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"EduPotStat" - Construction and Testing of A Low Cost Potentiostat

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IOSR Journal Of Applied Physics (IOSR-JAP)

e-ISSN: 2278-4861.Volume 12, Issue 5 Ser. III (Sep. – Oct 2020), PP 10-18
www.Iosrjournals.Org

“EduPotStat”: Construction and testing of a low cost potentiostat


R.M.D.P.K.Rathnayaka1, D. D.C. Wanniarachchi2, C. H. Manathunga3, R.
A.D.D. Dharmasiri3, W. K. I. L. Wanniarachchi3*
1
(Department of Biosystems Technology, Faculty of Technological Studies, UvaWellassa University of Sri
Lanka, Badulla, Sri Lanka)
2
(Instrument Center, Faculty of Applied Sciences, University of Sri Jayewardenepura, Nugegoda, Sri Lanka)
3
(Department of Physics, Faculty of Applied Sciences, University of Sri Jayewardenepura, Nugegoda, Sri
Lanka)

Abstract:
In this work we developed a low cost potentiostat to monitor redox processes using open source software and
hardware for undergraduate laboratories in the developing countries. The developed system consists of three
main modules namely user interface, triangular voltage generator, and current to voltage converter. Arduino
Uno, 12-bit digital to analog converter and nine operational amplifiers were used to construct the proposed
hardware. It operates in voltage range -2.5 V to +2.5 V and measure current in the range of ± 25 µA -0.025 A
with 10 nA resolution and 1 mV DC-potential resolution for the cyclic voltammetry measurements. The
performance of this system is compared with a commercially available potentiostat using K 3Fe(CN)6 solutions.
The three-electrode system reported here is screen-printed electrodes with aqueous KCl as the electrolyte.
Results are in good agreement with commercially available research grade potentiostat. Overall cost for
developed system is around $50 which make possible to use in undergraduate education.
Key Word:Cyclic voltammetry; Digital to analog conversion; Electrochemical measurements; Potentiostat;
Three-electrode system
----------------------------------------------------------------------------------------------------------------------------- ----------
Date of Submission: 30-09-2020 Date of Acceptance: 13-10-2020
----------------------------------------------------------------------------------------------------------------------------- ----------

I. Introduction
Commercially available potentiostats, often cost upwards of $5000/$6000 per channel or $1,000 for a
model with limited functionality1. In addition, these commercial instruments are typically impractical to use in
field researches. Therefore, teaching laboratories in the fields of both electronics and electrochemistry, and
developing teaching centers that cannot afford a commercial device are faced with more difficulty. While a low
cost potentiostat device cannot rival the quality and capabilities of research-grade potentiostats, many of the
features of top-of-the-line commercial instruments are unnecessary for environmental or public health
applications and portable applications1,2,3. However, high school students or university students will be
benefitted by inexpensive potentiostats which are used for teaching purposes. Therefore, desirable to design and
assemble a potentiostat which is easy in operation as well as economically cheap.
However, in order to reduce price, size and complexity, custom made potententiostats can be
implemented with limited functionality compared to the commercially available high grade potentiostats. In the
review of literature there were several low cost, open source, microcontroller unit (MCU) based, miniature
potentiostats have been described over the last decade 1,3–12. When the history of potentiostat is considered, the
first research paper about MCU based potentiostat was published by Vittal and Russell3in 2006 for cyclic
voltammetry. This is the first open source design of an inexpensive potentiostat that is field ready for long-term
chronoamperometry. PIC18F452 microcontroller was used in this potentiostat and there are some limitations
associated with design. More recent open-source potentiostat development has focused on miniature
potentiostats, often with implantation in mind 1, 4, 5,7, 8, 12–16. These devices offer additional options than Vttal and
Russel’s with minimizing drawbacks. A LabView based potentiostat was developed by Avdikos which is not an
open source platform9. But none of the above developed systems are not commercially available.
However, the “CheapStat: An Open-Source, “Do-It-Yourself”Potentiostat for Analytical and
Educational Applications” was built for under $60 (or < $80)1,5. This device is commercially available and
supports multiple measurements mode such as cyclic, square wave, linear sweep stripping voltammetry over the
potential range -990 mV to 990 mV. But this potential range is not enough for some experiments. Other
limitations associated with this potentiostat are having onboard LCD display and input parameters (Frequency,
starting voltage, end voltage, scan rate) must be set through that limited onboard LCD display and 5-way
joystick. Therefore, that device is lack of user-friendliness.

