces
July 2014
We report the synthesis of a low-cost carbon/sulfur nanocomposite using Ketjen black (KBC) as the carbon framework, encapsulated by thin graphene sheets using a simple process that relies on binding a functionalized KBC/S nanoparticle surface with graphene oxide (GO), which is reduced in situ. A slight excess of GO is employed to create a second layer of graphene wrapping around the KBC/S. This g-KBC/S sulfur cathode exhibits excellent cyclability over 200 cycles where the average stabilized fade rate is only 0.
View Article and Find Full Text PDFThe development of Li2S electrodes is a crucial step toward industrial manufacturing of Li-S batteries, a promising alternative to Li-ion batteries due to their projected two times higher specific capacity. However, the high voltages needed to activate Li2S electrodes, and the consequent electrolyte solution degradation, represent the main challenge. We present a novel concept that could make feasible the widespread application of Li2S electrodes for Li-S cell assembly.
View Article and Find Full Text PDFNew electrode materials of layered oxides, Na2/3Ni1/3Mn2/3-xTixO2 (0 ≤ x ≤ 2/3), are successfully synthesized, and their electrochemical performance is examined in aprotic Na cells. A Na//Na2/3Ni1/3Mn1/2Ti1/6O2 cell delivers 127 mA h g(-1) of reversible capacity and the average voltage reaches 3.7 V at first discharge with good capacity retention.
View Article and Find Full Text PDFThis article describes the synthesis and characterization of a novel crosslinked polymer with tricyanuric acid core bearing tetrasulfide bridges as a novel redox polymerization electrode material for rechargeable lithium-sulfur batteries. The new material was synthesized by reaction of stoichiometric sulfur monochloride amounts with trithiocyanuric acid and the structure of the redox polymer proven by the means of elementary analysis, infrared spectroscopy and Raman spectroscopy. Electrochemical evaluation of the polymer as electroactive cathode component showed cycling stability up to 140 cycles after initial capacity of 650 mAhg(-1) with 73% utilization of the theoretical specific capacity (893 mAhg(-1)) regarding the electroactive tetrasulfide moieties.
View Article and Find Full Text PDFPorous hollow carbon spheres with different tailored pore structures have been designed as conducting frameworks for lithium-sulfur battery cathode materials that exhibit stable cycling capacity. By deliberately creating shell porosity and utilizing the interior void volume of the carbon spheres, sufficient space for sulfur storage as well as electrolyte pathways is guaranteed. The effect of different approaches to develop shell porosity is examined and compared in this study.
View Article and Find Full Text PDFPolyether solvents are considered interesting and important candidates for Li-O2 battery systems. Discharge of Li-O2 battery systems forms Li oxides. Their mechanism of formation is complex.
View Article and Find Full Text PDFIn the search for room-temperature batteries with high energy densities, rechargeable metal-air (more precisely metal-oxygen) batteries are considered as particularly attractive owing to the simplicity of the underlying cell reaction at first glance. Atmospheric oxygen is used to form oxides during discharging, which-ideally-decompose reversibly during charging. Much work has been focused on aprotic Li-O(2) cells (mostly with carbonate-based electrolytes and Li(2)O(2) as a potential discharge product), where large overpotentials are observed and a complex cell chemistry is found.
View Article and Find Full Text PDFA route for the preparation of binder-free sulfur-carbon cathodes is developed for lithium sulfur batteries. The method is based on the impregnation of elemental sulfur into the micropores of activated carbon fibers. These electrodes demonstrate good electrochemical performance at high current density attributed to the uniform dispersion of sulfur inside the carbon fiber.
View Article and Find Full Text PDFNine non-noble-metal catalysts (NNMCs) from five different laboratories were investigated for the catalysis of O(2) electroreduction in an acidic medium. The catalyst precursors were synthesized by wet impregnation, planetary ball milling, a foaming-agent technique, or a templating method. All catalyst precursors were subjected to one or more heat treatments at 700-1050 degrees C in an inert or reactive atmosphere.
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