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DOI: 10.1002/adma.200501366

A Mesoporous Nanocomposite of TiO2 and Carbon Nanotubes as a High-Rate Li-Intercalation Electrode Material**
By Isamu Moriguchi,* Ryoji Hidaka, Hirotoshi Yamada, Tetsuichi Kudo, Hiroto Murakami, and Naotoshi Nakashima
There is growing interest in electrical/electrochemical energy-storage devices with both high power and high energy densities for possible application as auxiliary-power sources for electric and/or hybrid-electric vehicles.[1,2] Although lithiumion batteries are attractive power-storage devices with high energy density, their power density is generally low because of a large polarization at high chargingdischarging rates. The large polarization is thought to be due to slow lithium diffusion in the solid active material and increases in the resistance of the electrolyte and in the electric resistance of the active materials upon increasing the chargingdischarging rate. Therefore, in order to obtain high performance with both high power and high energy densities, it is important to design and fabricate nanostructured electrode materials that provide interconnected nanopaths for electrolyte-ion transport and electronic conduction. Mesoporous materials are quite attractive hosts for Li intercalation because of their large surface area, which decreases the current density per unit surface area; their thin walls, which shorten the Li-diffusion length in the solid phase; and their pores, which enable electrolyte ions to be transported smoothly. Actually, it has recently been reported that control of the porous structure of the active materials is effective in increasing the capacity of Li-intercalating electrode materials, even at high chargingdischarging rates.[36] Porous materials are often considered to have the disadvantage of having low

[*] Prof. I. Moriguchi, R. Hidaka Graduate School of Science and Technology Nagasaki University 1-14 Bunkyo-machi, Nagasaki 852-8521 (Japan) E-mail: mrgch@net.nagasaki-u.ac.jp Dr. H. Yamada, Prof. T. Kudo, Prof. H. Murakami Department of Applied Chemistry, Faculty of Engineering Nagasaki University 1-14 Bunkyo-machi, Nagasaki 852-8521 (Japan) Prof. N. Nakashima Graduate School of Engineering Kyushu University 6-10-1 Hakozaki, Fukuoka 812-8581 (Japan) [**] The study made use of instruments (elemental analysis, XRD, and TEM) in the Center for Instruments Analysis of Nagasaki University. This work was partly supported by a Grant-in-Aid for Scientific Research from the Ministry of Education, Culture, Science, Sports, and Technology of Japan, and by PRESTO of Japan Science and Technology Corporation.

