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DOI: 10.1002/adfm.200500937

A Hybrid Supercapacitor Fabricated with a Carbon Nanotube Cathode and a TiO2B Nanowire Anode**
By Qiang Wang, Zhenhai Wen, and Jinghong Li*
Recently, a new hybrid supercapacitor, integrating both the advantages of supercapacitors and lithium-ion batteries, was proposed and rapidly turned into state-of-the-art energy-storage devices with a high energy density, fast power capability, and a long cycle life. In this paper, a new hybrid supercapacitor is fabricated by making use of the benefits of 1D nanomaterials consisting of a carbon nanotube (CNT) cathode and a TiO2B nanowire (TNW) anode, and the preliminary results for such an energy-storage device operating over a wide voltage range (02.8 V) are presented. The CNTTNW supercapacitor is compared to a CNTCNT supercapacitor, and discussed with regards to available energy densities, power capabilities, voltage profiles, and cycle life. On the basis of the total weight of both active materials, the CNTTNW supercapacitor delivers an energy density of 12.5 W h kg1 at a rate of 10 C, double the value of the CNTCNT supercapacitor, while maintaining desirable cycling stability. The combination of a CNT cathode and a TNW anode in a non-aqueous electrolyte is proven to be suitable for highperformance hybrid supercapacitor applications; this can reasonably be assigned to the interesting synergistic effects of the two nanomaterials. It is hoped that the results presented in this study might renew interest in the design of nanomaterials that are applicable not only to hybrid supercapacitors, but also to energy conversion and storage applications of the future.

1. Introduction
Of the current energy-storage technologies, lithium-ion batteries provide the highest energy density (150200 W h kg1), but at the expense of a limited cycle life. On the other hand, while supercapacitors benefit from the highest known power capability (25 kW kg1) and long cycle life, they suffer from a modest energy density (36 W h kg1).[1,2] In order to combine the advantages of lithium-ion batteries and supercapacitors, a new hybrid supercapacitor was recently proposed, and this rapidly turned into a state-of-the-art energy-storage device, where a high energy-density, fast power capability, and long cycle life were established.[39] The hybrid supercapacitor utilizes a nonFaradaic capacitative cathode and a non-aqueous electrolyte, coupled with a Faradaic lithium-intercalation anode. As a result, the device stores charge by a reversible adsorption/desorption reaction of anions on the surface of the cathode material, and simultaneously utilizes a reversible insertion/extraction reaction of the lithium ions in the anode material to store the charge.[3] The combined effects provide an opportunity to enhance the energy density and power capability effectively,

[*] Prof. J. H. Li, Q. Wang, Z. H. Wen Department of Chemistry, Tsinghua University Beijing 100084 (P.R. China) E-mail: jhli@mail.tsinghua.edu.cn [**] This work was financially supported by the National Natural Science Foundation of China (No. 20125513), the Specialized Research Fund for the Doctoral Program of Higher Education (No. 20050003035), and the Foundation for the Author of National Excellent Doctoral Dissertation of China.

while maintaining an acceptable cycle life with respect to conventional supercapacitors. From a materials point of view, if the above desirable performance characteristics are to be successfully retained in a hybrid supercapacitor, then considerable effort will have to be invested in the challenging search for optimal electrode materials.[10] Fortunately, advancement in energy-storage technologies can benefit from moving from conventional to nanostructured electrodes. For supercapacitors, recent attention has focused on nanostructured carbon, such as aerogels,[11] nanotubes, and nanotemplates.[12,13] Of these materials, carbon nanotubes (CNTs) have been considered ideal for supercapacitors, owing to their advantages of chemical stability, unique pore structure, and low electrical resistivity. On the other hand, for the lithium-ion batteries, recent trends have involved the development of inorganic 1D nanomaterials, such as SnO2, TiO2, Co3O4, V2O5, MnO2, and Fe2O3, owing to their size- and dimensionality-dependent physicochemical properties.[1422] Taking into account the high specific capacity, extended cycle life, and fast rate capability,[2022] TiO2B nanowires (TNWs) seem to be extremely attractive, and should be a promising candidate for hybrid-supercapacitor applications. Additionally, Li4Ti5O12-based hybrid supercapacitors are characterized by an abrupt voltage decrease between 1.5 and 0 V during discharge, owing to a very flat 1.5 V potential plateau in nanostructured Li4Ti5O12consequently their typical working range is limited.[3,23,24] In contrast, relatively smooth charge discharge curves within a potential window of 12.5 V have been observed for TNWs,[22] which offers the possibility of extending the working range of related supercapacitors. Therefore, in this paper, making use of the benefits of the two 1D nanomaterials mentioned above, we report the first fabrication 2141

