Cyclic voltammetry (CV) is one type of potentiodynamic electrochemical measurements. Generally speaking, the operating process is a potential-controlled reversible experiment, which scans the electric potential before turning to reverse direction after reaching the final potential and then scans back to the initial potential, as shown in Figure 1a. When voltage is applied to the system changes with time, the current will change with time accordingly as shown in Figure 1b. Thus the curve of current and voltage, illustrated in Figure 1c, can be represented from the data, which can be obtained from Figure 1a and b.

Figure 1: Potential wave changes with time (a); current response with time (b); current-potential representations (c). Adapted from D. K. Gosser, Jr. Cyclic Voltammetry Simulation and Analysis of Reaction Mechanisms, Wiley-VCH, New York, (1993).

Cyclic voltammetry is a very important analytical characterization in the field of electrochemistry. Any process that includes electron transfer can be investigated with this characterization. For example, the investigation of catalytical reactions, analyzing the stoichiometry of complex compounds, and determining of the photovoltaic materials’ band gap. In this module, I will focus on the application of CV measurement in the field of characterization of solar cell materials.

Although CV was first practiced using a hanging mercury drop electrode, based on the work of Nobel Prize winner Heyrovský (Figure 2), it did not gain widespread until solid electrodes like Pt, Au and carbonaceous electrodes were used, particularly to study anodic oxidations. A major advance was made when mechanistic diagnostics and accompanying quantitations became known through the computer simulations. Now, the application of computers and related software packages make the analysis of data much quicker and easier.

Figure 2: Czech chemist and inventor Jaroslav Heyrovský (1890 – 1967).

As shown in Figure 3, the CV systems are as follows:

Figure 3: Components of cyclic voltammetry systems. Adapted from D. K. Gosser, Jr., Cyclic Voltammetry Simulation and Analysis of Reaction Mechanisms, Wiley-VCH, NewYork, (1993).

In order to better understand the electrodes mentioned above, three kinds of electrodes will be discussed in more detail.

Figure 4: The structure of (C₅H₅)₂Fe (ferrocene).

Cyclic voltammetry systems employ different types of potential waveforms (Figure 5) that can be used to satisfy different requirements. Potential waveforms reflect the way potential is applied to this system. These different types are referred to by characteristic names, for example, cyclic voltammetry, and differential pulse voltammetry. The cyclic voltammetry analytical method is the one whose potential waveform is generally an isosceles triangle (Figure 5a).

Figure 5: Examples of different waveforms of CV systems, illustrating various possible cycles. Adapted from D. K. Gosser, Jr., Cyclic Voltammetry Simulation and Analysis of Reaction Mechanisms, Wiley-VCH, New York (1993).

As mentioned above, there are two main parts of a CV system: the electrochemical cell and the epsilon. Figure 6 shows the schematic drawing of circuit diagram in electrochemical cell.

Figure 6: Diagram of a typical cyclic voltammetry circuit layout. Adapted from R. G. Compton and C. E. Banks, Understanding Voltammetry, World Scientific, Sigapore (2007).

In a voltammetric experiment, potential is applied to a system, using working electrode (W in Figure 6) and the reference electrode (R = Figure 6), and the current response is measured using the working electrode and a third electrode, the counter electrode (C in Figure 6). The typical current-voltage curve for ferricyanide/ferrocyanide, Equation 1, is shown in Figure 7.

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Figure 7: Typical curve of current-voltage curve for for ferricyanide/ferrocyanide, Equation 1.

Despite some limitations, cyclic voltammetry is very well suited for a wide range of applications. Moreover, in some areas of research, cyclic voltammetry is one of the standard techniques used for characterization. Due to its characteristic shapes of curves, it has been considered as ‘electrochemical spectroscopy’. In addition, the system is quite easy to operate, and sample preparation is relatively simple.

The band gap of a semiconductor is a very important value to be determined for photovoltaic materials. Figure 8 shows the relative energy level involved in light harvesting of an organic solar cell. The energy difference (E_g) between the lowest unoccupied molecular orbital (LUMO) and the highest occupied molecular orbital (HOMO), which determines the efficiency. The oxidation and reduction of an organic molecule involve electron transfers (Figure 9), and CV measurements can be used to determine the potential change during redox. Through the analysis of data obtained by the CV measurement the electronic band gap is obtained.

Figure 8: Diagram showing energy level and light harvesting of and organic solar cell. Adapted from S. B. Darling, Energy Environm. Sci., 2009, 2, 1266.

Figure 9: Diagram showing energy level and light harvesting of organic solar cell. Adapted from D. K. Gosser, Jr., Cyclic Voltammetry Simulation and Analysis of Reaction Mechanisms, Wiley-VCH, New York (1993).

The example of the analysis of CV data in solar cell material characterization

Graphene nanoribbons (GNRs) are long, narrow sheets of graphene formed from the unzipping of carbon nanotubes (Figure 10). GNRs can be both semiconducting and semi-metallic, depending on their width, and they represent a particularly versatile variety of graphene. The high surface area, high aspect ratio, and interesting electronic properties of GNRs render them promising candidates for applications of energy-storage materials.

Figure 10: Schematic for the “unzipping” of carbon nanotubes to produce graphene (Rice University).

Graphene nanoribbons can be oxidized to oxidized graphene nanoribbons (XGNRs), are readily soluble in water easily. Cyclic voltammetry is an effective method to characterize the band gap of semiconductor materials. To test the band gap of oxidized graphene nanoribbons (XGNRs), operating parameters can be set as follows:

• 0.1M KCl solution
• Working electrode: evaporated gold on silicon.
• Scan rate: 10 mV/s.
• Scan range: 0 ~ 3000 mV for oxidization reaction; -3000 ~ 0 mV for reduction reaction.
• Samples preparation: spin coat an aqueous solution of the oxidized graphene nanoribbons onto the working electrode, and dry at 100 °C.

To make sure that the results are accurate, two samples can be tested under the same condition to see whether the redox peaks are at the same position. The amount of XGNRs will vary from sample to sample, thus the height of peaks will vary also. Typical curves obtained from the oxidation reaction (Figure 9a) and reduction reaction (Figure 9b) are shown in Figure 11 and Figure 12, respectively.

Figure 11: Oxidation curves of two samples of XGNRs prepared under similar condition. The sample with lower concentration is shown by the red curve, while the sample with higher concentration is shown as a black curve.

Figure 12: Reduction curves of two samples of XGNRs prepared under similar condition. The sample with lower concentration is shown by the green curve, while the sample with higher concentration is shown as a black curve.

From the curves shown in Figure 11 and Figure 12 the following conclusions can be obtained:

• Two reduction peak and onset is about -0.75 V (i.e., Figure 9b).
• One oxidation peak with onset about 0.85 V (i.e., Figure 9a).
• The calculated band gap = 1.60 eV.

In conclusion, there are many applications for CV system, efficient method, and the application in the field of solar cell provides the band gap information for research.