volumetric energy density, but this is not always the case for high-rate use: because of the low diffusion coefficient in the solid phase (10111013 cm2 s1), only the thin surface layer of the host material is available for Li intercalation at high chargingdischarging rates for bulk materials. On the other hand, hosts for Li intercalation generally have a low electronic conductivity, and thus electronic conduction paths are also required in the host material to decrease the polarization. Although conducting additives, such as acetylene black can be mechanically mixed with the host material in conventional Libattery electrodes, it is difficult to mix such large-sized conducting additives with mesoporous host materials, because the wall of the mesoporous structure is easily destroyed by conventional mixing techniques. As a new approach, we have synthesized single-walled carbon nanotube (SWNT)-containing mesoporous TiO2 by a bicontinuous microemulsion-aided process using a dispersed aqueous solution of cut SWNTs (c-SWNTs) as the water phase of a water/surfactant/oil ternary bicontinuous microemulsion. Although there are some reports on surface modifications of carbon nanotubes with metal oxides,[710] this study is the first attempt to prepare a nanocomposite material with a mesoporous structure consisting of anatase TiO2 and c-SWNTs. We also demonstrate that the Li-intercalation capacity at high chargingdischarging rates increases dramatically for c-SWNT-containing mesoporous TiO2 compared with that of mesoporous TiO2 and other composites such as conventional solgel-derived SWNTs/TiO2 composites. Mesoporous TiO2 samples have been synthesized via sol gel reactions of titanium tetrabutoxide (TTB) or acetylacetone-stabilized TTB (TTB-acac) in a bicontinuous microemulsion of the ternary system hexane/didodecyldimethylammonium bromide (DDAB)/4 mM aqueous HCl according to a procedure reported previously.[3] Hereafter, the samples are denoted as TiO2(TTB) and TiO2(TTB-acac). A carbon nanotube-containing mesoporous TiO2, c-SWNT/TiO2(TTB-acac), was synthesized similarly using c-SWNTs dispersed in an aqueous solution as the water phase of the bicontinuous microemulsion and TTB-acac as the Ti source. The carbon content of c-SWNT/TiO2(TTB-acac), estimated by elemental analysis, was 0.86 wt.-%, which is larger than that of TiO2(TTB-acac) (0.41 wt.-%). Therefore, the amount of c-SWNTs incorporated into c-SWNT/TiO2(TTB-acac) was estimated to be 0.43 wt.-% from the ratio of [SWNT]/[TiO2]. This ratio is close to the initial mixing ratio of [SWNT]/[TiO2] (0.33 wt.-%) during the synthesis. In X-ray diffraction (XRD) measurements, broad peaks assigned to anatase TiO2 were observed for all the samples, while no distinct XRD peak was observed at 2h < 10. This indicates that the samples did not possess an ordered mesoporous structure like micelle-templated mesoporous silica. N2 adsorptiondesorption isotherms and BarrettJoynerHalenda (BJH) pore-size distribution of these samples are compared in Figure 1. An inflection characteristic due to capillary condensation into mesopores was observed at p/p0 = 0.20.5, 0.80.9, and 0.60.85 for TiO2(TTB), TiO2(TTB-acac), and c-SWNT/TiO2(TTB-acac), respectively.

