The interest of exploring environmentally benign and safe anode materials for lithium batteries has led to TiO 2 (anatase) nanostructures as promising candidates. However, the poor chemical diffusion of lithium in the materials still limits the rate capability. We report on the high rate capability of lithium storage with oxygen-deficient TiO 2−δ nanoparticles prepared by hydrogen reduction. A systematic study on the effect of electronic charge carrier concentration on the overall electrochemical lithium storage performance revealed that well-balanced Li + /e − transport is the key factor for high-performance TiO 2 anodes.
Dual-phase ceramic membranes with very high oxygen flux have been designed by taking into account the volume fraction of the fluorite phase, membrane thickness, and surface modification. The oxygen flux of Ce 0.9 Gd 0.1 O 2−δ −La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3−δ (GDC−LSCF) dual-phase membranes has been systematically investigated as a function of membrane thickness and volume fraction of the fluorite phase with or without surface modification. The percolation threshold of the composites for electronic conduction has been determined to be about 20 vol % of LSCF by general effective-medium theory. The oxygen flux of uncoated fluorite phase-rich membrane (80 vol % GDC−20 vol % LSCF) with 30-μm thickness exhibits a low oxygen flux (8.0 × 10 −3 mL• cm −2 •min −1 at 850 °C) under an air/He gradient, indicating that the permeation is controlled by only the surface-exchange kinetics of GDC. With both sides coated with La 0.6 Sr 0.4 CoO 3−δ (LSC), the flux of the membrane (3.6 mL•cm −2 •min −1 at 850 °C) has been dramatically enhanced by about 3 orders of magnitude in comparison with the oxygen flux of the membrane with a nonmodified surface. This observation implies that surface modification has a decisive role in dramatically enhancing the contribution of the GDC to the fluorite rich dual-phase membrane.
The oxygen permeation flux of dual-phase membranes, Ce0.9Gd0.1O2-δ-La0.7Sr0.3MnO3±δ (GDC/LSM), has been systematically studied as a function of their LSM content, thickness, and coating material. The electronic percolation threshold of this GDC/LSM membrane occurs at about 20 vol % LSM. The coated LSM20 (80 vol % GDC, 20 vol % LSM) dual-phase membrane exhibits a maximum oxygen flux of 2.2 mL·cm(-2)·min(-1) at 850 °C, indicating that to enhance the oxygen permeation flux, the LSM content should be adjusted to the minimum value at which electronic percolation is maintained. The oxygen ion conductivity of the dual-phase membrane is reliably calculated from oxygen flux data by considering the effects of surface oxygen exchange. Thermal cycling tests confirm the mechanical stability of the membrane. Furthermore, a dual-phase membrane prepared here with a cobalt-free coating remains chemically stable in a CO2 atmosphere at a lower temperature (800 °C) than has previously been achieved.
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