orous Electrodes and the Nomenclature That Will Be Used in This Paper.

Transmission Lines

Favorite Electrochemistry EIS Books Availalbe
What Are They?

Why Are They Useful?

 

Introduction

Porous electrodes offer a high surface area to volume or weight ratio which is highly beneficial to a number of energy generation or storage devices. (e.g. Dye-Sensitized Solar Cells, Super-Capacitors, Fuel Cells, etc). Transmission lines are heavily used in modeling in Electrochemical Impedance Spectroscopy (EIS) experiments where porous systems are employed.

Though transmission lines are commonly used, an introductory paper was hard to find. This paper is intended to serve that purpose. It assumes basic knowledge of EIS and modeling using equivalent circuits as covered in our EIS application note.

Nomenclature and Notation

We will distinguish between the base electrode and the porous electrode and the various interfaces as shown in Figure 1.

Based electrode vs porous electrode

Figure 1. Porous Electrodes and the Nomenclature That Will Be Used in This Paper.

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There is a description of potentiostat stability (written by DK Roe) in the Kissinger & Heineman book (

A Basic Understanding of iR Compensation

Some of the most common technical questions we hear have to do with iR compensation —

Dr. Bobs basic understanding of iR compensation.

  1. Where does uncompensated iR come from?
  2. Do I need to use iR compensation with my experiment?
  3. How should I set up the iR compensation parameters?
  4. Why doesn’t iR compensation work on my system?

In this post we’ll attempt to answer these questions and to give you a basic understanding of iR compensation.

[…]

ompliance voltage is the voltage available at the counter electrode that can be used to force current to flow and still maintain control of the working electrode voltage.

How to Speak Potentiostat Compliance

Dr. Bobs Speaking Potentiosta ComplianceWhat’s important in the selection of a potentiostat? That depends greatly on its intended use. This page addresses an often misunderstood term.

Compliance voltagePotentiostat: Compliance Voltage

Compliance voltage is the voltage available at the counter electrode that can be used to force current to flow and still maintain control of the working electrode voltage. The compliance should be specified in conjunction with a current value: “20V @ 250mA” or “20V @ full rated current”. An amplifier’s output voltage decreases at higher currents due to the output impedance of the amplifier.

[…]

EIS Short Course - Houston TX

Fall EIS Short Course

The 26th Annual Fall EIS Short Course:
Electrochemical Impedance Spectroscopy:
Theory – Applications – Laboratory Instruction

Dates:  November 10-14, 2014

Where:   Houston, Tx

Electrochemical Impedance Spectroscopy short course houston tx Nov 10-14Course Overview

Impedance spectroscopy is an extremely powerful non-destructive investigative technique that can obtain essential information about interfacial and bulk material parameters through the use of low energy, time varying electrical excitation. When applied to an electrochemical system, electrochemical impedance spectroscopy (EIS) can provide information on reaction parameters, corrosion rates, oxide characteristics and integrity, surface porosity, coating integrity, mass transport, and many other electrode/interface characteristics. EIS is possibly one of the most powerful methods available in electrochemistry today and is utilized in research and development in essentially every technical sector, e.g., transportation and infrastructure, batteries and fuel cells, medicine, among many others. However, effective utilization of this method has been hindered by the lack of a comprehensive and cohesive explanation of the theory, measurement, and analysis techniques. This course on EIS has been developed to fill this void.

This short course, now in its 26th year, was first taught in 1988 in Charlottesville, Virginia. It has recently had the tremendous fortune of moving to the vibrant and technologically rich city of Houston, Texas. Please read more about our course on this website, or contact us either by e-mail or telephone.

Course Objective […]

Potentiostats for Battery Research Testing

Potentiostats for Battery Research Testing

Take two different metals, place an ion transporting medium between them, wire them up to be connected outside the electrolyte solution (perhaps to a voltmeter or potentiostat) and you’ve made a battery. With the ever-increasing demand for portable power, batteries are becoming more and more important. As demands on battery performance increase, so do demands Read more about Potentiostats for Battery Research Testing[…]

Favorite Electrochemistry EIS Books Availalbe

Selecting a Reference Electrode

My favorite My favorite reference electrode is the Ag/AgCl reference.electrode. Due to its simplicity, it is quite robust, and can be easily and effectively ‘revived’ if it should dry out. Moderately high temperatures ( 100 °C ) can be tolerated, as long as the AgCl does not completely dissolve and the construction materials are suitably Read more about Selecting a Reference Electrode[…]