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incorporation of c-SWNTs with a tube diameter of 12 nm inside or beside gel do600 a 5 mains could be confirmed in Figure 2A. 5 160 4 Figure 2B confirms that the nanotubes still 4 c 500 140 3 remained inside or beside the TiO2 nano3 b 2 crytallites in the calcined sample. From 2 120 400 1 these results, it can be concluded that a 1 100 c-SWNT-containing mesoporous anatase 0 0 0 10 20 30 40 50 0 10 20 300 Pore diameter Pore diameter / nm 80 TiO2 sample with relatively high surface / nm area (100 m2 g1), containing 515 nm me60 200 a b c sopores has been synthesized successfully 40 by a bicontinuous microemulsion-aided 100 process. 20 Lithium-insertion/extraction properties 0 0 0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1 of the porous samples obtained have Relative pressure, P/P0 Relative pressure, P/P0 been investigated by cyclic voltammetry and galvanostatic chargingdischarging Figure 1. N2 adsorptiondesorption isotherms of TiO2(TTB) (curve a); c-SWNT/TiO2(TTBmeasurements. Lithium insertion/extracacac) (curve b) and TiO2(TTB-acac) (curve c). The insets show BJH pore-size distributions of tion to anatase TiO2 proceeds according these samples. to the following reversible reaction: TiO2 + xLi + xe = LixTiO2; the maximum value of x for a reversible reaction at room temperature was The parameters associated with the porous structure of the reported to be 0.5, which corresponds to a capacity of samples, BrunauerEmmettTeller (BET) surface area, pore 168 mA h g1.[11] Figure 3A shows galvanostatic lithium-inservolume, mesopore size range, and crystallite size, are summarized in Table 1. By using TTB-acac as the Ti source, the tion/extraction curves of TiO2(TTB-acac) at a charging rate of 140 C (1 C = 0.168 A g1). Since the plateaus around 1.7 V mesopore size and volume increased, compared to that of (insertion process) and 2.0 V (extraction process) are related TiO2(TTB). TTB-acac is more stable against hydrolysis and to the phase transition between the tetragonal and orthocondensation reactions than TTB, thus the microemulsion rhombic phases with Li intercalation into anatase TiO2,[12] the appearance of plateaus reconfirmed the formation of the anaTable 1. Parameters associated with the porous structure of the samples. tase TiO2 phase in the mesoporous samples. The chargingdischarging capacity of TiO2(TTB-acac) decreased steeply with Sample BET surface Pore volume Mesopore size Crystallite increasing current density and it reached zero above 40 C. On area [m2g1] [cm3g1] range [nm] size [nm] the other hand, the c-SWNT/TiO2(TTB-acac) shows extended TiO2(TTB) 189 0.16 24 5 plateaus and a larger chargingdischarging capacity than TiO2(TTB-acac) 218 0.83 1025 14 TiO2(TTB-acac), especially at high charging rate (Fig. 3B). It c-SWNT/TiO2(TTB-acac) 100 0.26 615 32 28 0.16 24 13 AB/TiO2(TTB-acac) has also been confirmed by cyclic voltammetry that c-SWNT/ 34 0.18 525 23 s-SWNT/TiO2 TiO2(TTB-acac) shows larger redox currents than TiO2(TTBacac). In addition, a larger decrease in peak separation between anodic and cathodic peaks with increasing sweep rate was observed for c-SWNT/TiO2(TTB-acac) compared to structure of TTB might change more easily during the proTiO2(TTB-acac). These results indicate that the polarization longed gelation time and this would cause the formation of larger mesopores in TiO2(TTB-acac). On the other hand, although the incorporation of c-SWNTs into the (A) (B) TiO2(TTB-acac) system results in a decrease in pore size and BET surface area compared with TiO2(TTB-acac), the c-SWNT/TiO2(TTB-acac) had a mesoporous structure, the mesopore 20 nm size of which was larger than that of TiO2(TTB). Figure 2 shows TEM images of a precursor gel and of a calcined 20 nm 100 nm 200 nm sample of c-SWNT/TiO2(TTB-acac). A bicontinuous gel-network structure Figure 2. TEM images of A) a gel precursor heated at 110 C and B) c-SWNT/TiO2(TTB-acac). could be observed in the precursor, and
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4.0
40C 30C 20C 10C 5C 1C

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3.5 Potential / (V vs. Li/Li+) 3.0 2.5 2.0 1.5 1.0 0 0.1 0.2 0.3 0.4 x in LiXTiO2 0.5 0.6

0.1

0.2

0.3 0.4 x in LiXTiO2

0.5

0.6

Figure 3. Galvanostatic Li-insertion/extraction curves of A) TiO2(TTB-acac) and B) c-SWNT/TiO2(TTB-acac).

increased upon increasing the chargingdischarging rate, but it was suppressed by the incorporation of c-SWNTs. The lithium-intercalation capacity has been determined by subtracting the electric double-layer capacitance, which was estimated from the anodic plateau region around 33.5 V versus Li/Li+ in the cyclic voltammogram, from the capacitance of the third extraction curve in galvanostatic measurements. Figure 4 shows the lithium intercalation capacity of the samples synthesized in this work as a function of charging rate. At low charging rate below 10 C, the capacity of TiO2(TTB) was largCurrent density / A g-1 3 4 5 6

0.6 0.5

200

150 x in LiXTiO2 0.4 0.3 0.2 50 0.1 0 0 50 100 Capacity / mA h g-1

10

20 C rate

30

40

Figure 4. Li-intercalation capacities of the samples as a function of charging rate: () TiO2(TTB), (&) TiO2(TTB-acac), () c-SWNT/TiO2(TTBacac), (~) AB/TiO2(TTB-acac), and (~)s-SWNT/TiO2.

