ARTICLE pubs.acs.

org/JPCC

Preparation of Carbon Nano-Onions and Their Application as Anode Materials for Rechargeable Lithium-Ion Batteries
Fu-Dong Han, Bin Yao, and Yu-Jun Bai*
Key Laboratory for LiquidÀSolid Structural Evolution and Processing of Materials (Ministry of Education), Shandong University, Jinan 250061, P. R. China
S b Supporting Information

ABSTRACT: Carbon nano-onions (CNOs) were prepared at 600 °C by a simple reaction between copper dichloride hydrate (CuCl2 3 2H2O) and calcium carbide (CaC2). The morphology and structure of the obtained products were investigated by field-emission scanning electron microscope, high-resolution transmission electron microscopy, X-ray diffraction, Raman spectrum, and nitrogen adsorption. Large quantities of CNOs consisting of quasi-spherically concentric graphitic shells with high purity and uniform size distribution (about 30 nm) were obtained. The crystal water in CuCl2 3 2H2O plays an important role in the formation of CNOs. The CNOs as-obtained exhibit high capacity and excellent cycling performance as anode materials for lithium-ion batteries, which can deliver a reversible capacity of 391 mAh gÀ1 up to 60 cycles.

’ INTRODUCTION Carbon nano-onions (CNOs), which consist of concentric graphitic shells, represent another new allotropic nanophase of carbon materials. CNOs have already been shown to offer a variety of potential applications such as solid lubrication,1 electromagnetic shielding,2 fuel cells,3 heterogeneous catalysis,4 gas and energy storage,5 and electro-optical devices6 owing to their outstanding chemical and physical properties. According to a recent study, CNOs can also be used to produce ultrahighpower micrometer-sized supercapacitors due to their accessible external surface area for ion adsorption.7 Since the first observation of the onion-like structure by Iijima in vacuum deposited amorphous carbon films in 1980,8 several methods have been reported to prepare CNOs. For example, Ugarte examined the formation of CNOs in a transmission electron microscope (TEM) by irradiating carbon material consisting of different carbon nanostructures (fullerenes, nanotubes, amorphous carbon).9 Kuznetsov et al. obtained CNOs by high-temperature annealing of diamond nanoparticles under vacuum.10 Cabioc’h et al. prepared CNOs by high-dose carbon ion implantation into copper and silver.11 Sano et al. fabricated CNOs by arc discharge between two graphite rods immersed in water.12 Recently, Hou et al. reported the high-yield synthesis of CNOs in counterflow diffusion flames.13,14 In addition, chemical vapor deposition was also considered as a viable method to synthesize CNOs by lots of scientists.15À18 Other ways have also been proposed to synthesize CNOs, such as laser irradiation,19 shock compression,20 and high-energy ball-milling.21 However, most of the methods above-mentioned require high energy input, and CNOs are sometimes of low yield or just as a
r 2011 American Chemical Society

byproduct.16,22 For applications such as fuel-cell electrodes, large quantities (kilograms) of the material are desired. Nevertheless, CNOs can only be produced in minute quantities by lots of methods such as electron beam irradiation of carbon materials. Moreover, it is not practical to use the CNOs obtained by some methods requiring high investment and running costs for ordinary applications such as solid lubrication. Therefore, how to economically synthesize CNOs in large scale is of great importance for their wide applications. In this article, we reported a simple, efficient, and economical route for large-scale preparation of CNOs with uniform morphology and size. The CNOs were obtained via the reaction between CaC2 and CuCl2 3 2H2O at 600 °C. In addition, the electrochemical properties of the as-obtained CNOs as anode materials for lithium-ion battery have also been evaluated.

’ EXPERIMENTAL SECTION
Materials and Synthesis. The raw materials used are chemically pure copper dichloride hydrate (CuCl2 3 2H2O) and calcium carbide (CaC2). In a typical procedure, 10 g (0.059 mol) CuCl2 3 2H2O and 3.2 g (0.05 mol) CaC2 were put into a stainless steel autoclave of 30 mL capacity. Because the removal of CuCl2 3 2H2O is easier than that of CaC2, the amount of CuCl2 3 2H2O was slightly in excess to ensure the complete reaction of CaC2. The autoclave containing the raw materials was sealed
Received: January 24, 2011 Revised: March 29, 2011 Published: April 14, 2011
8923
dx.doi.org/10.1021/jp2007599 | J. Phys. Chem. C 2011, 115, 8923–8927

