ABSTRACT
Although Li-ion batteries have attracted significant interest due to their higher energy density, lack of high rate performance electrode materials and intrinsic safety issues challenge their commercial applications. Herein, we demonstrate a simple photocatalytic reduction method that simultaneously reduces graphene oxide (GO) and anchors (010)-faceted mesoporous bronze-phase titania (TiO2-B) nanosheets to reduced graphene oxide (RGO) through Ti(3+)-C bonds. Formation of Ti(3+)-C bonds during the photocatalytic reduction process was identified using electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS) techniques. When cycled between 1-3 V (vs Li(+/0)), these chemically bonded TiO2-B/RGO hybrid nanostructures show significantly higher Li-ion storage capacities and rate capability compared to bare TiO2-B nanosheets and a physically mixed TiO2-B/RGO composite. In addition, 80% of the initial specific (gravimetric) capacity was retained even after 1000 charge-discharge cycles at a high rate of 40C. The improved electrochemical performance of TiO2-B/RGO nanoarchitectures is attributed to the presence of exposed (010) facets, mesoporosity, and efficient interfacial charge transfer between RGO monolayers and TiO2-B nanosheets.
ABSTRACT
Microcrystalline and submicrometer powders of Zn(1-x)Cu(x)WO(4) (0 ≤ x ≤ 1) have been prepared by a solid-state synthesis from stoichiometric quantities of the constituent d-block metal oxide and tungsten oxide as well as from a Pechini sol-gel synthesis starting from the d-block metal nitrate and ammonium metatungstate. The stoichiometry of the product is confirmed by inductively coupled plasma-atomic emission spectrometry (ICP-AES) analysis. X-ray diffraction shows that for the entire range of compositions, a single-phase product crystallizes in the wolframite structure, with a symmetry-lowering transition from P2/c to P1[overline] at x = 0.20, concomitant with the first-order Jahn-Teller distortion of Cu(2+). Far-IR spectroscopy corroborates that symmetry lowering is directly related to the tetragonal distortion within the CuO(6) octahedra, with the Zn-O A(u) symmetry mode at 320 cm(-1) (x = 0) splitting into two stretches at 295 and 338 cm(-1) (x = 0.3). UV-vis-NIR spectroscopy shows an optical absorption edge characteristic of an indirect band gap that linearly decreases in energy from 3.0 eV (x = 0) to 2.25 eV (x = 1). SQUID magnetometry shows that Zn(1-x)Cu(x)WO(4) (0.1 ≤ x ≤ 1) has an effective moment of 2.30 ± 0.19 µ(B) per mol copper, typical of Cu(2+) in extended solids. For high concentrations of copper (x ≥ 0.8), two transitions are observed: one at high-temperature, 82 K (x = 1.0) that decreases to 59 K (x = 0.8), and the Néel temperature, 23.5 K (x = 1.0) that decreases to 5.5 K (x = 0.8). For x < 0.8, no long-range order is observed. A physical 1:1 mixture of both CuWO(4):ZnWO(4) shows magnetic ordering identical to that of CuWO(4).
