Rupesh S.
Devan
*abc,
Yuan-Ron
Ma
*c,
Ranjit A.
Patil
c and
Schmidt-Mende
Lukas
d
aCentre for Physical Sciences, School of Basic and Applied Sciences, Central University of Punjab, Bathinda, Punjab 151001, India. E-mail: devan_rs@yahoo.co.in
bDepartment of Physics, Savitribai Phule Pune University (Formerly, University of Pune), Pune 411007, India
cDepartment of Physics, National Dong Hwa University, Hualien 97401, Taiwan, Republic of China. E-mail: ronma@mail.ndhu.edu.tw
dDepartment of Physics, University of Konstanz, 78457 Constance, Germany
First published on 22nd June 2016
We report the highly stable supercapacitive performance of one-dimensional (1D) nanoneedles of brookite (β) TiO2 synthesized on a conducting glass substrate. The 1D β-TiO2 nanoneedles synthesized over a large area array utilizing hot-filament metal vapor deposition (HFMVD) were ∼24–26 nm wide, ∼650 nm long and tapered in a downward direction. X-ray photoemission spectroscopy (XPS) revealed their chemical properties and stoichiometric Ti and O composition. The 1D β-TiO2 nanoneedles execute as parallel units for charge storage, yielding a specific capacitance of 34.1 mF g−1. Electrochemical impedance spectroscopy revealed that the large surface area and brookite crystalline nature of the 1D nanoneedles provided easy access to Na+ ions, and resulted in low diffusion resistance, playing a key role in their stable charging–discharging electrochemical mechanism. Moreover, the non-faradic mechanism of these nanoneedles delivered better durability and high stability up to 10000 cycles, and a columbic efficiency of 98%. Therefore, 1D β-TiO2 nanoneedles hold potential as an electrode material for highly stable supercapacitive performance with long cycle lifetime.
Over the past few decades, titanium dioxide (TiO2) is one of the most fascinating functional materials in the fabrication of supercapacitor because of the low processing cost, high chemical stability compared to most alternative materials, abundance and non-toxic nature. In the form of ultra-thin films or nanoparticles of size below 10 nm, mesoporous TiO2 films dramatically increase the ion transport and provide the high specific capacitance of 90–120 μF cm−2 at the normalized surface area.6 Highly ordered arrays of TiO2 nanotubes provide large surface area were found interesting alternative morphology for charge storage.3,7,8 However, the discontinuous and polycrystalline morphology of TiO2 nanotubes offers relatively poor conductivity and low electrochemical activity, limit its use in high-performance supercapacitors. Therefore, significant efforts have been made to synthesize TiO2 nanorods, nanowires, nanotubes and nanofibers, etc. and improve their supercapacitive performance in combination with various electrolytes such as H2SO4, NaOH, Na2SO4, LiClO4, and LiPF6, etc.3,5,7–11 Mainly three different polymorphs, rutile, anatase and brookite (β) are described regarding crystal structural arrangements of distorted TiO6 octahedra. Chains of edge-shared distorted octahedra running parallel to the c-axis yielding in β-phase of 1D nanoneedles. The shared edges of distorted TiO6 octahedra provide abundant enough vacant sites to accommodate Na+ ions. Therefore, especially β-TiO2 promises a electrode material for electrochemical processes. In nanocrystalline form, the β-phase is thermodynamically most stable with dimensions between 11 and 35 nm,12 and crystallographic data in brookite are intermediate between rutile and anatase phases.13 Moreover, β-TiO2 is promising dielectrics with much larger static dielectric constant14 and also known to exhibit markedly higher catalytic activities12 than anatase and rutile TiO2. Therefore, the β-phase is expected to offer high stability and long cycle lifetime.