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“EduPotStat”: Construction and testing of a low cost potentiostat
The system developed in this work use open source hardware and software. It is a low cost three-
electrode potentiostat for electrochemistry measurements capable to run cyclic voltammetry measurements. The
system consists of three main modules namely a user interface, a triangular voltage generator, and a current to
voltage converter. User inputs of scanning voltage range and scanning rate can be input through the user
interface. Triangular voltage generator consists of four sub circuits such as ATmega328p microcontroller based
12-bit step counter, digital to analog converter (MCP 4725 12-bit DAC), difference amplifier and inverting
summing amplifier. This module outputs a triangular voltage in the range of -2.5 V to +2.5 V at a user given rate
where it connects to the counter electrode of the three-electrode system.

II. Material And Methods


The potentiostat has two main tasks: The first task is to measure the potential difference between the
working electrode (WE) and the reference electrode without polarizing the reference electrode. The second task
is to compare the potential difference to a preset voltage and force a current through the counter electrode (CE)
towards the WE in order to counteract the difference between preset voltage and existing WE potential. To
perform cyclic voltammetry, a triangular voltage is applied to the WE. During the voltage waveform applied
time electron transfer occurs withinthe electrochemical cell; this current is measured at the WE and recorded for
analysis.

Basic Potentiostat circuit


A basic potentiostat circuit is presented in Fig. 1 The reference electrode (RE) is connected to the “OP
Amp B” which is a voltage follower and has near infinite input resistant, therefore no significant current transfer
can occur at this electrode. The voltage-follower circuit helps in maintaining a constant potential at the RE
without drawing much current. Input triangular voltage waveform is applied to the electro chemical cell at the
CE respect to the RE using the current buffer “Op Amp A” (control amplifier). The input of the current buffer is
isolated from the output, therefore the current at the output of the op amp is not limited by the input current and
is capable of providing infinite current (effectively infinite, practically 1 A) to electro chemical system which is
needed to undergo chemical reactions. The current flow between the CE and the WE.

Fig. 1.Basic Potentiostat Circuit

By applying the voltage waveform, the potential difference is controlled between the WE and the CE
and also the potential difference is measured between the WE and the RE. Because the WE is kept fixed stable
potential (pseudo ground) by controlling the polarization of the CE, the potential difference between the WE and
the RE is controlled all the time. The potential difference between the WE and the RE will be equal to the
applied triangular voltage waveform. This configuration allows the potential across the electrochemical interface
at the WE to be controlled with respect to the RE. For a potentiostat to operate correctly, the WE must maintain
a zero potential. Therefore, the WE is connected to the inverting terminal of the “Op Amp C” while the non-
inverting terminal is connected to the ground. In this configuration virtual ground creates at the WE and that
also creates a negative voltage across the measuring resistor at the “Op Amp C”. The current generated from the
electrochemical cell is forced to flow through the resistor of “Op Amp C”. When the resistor value is known and

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“EduPotStat”: Construction and testing of a low cost potentiostat
the voltage across the resistor is measured, can calculate the current through the cell. In this case, “Op Amp C”
acts as a current to voltage converter.

Electronics in Potentiostat design


The block diagram of the EduPotStat is presented in Fig. 2 The developed system consists of four
distinct parts: (i) Microcontroller Unit (MCU – ATmega328p), which serve as a central processing unit,
generates the triangular waveform in digitally, measure the voltages and running all other functions, (ii) 12 bit
Digital to Analog Converter (DAC -MCP 4725 breakout board, control it via I2C ), which converts the digitally
generate triangular waveform to analog signal, (iii) external circuit (consist of operational amplifiers, resistors,
capacitors..etc), which provides the core of the potentiostat and interface between the MCU and the electrodes,
(iv) personal computer, which provides the user interface to control the potentiostat from the GUI.

Fig. 2. Block diagram of the EduPotStat

The schematic of the developed EduPotStat is presented in Fig. 3 MCU programmed to generate a
triangular waveform as digital form according to user input using a 12 bit up-down counter. The output of the
MCU‟s digital signal will convert to analog triangular voltage waveform by DAC. The output of the DAC is fed
to the external circuit through a voltage follower (Op-1, Fig. 3). The voltage follower circuit is used to isolate
the external circuit from the MCU with DAC. But the output of the DAC is unipolar (between 0 V and +5 V
Fig. 4); to change the output voltage to bipolar (between -2.5 V and +2.5 V, Fig. 5) an op amp difference
amplifier circuit (Op-2 and Op-3, Fig. 3) is used as a level shifter.

