Characterization and Electrochemical Properties of Nanostructured Zr-Doped Anatase TiO2 Tubes Synthesized by Sol-Gel Template Route

doi:10.1016/j.jmst.2016.11.011

Abstract

Abstract:

A series of nanostructured Zr-doped anatase TiO₂ tubes with the Zr/Ti molar ratio of 0.01, 0.02, 0.03, and 0.09 were prepared by a sol-gel technology on a carbon fiber template. The electrochemical performance of Zr-doped anatase TiO₂ as anodes for rechargeable lithium batteries was investigated and compared with undoped titania. Tests represented that after 35-fold charge/discharge cycling at C/10 the reversible capacity of Zr-doped titania (Zr/Ti = 0.03) reaches 135 mA h g^-1, while the capacity of undoped titania (Zr/Ti = 0) yielded only 50 mA h g^-1. Based on the results of the physicochemical investigation, three reasons of improving electrochemical performance of Zr-doped titania were suggested. According to the scanning electron microscopy and transmission electron microscopy, Zr⁴⁺ doping induces a decrease in nanoparticle size, which facilitates the Li⁺ diffusion. The Raman investigations show the more open structure of Zr-doped TiO₂ as compared to undoped titania due to changing of the unit cell parameters, that significantly affects on the reversibility of the insertion/extraction process. The electrochemical impedance spectroscopy results indicate that substitution of Zr⁴⁺ for Ti⁴⁺ into anatase TiO₂ has favorable effects on the conductivity.

Key words: Li-ion batteries, Anatase titania, Nanostructured materials, Sol-gel template process, Doping, Electrochemical performance

Opra Denis P., Gnedenkov Sergey V., Sinebryukhov Sergey L., Voit Elena I., Sokolov AlexanderA., Modin Evgeny B., Podgorbunsky Anatoly B., Sushkov Yury V., Zheleznov Veniamin V.. Characterization and Electrochemical Properties of Nanostructured Zr-Doped Anatase TiO₂ Tubes Synthesized by Sol-Gel Template Route[J]. J. Mater. Sci. Technol., 2017, 33(6): 527-534.

Figures/Tables 11

Fig. 1. SEM images of ZT-0, ZT-1, ZT-2, ZT-3, ZT-4 materials at different magnifications.

Fig. 2. TEM images of ZT-0 (a) and ZT-3 (b) samples. Electron diffraction pattern of ZT-4 (c).

Table 1. EDX results for the as-synthesized materials

Sample	Concentration (at.%)			Zr/Ti ratio
Sample	Ti	Zr	Si	Zr/Ti ratio
ZT-0	31.0	0.0	2.0	0.00
ZT-1	30.7	0.3	2.0	0.01
ZT-2	30.4	0.6	2.0	0.02
ZT-3	30.0	1.0	2.0	0.03
ZT-4	28.4	2.6	2.0	0.09

Fig. 3. Elemental mapping of Ti (a), Zr (b), O (c), Si (d) and area of analysis (e) for ZT-3 sample.

Fig. 4. XRD spectra of ZT-3 and ZT-4 samples heat treated at 550 and 700 °C, respectively.

Fig. 5. Raman spectra of ZT-0, ZT-1, ZT-2, ZT-3, ZT-4 samples. The inset displays the enlarged Raman spectrum of ZT-3.

Table 2. Dependence of Eg(1), B1g(1), and Eg(3) peaks positions on Zr/Ti molar ratio

Zr/Ti ratio	Peak maximum (cm^-1)
Zr/Ti ratio	E_g₍₁₎	B₁_g₍₁₎	E_g₍₃₎
0.00	147.5	396.7	638.7
0.01	144.4	395.1	638.1
0.02	143.8	394.5	637.7
0.03	143.2	392.2	637.4
0.09	144.7	395.7	638.0

Fig. 6. Impedance spectra of ZT-0 (□), ZT-1 (▼), ZT-2 (○), ZT-3 (?), and ZT-4 (●) pellets at room temperature. The frequencies of 0.1 Hz and 0.01 Hz are marked by solid symbols.

Fig. 7. Nyquist plots of half-cells with ZT-0 (□), ZT-1 (▼), ZT-2 (○), ZT-3 (?), and ZT-4 (●) electrodes (a). Symbols are the experimental data, while the solid lines are the fitted curves calculated with the use of equivalent electric circuit (b). The frequencies of 0.1 Hz and 0.01 Hz are marked by solid symbols.

Fig. 8. Charge/discharge profiles of ZT-0, ZT-1, ZT-2, ZT-3, ZT-4 electrodes for the 1st (solid), 2nd (dashed), and 10th (dotted) cycles at a C/10-rate.

Fig. 9. Li+ ions insertion into (a) and extraction from (b) ZT-0 (■), ZT-1 (▼), ZT-2 (●), ZT-3 (?), and ZT-4 (●) during 35 cycles.

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Characterization and Electrochemical Properties of Nanostructured Zr-Doped Anatase TiO₂ Tubes Synthesized by Sol-Gel Template Route

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