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of a supercapacitor in which CNTs are used as the cathode and TNWs as the anode, and we report its performance characteristics over a wide voltage range: 02.8 V. This is vital for understanding the interesting combined effects of CNTs and TNWs in a hybrid supercapacitor, and for further design of new nanomaterials to satisfy increasing worldwide demand for energy conversion and storage.

2. Results and Discussion

A nanoagglomerate fluidized-bed catalytic technique[25,26] and a modified hydrothermal method[27] were utilized to synthesize the multiwalled CNTs and single-crystal TNWs, respectively. As shown by the scanning electron microscopy (SEM) images in Figure 1A, the CNTs have a morphology characterized by a randomly entangled and crosslinked nanotubular structure. Furthermore, a large variety of tube diameters, with inner diameters of 310 nm and outer diameters of 620 nm were observed. It is widely accepted that such an open structure permits easy access for ions to the electrode/electrolyte interface, which is crucial for a non-Faradaic capacitative electrode material.[1113] Transmission electron microscopy (TEM) images (Fig. 1B and C) clearly show that the TNWs have diameters in the range 2050 nm and lengths of up to several micrometers. The selected-area electron diffraction (SAED) pattern (Fig. 1C, inset) recorded from a single TNW reveals its single-crystalline nature. Generally, nanostructured materials are essential for lithium-intercalation kinetics, owing to their reduced diffusion paths and increased specific surface area, especially at high rates of chargedischarge.[28] Figure 2 shows the X-ray diffraction (XRD) patterns of the CNTs and TNWs. After treatment with HNO3/H2SO4, the CNTs exhibited excellent graphitic properties with obvious polyaromatic, turbostratic structural features with (002) and (100) peaks, as well as clear (004) peaks (Fig. 2A).[29] It is well known that a high degree of graphitization (which results in good electronic conductivity) is important for electron transport during the electrochemical reaction.[30] Moreover, the nano-

Figure 2. XRD patterns of A) CNTs B) TNWs.

tubes were uncontaminated by other forms of carbon residue, except for small amounts of catalyst residue that were entrapped by CNTs, as is evident in Figure 1A. All the diffraction peaks of the TNWs (Fig. 2B) can be indexed as the TiO2B structure, which is characterized by corrugated sheets of corner- and edgesharing TiO6 octahedra linked together by bridging oxygen atoms.[21] As a consequence of this connection, TNWs have freely accessible parallel channels, in which lithium ions can be accommodated without any remarkable distortion of the structure.[20] Thermogravimetric analysis (TGA) and X-ray fluorescence (XRF) spectroscopy were employed for the quantitative evaluation of the quality of the CNTs and TNWs. On the basis of the TGA analysis, the purity of the CNTs is about 91.7 % (considering the weight percent of Fe in the catalyst and its conversion to metal oxide in the TGA process). From the XRF results, the content of TiO2 in TNWs is as high as 98.58 %. The nitrogen absorption/desorption isotherms at 77 K and pore size distributions of CNTs and TNWs are presented in Figure 3. Considering the absence of nitrogen absorption at very low pressure, it can be concluded that the micropore contribution to the total pore volume was negligible for the two materials. As seen in Figure 3A, the adsorption curve gradually increased in the middle-pressure region and then increased abruptly in the high-pressure region (> 0.8 P/P0; P/P0: relative pressure) so the adsorption behavior of CNTs can be attributed to capillary condensation and multilayer adsorption of nitrogen in the mesopores or macropores.[26] TNWs (Fig. 3B) exhibited the adsorption characteristics of nonporous or macroporous materials. These conclusions are in good agreement with the BarrettJoyner Halenda (BJH) pore size distributions of the CNTs and TNWs. The Brunauer EmmettTeller (BET) surface areas were Figure 1. A) Representative SEM images of carbon nanotubes; inset shows magnified image. as high as 177.2 and ca. 17.8 m2 g1 for the B,C) Representative transmission electron microscopy (TEM) images of TiO2B nanowires; inset (C) shows the selected-area electron diffraction (SAED) pattern. CNTs and TNWs, respectively. 2142 www.afm-journal.de