Center for Electrochemical Engineering Research

Ohio University Receives Electrochemical Engineering Grant

Ohio University Electrochemical Engineering Research Center Receives $379,000 NIST Grant .S. Department of Commerce and National Institute of Standards and Technology (NIST). The award will be used to establish a consortium to support, sustain, and enhance U.S. manufacturing capacity in the nation’s chemical industry and allied sectors through innovative electrochemical processes. Under the Advanced Manufacturing Read more about Ohio University Receives Electrochemical Engineering Grant[…]

equation for a Warburg's impedance

Fitting EIS Data – Diffusion Elements

Whenever you look at a Complex-Plane Impedance Plot ( Nyquist or Cole-Cole plot) and see a 45° line, or fit data to an equivalent circuit and find a Constant Phase Element (CPE) with an n-value close to 0.5, you should consider diffusion as a possible explanation.

Diffusion Circuit Elements – Warburg

The most common diffusion circuit is the so-called “Warburg” diffusion element, but it is not the only one! A Warburg impedance element can be used to model semi-infinite linear diffusion, that is, unrestricted diffusion to a large planar electrode. This is the simplest diffusion situation because it is only the linear distance from the electrode that matters.
The Warburg impedance is an example of a constant phase element for which the phase angle is a constant 45° and independent of frequency. The magnitude of the Warburg impedance is inversely proportional to the square root of the frequency
as you would expect for a CPE with an n-value of 0.5. The Warburg is unique among CPE’s because the real and imaginary components are equal at all frequencies and both depend upon warburg-equations - 1
[…]

Reference Electrode for Ionic Liquids

Reference Electrode for Ionic Liquids

Room temperature ionic liquids or simply ionic liquids (some even call them molten salts) can act as a great solvent for electrochemistry but they bring along a challenge of what to use for the reference electrode. Traditional saturated calomel or Ag/AgCl reference electrodes use water as a solvent which can cause trouble for ionic liquids. Read more about Reference Electrode for Ionic Liquids[…]

CPE in parallel with a resistance

The Constant Phase Element (CPE)

What is a Constant Phase Element?

The Constant Phase Element (CPE) is a non-intuitive circuit element that was discovered (or invented) while looking at the response of real-world systems. In some systems the Nyquist plot (also called the Cole-Cole plot or Complex Impedance Plane plot) was expected to be a semicircle with the center on the x-axis. However, the observed plot was indeed the arc of a circle, but with the center some distance below the x-axis.
These depressed semicircles have been explained by a number of phenomena, depending on the nature of the system being investigated. However, the common thread among these explanations is that some property of the system is not homogeneous or that there is some distribution (dispersion) of the value of some physical property of the system.

CPE equations

Mathematically, a CPE’s impedance is given by

1 / Z = Y = Q° ( j omega )n

where Q° has the numerical value of the admittance (1/ |Z|) at omega =1 rad/s. The units of Q° are S•sn (ref 1).
A consequence of this simple equation is that the phase angle of the CPE impedance is independent of the frequency and has a value of -(90*n) degrees. This gives the CPE its name.

When n=1, this is the same equation as that for the impedance of a capacitor, where Q° =C.

1 / Z = Y = j omega Q° = j omega C

When n is close to 1.0, the CPE resembles a capacitor, but the phase angle is not 90°. It is constant and somewhat less than 90° at all frequencies. In some cases, the ‘true’ capacitance can be calculated from Q° and n
The Nyquist (Complex Impedance Plane) Plot of a CPE is a simple one. For a solitary CPE (symbolized here by Q), it is just a straight line which makes an angle of (n*90°) with the x-axis as shown in pink in the Figure. The plot for a resistor (symbolized by R) in parallel with a CPE is shown in green. In this case the center of the semicircle is depressed by an angle of (1-n)*90°

What Causes a CPE?

[…]

The Working electrode is not at Virtual Ground

Potentiostat Architectures – Passive I/E Converters

A Common Potentiostat Design

This style of I/E Converter is well suited to potentiostats with output currents of a few tenths of an ampere up to several A Common Potentiostat Designamperes. This scheme has been used by Gamry, PAR, Solartron, and perhaps others.

The I/E Converter is a “passive” design

The current path through the I/E converter only traverses passive components such as wires and resistors. No active components (such as op amps or transistors) are in the current path. The current measurement resistor is connected between the Working electrode and the potentiostat’s power supply ground (or “current return”).

The Working electrode is not at Virtual Ground

This is a consequence of the passive design. The working electrode voltage (vs the potentiostat’s internal ground) depends on the current flowing. In the sketch shown to the right, the working electrode will be at (i*Rm) volts. The actual voltage may be higher due to the resistance of the cell cable connecting the potentiostat to the working electrode!

Potentiostat with differential electrometer

[…]

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