The cell performance was estimated galvanostatically at a current density of C/10 (one Li per six formula units (LiC6) in 10 h)) for both charge (Li extraction) and discharge (Li insertion) at room temperature. The product is comprised of numerous quasi-spheres about 30 nm in diameter. a little amorphous carbon can be found on the surface of CNOs. The corresponding selected area electron diffraction (SAED) pattern (insert in part d of Figure 1) reveals the poor graphitization of the CNOs. C 2011. Raman spectra were collected on a Renishaw confocal Raman microspectroscopy (Renishaw Co. and Celgard 2300 was used as the separator. which may imply that the formation of CNOs was not by virtue of encapsulating Cu. and polyvinylidene fluoride (PVDF) (10 wt %) dissolved in n-methyl pyrrolidinone (NMP) onto a Cu foil substrate and dried in a vacuum oven at 120 °C for 12 h. and HRTEM images (cÀe) of the as-obtained CNOs. Electrochemical experiments were carried out in 2025 coin-type cells. 115. EDX spectrum (b). When the autoclave was cooled naturally to ambient temperature. The main peak at 2θ = 25.doi. The short-range order or turbostratic graphite structure gives rise to concentric graphite layers around a hollow and irregular core about 5 nm in diameter. further confirming the high purity of CNOs. Half-cells were assembled in an argon-filled glovebox.The Journal of Physical Chemistry C tightly and heated in an electric oven to 600 °C and maintained for 10 h at this temperature. indicating the high purity of the spheres. carbon black (5 wt %). Electrochemical Measurement. black powders were ultimately obtained. It is worthwhile to note that Cu-encapsulating CNOs can hardly be observed in the product even by careful TEM examination. Ltd. ARTICLE Figure 1.1021/jp2007599 |J.org/10. The broadening nature of the peak is indicative of the long-range disorder structure of the 8924 dx. Characterization. from which there is no detectable metal catalyst (Cu) or other impurities except for C and a little O resulting from absorption. XRD pattern (a) and Raman spectrum (b) of the as-obtained CNOs. In addition. I = 50 mA) at a scanning rate of 4°/min. U.02À3 V (versus Li/Liþ). The interplanar spacing of 0. The specific surface area was calculated with the BrunauerÀEmmettÀTeller (BET) model. To determine the structure of the as-obtained product.) with a laser excitation wavelength of 780 nm. The insert in (d) is the corresponding SAED pattern. Figure 2. ’ RESULTS AND DISCUSSION The morphology of the asÀobtained product was observed by FESEM. The working electrodes were prepared by coating the slurry of CNOs (85 wt %). The morphology of the product was examined using a Hitachi SU-70 field-emission scanning electron microscope (FESEM) with an energy-dispersive X-ray spectrometer (EDX) and a JEOL JEM-2100 high-resolution transmission electron microscope (HRTEM).. Chem.8° can be attributed to the (002) diffraction of hexagonal graphite. and this will be discussed in detail. which may result from the deposition of vaporous carbon atoms around the CNOs. The electrolyte was a mixture of 1 M LiPF6 in ethylene carbonate (EC) and dimethyl carbonate (DMC) (1:1 by volume).34 nm corresponds to that of the (002) plane of graphite.K. The samples were outgassed at 300 °C for 3 h under a vacuum in the degas port of the analyzer. Part b of Figure 1 is the EDX spectrum taken from the spheres. Phys. Nitrogen adsorption and desorption isotherms were carried out at 77 K on a Quadrasorb (Supporting Information) sorption analyzer. The examination by HRTEM (parts cÀe of Figure 1) demonstrates that the spheres have an onion-like structure. and the pore-size distribution was calculated from the adsorption/desorption data by using the DFT method. Lithium metal foil was utilized as the counter electrode. 8923–8927 . X-ray powder diffraction (XRD) patterns were obtained on a Rigaku Dmax-rc diffractometer with Ni-filtered Cu KR radiation (V = 40 kV. FESEM image (a). and no other carbon nanostructures such as carbon nanotubes can be detected. After drying at 60 °C for 10 h. the products in the autoclave were collected and primarily washed several times with a mixed solution of ammonia (NH3 3 H2O) and carbon tetrachloride (CCl4) to remove the byproduct copper23 and then rinsed successively with dilute hydrochloric acid and deionized water until all soluble materials were removed. XRD measurements were conducted. The cells were cycled in the voltage range of 0. as shown in part a of Figure 1. Gloucestershire. as shown in part a of Figure 2.

