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In situ Raman spectro-electrochemistry study of single-wall carbon nanotube mat

机译:单壁碳纳米管垫的原位拉曼光谱电化学研究

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A carbon nanotube-based electrochemical actuator has been investigated using in situ Raman spectro-electrochemistry. A sheet of single-wall carbon nanotubes (SWNTs) is dipped into an electrolyte and it expands or contracts if a voltage is applied between them and a counter electrode. It has been predicted that actuation is primarily due to changes in orbital occupation and band structure with a secondary contribution arising from double-layer electrostatic effects. However, the relative contribution and interaction between each of these mechanisms are unclear. We built a linear actuator from SWNT mat and studied its actuation in several alkali (Li, Na, K) and Ca halide and sulfate solutions in order to clarify the role of cation as mobile ions in the film. The variation of bonding with applied potential was monitored using in situ Raman spectroscopy. Raman can detect changes in C-C bond length, because the radial breathing mode at approx 190 cm~(-1) varies inversely with the nanotube diameter and the G band at approx 1590 cm~(-1) varies with the axial bond length. In addition, the intensities of both the modes vary with the emptying or filling of the bonding and anti-bonding states. We discuss the variation of spectroscopic observables (intensity/frequency) of these modes providing valuable information on the charge transfer dynamics on the SWNTs mat surface and indirectly quantify some of the parameters that include in-plane compressive strain (approx -0.25 percent) and the charge transfer per carbon atom (f_c approx -0.005). The cyclic voltammetry and a.c. impedance spectroscopy are described briefly and help to demonstrate well-developed capacitive behavior of SWNT mat.
机译:已经使用原位拉曼光谱电化学研究了基于碳纳米管的电化学致动器。将单壁碳纳米管(SWNT)片浸入电解质中,如果在它们和对电极之间施加电压,则它会膨胀或收缩。可以预料的是,致动主要是由于轨道占据和能带结构的变化,以及由于双层静电效应引起的次要贡献。但是,这些机制之间的相对作用和相互作用尚不清楚。我们用SWNT毡构建了线性致动器,并研究了其在几种碱(Li,Na,K)以及卤化钙和硫酸盐溶液中的致动作用,以阐明阳离子在薄膜中作为移动离子的作用。使用原位拉曼光谱法监测结合电位的变化。拉曼可以检测C-C键长度的变化,因为在大约190 cm〜(-1)处的径向呼吸模式与纳米管直径成反比,而在大约1590 cm〜(-1)处的G波段随轴向键长而变化。另外,两种模式的强度随着结合和反结合状态的排空或填充而变化。我们讨论了这些模式的光谱可观测值(强度/频率)的变化,从而提供了有关SWNTs垫表面上电荷转移动力学的有价值的信息,并间接量化了一些参数,包括平面内压缩应变(约-0.25%)和每个碳原子的电荷转移(f_c约为-0.005)。循环伏安法和交流电简要介绍了阻抗谱,有助于证明SWNT垫的良好电容性能。

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