Simple computercontrolled potentiostat for the characterization of electrochromic films

L. Kirkup, J. M. Bell, D. C. Green, G. B. Smith, and K. A. MacDonald Citation: Review of Scientific Instruments 63, 2328 (1992); doi: 10.1063/1.1143795 View online: http://dx.doi.org/10.1063/1.1143795 View Table of Contents: http://scitation.aip.org/content/aip/journal/rsi/63/4?ver=pdfcov Published by the AIP Publishing

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Simple computer-controlled of electrochromic films

potentiostat

for the characterization

L. Kirkup, J. M. Bell, D. C. Green, G. B. Smith, and K. A. MacDonald

Department of Applied Physics, University of Technology, Sydney, P. 0. Box 123, Broadway, N. S. W. 2007, Australia

(Received 9 October 1991; acceptedfor publication 9 December 1991) We describe a simple and inexpensivepotentiostat, incorporating current boosting and filtering circuitry for use in the study of coloration and bleaching in electrochromic thin films. The system is sufficiently flexible to permit utilization in other electrochemical applications.

Three electrode potentiostats are widely used in electrochemical studies to establishthe potentials at which specific reactions occur. A potentiostat may be used to study the coloration and bleaching that occurs in an electrochromic film when charged species are injected into, or removed from, a film. This application requires that a linear ramp voltage be applied to the potentiostat so that the potential of the reference electrode with respect to the working electrode varies within the range 3 to - 3 V with a period of the order of 100 s. Though it is possible to acquire expensive proprietary potentiostats to accomplish this task, the availability of low cost, high performance, integrated circuits and microcomputers permits the construction of a high quality, inexpensive electrochemical analysis system. Figure 1 shows the potentiostat circuit designedfor the electrical characterization of electrochromic films. When a voltage Vi is applied to the noninverting input of the f OPA2 111 operational amplifier (op-amp), labeled ICI A, the feedbackloop around that op-amp (which contains the electrochemicalcell) ensuresthat the referenceelectrodeis held at the same potential. The other half of this dual op-amp ( IClB) acts as a current to voltage converter permitting the current through the electrochemical cell to be established.In this configuration the working electrode of the potentiostat is held at virtual ground. The current through the cell is given by -V&Z/, where Rf is the feedbackresistor in the circuit containing IClB. V0 may be measuredusing a chart recorder or input to an analog to digital converter. The very high input impedance of the OPA2111 ( > 10 a) ensuresthat no current is drawn by the referenceelectrode and the offset voltage ( < 0.3 mV) is sufficiently low that no offset adjustments are required. The amount of current that must flow betweencounter electrodeand working electrodeto force the referenceelectrode to the samepotential as Vi, dependsupon the surface area of the film (which is attached to the working electrode). In some situations this current may exceed 10 mA which is the limit of the current that a precision op-amp, such as the OPA 2111, can supply. To provide currents to the electrochemical cell in excessof 10 mA, and in order that these currents may be measured,a simple push-pull arrangement of complementary bipolar transistors is used at both outputs of the OPA2111. The current boosting
2328 Rev. Sci. Instrum. 83 (4), April 1992

circuitry shown in Fig. 1 is capable of supplying up to 0.1 A. Such a push-pull circuit is susceptible to cross over distortion at high frequencies.3 In the application discussed here signal frequenciesare of the order of 0.01 Hz and such distortion is negligible. As frequenciesof interest are close to dc, a simple first order low pass filter is used to attenuate frequenciesabove about 20 Hz. At low levels of current through the cell, 50 Hz interference was found to be a problem. This is associated with the distributed nature of the feedback path around the ICl A op-amp and the fact that no attempt has been made to shield any part of the circuit from the intrusive effect of electrical mains interference. The effect of such interference is reduced dramatically by the use of an active notch filter which discriminates strongly against signals at or close to the notch frequency.4To adjust the filter for optimum performance, a signal frequency of 50 Hz is applied to Vi,. The 20 kfi potentiometer is adjusted until the 50 Hz component of the output is minimized. In the situation where it is desired to monitor the referenceelectrode directly with a conventional voltmeter or oscilloscope, it is important to buffer the electrode with a high input impedanceop-amp such as the 071 (IC2) shown in Fig. 1 otherwise the electrode will be loaded by the measuring device. The OP77 (IC3) performs a similar buffering function to the output of the current to voltage converter. Though the circuit shown in Fig. 1 may be used with a signal generator to provide a linear ramp voltage Vi, and a chart recorder used to plot the current through the cell as a function of potential at the working electrode, greater flexibility in terms of control, data storage and data manipulation is offered by using a multipurpose interfacing card in conjunction with a microcomputer. For example, the amount of charge injected into, or extracted from, a film can be establishedby simply integrating with respect to time the current supplied to the film. A Sunset Laboratory interfacing board5situated within an IBM compatible PC is used to provide digital to analog functions so that a ramp voltage may be generatedand analog to digital functions so that the current through the cell may be measured. The hardware is controlled by software written in Quick-Basic.6The circuit was designedto operate from an external bipolar power supply ( f 15 V at 0.5 A) or from the f 12 V supply of a microcomputer.
0 1992 American Institute of Physics 2328

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9034-8748/92/042328-02$92.00

FIG. 1. Circuit diagram for potentiostat.

Figure 2 shows a cyclic voltammogram obtained with the system. An Ag/AgCl electrode was used as a reference electrode, a platinum rod as counter electrode and the working electrode consisted of a tungsten oxide film deposited by the sol-gel technique2 on an indium-tin oxide sub-

strate. The feedback resistor, RP shown in Fig. 1 was chosen to be 1 kfi. The electrolyte is LiClO, in propylene carbonate. The curve represents a single cycle from - 1.5 to 1.5 V and back. As can be seen, the drift of the system is minimal and the noise intrusion negligible. The potentiostat described here is suitable for other electrochemical applications such as the study of corrosion in metals7 or the investigation of reaction rates. The authors gratefully acknowledge Mr. Alan Coelho and Mr. Robert Graves for their assistance in computing and electronic matters, respectively.
D. D. MacDonald, Transient Techniques in Electrochemistry (Plenum, New York, 1977). 5. M. Bell, D. C. Green, A. Patterson, G. B. Smith, K. A. MacDonald, K. Lee, L. Kirkup, J. D. Cullen, B. 0. West, L. Spiccia, M. J. Kenny, and L. S. Wielunski, Proc. SPIE Vol. 1536 (in press). 3G. B. Clayton, Operational AmpIifirs, 2nd ed. (Butterworths, London, 1979), Chap. 9. 4P. Horowitz and W. Hill, The Art of Electronics, 2nd ed. (Cambridge University, Cambridge, 1989). 5Sunset Laboratory, Forest Grove, Oregon, 1989. Microsoft BASIC version 7.0 ( 1990). 7M. G. Hocking and V. Vasantasree, Br. Corros. J. 10, 160 (1975). 5. A. Fraunhofer and C. H. Banks, Potentiostat and its Applications (Butterworths, London, 1972), Chap. 9.

FIG. 2. Cyclic voltammogram for coloring and bleaching of a WOs solgel film on indium-tin oxide. The inset of this figure shows the variation of the potential of the working electrode with respect to the reference electrode and the current density through the film with respect to time.

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitationnew.aip.org/termsconditions. Downloaded to IP: 2329 Rev. Sci. lnstrum., Vol. 83, No. 4, April 1992 Notes 2329 163.10.198.122 On: Wed, 26 Feb 2014 12:16:13