Physical and electrochemical properties of synthesized carbon nanotubes [CNTs] on a metal substrate by thermal chemical vapor deposition
© Gwon et al; licensee Springer. 2012
Received: 21 September 2011
Accepted: 5 January 2012
Published: 5 January 2012
Multi-walled carbon nanotubes were synthesized on a Ni/Au/Ti substrate using a thermal chemical vapor deposition process. A Ni layer was used as a catalyst, and an Au layer was applied as a barrier in order to prevent diffusion between Ni and Ti within the substrate during the growth of carbon nanotubes. The results showed that vertically aligned multi-walled carbon nanotubes could be uniformly grown on the Ti substrate (i.e., metal substrate), thus indicating that the Au buffer layer effectively prevented interdiffusion of the catalyst and metal substrate. Synthesized carbon nanotubes on the Ti substrate have the diameter of about 80 to 120 nm and the length of about 5 to 10 μm. The Ti substrate, with carbon nanotubes, was prepared as an electrode for a lithium rechargeable battery, and its electrochemical properties were investigated. In a Li/CNT cell with carbon nanotubes on a 60-nm Au buffer layer, the first discharge capacity and discharge capacity after the 50th cycle were 210 and 80 μAh/cm2, respectively.
Keywordscarbon nanotubes metal substrate electrochemical property Au layer catalyst
Carbon nanotubes [CNTs] have recently attracted considerable attention as promising electrode materials for lithium-ion batteries due to their exceptional structure . CNTs have been studied extensively and found to be promising as a new nanoscale material for a variety of potential applications owing to their excellent electrical properties, mechanical strength, and high resistance to chemical attacks [2–6]. Among various processes of CNT synthesis, chemical vapor deposition is particularly promising because CNTs can be synthesized with high yield and high purity. This process also allows direct growth of CNTs on substrates with a selective area and vertical alignment. In order to fabricate various nanodevices, controlled growth of CNTs on suitable substrates is a key issue. For such practical applications, a high-quality contact between the CNTs and conductive substrates is essential to provide an in-situ electrical connection for individual CNTs. Non-conductive substrates, such as silicon wafers and quartz plates, have thus far usually been used to synthesize CNTs. However, in applications such as electrodes, it is desirable to grow CNTs directly on conductive substrates, especially metallic substrates. The growth of CNTs directly on metallic substrates also resolves the problem of adhesion of nanotube layers and fulfills the requirement of substrate electroconductivity [7, 8]. Such a one-step method is also advantageous in electrode preparation for lithium battery application. When metal is used as a substrate for CNT growth by CVD, a buffer layer should be deposited between the metal substrate and catalyst film (e.g., Ni, Co, or Fe) to prevent interdiffusion and interaction between the catalyst and substrate. Also, a conductive buffer layer must be used to establish electroconductivity between the CNTs and the substrate after synthesis of CNTs.
In this work, a Ni/Au/Ti substrate was used to grow vertically aligned CNTs by thermal chemical vapor deposition with acetylene gas as a carbon source. Au was applied as a barrier layer to prevent interdiffusion between the Ni layer, employed as a catalyst material, and the Ti substrate, and the effect of the Au layer according to thickness on the CNT growth was investigated. Electrochemical properties of a Ti substrate covered with CNTs were also evaluated.
CNTs were grown on Ni-coated Ti substrates with an Au buffer layer by TCVD. A catalyst Ni layer with a thickness deposition of 10 nm and buffer layers with thicknesses of 20, 40, or 60 nm were deposited using a radiofrequency magnetron sputtering system. To produce Ni particles, NH3 gas was introduced at 873 K for 15 min. After the pretreatment processes, CNTs were grown at 1173 K for 10 min using a mixture of acetylene and ammonia flowed to the reactor chamber. The morphology, density, and quality of the CNTs were analyzed using a field emission scanning electron microscope [FE-SEM] (XL30 S FEG, Philips, Amsterdam, The Netherlands) and a high-resolution micro-Raman spectrometer (Ar+ laser, 514 nm, LabRAM HR800 UV, HORIBA, Japan). One molar of LiPF6 dissolved in a mixture of ethylene carbonate and diethyl carbonate (1:1 by volume) was employed as a liquid electrolyte to evaluate the electrochemical properties. To investigate the electrochemical properties, a test cell was assembled in a stainless steel case (Swagelok®, Seoul, South Korea) by stacking, in the following order: a lithium foil, a polypropylene separator (Celgard 2400, Cheongwon-gun, South Korea) containing the liquid electrolyte, and a CNT electrode. The cell was tested in a voltage range of 0.01 to 2.0 V with a current of 50 μA. Charge/discharge tests were carried out via the galvanostatic method using a WBCS3000 battery cycler (WonATech, Seoul, South Korea).
Results and discussion
Vertically aligned CNTs were uniformly grown on a large area of a Ni/Au/Ti substrate by a thermal chemical vapor deposition process. The CNTs prepared on an Au buffer layer with a thickness exceeding 40 nm were more uniform and abundant compared to those grown on substrates without a buffer layer or with a 20-nm Au buffer layer. A Li/CNT cell consisting of CNTs on a 60-nm Au buffer layer/Ti substrate exhibited a lower irreversible capacity and better cycle performance than a cell with CNTs on a Ti substrate. The present findings suggest that an Au buffer layer is a good candidate for a barrier of interdiffusion between the catalyst layer and metal substrate for CNT synthesis. This work also provides an enhanced approach for secondary battery electrode fabrication.
This work was supported by the Pioneer Research Center for Nano-morphic Biological Energy Conversion and Storage and the World Class University (WCU) program through the National Research Foundation of Korea funded by the Ministry of Education, Science and Technology (grant number: R32-20093). The authors are also grateful to the Brain Korea (BK) 21 Project for supporting a fellowship.
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