Phase transformation of TiO2 from anatase to rutile is studied by UV Raman spectroscopy excited by 325 and 244 nm lasers, visible Raman spectroscopy excited by 532 nm laser, X-ray diffraction (XRD), and transmission electron microscopy (TEM). UV Raman spectroscopy is found to be more sensitive to the surface region of TiO2 than visible Raman spectroscopy and XRD because TiO2 strongly absorbs UV light. The anatase phase is detected by UV Raman spectroscopy for the sample calcined at higher temperatures than when it is detected by visible Raman spectroscopy and XRD. The inconsistency in the results from the above three techniques suggests that the anatase phase of TiO2 at the surface region can remain at relatively higher calcination temperatures than that in the bulk during the phase transformation. The TEM results show that small particles agglomerate into big particles when the TiO2 sample is calcined at elevated temperatures and the agglomeration of the TiO2 particles is along with the phase transformation from anatase to rutile. It is suggested that the rutile phase starts to form at the interfaces between the anatase particles in the agglomerated TiO2 particles; namely, the anatase phase in the inner region of the agglomerated TiO2 particles turns out to change into the rutile phase more easily than that in the outer surface region of the agglomerated TiO2 particles. When the anatase particles of TiO2 are covered with highly dispersed La2O3, the phase transformation in both the bulk and surface regions is significantly retarded, owing to avoiding direct contact of the anatase particles and occupying the surface defect sites of the anatase particles by La2O3.
Urchin‐like CoSe2 assembled by nanorods has been synthesized via simple solvothermal route and has been first applied as an anode material for sodium‐ion batteries (SIBs) with ether‐based electrolytes. The CoSe2 delivers excellent sodiation and desodiation properties when using 1 m NaCF3SO3 in diethyleneglycol dimethylether as an electrolyte and cycling between 0.5 and 3.0 V. A high discharge capacity of 0.410 Ah g−1 is obtained at 1 A g−1 after 1800 cycles, corresponding to a capacity retention of 98.6% calculated from the 30th cycle. Even at an ultrahigh rate of 50 A g−1, the capacity still maintains 0.097 Ah g−1. The reaction mechanism of the as‐prepared CoSe2 is also investigated. The results demonstrate that at discharged 1.56 V, insertion reaction occurs, while two conversion reactions take place at the second and third plateaus around 0.98 and 0.65 V. During the charge process, Co first reacts with Na2Se to form NaxCoSe2 and then turns back to CoSe2. In addition to Na/CoSe2 half cells, Na3V2(PO4)3/CoSe2 full cell with excessive amount of Na3V2(PO4)3 has been studied. The full cell exhibits a reversible capacity of 0.380 Ah g−1. This work definitely enriches the possibilities for anode materials for SIBs with high performance.
We report room-temperature rechargeable potassium-sulfur (K-S) batteries using ordered mesoporous carbon (CMK-3)/sulfur and polyanilime (PANI) coated CMK-3/sulfur composites as the cathode and metallic potassium as the anode. The electrochemical reaction mechanism was investigated by electrochemical tests, TEM, XRD, and Raman spectra. It was found that K-S batteries delivered two reduction peaks located at about 2.1 and 1.8 V and one oxidation peak at about 2.2 V, respectively. Meanwhile, K2S3 was the major discharge product that could be charged to reversibly form S and K ion. Through optimization of sulfur content, the CMK-3/sulfur composite with 40.8 wt % S displayed an initial discharge capacity of 512.7 mAh g(-1) and a capacity of 202.3 mAh g(-1) after 50 cycles at a current density of 50 mA g(-1). A coating of conductive polyanilime (PANI) on the CMK-3/sulfur composite is effective in enhancing the cycling performance. In comparison, PANI@CMK-3/sulfur composite showed a capacity of 329.3 mAh g(-1) after 50 cycles at 50 mA g(-1). The results shed light on the basic study of rechargeable K-S batteries.
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