Vanadium-doped TiO2-B/anatase mesoporous nanotubes with improved rate and cycle performance for rechargeable lithium and sodium batteries

doi:10.1016/j.jmst.2020.02.068

Abstract

Abstract:

TiO₂-B/anatase nanotubes doped by vanadium have been synthesized through a facile one-step hydrothermal reaction. The material shows a mesoporous structure with a specific surface area of 179.1 m² g^-1. XPS data presume the presence of V³⁺, V⁴⁺, V⁵⁺, and Ti³⁺ in doped TiO₂-B/anatase. As found by XRD and EIS investigations, the vanadium expands bronze titania crystal structure and enhances the conductivity of material by three orders of magnitude. When tested for lithium storage, the V-modified titania nanotubes show a specific capacity of 133 mA h g^-1 after 100 charge/discharge cycles at the current density of 3000 mA g^-1 with a Coulombic efficiency of around 98.9%, resulting in its good cycleability. The material still possesses a reversible capacity of 114 mA h g^-1 at a very high current load of 6000 mA g^-1, demonstrating superior rate characteristics for secondary lithium batteries. Furthermore, V-doped TiO₂-B/anatase mesoporous nanotubes show promise performance as anode material for sodium-ion batteries, delivering about 119 mA h g^-1 and 101 mA h g^-1 at the current loads of 10 and 1500 mA g^-1, respectively.

Key words: Lithium-ion battery, Sodium-ion battery, Anode, TiO₂-B Anatase, Doping, Nanotubes, Mesoporosity

D.P. Opra, S.V. Gnedenkov, A.A. Sokolov, A.B. Podgorbunsky, A.Yu. Ustinov, V.Yu. Mayorov, V.G. Kuryavyi, S.L. Sinebryukhov. Vanadium-doped TiO₂-B/anatase mesoporous nanotubes with improved rate and cycle performance for rechargeable lithium and sodium batteries[J]. J. Mater. Sci. Technol., 2020, 54: 181-189.

Figures/Tables 10

Table 1 EDX results (atomic ratio), fraction of anatase phase, and conductivity for pristine and V-modified samples.

Sample	V/Ti ratio	Anatase content	Conductivity, S cm^-1
pristine	-	9.5%	1.54·10^-11
VTO-1	0.011	12.3%	9.29·10^-9
VTO-2	0.034	11.6%	1.70·10^-8
VTO-3	0.049	12.9%	4.89·10^-9

Fig. 1. Microphotographs of surface for VTO-2 sample, recorded in SEM (a, b, c) and STEM (d) modes.

Fig. 2. N2 adsorption-desorption isotherms at 77 K and corresponding pore size distributions of (a) VTO-2 and (b) pristine sample.

Fig. 3. XPS spectra of VTO-2 material: (a) survey; (b) Ti 2p; (c) V 2p; (d) O 1s, and (e) C 1s.

Table 2 XPS data for the VTO-2 sample.

Element	Concentration, at%	Chemical state
Ti	20.8	Ti-O-Ti Ti-O-V
V	1.0	Ti-O-V V-O-V
O	43.4	Ti-O-Ti Ti-O-V V-O-V
O	9.3	O-H C=O O-C=O
C	1.5	C=O
	3.2	O-C=O
	20.8	C-C, C-H

Fig. 4. XRD patterns of pristine and V-substituted titania samples.

Table 3 Structural analysis for pristine and V-doped TiO2-B/anatase samples.

Sample	a (?)	b (?)	c (?)	β (°)	V (?³)	R_wp^a	R_p^b	χ^2c
pristine	12.274(2)	3.7795(8)	6.573(1)	109.59(1)	287.27(6)	8.01	6.07	1.11
VTO-1	12.301(2)	3.7861(9)	6.565(1)	109.32(2)	288.55(6)	8.18	6.30	1.09
VTO-2	12.317(2)	3.797(1)	6.582(1)	109.62(2)	290.00(6)	8.86	6.65	1.09
VTO-3	12.314(3)	3.744(1)	6.438(2)	107.36(3)	283.31(8)	10.45	8.00	1.07

Fig. 5. Impedance spectra of pristine and V-doped samples at the room temperature (experimental data are marked by symbols, while solid lines present fitting results).

Fig. 6. (a) Cyclic voltammograms of the VTO-2 electrode for the first ten cycles at a scan rate of 0.1 mV s-1, (b) initial charge/discharge voltage profiles of pristine and V-modified samples at a current load of 150 mA -1, dependence of reversible capacity on applied current load (shown in the figure) for (c) VTO-2 and (d) pristine electrodes, (e) cycling performance of VTO-2 at 3000 mA g-1 between 1 and 3 V (the processes of lithium insertion and extraction are marked, respectively, by open and filled symbols).

Fig. 7. (a) CV curves of the VTO-2 material (b) and initial charge/discharge profiles, (c) cycling performance, (d) rate capability of the pristine and V-doped TiO2-B/anatase electrodes for SIBs.

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Vanadium-doped TiO₂-B/anatase mesoporous nanotubes with improved rate and cycle performance for rechargeable lithium and sodium batteries

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