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Figure 3. The N2 adsorption and desorption isotherms of A) CNTs; B) TNWs. The volume adsorbed of B is multiplied by a factor of five. Solid circles: adsorption; hollow circles: desorption. The inset shows the BarrettJoynerHalenda (BJH) pore size distributions of the two materials.

Electrochemical measurements were carried out using twoelectrode cells without a reference electrode. For the assembly of the supercapacitors, pellets of the same mass were selected. Cyclic voltammetry (CV) was considered to be a suitable tool for estimating the difference between the non-Faradaic and Faradaic reactions. In addition, this technique can also be used for preliminary determination of the power density and energy density of the supercapacitors.[31] Figure 4 presents the steadystate cyclic voltammograms of CNTCNT and CNTTNW supercapacitors, obtained by applying a potential varying from 0 to 2.8 V with various sweep rates (from 20 to 120 mV s1). According to the shapes of these curves, it can be assumed that their current responses are sweep-rate dependent. The cyclic voltammograms of the CNTCNT supercapacitor (Fig. 4A) maintained good rectangular shapes, even at a sweep rate of 120 mV s1, indicating its excellent capacitative behavior. In contrast, the CNTTNW supercapacitor (Fig. 4B) exhibited a gradual deviation from the ideal rectangular shape with increasing sweep rate, directly owing to the overlapping effect of two different energy-storage mechanisms. In contrast to the CNT electrode, where energy is stored by electrostatic surfacecharge accumulation at its electrode/electrolyte interface, the TNW electrode stores energy by utilizing a lithium-intercalation reaction involving Faradaic electron transfer and reversible phase transformation.[3] Such a conclusion is consistent with the interpretation of the deviation of the voltammetry characteristics in the CV results. Ragone plots (Fig. 5), which are used to relate the power density to the energy density, were calculated from the cyclic voltammograms using the equations of Xing et al.[31] In comparison to the CNTCNT supercapacitor, the energy densities of the CNTTNW supercapacitor were dramatically higher, especially in cases with lower power densities. A maximum energy density of 12.5 W h kg1 was obtained for the CNTTNW supercapacitor, which is more than twice that (6.1 W h kg1) of the CNTCNT supercapacitor. It is important to mention that

Figure 4. Steady-state cyclic voltammograms of A) CNTCNT supercapacitor; B) CNTTNW supercapacitor at various sweep rates. Arrows indicate the direction of increasing sweep rate (20, 40, 60, 80, 100, and 120 mV s1).