So far, supercapacitor properties of anatase and rutile structures are studied extensively15–17 and seem to have reached their limit. Because of the difficulties encountered in the synthesis, most of the times β-phases was accompanied with anatase or/and rutile phases.12,18,19 Therefore, high temperature calcinations19 (700 °C) and annealing18 (800 °C) treatment was employed to obtain β-TiO2 nanorods. Nevertheless, the properties of the nanostructure of pure β-TiO2 phase seem to be interesting. To the best of our knowledge, supercapacitor properties of pure 1D β-TiO2 nanoneedles have not been reported yet in the literature. Therefore, in this paper, we report stable supercapacitive performance of 1D β-TiO2 nanoneedles synthesized in a large area via hot-filament metal vapor deposition (HFMVD) technique without additional heat treatment. The HFMVD technique is unique and useful for the synthesis of the variety of metal oxide nanostructures with diverse morphologies and crystalline phases.20–24 The structural morphology and chemical composition of the 1D β-TiO2 nanoneedles was examined utilizing field-emission scanning electron microscopy (FESEM) and X-ray photoemission spectroscopy (XPS), respectively. The electrochemical characterizations of the large-area array of the 1D β-TiO2 nanoneedles were carried out by cyclic voltammetry (CV), galvanostatic charge/discharge method, and AC impedance analysis in the electrolyte of Na2SO4. The results strongly indicated that 1D β-TiO2 nanoneedles provide columbic efficiency of 98%, high stability, greater retentivity (∼88.2%) and long cycle lifetimes up to 10000 cycles in Na2SO4 electrolyte. Therefore, the large area array of 1D β-TiO2 nanoneedles is an attractive material for fabrication of highly stable supercapacitors of long cycle lifetime.
(1) |
Further, the crystalline structure of these well-defined TiO2 nanoneedles was confirmed by XRD and discussed elsewhere.25 The corresponding XRD spectra evidences that the 1D TiO2 nanoneedles are exclusively of orthorhombic crystal structure in brookite phase, which is assigned to the space group Pbca (JCPDS-761936) with lattice constants a = 0.919 nm, b = 0.546 nm, c = 0.516 nm and α = β = γ = 90°. Altogether, it demonstrates that our HFMVD technique can be successfully employed for the synthesis of 1D TiO2 nanostructures with optimal dimensions and required thickness. According to our literature survey, rutile and anatase phases are commonly synthesized and widely studied TiO2 phases. Only brookite is investigated rarely, even though it has exciting properties. Therefore, the large area array of 1D TiO2 nanoneedles of brookite phase reported here is of special importance in scientific and technological application point of view.
XPS was used to perform quantitative analysis of the electronic structure and chemical properties of the 1D β-TiO2 nanoneedles. Fig. 2 illustrate two Ti(2p) and O(1s) XPS spectra obtained for the large area array of 1D TiO2 nanoneedles. Fig. 2(a) shows the double peak features in the Ti(2p) XPS spectrum. To precisely determine the features of the double peaks of Ti(2p3/2) and Ti(2p1/2), the Ti(2p) XPS spectra was decomposed via Voigt curve fitting with the Shirley background. The deconvolution shows a perfect fit for two peaks located at binding energies of 458.56 and 464.24 eV, respectively, corresponding to the Ti(2p3/2) and Ti(2p1/2) core levels of Ti4+ cations and not of Ti3+.17,26 The energy separation between Ti(2p3/2) and Ti(2p1/2) peaks is 5.68 eV, and their area ratio is 2.48, which reflects a strong bonding between the Ti and O atoms. The full width at half-maximum (FWHM) of the Ti(2p3/2) and Ti(2p1/2) peak are 1.29, 2.27, respectively, indicating the high resolution of the Ti(2p) XPS spectrum in comparison with previous studies.26,27 Similarly, the O(1s) XPS spectrum of the 1D nanoneedles shown in Fig. 2(b) was decomposed via Voigt curve fitting with the Shirley background. The results demonstrate a perfect fit to two peaks located at 529.89 and 531.31 eV, with FWHM's of 1.38 and 2.19 eV, respectively. The lower binding energy peak at 530.14 eV corresponds to the O(1s) core level of the O2− anions in the 1D β-TiO2 nanoneedles. However, the higher binding peak at 531.61 eV is ascribed to surface contamination, such as carbon oxides or hydroxides20,21 of the 1D nanoneedles. The O(1s) peak observed at a binding energy of 529.89 eV is associated with the Ti–O chemical bonding.17 The atomic ratio of titanium and oxygen (i.e. Ti/O ratio) estimated by integrating the area beneath the decomposed peaks of O(1s) (530.14 eV) and Ti(2p3/2) (458.74 eV) is ∼0.51 (i.e. Ti:O = 1.02:2), which is very close to the stoichiometric ratio (i.e. 1:2) of pure TiO2. This analysis confirms that all 1D nanoneedles in the large area array were fully oxidized, and were composed of pure stoichiometric TiO2 without any traces of sub-oxides (TiOx). Moreover, the binding energy difference (ΔE) of 71.33 eV between the O(1s) and Ti(2p3/2) peaks is very close to that of 71.5 eV for TiO2, and significantly smaller than 73.4 eV for Ti2O3 and 75.0 eV for TiO.28 This confirms again that the 1D nanoneedle array over a large area is formed exclusively of stoichiometric TiO2.
