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2.3. Potentiostats

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57 views6 pages

2.3. Potentiostats

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macaco9855
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Sensors in Neural Engineering – An Introduction to

Potentiostats
Henry Lancashire

February 2024

Contact details:
Implanted Devices Group
Malet Place Engineering Building, room 8.03
Phone: 020 3108 1611
Email: h.lancashire@ucl.ac.uk

1 Overview
Overview
• What is a Potentiostat?
• Three Electrode Setup

• Potentiostat Design
• What is a Galvanostat?
• Input signals

2 The Potentiostat
What is a Potentiostat?
• A scientific instrument which: Measures and controls electrode potential.

• By controlling electrode current.


• With a feedback circuit.

Why use a Potentiostat?


• We know that electrodes polarise when current is passed through them.
• Can we observe this polarisation?

• To apply current to an electrode under test (the Working Electrode (WE)) we need to complete the circuit.
• We can use a Counter Electrode (CE) to complete the circuit.
• If we apply a current through the WE and CE and measure the potential difference between them ...
• Both electrodes polarise.

• Voltage drops across the electrolyte.


• We cannot observe polarisation of the WE alone.
• We need a stable potential point which does not pass current.
• This third electrode is the Reference Electrode (RE).
Potentiostats

Figure 1: Two electrode cell, from Bard and Faulkner, 2001, Electrochemical Methods.

3 Three Electrodes - The Electrochemical Cell


The Three Electrode Cell
• Current is passed between the Working Electrode and the Counter Electrode.
• The Working Electrode potential is measured with respect to the Reference Electrode.
• No or we hope very little current passes through the Reference Electrode.

• The Reference Electrode remains unpolarised with a stable electrode potential.


• The measurements concern only the Working Electrode. (At least in a well designed system, a poorly designed
system can interfere with measurements).
• There are rare cases where a two electrode cell is appropriate.

• The Counter Electrode is usually much larger than the Working Electrode to ensure that the CE has a low
impedance, and to ensure that it does not polarise much and therefore does not generate chemical products which
will interfere with the electrolyte.
• The Reference Electrode impedance is important, RE impedance must be low to ensure a stable feedback loop.

Figure 2: Three electrode cell, consider the standard cell notation for each electrode type. From Bard and Faulkner,
2001, Electrochemical Methods.

Version of January 31, 2024 2


Potentiostats

Uncompensated Resistance

• We assume that the measurements only concern the WE, this is not true.
• There is still some resistance due to the electrolyte which is uncompensated (Ru ).
• This is the Access Resistance from the WE to the RE only.
• We can reduce this by:

– Moving the RE closer to the WE.


– Increasing the solution conductivity.

Figure 3: Uncompensated resistance (Ru ) creates a potential drop (iRu ) due to the access resistance (solution resistance)
between the working electrode and the reference electrode, considered as a cell (a) and as as potentiometer (b). From
Bard and Faulkner, 2001, Electrochemical Methods.

4 Potentiostat Design
Feedback Loops
• If we apply a potential to a cell, current will flow, this current causes the electrodes to polarise, and alters the
applied potential.
• Do you recognise this system?

• We need a feedback loop to control the Working Electrode potential.


• A Potentiostat provides this feedback.
– Made up of potenti al,
– and static.

An “Adder” Potentiostat
• The WE is held at virtual ground by a current follower (CF) which measures the cell current with a transimpedance
amplifier.
• The RE potential is measured by a high input impedance voltage follower (F). WE is grounded, therefore RE floats,
and eF = −eW E .
• A waveform is created by an adder circuit from e1 , e2 , and e3 .

• The waveform is summed with the working electrode potential at S, by an adder using a potential control amplifier
(PC) to provide a low impedance output voltage.

Version of January 31, 2024 3


Potentiostats

• A booster (B) may be used to extend the cell voltage, and a similar booster can be used to extend the current
range.

• HOW DOES IT WORK?


• e1 + e2 + e3 form a set potential eset at which we want to hold WE.
• If eW K = eset then S = 0V , because eF = −eW K and S = eset − eW K .
• If eW K > eset then S < 0V , because S = eset − eW K , and PC applies a negative WE current (a positive CE
current). Note the inversion between S and CE current because PC is an inverting amplifier.
• If eW K < eset then S > 0V , because S = eset − eW K , and PC applies a positive WE current (a negative CE
current).

Figure 4: A potentiostat schematic showing a control amplifier (PC) with a voltage range booster (B). A voltage follow
(F) provides a high input impedance measurement point for the reference electrode. A current follow (CF) holds the
working electrode at a virtual ground and measures the cell current. From Bard and Faulkner, 2001, Electrochemical
Methods.

5 What is a Galvanostat?
What is a Galvanostat?
• A galvanostat is a scientific instrument which: measures and controls electrode current.
• And measures electrode potential.

• Does not need a feedback circuit.


– Made up of Galvanism, (chemical direct current, after Luigi Galvani),
– and static.

Version of January 31, 2024 4


Potentiostats

The Galvanostat

• Galvanostats can be much simpler than potentiostats because only the working and counter electrodes are consid-
ered in the control circuit.
• In the given example a current through the cell flows from CE to WE and is set by icell = R .
−ei

• Electrode potential is measured differentially because WE is at −ei w.r.t. ground (so system ground cannot be
used to measure the RE potential).

• There are lots of other ways to make a galvanostat, but the principle is the same: apply a current through WE
and CE, and measure potential w.r.t. RE.

Figure 5: A simple galvanostat design. From Bard and Faulkner, 2001, Electrochemical Methods.

Version of January 31, 2024 5


Potentiostats

6 What are all these ei s?


Input Signals
• A little bit more information about “Adder” Potentiostats.
• We want to alter the electrode potential by a known amount. This might be a pulse, ramp, or a sinusoid. You
will encounter examples which use all of these.
• We often want some voltage offset, for example holding an electrode at around equilibrium to ensure icell = 0.
• A DAC is usually not smooth enough for electrochemistry, so we use an adder or summing amplifier.

Figure 6: Creating a complex waveform by adding primitives. This is usually not possible with a standard DAC because
the resolution creates "jumps", which are especially apparent in sinusoidal and ramp waveforms. Therefore separate
specialist circuits are used to create the primitives which are then combined with an adder or summing amplifier. From
Bard and Faulkner, 2001, Electrochemical Methods.

Version of January 31, 2024 6

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