Discharging of the aprotic Li−O 2 battery relies on the oxygen reduction reaction (ORR) producing Li 2 O 2 in the positive electrode, which remains incompletely understood. Here, we report a mechanistic study of the Li-ORR on a model system, i.e., an Au electrode in a Li + dimethyl sulfoxide (DMSO) electrolyte. By spectroscopic identification of the reaction intermediates coupled with density functional theory calculations, we conclude that the formation of O 2 − and LiO 2 in the Li-ORR critically depends on electrode potentials and determines the Li 2 O 2 formation mechanism. At low overpotentials (> 2.0 V vs Li/ Li + ) O 2− is identified to be the first surface intermediate, which diffuses into the bulk electrolyte and forms Li 2 O 2 therein via a solution-mediated disproportionation mechanism. At high overpotentials (ca. 2.0−1.6 V vs Li/Li + ) LiO 2 has been observed, which can rapidly transform to Li 2 O 2 by further electro-reduction, suggesting a surface-mediated mechanism. The solution-mediated Li 2 O 2 formation that can account for the widely observed toroid-shaped discharged Li 2 O 2 particles has also been thoroughly examined. Thus, O 2 − formation controls the overall reaction onset potential, and LiO 2 formation demarcates the change from a solution-to surface-mediated reaction mechanism. The new findings and improved understandings of the Li-ORR in DMSO will contribute to the further development of aprotic Li−O 2 batteries.
When aprotic Li-O2 batteries discharge, the product phase formed in the cathode often contains two different morphologies, that is, crystalline and amorphous Li2 O2 . The morphology of Li2 O2 impacts strongly on the electrochemical performance of Li-O2 cells in terms of energy efficiency and rate capability. Crystalline Li2 O2 is readily available and its properties have been studied in depth for Li-O2 batteries. However, little is known about the amorphous Li2 O2 because of its rarity in high purity. Herein, amorphous Li2 O2 has been synthesized by a rapid reaction of tetramethylammonium superoxide and LiClO4 in solution, and its amorphous nature has been confirmed by a range of techniques. Compared with its crystalline siblings, amorphous Li2 O2 demonstrates enhanced charge-transport properties and increased electro-oxidation kinetics, manifesting itself a desirable discharge phase for high-performance Li-O2 batteries.
The protonated acetylene cation, C2H3+, (also known as the vinyl cation) and the proton-bound acetylene dimer cation (C4H5+) are produced by a pulsed supersonic nozzle/pulsed electrical discharge cluster source. The parent ions are also generated with weakly attached argon "tag" atoms, e.g., C2H3+Ar and C4H5+Ar. These ions are mass selected in a specially designed reflectron time-of-flight mass spectrometer and studied with infrared laser photodissociation spectroscopy in the 800-3600 cm-1 region. Vibrational resonances are detected for both ions in the C-H stretching region. C2H3+ has a strong vibrational resonance near 2200 cm-1 assigned to the bridged proton stretch of the nonclassical ion, while C4H5+ has no such free-proton vibration. Instead, C4H5+ has resonances near 1300 cm-1, consistent with a symmetrically shared proton in a di-bridged structure. Although the shared proton structure is not the lowest energy isomer of C4H5+, this species is apparently stabilized under the supersonic beam conditions. Larger clusters containing additional acetylene units are also investigated via the elimination of acetylene. These species have new IR bands indicating that rearrangement reactions have taken place to produce core C4H5+ ions with the methyl cyclopropane cation structure and/or the protonated cyclobutadiene isomer. Ab initio (MP2) calculations provide structures and predicted spectra consistent with all of these experiments.
Utilization of LiFePO4 as a cathode material for Li-ion batteries often requires size nanonization coupled with calcination-based carbon coating to improve its electrochemical performance, which, however, is usually at the expense of tap density and may be environmentally problematic. Here we report the utilization of micron-sized LiFePO4, which has a higher tap density than its nano-sized siblings, by forming a conducting polymer coating on its surface with a greener diazonium chemistry. Specifically, micron-sized LiFePO4 particles have been uniformly coated with a thin polyphenylene film via the spontaneous reaction between LiFePO4 and an aromatic diazonium salt of benzenediazonium tetrafluoroborate. The coated micron-sized LiFePO4, compared with its pristine counterpart, has shown improved electrical conductivity, high rate capability and excellent cyclability when used as a ‘carbon additive free' cathode material for rechargeable Li-ion batteries. The bonding mechanism of polyphenylene to LiFePO4/FePO4 has been understood with density functional theory calculations.
We use comparative natural bond orbital (NBO) and quantum theory of atoms in molecules (QTAIM) methods to analyze the proximal bay-type H···H interactions in cis-2-butene and related species, which lead to controversial interpretation as attractive "HH bonding" in the QTAIM framework. We address the challenging questions concerning well established structural, conformational, and vibrational properties of such species that appear to be sharply at odds with the QTAIM interpretation. In contrast to the purported "HH bonding" of QTAIM theory, NBO-based evaluation of steric (donor-donor) and hyperconjugative (donor-acceptor) interactions unambiguously portrays such H···H contacts as dominated by steric clashes that are only partially softened by weak secondary hyperconjugative interactions, contributing negligibly (bHH < 0.01) to H···H bond order. Additional details of NBO-based versus QTAIM-based description are provided by natural bond critical point analysis of topological bond critical point properties, which further emphasizes the contrast between the problematic bay-type H···H contacts and remaining noncontroversial (consensus) chemical bonds. NBO analysis is thereby shown to be fully consistent with the traditional physical organic concept of repulsive bay-type H···H contacts, including the corollary array of structural, conformational, and vibrational properties. © 2014 Wiley Periodicals, Inc.
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