er than that of TiO2(TTB-acac). Upon increasing the rate, the capacity of TiO2(TTB) decreased more steeply than TiO2(TTB-acac). Therefore, TiO2(TTB-acac) has a superior lithium-intercalation capacity at high rates above 10 C. The high capacity of TiO2(TTB) at the low rate in this case would be due to the small crystallite size, which means a shortened diffusion length in the solid phase; the surface area of

TiO2(TTB) is smaller than that of TiO2(TTB-acac). At high rates, an increase in electrolyte resistance in the TiO2(TTBacac) electrode would be suppressed more than that in the TiO2(TTB) electrode, that is, mesoporous materials with large pore sizes are better for a smooth transport of electrolyte ions. On the other hand, a remarkable increase in capacity, especially at high charging rates, was observed for c-SWNT/ TiO2(TTB-acac) compared to mesoporous TiO2 samples without SWNT, suggesting that electron-conducting paths are also indispensable for a high rate of chargingdischarging. When acetylene black was mixed into the c-SWNT/TiO2(TTB-acac) system instead of c-SWNTs (using the same mixing procedure), the sample obtained, AB/TiO2(TTB-acac), possessed a low surface area (Table 1), and its ability to intercalate Li was much inferior to that of c-SWNT/TiO2(TTB-acac). The size of acetylene black particles is much larger than the width of the oil and water nanochannels in the bicontinuous microemulsion used for the reaction medium, thus effective ion- and electron-transport nanopaths cannot be formed in AB/ TiO2(TTB-acac). In addition, s-SWNT/TiO2, synthesized by a solgel reaction without a bicontinuous microemulsion, also showed inferior capacitive property, similar to AB/TiO2(TTBacac). From these results, it can be concluded that the present bicontinuous microemulsion-aided process is useful for the synthesis of mesoporous nanocomposite materials with effective nanopaths of both electron conduction (c-SWNTs) and ion transport (mesopores). In addition, it has also been confirmed that the intercalation capacity of c-SWNT/TiO2(TTBacac) of 10 C was maintained during the 70 cycles measured (Fig. 5), suggesting stable cyclability of the composite electrode. In conclusion, c-SWNT-containing mesoporous TiO2, c-SWNT/TiO2(TTB-acac), has been successfully synthesized by a bicontinuous microemulsion-aided process. Since this process basically consists of mixing a metal source and c-SWNTs in a bicontinuous microemulsion and heating, it is relatively simple and can be scaled-up for a practical application. The incorporation of c-SWNTs inside or beside an ana-

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0.6 0.5 0.4 0.3 0.2 0.1 0

20

40 60 Cycle number

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Figure 5. Cycle performance of a c-SWNT/TiO2(TTB-acac) electrode at 10 C.

tase TiO2 nanophase while keeping a mesoporous structure by means of the bicontinuous microemulsion-aided process effectively improves the chargingdischarging property of anatase TiO2, especially at high rates. Recently, TiO2 nanowires with a TiO2-B crystalline phase have been reported to have high capacities ( 305 mA h g1 at 50 mA g1).[13,14] Although the theoretical capacity of TiO2-B is inherently higher than that of anatase TiO2, the capacity of TiO2-B nanowires at a high rate (85 mA h g1 at 3.0 A g1) was lower than that of the present c-SWNT/TiO2(TTB-acac). The methodology reported in this work can contribute to the development of high-power chargingdischarging devices by providing effective paths for both ion transport and electronic conduction in electrode materials. In addition, it could potentially be applied to other metal-oxide systems.