Fig. 3. Schematic diagram for the external circuit of the developed potentiostat. All Op-Amps are powered with
± 12 V power supply. (CE – Counter Electrode, WE – Working Electrode, RE – Reference Electrode)

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“EduPotStat”: Construction and testing of a low cost potentiostat

Fig. 4. Output voltage waveform of the Digital to Analog Converter

Fig. 5.Graph (A) - Output wave form at the DAC; Graph (B) - Output of the level shifted difference amplifier

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“EduPotStat”: Construction and testing of a low cost potentiostat

Fig.6. Triangular Waveform at the working electrode which is used to perform cyclic voltammetry

Another two-voltage follower circuit (Op-4 and Op-5, Fig. 3) is used in an external circuit. The RE is
connected to the non-inverting terminal of a voltage follower circuit (Op-5, Fig. 3). The voltage-follower circuit
helps in maintaining a constant potential at the RE without drawing much current (RE will be polarized when
current passes through the RE and cannot maintain a constant potential. Voltage follower circuit will prevent
that phenomena.) An inverting summing amplifier is inserted between the level shifted voltage and CE; the
inverting summing amplifier (Op-6, Fig. 3) is fed the level shifted voltage to the electro chemical cell respect to
the RE. The WE is connected to the inverting terminal of a current-to-voltage converter (Op-7, Fig. 3); feedback
resistor of the current to voltage converter will produces a voltage equivalent of the electrochemical current at
the output of the voltage converter. The electrochemical current, now converted to a voltage, is level-shifted
usinganother difference amplifier circuit (Op-8, Op-9 Fig. 3) and attenuated/amplified to bring the voltage into
the 0 V to ± 5 V range which can readable at the Analog to Digital Converter (ADC) in MCU. Because the
inbuilt 10-bit ADC of the MCU can read voltage between 0 V and +5 V. ATmega 328p microcontroller uses its
own voltage references. But they are not very precise. Limit of the analog measurement accuracy depends on the
used voltage reference. Here, microcontroller used allows to providing a substitute for its default voltage
reference byproviding an Analog Reference (AREF) input. Therefore, an external voltage reference (REF-02,
LINEAR TECHNOLOGY) (Fig. 7) was used to improve the accuracy of the analog voltage measurements. The
same external voltage reference was used to supply voltage to DAC to get accurate analog voltage waveform as
well. Microcontroller was programmed such that the user can set initial voltage and peak voltage of the required
triangular waveform and also can select the scan rate using the Arduino Serial Monitor.

Fig. 7.External voltage reference circuit

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“EduPotStat”: Construction and testing of a low cost potentiostat
Software design
Arduino IDE used to program the MCU where the program consists of three parts: (i) providing user
input to control the EduPotStat (ii) generating a voltage waveform to the analog circuit (iii) read and record
input voltages to the electrochemical cell and the current received at the ADC as a voltage which then converted
to current. User can connect the EduPotStat to one of the PC‟s USB ports. Then the user will be guided for
required user inputs when opening the Arduino IDE serial monitor.

Electrodes

Fig. 8.Pine screen printed electrode. (a)-Counter Electrode,(b)-Working Electrode,(c)-Reference Electrode

In this work “Pine Screen Printed Electrodes” were used as three electrode system 17,18. These offer some
advantages over traditional electrodes in the areas of cost, solution volume, and operating temperature.

System testing
The EduPotStat‟s performance was compared with an Autolab PGSTAT204 potentiostat/galvanostat
which is commercially available. For testing the potentiostat, cyclic voltamagmogram was recorded for 1
mol/dm3 solution of potassium ferricyanide in 0.1 mol/dm3 electrolyte solution of potassium chloride. A beaker
(50 mL) was used as the electrochemical cell where three electrodes were set up. The current (i) vs. voltage (v)
was recorded for -0.7 V as the starting voltage and 1 V as the switching voltage. The experiment was conducted
using two scan rates 100 mV/s and 200 mV/s.