Figure 5. Ragone plots of power density versus energy density for A) CNTCNT supercapacitor; B) CNTTNW supercapacitor.

our values for the energy and power densities delivered by the CNTTNW supercapacitor have not been optimizedfurther enhancement can be easily envisioned through the balancing of active masses, of power densities, and the choice of proper www.afm-journal.de 2143

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states of discharge.[6] As observed in Figure 5, higher energy densities were achieved at the expense of power capability in the CNTTNW supercapacitor, which can mostly be attributed to the relatively poor rate capability of the TNW electrode. Since the CNT electrode is more kinetically reversible than the TNW electrode, especially at higher power densities,[9] one can conclude that the power capability of the CNTTNW supercapacitor is determined by the TNW electrode. The applicability of supercapacitors can be directly evaluated by means of the galvanostatic chargedischarge method. Plots of voltage versus time for the CNTCNT and CNTTNW supercapacitors at a rate of 10 C are given in Figure 6. As expected, the discharge curves of the CNTCNT (Fig. 6A) were symmetric with their corresponding charge counterparts, and

overall operating voltage of the latter was significantly raised; this can be explained taking into account the fact that the Faradaic lithium-intercalation reaction occurring at the TNW electrode was more stable thermodynamically than the non-Faradaic capacitative reaction occurring at the CNT electrode,[8] effectively flattening the output voltage and resulting in substantially higher energy densities. Figure 7 shows the variation in energy density as a function of cycle number (cycled between 0 and 2.8 V, at a rate of 10 C). For CNTCNT and CNT TNW supercapacitors, the trend in energy-density variation

Figure 7. Variation of the energy density with the number of cycles for A) CNTCNT supercapacitor; B) CNTTNW supercapacitor at a rate of 10 C.

Figure 6. Representative galvanostatic chargedischarge curves of A) CNTCNT supercapacitor; B) CNTTNW supercapacitor at a rate of 10 C.

the slope of every curve was almost potential independent and retained a constant value. As for the CNTTNW (Fig. 6B), it should be noted that its currentresistance (IR) drop was relatively obvious, and was mainly derived from the low electronic conductivity of the TNWs, and slightly narrowed the voltage range in which energy was stored and delivered. However, the 2144 www.afm-journal.de

with cycle was similar: both showed a small loss in the first hundred cycles, and then remained almost constant as cycling continued. On the basis of the mass of both active materials, the CNTTNW supercapacitor (Fig. 7B) not only delivered an energy density of 12.5 W h kg1 at a rate of 10 C (double the values of the CNTCNT supercapacitor; Fig. 7A), but also maintained an excellent cycling stability comparable to that of the CNTCNT supercapacitor. Obviously, the good cycling stability of the TNW electrode utilized in the hybrid supercapacitor complements the intrinsic cycling stability of CNT electrode. The cycle life of a TNW electrode usually depends on the operating rates and depth-of-discharge, which determine the available energy density. Hence, it is desirable that this behavior be factored into mass- and charge-balance calculations in fabricating CNTTNW supercapacitors in our future work, in order to maintain cathode-limitation conditions and a good anode cycle life of the resulting device. For the first time, the combination of a CNT cathode and TNW anode in a non-aqueous electrolyte has been proven to be suitable for high-performance hybrid supercapacitor applications; this result can reasonably be ascribed to the interesting synergistic effects of the two nanomaterials, as will be discussed later. Electrochemical impedance spectroscopy (EIS) was utilized to obtain information on the supercapacitors performance, such as their frequency dependence and equivalent series resistance (ESR).[32] Figure 8 illustrates the Nyquist plots of the

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CNTCNT and CNTTNW supercapacitors before and after 600 cycles. At very high frequencies, the intercept at the real axis (ZRe) is the ESR. Only a slight ESR increase was observed for the CNTCNT supercapacitor (Fig. 8A) after cycling,

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Figure 8. Nyquist plots of A) CNTCNT and B) CNTTNW supercapacitors before and after 600 cycles. Hollow circles: before cycling; solid circles: after cycling. Inset: enlarged Nyquist plots.