ple, c-SWNT/TiO2(TTB-acac), was synthesized by the same procedure using an aqueous HCl dispersion of c-CNTs as the water phase of the bicontinuous microemulsion and TTB-acac as the Ti source. The concentration of c-SWNTs and HCl in the aqueous solution was 1 mg/3 mL and 2.7 103 mol dm3, respectively; the mixing ratio of [SWNTs]/[TiO2] at the start was 0.33 wt.-%. As a reference, acetylene black was used instead of c-SWNTs, maintaining the same synthetic procedure, to yield AB/TiO2(TTB-acac). In addition, a composite of as-received SWNT and TiO2, s-SWNT/TiO2, was also synthesized by a solgel process without a bicontinuous microemulsion; as-received SWNTs were suspended in the aqueous HCl solution (4 103 mol dm3), and TTB-acac was added dropwise under vigorous stirring. The work-up procedure to yield the composite was the same as that for c-SWNT/TiO2(TTB-acac). Instrumental Analysis: Elemental analysis was carried out by using a Perkin-Elmer 2400II analyzer. XRD patterns of samples were obtained on a Rigaku RINT-2200 diffractometer using Cu Ka radiation. The crystallite size of TiO2 in the samples was estimated from the full width at half maximum (FWHM) of XRD peaks by using the Scherrer equation.[17] The morphology of the porous structure was observed by transmission electron microscopy (TEM, JEOL JEM-100). Adsorptiondesorption isotherms of N2 were measured at 77 K (Micromeritics Co. Ltd. Gemini 2370). The specific surface area and mesoporediameter distribution of the samples were analyzed by BET and BJH methods, respectively, from the N2 adsorption branch. The lithium insertion/extraction property of the TiO2 samples was investigated at room temperature by cyclic voltammetry and a galvanostatic technique (Hokuto Denko, HZ-3000) using a sealed three-electrode cell equipped with metallic lithium counter and reference electrodes. Mesoporous TiO2 or a composite sample (5 mg) was mixed mechanically with acetylene black (Denka Co. Ltd.), as an electron-conducting additive (20 mg) and poly(tetrafluoroethylene) as a binder (2 mg), and then pressed onto a nickel mesh to form a working electrode. The apparent electrode area and volume were ca. 11.5 cm2 and ca. 0.1 cm3, respectively. The electrolyte was a 1 mol dm3 solution of LiClO4 in PC + DME (1:1 v/v) (Kishida Chemical Co. Ltd). To minimize the effect of IR drop associated with the electrolyte resistance, the tip of a capillary connected to the reference electrode was placed as close as possible to the working electrode. The lithium-insertion/extraction measurement was carried out between 3.6 and 1.4 V versus Li/Li+ at a constant current density ranging from 0.168 to 6.72 A g1 (140 C). Received: July 4, 2005 Final version: August 16, 2005 Published online: November 15, 2005

Experimental
Purification and Cutting of SWNTs: SWNTs were obtained from Carbon Nanotechnologies Inc. (HiPco). The SWNTs were purified and cut into short pieces following a previously procedure [15]. The nanotubes were sonicated at 50 C for 5 h in a 3:1 (v/v) mixture of concentrated sulfuric acid (97 wt.-%) and nitric acid (69 wt.-%) using a bath sonicator (180 W, 40 kHz); the material collected by a filtration was washed copiously with aqueous sodium hydrogen carbonate until the pH of the filtrate became neutral. The purified c-SWNTs were dispersed in pure water to yield a 1 mg mL1 dispersion that was used as the water phase of a bicontinuous microemulsion, as described below. Synthesis of Mesoporous TiO2 and Nanocomposites: A bicontinuous microemulsion was prepared by mixing DDAB, hexane as an oil phase, and aqueous HCl (4 103 mol dm3), at 34 wt.-%, 36 wt.-%, and 30 wt.-%, respectively. The composition of DDAB/oil/water used here is in the bicontinuous microemulsion region of the phase diagram reported by Ninham and co-workers [16]. TTB or a mixture of TTB and acetylacetone with a molar ratio of 1:3 (TTB-acac) was added dropwise to the stirred bicontinuous microemulsion with a weight ratio of DDAB/TTB = 3.4:1.4. After further stirring for 30 s, the mixture solution was aged at 25 C for 1 day in a N2 atmosphere [3,4]. The resulting gel was filtered off, washed thoroughly with hexane, dried in an oven at 110 C for 12 h, and finally calcined at 350 C for 6 h in a N2 gas flow. A c-SWNT-containing mesoporous TiO2 sam-