III. Result
The cyclic voltammetry for the test species Fe2+/Fe3+ has the theoretically predicted shape as a
reversible redox couple. In this study K3[Fe(CN)6] is used to test the EduPotStat due to the water solubility of
the redox couple. Here, commonly used internal standard, ferrocene was not used due to the water insolubility
of the compound. Though, the expected redox Fe2+/Fe3+ couple of K3[Fe(CN)6] is not reversible to the limits of
ferrocene it is qualitatively sufficient to test the system. The cyclic voltamagmogram was recorded using
EduPotStat and Autolab potentiometers for the same solution containing K 3[Fe(CN)6] and KCl. The CV
recorded for using 100 mV/s and 200 mV/s scan rates are given in the following Figures 09 and 10 respectively.
The reversibility of the redox couple can be evaluated by calculating the ratio between anodic peak current and
anodic peak current as well as the difference between anodic and cathodic peak potentials.

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“EduPotStat”: Construction and testing of a low cost potentiostat

Fig. 9.Cyclic voltammogram for 1 M potassium ferricyanide solution for developed CV system and commercial
potentiostat with 0.100 V/s scan rate; Blue colour:Commercial potentiostat, Red colour: developed potentiostat.

Fig. 10.Cyclic voltammogram for 1 M potassium ferricyanide solution for developed CV system and
commercial potentiostat with 0.200 V/s scan rate; Blue colour: Commercial potentiostat, Red colour:developed
potentiostat.

Criteria for reversibility are;


ipc  ipa (1)
Ep   Epa  Epc   0.0592 / n ; Where n is the number of electrons in reaction (2)

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“EduPotStat”: Construction and testing of a low cost potentiostat
Furthermore, the potential of the redox couple can be given as,
E1 / 2   Epa  Epc  / 2 (3)

Table 01: Comparison of redox parameters for the EduPotStat and commercially available Autolab
potentiometers for 0.1 V/s scan rate.
𝑖𝑝𝑎
E1/2 (mV) 𝑖𝑝𝑐 |𝐸𝑝𝑐 −𝐸𝑝𝑎 | (mV)

EduPotStat 86.79 0.750 297.81


AutoLab 81.05 0.717 309.3

According to Table 01, the E1/2 values obtained for the Fe2+/Fe3+ redox couples are 86.79 mV and 81.05
mV for the EduPotStat and Autolab respectively. Furthermore, the ratios between anodic and cathodic peak
currents are 0.750 (EduPotStat) and 0.717 (AutoLab). Therefore, the system tested in this study is in good
agreement with a commercially available CV systems.
When constructing the system, TL074 IC and 741 IC were used for the external circuit because they
have high-Input Impedance, low power consumption, wide common-mode and differential voltage ranges, low
Input bias and offset currents. The analog circuit is the heart of the potentiostat. Where the EduPotStat supports
only for cyclic voltammetry currently. But other operation modes (linear sweep, stripping, square wave
voltammetry) can be added with simple microcontroller program algorithms. And also above mentioned
operation range can be expanded with simple hardware adjustments. We noted that different power supplies
produce slightly different outputs. This is an issue that arose which affected the accuracy of the resulting current
since all data is scaled proportionally to Vcc of the DAC. Therefore, a REF-02 (LINEAR TECHNOLOGY)
precision 5 V voltage reference was used to improve the accuracy of the analog voltage measurements.
The constructed system can operate voltage range between -2.5 V to 2.5 V, while user can select desire
scan rate. Also, the proposed light weight system can construct with low budget. Therefore, this EduPotStat is
very field portable and can be used in undergraduate laboratory experiments and analytical applications in
developing countries.

IV. Conclusion
In this work we presented that the design of a low cost three electrode potentiostat which operates
voltage range in the -2.5 V to +2.5 V for cyclic voltammetry applications with uccessful scanning in both
positive and negative voltages. This allows to measure current between ± 0.000025 A -0.025 A ranges with 10
nA resolution and 1 mV DC-potential resolution for voltage measurments with low noise. Test results were
good agreement with the commercially available potentiostat. The simple design, construction, easy to operate,
low cost (< $50), low power consumption, field portable and good performance are the advantages of the
instrumentation. The next steps include creating a graphical user interface to control the device and optimize the
potentiostat for provide multiple techniques.

Acknowledgment
The authors wish to acknowledge the facilities provided by the Department of Physics, University of Sri
Jayewardenepura and Department of Science and Technology,UvaWellassa University to carry out this
research. Furthermore, funding supported by NRC 17-038 is also acknowledged.

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R.M.D.P.K.Rathnayaka, et. al. “EduPotStat”: Construction and testing of a low cost potentiostat.”
IOSR Journal of Applied Physics (IOSR-JAP), 12(5), 2020, pp. 10-18.

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