whereas a different situation appeared for the CNTTNW supercapacitor (Fig. 8B), where the ESR increased remarkably, probably owing to the gradual decrease in the electric conductivity of the TNWs as cycling continued. At high frequencies, the CNTCNT supercapacitor showed a Warburg region with a 45 slope that was explained as arising from the diffusion of ions in the CNT electrode, whereas in the low-frequency range its ideally capacitative characteristics gave rise to a close-tovertical line along the imaginary axis (ZIm).[11] In comparison,

the Nyquist plot of the CNTTNW supercapacitor revealed some interesting differences. A major difference was the semicircle at high frequencies, which represented the charge-transfer resistance at the TNW electrode/electrolyte interface. As shown in Figure 8B, the charge-transfer resistance increased noticeably before and after 600 cycles: a possible reason could be the decrease in the electronic conductivity of the TNWs. Another difference was the straight line inclined at an angle of around 45 to the real axis (ZRe) in the low-frequency range, corresponding to the semi-infinite ion diffusion resistance in the TNW electrode.[33] Arguably, the differences between the Nyquist plots of the two supercapacitors reflect the differences between the energy-storage mechanisms of the CNT and TNW electrodes. Therefore, on the basis of these differences, it can be assumed that the overall kinetics of the CNTCNT supercapacitor could be an energy-limited process, whereas that of the CNTTNW supercapacitor could predominantly be a powerlimited process, in good agreement with the Ragone plots. As previously shown, this combination of a CNT cathode and TNW anode in a hybrid supercapacitor introduces the advantages of the synergism between the two nanomaterials. First, the disadvantage of the relatively low energy density of the CNT electrode is compensated for by the relatively high energy density of the TNW electrodethus the CNTTNW supercapacitor would have a substantially improved energy density over that of a CNTCNT supercapacitor. Secondly, the disadvantage of the relatively poor cycle life of the TNW electrode is compensated for by the excellent cycle life of the intrinsically more reversible CNT electrode, hence a CNTTNW supercapacitor provides an advantageous opportunity for optimizing cycle life. Finally, the disadvantage of the two capacitative electrodes in the CNTCNT supercapacitor, each having intrinsically declining electrode potentials on discharge, is halved in the CNTTNW supercapacitor, since the TNW electrode has a relatively flat electrode potential that is determined by the electrode reactions thermodynamically, thus the operating voltage profile of the latter on discharge remains higher and longer compared to the former.[8] CNTs have the following advantages: open mesopore architecture and high electrical conductivity for ion/electron transport, to achieve fast power capability; good mechanical properties; and chemical stability for an excellent cycle life. Recently, several modified methods have been proposed to further improve its capacitance values, such as the combination of CNTs with conducting polymers or transition-metal oxides at the nanoscale level.[34,35] TNWs have the following potential advantages: suppression of structural distortion, to improve reversibility and cycling stability; and more active sites for lithium ions to deliver a higher energy-density. The utilization of TNWs is an important development for hybrid supercapacitor applications, and there still exists great opportunities to raise its electrical conductivity further. In this way, a deeper understanding of TNWs, and optimization of its performanceespecially in terms of power capabilityare expected to be achieved.

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3. Conclusions
A new hybrid supercapacitor, in which a CNT cathode and TNW anode were well matched, exhibited the synergistic effects of two 1D nanomaterials, and represents a very promising energy-storage system. It should be noted that the observed energy density of the CNTTNW supercapacitor (12.5 W h kg1) is comparable to that of an ACLi4Ti5O12 supercapacitor (1013 W h kg1), and is twice as high as a CNTCNT supercapacitor (6.1 W h kg1). Considering that the specific capacitance of CNTs is usually lower than that observed with AC, our energy-density value is a promising starting point. Also, the results illustrated in our preliminary experiments have not been optimizedwe believe that this hybrid supercapacitor deserves further investigation. It is generally accepted that breakthroughs in materials hold the key to new generations of energystorage and conversion devices. In this respect, the CNTTNW hybrid supercapacitor is expected to extend the palette of available candidates in hybrid supercapacitor research, and other nanomaterials, such as composite, coreshell, and more complex nanostructures, might also find encouraging applications.