x in LiXTiO2

[1] B. Scrosati, Nature 1995, 373, 557. [2] R. F. Nelson, J. Power Sources 2001, 91, 2. [3] I. Moriguchi, Y. Katsuki, H. Yamada, T. Kudo, T. Nishimi, Chem. Lett. 2004, 33, 1102. [4] I. Moriguchi, R. Hidaka, H. Yamada, T. Kudo, Solid State Ionics 2005, 176, 2361. [5] H. Yamada, T. Yamato, I. Moriguchi, T. Kudo, Solid Sate Ionics 2004, 175, 195. [6] H. Yamada, T. Yamato, I. Moriguchi, T. Kudo, Chem. Lett. 2004, 33, 1548. [7] J. Sun, M. Iwasa, L. Gao, Q. Zhang, Carbon 2004, 42, 885. [8] A. Jitianu, T. Cacciaguerra, R. Benoit, S. Delpeux, F. Beguin, S. Bonnamy, Carbon 2004, 42, 1147. [9] M. H. Chen, Z. C. Huang, G. T. Wu, G. H. Zhu, J. K. You, Z. G. Lin, Mater. Res. Bull. 2003, 38, 831. [10] J. S. Sakamoto, B. Dunn, J. Electrochem. Soc. 2002, 149, A26. [11] H. Lindstrom, S. Sodergrem, A. Solbrand, H. Rensmo, J. Hjelm, A. Hagfeldt, S. E. Lindquist, J. Phys. Chem. B 1997, 101, 7717. [12] R. van de Krol, A. Goossens, E. A. Meulkenkamp, J. Electrochem. Soc. 1990, 146, 3150. [13] A. R. Armstrong, G. Armstrong, J. Canales, R. Garcia, P. G. Bruce, Adv. Mater. 2005, 17, 862.

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[14] X. Gao, H. Zhu, G. Pan, S. Ye, Y. Lan, F. Wu, D. Song, J. Phys. Chem. B 2004, 108, 2868. [15] J. Liu, A. R. Rinzler, H. Dai, J. H. Hafner, R. K. Bradley, P. J. Boul, A. Lu, T. Iverson, K. Shelimov, C. B. Hoffamn, F. R. Macias, Y.-S. Shon, T. R. Lee, D. T. Colbert, R. E. Smalley, Science 1998, 280, 1253. [16] M. Allen, D. F. Evans, D. J. Mitchell, B. W. Ninham, J. Phys. Chem. 1987, 91, 2320. [17] Elements of X-ray Diffraction, (Ed: B. D. Cullity), Addison-Wesley, Reading, MA 1956.

DOI: 10.1002/adma.200501217

Growth of Carbon Nanotubes on Clay: Unique Nanostructured Filler for High-Performance Polymer Nanocomposites**
By Wei-De Zhang,* In Yee Phang, and Tianxi Liu*
Clay minerals have a layered structure with unit layers about 1 nm thick and sizes ranging from several nanometers to several micrometers. Each layer is formed of tetrahedrally coordinated Si atoms fused into an edge-sharing octahedral plane of either alumina or magnesia.[1] As a natural product, clay can be obtained in large amounts at low cost and has been used for a wide range of applications. Because of its large surface area, strong acidity, and strong adsorption and ion-exchange ability, clay has been widely used as a catalyst and catalytic support for years.[13] For example, clay-supported cobalt oxide is the catalyst for the de-NOx reaction,[4] while clay-supported iron oxide has been used as a FischerTropsch catalyst.[5] As has been demonstrated, iron, nickel, or cobalt nanoparticles supported on oxides are efficient catalysts for the synthesis of carbon nanotubes (CNTs) by chemical vapor deposition (CVD), which has proven to be a cost-efficient