The supercapacitor behavior of 1D β-TiO2 nanoneedles is confirmed with CV, galvanostatic charge/discharge and impedance measurements. The CV measurements useful to investigate supercapacitor behavior are recorded for 1D β-TiO2 nanoneedles within the operating potential range of 0 to 0.8 V and at various scan rates ranging from 15 to 150 mV s−1. Fig. 3(a) shows the CV graphs of the 1D β-TiO2 nanoneedles. Irrespective of variation in the scan rates, the CV graph shows well rectangular shape in 1 M Na2SO4 electrolyte, indicating good capacitive behavior and high rate capability of the β-TiO2 nanoneedles. No evidence of any faradic reaction on well rectangular CV curve is found to ensure the reduction of Ti4+ to Ti3+. This confirms the pure double layer capacitor behavior of the β-TiO2 nanoneedles. Moreover, the well rectangular shape of CV graph confirms that the large surface area of the nanoneedle morphology of β-TiO2 with clearly visible textural boundaries offers abundant diffusion of Na+ ions and charge transport during non-faradic reaction along the nanoneedle sides. The negative and positive current density occurred due to the insertion and extraction of Na+ ions on the surface of β-TiO2 nanoneedles. A little bit more negative current density is observed than that of positive current density at applied potential. It is accepted that the large surface area of nanostructure morphology acts as traps to capture free electrons or ions when they pass through. Likewise, the large surface area of 1D TiO2 nanoneedles possibly provides a number of trap levels. Therefore, trapping–detrapping of free electrons at trap levels enhances the ionic conductivity17 and results in a more negative current density at applied potential. The current density of CV increased with increase in scanning rate from 15 to 150 mV s−1. Likewise, the area under CV graph increased proportionally with the scan rate. The variation in current density can be well understood via the Randles–Sevcik equation-
ip = 2.69 × 105n3/2Coν1/2D1/2 | (2) |
The specific capacitance is shown in the Fig. 3(c) is calculated from CV graph at various scan rates (Fig. 3(a)) from the equation,
(3) |
The galvanostatic charging–discharging (Fig. S1, ESI†) of 1D β-TiO2 nanoneedles was studied at various current densities of 166.7, 250, 333.3 and 416.7 μA g−1. Obviously, the charging curves were relatively symmetric to their discharge counterpart implying that a highly reversible ion transportation is efficiently taking place along the textural boundaries of 1D β-TiO2 nanoneedles. Furthermore, the overall performance of 1D β-TiO2 nanoneedles was illustrated with a Ragone plot (ESI, Fig. S2†). A Ragone plot manifests a high energy density and power density of 3.04 W h kg−1, and 1683 W kg−1, respectively.