2.8 V at various sweep rates, using a CHI 802B electrochemical workstation (CHI Inc., USA). Dischargecharge curves were recorded from 0 to 2.8 V at a rate of 10 C, using a Roofer Battery Tester (Shenzhen, China). Electrochemical impedance measurements were carried out on a PARSTAT 2273 Potentiostat/Galvanostat (Advanced Measurement Technology Inc., USA). The Nyquist plots were recorded potentiostatically (0 V) by applying an AC voltage of 5 mV amplitude in the 100 kHz 10 mHz frequency range. All electrochemical measurements were carried out at room temperature. Received: December 17, 2005 Final version: February 24, 2006 Published online: September 19, 2006

[1] A. D. Pasquier, I. Plitz, S. Menocal, G. G. Amatucci, J. Power Sources 2003, 115, 171. [2] A. D. Pasquier, I. Plitz, J. Gural, F. Badway, G. G. Amatucci, J. Power Sources 2004, 136, 160. [3] G. G. Amatucci, F. Badway, A. D. Pasquier, T. Zheng, J. Electrochem. Soc. 2001, 148, A930. [4] F. Chen, R. G. Li, M. Hou, L. Liu, R. Wang, Z. H. Deng, Electrochim. Acta 2005, 51, 61. [5] H. Q. Li, L. Cheng, Y. Y. Xia, Electrochem. Solid-State Lett. 2005, 8, A433. [6] J. P. Zheng, J. Electrochem. Soc. 2003, 150, A484. [7] Y. G. Wang, Y. Y. Xia, Electrochem. Commun. 2005, 7, 1138. [8] W. G. Pell, B. E. Conway, J. Power Sources 2004, 136, 334. [9] B. E. Conway, W. G. Pell, J Solid State Electrochem. 2003, 7, 637. [10] A. S. Arico, P. Bruce, B. Scrosati, J.-M. Tarascon, W. V. Schalkwijk, Nat. Mater. 2005, 4, 366. [11] E. Frackowiak, F. Beguin, Carbon 2001, 39, 937. [12] C. Liu, H. M. Cheng, J. Phys. D: Appl. Phys. 2005, 38, R231. [13] A. B. Fuertes, G. Lota, T. A. Centeno, E. Frackowiak, Electrochim. Acta 2005, 50, 2799. [14] X. P. Gao, J. L. Bao, G. L. Pan, H. Y. Zhu, P. X. Huang, F. Wu, D. Y. Song, J. Phys. Chem. B 2004, 108, 5547. [15] Y. Wang, J. Y. Lee, J. Phys. Chem. B 2004, 108, 17 832. [16] W. Y. Li, L. N. Xu, J. Chen, Adv. Funct. Mater. 2005, 15, 851. [17] K. Takahashi, S. J. Limmer, Y. Wang, G. Z. Cao, J. Phys. Chem. B 2004, 108, 9795. [18] R. H. Ma, Y. Bando, L. Q. Zhang, T. Sasaki, Adv. Mater. 2004, 16, 918. [19] J. Chen, L. N. Xu, W. Y. Li, X. L. Gou, Adv. Mater. 2005, 17, 582. [20] M. Zukalova, M. Kalbac, L. Kavan, I. Exnar, M. Graetzel, Chem. Mater. 2005, 17, 1248. [21] A. R. Armstrong, G. Armstrong, J. Canales, R. Garcia, P. G. Bruce, Adv. Mater. 2005, 17, 862. [22] A. R. Armstrong, G. Armstrong, J. Canales, P. G. Bruce, Angew. Chem. Int. Ed. 2004, 43, 2286. [23] A. D. Pasquier, A. Laforgue, P. Simon, G. G. Amatucci, J. F. Fauvarque, J. Electrochem. Soc. 2002, 149, A302. [24] A. D. Pasquier, A. Laforgue, P. Simon, J. Power Sources 2004, 125, 95. [25] Y. Wang, F. Wei, G. H. Luo, H. Yu, G. S. Gu, Chem. Phys. Lett. 2002, 364, 568. [26] F. X. Li, Y. Wang, D. Z. Wang, F. Wei, Carbon 2004, 42, 2375. [27] B. M. Wen, C. Y. Liu, Y. Liu, New J. Chem. 2005, 29, 969. [28] J. Jamnik, J. Maier, Phys. Chem. Chem. Phys. 2003, 5, 5215. [29] M. Monthioux, J. G. Lavin, Carbon 1994, 32, 335. [30] K. W. Park, Y. E. Sung, S. Han, Y. Yun, T. Hyeon, J. Phys. Chem. B 2004, 108, 939. [31] W. Xing, S. Z. Qiao, R. G. Ding, F. Li, G. Q. Lu, Z. F. Yan, H. M. Cheng, Carbon 2006, 44, 216. [32] W. Sugimoto, H. Iwata, K. Yokoshima, Y. Murakami, Y. Takasu, J. Phys. Chem. B 2005, 109, 7330. [33] P. R. Bueno, E. R. Leite, J. Phys. Chem. B 2003, 107, 8868. [34] F. Beguin, K. Szostak, G. Lota, E. Frackowiak, Adv. Mater. 2005, 17, 2380. [35] C. F. Zhou, S. Kumar, Chem. Mater. 2005, 17, 1997.

