Titania nanotube synthesized by a facile, scalable and cheap hydrolysis method for reversible lithium-ion batteries
Graphical abstract
Highlights
► Titania nanotubes were prepared by using the cellulose filter paper as the template. ► The synthetic process is simple, cheap and scalable. ► Titania nanotubes showed better cycling and rate performances than titania nanoparticles.
Introduction
Lithium-ion batteries (LIBs) have been widely used in many aspects of our society, such as mobile phone, laptop computer, and digital camera. However, the sustainable energy density and power density of LIBs are still much lower than the requirements of vehicle application, especially for electric vehicles (EV) and plug-in hybrid electric vehicles (PHEV) [1], [2], [3], [4], [5], [6], [7]. As for commercial LIBs, graphite is typically used as an anode material. However, there are inevitably safety problems for LIBs due to the possible production of lithium metal dendrites during continuous charge–discharge process. So much work has been done to investigate the electrochemical performance of potential anode for satisfying the requirements of high-performance batteries for EV and PHEV. Among the potential anode candidates, TiO2 has been widely investigated because it can be versatile used in many different fields, such as semiconductors, photocatalysts, photovoltaic devices, gas sensing, and energy storage and conversion [8], [9], [10], [11], [12]. Especially, TiO2 as an anode of LIB has attracted much attention due to its high lithium insertion potential to avoid the formation of lithium dendrite, high stability, environmental benign, low cost and the ability to be prepared with different morphology, such as spheres [12], [13], [14], nanofibers [15], nanoribbons [16], and nanotubes [17], [18], [19]. Compared with the conventional materials, nanostructure materials have some substantial advantage. Both electron and Li-ion transport path are much shorter, which can facilitate the electrochemical process. At the same time, they can accommodate the volume expansion during the intercalation/deintercalation process. Furthermore, higher electrode–electrolyte contact area helps to get better electrochemical performance. Among the one-dimensional nanostructures, nanotubes are better than nanofibers and nanorods as electrode materials because both their inner and outer surfaces can contact with the electrolyte, which is beneficial to the electrochemical performance. Furthermore, the void spaces inside the nanotubes also eliminate the stress of volume change during the intercalation/deintercalation process and hence provide good performance. Wang et al. [19] prepared mesoporous titania nanotube by using the anodic aluminum oxide (AAO) and P123 as the hard and soft template, respectively. The electrochemical testing results show that mesoporous titania nanotubes have a good performance. Recently, Kyeremateng et al. [20] investigated the performance of titania nanotube electrodes with electropolymerized copolymer electrolyte for 3D microbatteries. Bae et al. [21] demonstrated the improved performance of amorphous titania nanotubes with self-branched crystalline nanorods prepared by atomic layer deposition combined with the template-directed approach. Furthermore, several studies have shown that carbon coated [22] or nitridated [23] TiO2 nanotubes can improve reversible capacity by suppression the nanotube agglomeration. More recently, Pandaa et al. [24] reported the performances of TiO2 nanotubes with different wall thickness by atomic layer deposition using AAO membranes as the template. However, most of them take advantage of the expensive hard-template such as AAO or the molecular soft template such as polymer/copolymer surfactant combined with complex process. The simple, inexpensive and scalable fabrications of TiO2 nanotubes are still a challenge because of the cost of template, limited product yield, and the complexity of the methods. Herein, we report a simple and inexpensive method to prepare the titania nanotubes by using ordinary ashless cellulose filter paper as the template and their application in a rechargeable lithium ion battery. When titania nanotube used as anode of LIB, it shows excellent electrochemical charge/discharge behavior.
Section snippets
Preparation of nanotube
0.255 g of Ti(OBu)4 were dissolved in 25 mL of an anhydrous ethanol solvent with small amount of acetic acid. A piece of filter paper was placed in this solution for a while to ensure certain adsorption amount of titanate on the surface of filter paper, and was washed by ethanol, followed by drying with nitrogen flow. Then the filter paper was transferred into a beaker with copious de-ionized water, covered and kept for several hours to let the titanate hydrolysis thoroughly at room temperature.
Results and discussion
Compared to the reported preparation processes [18], [19], [26], the titania nanotubes in this study were produced directly by the hydrolysis of titanate without adding any additional capping agent to form a homogeneous precursor. The schematic illustration of the synthetic procedure used for preparing the titania nanotube by a simple hydrolysis route is shown in Fig. 1. The reaction processes involving the hydrolysis and condensation between TiO2 precursor and the hydroxyl groups from the
Conclusions
In summary, we report a facile method for large-scale synthesis of TiO2 nanotubes by using cheap and commercial cellulose filter paper as the template. The obtained titania nanotubes used as anode material of LIB show excellent electrochemical charge/discharge behavior with a good rate capability. Although several researches of titania nanotubes by hard or soft template have been reported, the titania nanotubes synthesized by cellulose filter paper as the template have inherent advantage in
Acknowledgment
Financial support from National Basic Research Program of China (973 Program No: 2007CB209702) is greatly appreciated.
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