Not only the amount of active material and electrolyte plays a critical role in the capacitive behavior, but a dominant role is attributed to the electrical properties, textural boundaries, and the core of the nanostructures. Therefore, electrochemical impedance spectroscopy (EIS) was employed to investigate the mechanistic aspects such as electrical resistance involved in the ion diffusion of 1D β-TiO2 nanoneedle arrays. Typical Nyquist plots of the 1D β-TiO2 nanoneedle in 1 M Na2SO4 solutions at various electrode potentials are presented in Fig. 4. All the impedance spectra consist of partial semicircles (arc) and straight lines having slopes at the higher and lower frequencies, respectively. In high-frequency region, the distorted semicircle corresponds to the charge-transfer resistance of the interface between the 1D β-TiO2 nanoneedles and electrolyte. The intercept of this semicircle yields the electrolyte resistance (Re), and the diameter provides the charge transfer resistance (Rct). As noticed from the diameter of the semi-circle, the value of the Rct increased with the applied potential which reduces Cs. However, the low-frequency regime in the form of the straight line corresponds to diffusion resistance from the textural boundaries. Extrapolation of this gives larger resistance compare to that of the core of the nanoneedle since the 1D nanoneedle morphology of β-TiO2 provides large surface area. These observations are within the expectation and are supporting the calculated values of Cs. Moreover, the straight line observed in low-frequency regime represents Warburg behavior. The angle made by the low-frequency data on the real axis decreases gradually from 67.4° to 50.03° on increasing the applied potential from 0.2 to 0.8 V. This indicates gradual transition from capacitance to Warburg behavior between 0.2 and 0.8 V. The Warburg behavior (Warburg resistance Zw) results from the diffusion-controlled insertion and extractions of anions/cations in the electrode. This trend is in good agreement with the reports based on rutile TiO2 nanowires and TiO2@C core–shell nanowires,35 and anatase TiO2 nanotubes.8 The equivalent circuit for these electrochemical impedance measurements is composed of electrolyte resistance (Re), a charge transfer resistance (Rct), finite length Warburg diffusion element (Zw), and a constant phase element (CPE). It is represented in the inset of Fig. 4. Thus, nanoneedle morphology with large surface area and clearly visible textural boundaries improve the accessibility of the Na+ ions from the electrolyte. The time constant (τ) is calculated from the equation-
(4) |
Good cycling stability, durability and lifetime are important characteristics for the highly stable performance of supercapacitors. The 1D β-TiO2 nanoneedles were tested at a scan rate of 100 mV s−1 and the current density of 250 μA g−1 for 10000 cycles and 5000 cycles, respectively (Fig. 5). The Cs evaluated from the CV measurements at a scan rate of 100 mV s−1 drops from 32.1 to 28.3 mF g−1 after 10000 cycles. Significantly, the 1D β-TiO2 nanoneedles exhibit long-term stability with only 11.8% reduction of Cs after 10000 continuous cycles (Fig. 5(a)). The CV graphs of selected cycles (Fig. S3†) used to evaluate the Cs retention are almost identical, indicating extremely stable performances of the 1D β-TiO2 nanoneedles. Furthermore, Cs measurements were performed for 5000 continuous cycles of galvanostatic charging–discharging at current density of 250 μA cm−2 in 200000 s (55.6 h) (Fig. 5(b)). Galvanostatic charging–discharging cycles were relatively symmetric to their discharge counterpart. First, 50 cycles are shown in Fig. S4.† With increased number of charging–discharging cycles and time, the calculated Cs drops from 109.9 to 96.7 mF g−1 after 5000 cycles. This small relative decrease indicates that 1D β-TiO2 nanoneedles exhibit long-term stability with only 12.04% reduction of Cs after continuous galvanostatic charging–discharging for 55.6 h (i.e. 5000 cycles). This ∼12% reduction of Cs of 1D β-TiO2 nanoneedles observed is much better than the value for amorphous TiO2 nanotubes (34.8% reduction after 10000 cycles) which were further annealed at 400 °C to form anatase TiO2 nanotubes (44.3% reduction after 10000 cycles),7 hydrothermally synthesized rutile TiO2 nanorods (20% reduction even after only 1000 cycles),9 sonochemically carbon activated TiO2 (β) nanowires mixed with polyaniline (57.5% reduction after 2000 cycles),4 polythiophene infiltrated TiO2 nanotubes (11% reduction after 1100 cycles),3 and arrays of anodic TiO2 nanotubes layered with Co(OH)2 by cathodic deposition (18% reduction after 1000 cycles).8 Moreover, these nanoneedles showed comparatively better stability than other metal oxides listed in ESI; Table S1.† Even after such a large number of cycles continued continuously for couples of days, 1D β-TiO2 nanoneedles were still intact and did not appear degraded or damaged by electrochemical interactions. This remarkable cycling performance of 1D β-TiO2 nanoneedles confirms their superior durability, the longer lifetime, high stability, and excellent electrochemical reversibility in Na2SO4 electrolyte. This is ascribed to their nanostructure, large surface area, clearly visible textural boundaries, enhanced electrical conductivity, and well stable electrochemical reactions. Therefore, the core–shell formation of 1D β-TiO2 nanoneedles with carbon based materials or conducting polymers may be helpful to overcome their swelling and shrinking and to further improve their stability at large extent.
Footnote |
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c6ra11348f |
This journal is © The Royal Society of Chemistry 2016 |