[*] Prof. W.-D. Zhang Nano Science Research Center College of Chemistry South China University of Technology Guangzhou 510640 (P.R. China) E-mail: zhangwd@scut.edu.cn Prof. T. X. Liu, I. Y. Phang Laboratory of Advanced Materials Fudan University 220 Handan Road, Shanghai 200433 (P.R. China) E-mail: txliu@fudan.edu.cn I. Y. Phang Department of Materials Science and Technology of Polymers MESA Institute for Nanotechnology University of Twente PO Box 217, NL-7500 AE Enschede (The Netherlands) [**] This work was supported by a grant from South China University of Technology to Prof. W. D. Zhang.

way of mass producing CNTs.[6] Naturally, clay has also been used as the support for catalytic CVD growth of CNTs.[7,8] In addition, clay platelets are typical two-dimensional (2D) nanofillers for incorporation into polymeric matrices, which have been intensively studied in the past few decades.[911] Carbon nanotubes, as one-dimensional (1D) nanomaterials, have also been considered as ideal enhancement fillers for making polymer nanocomposites because of their extremely high mechanical strength and high electrical and thermal conductivity.[1216] For both 1D and 2D nanofillers, homogeneous dispersion in polymeric matrices and strong interactions with the matricesso as to enhance the as-obtained nanocomposites with the intrinsic properties of the nanofillersare the most important issues. Much effort has been made in study of intercalation and exfoliation of clay in polymeric matrices,[911] while many studies have also been conducted on modification and dispersion of CNTs for incorporation in polymeric matrices.[1719] Here we demonstrate the use of clay-supported iron nanoparticles as a catalyst for the growth of CNTs followed by incorporation of the as-prepared CNT clay hybrid nanofillers into a nylon-6 (PA6) matrix to make PA6/CNTclay composites. The results indicate that the clay has been swollen and exfoliated by the intercalation of iron ions into the clay interlayers and the growth of CNTs on the clay platelets by CVD. The as-prepared CNTclay hybrid, which is the combination of a 2D nanoclay platelet and several 1D nanotubes, effectively promotes the homogeneous dispersion of both clay platelets and nanotubes in the polymeric matrix by simple melt blending. This method greatly simplifies the overall procedure for preparation of polymer nanocomposites with improved mechanical properties. Figure 1 depicts the procedure for making the nanofiller and the polymer nanocomposites. Firstly, the sodium montmorillonite (Na+MMT) was modified by impregnation with a Fe(NO3)3 solution. Fe3+ ions were intercalated into the layers of montmorillonite and changed to Fe2O3 particles by calcination. During CVD growth of CNTs, the Fe2O3 particles were reduced to Fe particles in situ, which served as seeds for the growth of CNTs. The platelets of the clay were further delaminated as the CNTs grew on them, forming a 3D nanostructure consisting of a 2D nanoclay platelet and several attached nanotubes. The obtained CNTclay hybrid was directly used as a filler by being incorporated into PA6 for preparation of PA6/CNTclay nanocomposites by melt-blending. The X-ray diffraction (XRD) patterns of the Na+MMT and the samples derived from Na+MMT are shown in Figure 2. For the pristine Na+MMT (curve a), the peak at 2h = 7.5 is obvious, which is a sign of the stacked-layer structure of the clay (i.e., the 001 reflection). Another peak at 2h = 19.6 is assigned to the 100 and 020 reflections.[20] The peak at 2h = 33.2 for the iron-modified Na+MMT (Feclay) (curve b) corresponds to the 104 reflection of rhombohedral Fe2O3.[21] The peak at 2h = 28.5 appeared in both Na+MMT and Feclay, and can be assigned to (Mg,Fe)SiO3 salts.[20] Fe2O3 disappeared after growth of CNTs (as indicated by the absence of the reflection peak at 2h = 33.2) since it was reduced to Fe

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