which is significantly higher than the theoretical capacity of graphite (372 mAh gÀ1). this process can also result in the elimination of dangling bonds at the edge of the flakes.31.393 kJ molÀ1. and 5 can occur readily. the disorder structure can be also reflected by the indistinguishability of the (100) and (101) peaks centered at 2θ = 43. Moreover.30 In our experiment. According to free energy calculations.16 cm3 gÀ1. giving rise to the formation of CNOs. respectively. a comparative experiment was performed using CuCl2 without crystal water as the reactant. According to previous reports. In contrast. as shown in part b of Figure 2. a first reversible capacity as high as 501 mAh gÀ1 can be observed. these defects would possibly act as nucleation sites for further deposition of vaporous carbon atoms on the surface of CNOs. Galvanostatic discharge/charge experiments were carried out to evaluate the electrochemical performance of the as-obtained CNOs.36 However. eq 4 is also thermodynamically spontaneous (ΔrGΘ = À223. Phys.24 Raman spectra were measured to identify the bonding and structure of the CNOs as-obtained. CuCl2 þ CaC2 ¼ Cu þ 2C þ CaCl2 ð1Þ The overall reaction can be concluded according to the above reactions: CuCl2 3 2H2 O þ CaC2 ¼ CaCl2 þ Cu þ 2C þ 2H2 O ð6Þ Thus. during which large quantities of carbon and Cu atoms are simultaneously produced. CuCl2 3 2H2O acts as a reactant to form CNOs because Cu can be detected in the products washed just by deionized water. 3.35 that is the highly stable spherical shape of carbon species and the multiple shell structure are more energetically favorable than a single or tubular shell. 8923–8927 .32 Accordingly. The pore-size distribution shown in part b of Figure 3 indicates that the size of pores is primarily between 1 and 5 nm.7°.25 The intensity ratio of ID to IG in Raman spectra is a typical parameter to quantify the disorder degree of carbon materials.539 m m kJ molÀ1) also demonstrates that the reaction between CuCl2 3 2H2O and CaC2 could happen under the reaction conditions. so no CaC2 could be left for the further reaction between CaC2 and CuCl2 under the experimental conditions. however. Nitrogen adsorption/desorption isotherms and DFT pore size distribution of the as-obtained CNOs are displayed in Figure 3. respectively. It is well-known that Cu has a very strong effect on graphitization of carbon.The Journal of Physical Chemistry C ARTICLE the reaction between CaC2 and CuCl2.org/10.9.92 kJ molÀ1).5 kJ molÀ1) and experimentally feasible. According to the molar ratio of approximately 5.9 m kJ molÀ1) and highly exothermic (ΔrHΘ = À191. the crystal water in CuCl2 3 2H2O plays an important role in the formation of the CNOs. The above-mentioned process can be expressed by the following reactions: Figure 3. The heat generated further prompts the progress of the reactions. Although the reaction between CuCl2 and CaC2 is both thermodynamically (ΔrGΘ = À508. These graphitic flakes obtained are the combination of pentagonal and heptagonal structures together with the planar hexagonal structure of graphene so that they can accommodate the curvature of the CNOs. m ΔrHΘ = À515.1021/jp2007599 |J. a redox reaction between C2H2 and CuCl2 will happen. the isotherms exhibit a typical IV-type curve with a small hysteresis loop at higher relative pressure.33 With continuous heating treatment. few CNOs were obtained. m indicating the feasibility of the above-mentioned chemical processes. the chemical reactions described by eqs 2. As to the as-obtained CNOs.2 kJ molÀ1. The driving force for the graphitic flake aggregation has been discussed in terms of a free energy minimization theory. a possible chemical reaction mechanism is proposed as follows. as m expressed by eq 1. instead. suggesting the diversity of pores and the presence of micropores and mesopores in the product. the formation of the CNOs cannot be just ascribed to the simple redox reaction between CaC2 and CuCl2. in good agreement with the HRTEM and XRD results. some defects such as dangling bonds also exist on the surface of the CNOs. as confirmed by XRD analysis (Figure S1 of the Supporting Information). the carbon atoms generated will grow into graphitic flakes under the catalysis of Cu. at this current density. The two broad peaks centered at about 1303 and 1571 cmÀ1 are ascribed to the D peak for disordered carbon and the G peak for graphite carbon. the calculated value of 1.10 for ID/IG implies a low graphitization degree resulted from the long-range disorder structure of the CNOs. Surprisingly. Meanwhile. C 2011. some hollow structures with various sizes and a few nanoparticles could be observed (Figure S2 of the Supporting Information). The crystal water in CuCl2 3 2H2O will be lost at 110 °C during heating and will immediately react with CaC2 to produce acetylene (C2H2).26À29 CuCl2 is sometimes used as a promoter in the formation of carbon nanostructures.9:5 for CuCl2 3 2H2O to CaC2. which could account for the amorphous carbon observed on the surface of CNOs under HRTEM. On the basis of the information acquired. At the end of the growth of CNOs. From part a of Figure 3. Nitrogen adsorption/desorption isotherms (a) and the DFT pore-size distributions (b) of the as-obtained CNOs. which can undoubtedly lower the energy of the system. The specific surface area and pore volume are 101 m2 gÀ1 and 0. Moreover. Part a of Figure 4 shows the discharge/charge curves of the as-obtained CNOs for the first four cycles at a rate of C/10.34. the graphitic flakes aggregate into quasi-spherical graphitic shells. the H2O generated from the CuCl2 3 2H2O is excess enough to consume the CaC2 thoroughly. 8925 dx. The reaction between water and CaC2 occurs quite readily even under ambient atmosphere and thus is prior to As has been known. For insight into the formation mechanism of the CNOs.doi. Chem. CaC2 can be used as carbon source to synthesize carbon spheres under appropriate conditions. With the increase of temperature. ΔrHΘ = À353. that is a greater value of ID/IG ratio means a higher disorder degree for graphite. the thermodynamic calculation for the overall reaction of eq 6 (ΔrGΘ = À631. CuCl2 3 2H2 O ¼ CuCl2 þ 2H2 O CaC2 þ 2H2 O ¼ CaðOHÞ2 þ C2 H2 CuCl2 þ C2 H2 ¼ Cu þ 2C þ 2HCl CaðOHÞ2 þ 2HCl ¼ CaCl2 þ 2H2 O ð2Þ ð3Þ ð4Þ ð5Þ as-obtained CNOs due to their small sizes. resulting in the formation of carbon and Cu. 115.

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