Elsevier

Journal of Alloys and Compounds

Volume 651, 5 December 2015, Pages 685-689
Journal of Alloys and Compounds

Fabrication of TiO2 hollow nanostructures and their application in Lithium ion batteries

https://doi.org/10.1016/j.jallcom.2015.08.168Get rights and content

Highlights

  • The diameter of TiO2 hollow nanostructures is about 10–15 nm.

  • The preparation condition is cheap, convenient and scalable.

  • TiO2 hollow nanostructures exhibit excellent electrochemical properties.

Abstract

A facile hydrothermal route is used for the synthesis of TiO2 hollow nanostructures. The choice of LiOH plays an important role in the formation of TiO2 hollow nanocrystals. XRD and HRTEM patterns show that TiO2 hollow nanostructures are anatase and TiO2 (B) structure. The electrochemical performance measurement demonstrated that the as-prepared TiO2 hollow nanostructures exhibit good lithium storage performance and excellent cyclability (which delivers a higher reversible capacity of 227 mAhg−1 at 0.5 C after 100 cycles). The unique architecture should be responsible for the superior electrochemical performance.

Graphical abstract

TiO2 hollow nanostructures have been successfully prepared by using a simple hydrothermal process without using any template. The structure of TiO2 hollow nanostructures is non-monolithic phase (anatase and TiO2 (B)). The test results of electrochemical performance show that these unique TiO2 hollow nanostructures exhibit good electrochemical performance with high reversible capacity, long cycle life, high rate performance, and their low cost synthesis and non-polluting nature make them promising candidates for the next generation Lithium ion batteries.

  1. Download : Download high-res image (465KB)
  2. Download : Download full-size image

Introduction

Crystalline TiO2 has been attracted much attention in recent years because of its excellent physicochemical properties and potential application in lithium-ion batteries [1], [2], [3], [4]. In lithium-ion batteries, the TiO2 is an attractive alternative anode material to graphite because of its sufficiently high operating voltage 1.8 V vs Li/Li+ [5]. However, the poor rate capability of TiO2 electrodes results from their intrinsically low Li-ion diffusivity and low electronic conductivity, which limits their practical use [6], [7], [8]. Considerable efforts have been made by predecessors to synthesize the nanostructures of TiO2 which enhances the rate performance. For example, producing hollow nanostructures have been synthesized, which possess many advantages such as enough storage space Li+, high contact area between electrolyte and electrode, short diffusion distance for Li+ transport, and the ability to accommodate strain during cycling [9], [10], [11], [12]. TiO2 hollow nanostructures prepared by Lou et al. [13] have excellent capacity retention over extended cycling, and they are able to deliver a reversible Li storage capacity of 172 mAhg−1 after 35 cycles. Wang et al. [14] used carbon spheres as template to prepare TiO2 hollow spheres that their lithium storage properties were improved greatly.

Numerous TiO2 hollow nanostructures synthesis often relies on templating approaches, in which hard (e.g., inorganic, metal, and polymer particles) or soft sacrificial templates (e.g., supramolecular assemblies of surfactant and polymer) were used to create a hollow structure [15], [16], [17], [18], [19], [20], [21], [22]. However, hollow nanostructures prepared by template are limited to application due to the high cost, not friendly to the environment.

Here, we describe a simple hydrothermal method for the synthesis of TiO2 hollow nanostructures without any template. The preparation condition is cheap, convenient and scalable, while the produced TiO2 hollow nanostructures exhibit excellent electrochemical properties. TiO2 hollow nanostructures give rise to significant improvements in the cycling stability and rate performance.

Section snippets

Experimental

The TiO2 hollow nanostructures were obtained by a hydrothermal reaction without any template. In a typical experiment, a solution of NaOH was added dropwise to a solution of Ti(SO4)2 under stirring at room temperature. The mole ratio of Ti(SO4)2 to NaOH was kept to be 1: 4. A gelatinous white precipitate was formed instantly. The resulting white precipitates were washed several times with deionized water until the absence of residual SO42 (tested by reaction with a BaCl2 solution).

Results and discussion

Fig. 1 shows the XRD patterns of the TiO2 hollow nanostructures prepared by different concentration of lithium hydroxide in the hydrothermal reaction. The diffraction peaks for the as-formed samples could be easily indexed to anatase (JCPDS No. 21-1272) and TiO2(B) (space group C2/m, JCPD No. 35-0088). The framework of the TiO2(B) structure is constructed from corrugated sheets of edge and corner-sharing TiO6 octahedra that are linked by bridging oxygen atoms to form a three-dimensional

Conclusions

In summary, TiO2 hollow nanostructures have been successfully prepared by using a simple hydrothermal process without using any template. The structure of TiO2 hollow nanostructures is non-monolithic phase (anatase and TiO2 (B)). The test results of electrochemical performance show that these unique TiO2 hollow nanostructures exhibit good electrochemical performance with high reversible capacity, long cycle life, high rate performance, and their low cost synthesis and non-polluting nature make

Acknowledgment

This work was financially supported by the Key Scientific and Technological Project of Jilin Province (Project Grant No. 20140204052GX) and the Opening Research Funds Projects of the state Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University (201505).

References (26)

  • G.N. Zhu et al.

    Ti-based compounds as anode materials for Li-ion batteries

    Energy Environ. Sci.

    (2012)
  • W. Wang et al.

    Porous TiO2/C nanocomposite shells as a high-performance anode material for lithium-ion batteries

    ACS Appl. Mater. Interfaces

    (2013)
  • J.S. Chen et al.

    Constructing hierarchical spheres from large ultrathin anatase TiO2 nanosheets with nearly 100% exposed (001) facets for fast reversible lithium storage

    J. Am. Chem. Soc.

    (2010)
  • Cited by (36)

    • Hollow nano- and microstructures: Mechanism, composition, applications, and factors affecting morphology and performance

      2022, Coordination Chemistry Reviews
      Citation Excerpt :

      Based on these factors, the hollow nano- and microstructures exhibit much lower density and larger surface area compared to dense solid materials with equal volumes [5]. It is obvious that, the fashioned cavities and voids with enhanced surface area, pore size, elevated loading capacity, and supplementary active sites can be potentially utilized in various applications including supercapacitors (SCs) [8–11], lithium-ion batteries (LIBs) [12–15], sensors [16–19], dye-sensitized solar cells [20–22], drug delivery [23–25], water treatment [26–27], catalysis [28–30], and many more. Hollow nano- and microstructures can be classified into multitudinous groups on the basis of different perception [7] as shown in Scheme 1.

    • Ultrafine TiO<inf>2</inf> nanocrystalline anchored on nitrogen-doped amorphous mesoporous hollow carbon nanospheres as advanced anode for lithium ion batteries

      2019, Electrochimica Acta
      Citation Excerpt :

      However, practical application of TiO2 as an anode material in LIBs is always hindered owing to its sluggish Li+ diffusivity and poor electrical conductivity [7,8]. To improve Li+ insertion/extraction kinetics of TiO2, one effective strategy is to substantially decrease the particle size of TiO2, which can remarkably shorten Li-ion diffusion length in the solid phase [9]. By now, various low-dimensional nanostructured TiO2, such as nanosphere [10], nanosheet [11], nanotube [12] and nanocable [13], have been investigated to improve the electrochemical performance of TiO2.

    View all citing articles on Scopus
    View full text