4. Experimental
CNTs were prepared by the catalytic decomposition of ethylene on a Fe/Al2O3 catalyst in a nanoagglomerate fluidized-bed reactor (NAFBR). Details of the NAFBR are described elsewhere [25]. In our experiments, the catalyst (10 g) was packed into the reactor and reduced by hydrogen at 823 K for 2 h. Then, a mixture of nitrogen and ethylene (2:3 volume ratio of nitrogen to ethylene; total gas velocity, 0.1 m s1) was fed into the reactor. The reaction was conducted at 823 K under atmospheric pressure for 5 h. The resulting products were pretreated by refluxing in HNO3/H2SO4 solution (1:3) for 1 h, followed by an extensive washing with deionized water to pH 7. TiO2 nanowires were synthesized by adding 1 g TiO2 (Degussa P25) to 30 mL of a mixture of aqueous 10 M NaOH and ethanol (1:1 volume ratio). After stirring for 1 h, the resulting suspension was transferred into a Teflon-lined stainless-steel autoclave. The autoclave was maintained at 180 C for 18 h and then cooled to room temperature naturally. The resulting products were filtered, washed with 0.1 M HCl solution, then deionized water to pH 7, and finally heated at 400 C for 4 h in air. Powder XRD was performed on a Bruker D8-Advance X-ray powder diffractometer with monochromatized Cu Ka radiation (k = 1.5418 ). The 2h range used in the measurements was from 10 to 70. TEM and SEM images were taken with an Hitachi model H-800 transmission electron microscope and a JSM-7401F scanning electron microscope, respectively. Specific surface areas were measured by BET nitrogen adsorptiondesorption (Shimadzu, Micromeritics ASAP 2010 Instrument), and pore size distributions were calculated from the desorption branch of the N2 adsorption isotherm using the BJH formula. TGA was carried out using a TA Instruments Mettler TGA/SDTA 851 from 80 to 800 C at 20 C min1 under air at a flow rate of 20 mL min1. XRF spectroscopy was collected on a SHIMADZU XRF-1700 XRF spectrometer. Electrochemical measurements were carried out using two-electrode Swagelok-type cells without a reference electrode. The cathode and anode pellets were fabricated in the same way, by pressing a mixture of 80 wt % active materials, 10 wt % non-activated acetylene black, and 10 wt % polytetrafluoroethylene (PTFE) onto a piece of aluminum foil. Pellets of the same mass were selected and then assembled as supercapacitors in an Ar-filled Labconco glove-box. The electrolyte solution was 1 M LiPF6 dissolved in a mixture of ethylene carbonate (EC), dimethyl carbonate (DMC), and diethyl carbonate (DEC), in a volume ratio of EC/DMC/DEC = 1:1:1. Cyclic voltammograms were recorded from 0 to

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