Faradaic impedance

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In electrochemistry, faradaic impedance [1] [2] is the resistance and capacitance acting jointly at the surface of an electrode of an electrochemical cell. The cell may be operating as either a galvanic cell generating an electric current or inversely as an electrolytic cell using an electric current to drive a chemical reaction. In the simplest nontrivial case faradaic impedance is modeled as a single resistor and single capacitor connected in parallel, as opposed say to in series or as a transmission line with multiple resistors and capacitors.

Contents

Mechanism

The resistance arises from the prevailing limitations on availability (local concentration) and mobility of the ions whose motion between the electrolyte and the electrode constitutes the faradaic current. The capacitance is that of the capacitor formed by the electrolyte and the electrode, separated by the Debye screening length and giving rise to the double-layer capacitance at the electrolyte-electrode interface. When the supply of ions does not meet the demand created by the potential the resistance increases, the effect being that of a constant current source or sink, and the cell is then said to be polarized at that electrode. The extent of polarization, and hence the faradaic impedance, can be controlled by varying the concentration of electrolyte ions and the temperature, by stirring the electrolyte, etc. The chemistry of the electrolyte-electrode interface is also a crucial factor.

Electrodes constructed as smooth planar sheets of metal have the least surface area. The area can be increased by using a woven mesh or porous or sintered metals. In this case faradaic impedance may be more appropriately modeled as a transmission line consisting of resistors in series coupled by capacitors in parallel.

Dielectric spectroscopy

Over the past two decades faradaic impedance has emerged as the basis for an important technique in a form of spectral analysis applicable to a wide variety of materials. This technique depends on the capacitive component of faradaic impedance. Whereas the resistive component is independent of frequency and can be measured with DC, the impedance of the capacitive component is infinite at DC (zero admittance) and decreases inversely with frequency of an applied AC signal. Varying this frequency while monitoring the faradaic impedance provides a method of spectral analysis of the composition of the materials at the electrode-electrolyte interface, in particular their electric dipole moment in the role of dielectric of a capacitor. The technique yields insights into battery design, the performance of novel fuel cell designs, biomolecular interactions, etc.

See also

Related Research Articles

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Electrolytic capacitor Type of capacitor

An electrolytic capacitor is a polarized capacitor whose anode or positive plate is made of a metal that forms an insulating oxide layer through anodization. This oxide layer acts as the dielectric of the capacitor. A solid, liquid, or gel electrolyte covers the surface of this oxide layer, serving as the cathode or negative plate of the capacitor. Due to their very thin dielectric oxide layer and enlarged anode surface, electrolytic capacitors have a much higher capacitance-voltage (CV) product per unit volume than ceramic capacitors or film capacitors, and so can have large capacitance values. There are three families of electrolytic capacitor: aluminum electrolytic capacitors, tantalum electrolytic capacitors, and niobium electrolytic capacitors.

Practical capacitors and inductors as used in electric circuits are not ideal components with only capacitance or inductance. However, they can be treated, to a very good degree of approximation, as being ideal capacitors and inductors in series with a resistance; this resistance is defined as the equivalent series resistance (ESR). If not otherwise specified, the ESR is always an AC resistance, which means it is measured at specified frequencies, 100 kHz for switched-mode power supply components, 120 Hz for linear power-supply components, and at its self-resonant frequency for general-application components. Additionally, audio components may report a "Q factor", incorporating ESR among other things, at 1000 Hz.

Internal resistance

A practical electrical power source which is a linear electric circuit may, according to Thévenin's theorem, be represented as an ideal voltage source in series with an impedance. This impedance is termed the internal resistance of the source. When the power source delivers current, the measured voltage output is lower than the no-load voltage; the difference is the voltage drop caused by the internal resistance. The concept of internal resistance applies to all kinds of electrical sources and is useful for analyzing many types of electrical circuits.

Dielectric spectroscopy

Dielectric spectroscopy measures the dielectric properties of a medium as a function of frequency. It is based on the interaction of an external field with the electric dipole moment of the sample, often expressed by permittivity.

Capacitor types Customary components for use in electronic equipment

Capacitors are manufactured in many forms, styles, lengths, girths, and from many materials. They all contain at least two electrical conductors separated by an insulating layer. Capacitors are widely used as parts of electrical circuits in many common electrical devices.

Capacitor Passive two-terminal electronic component that stores electrical energy in an electric field

A capacitor is a device that stores electrical energy in an electric field. It is a passive electronic component with two terminals.

Test probe

A test probe is a physical device used to connect electronic test equipment to a device under test (DUT). Test probes range from very simple, robust devices to complex probes that are sophisticated, expensive, and fragile. Specific types include test prods, oscilloscope probes and current probes. A test probe is often supplied as a test lead, which includes the probe, cable and terminating connector.

Ceramic capacitor

A ceramic capacitor is a fixed-value capacitor where the ceramic material acts as the dielectric. It is constructed of two or more alternating layers of ceramic and a metal layer acting as the electrodes. The composition of the ceramic material defines the electrical behavior and therefore applications. Ceramic capacitors are divided into two application classes:

Randles circuit

A Randles circuit is an equivalent electrical circuit that consists of an active electrolyte resistance RS in series with the parallel combination of the double-layer capacitance Cdl and an impedance of a faradaic reaction. It is commonly used in Electrochemical impedance spectroscopy (EIS) for interpretation of impedance spectra, often with a Constant phase element (CPE) replacing the double layer capacity (Cdl). The Randles equivalent circuit is one of the simplest possible models describing processes at the electrochemical interface. In real electrochemical systems, impedance spectra are usually more complicated and, thus, the Randles circuit may not give appropriate results.

Double layer (surface science) Condensed matter physics

A double layer is a structure that appears on the surface of an object when it is exposed to a fluid. The object might be a solid particle, a gas bubble, a liquid droplet, or a porous body. The DL refers to two parallel layers of charge surrounding the object. The first layer, the surface charge, consists of ions adsorbed onto the object due to chemical interactions. The second layer is composed of ions attracted to the surface charge via the Coulomb force, electrically screening the first layer. This second layer is loosely associated with the object. It is made of free ions that move in the fluid under the influence of electric attraction and thermal motion rather than being firmly anchored. It is thus called the "diffuse layer".

Applications of capacitors Uses Of Capacitors In Daily Life.

Capacitors have many uses in electronic and electrical systems. They are so ubiquitous that it is rare that an electrical product does not include at least one for some purpose.

Tantalum capacitor

A tantalum electrolytic capacitor is an electrolytic capacitor, a passive component of electronic circuits. It consists of a pellet of porous tantalum metal as an anode, covered by an insulating oxide layer that forms the dielectric, surrounded by liquid or solid electrolyte as a cathode. Because of its very thin and relatively high permittivity dielectric layer, the tantalum capacitor distinguishes itself from other conventional and electrolytic capacitors in having high capacitance per volume and lower weight.

Polymer capacitor Solid conductive electrolyte

A polymer capacitor, or more accurately a polymer electrolytic capacitor, is an electrolytic capacitor (e-cap) with a solid conductive polymer electrolyte. There are four different types:

Supercapacitor Electrochemical capacitor

A supercapacitor (SC), also called an ultracapacitor, is a high-capacity capacitor with a capacitance value much higher than other capacitors, but with lower voltage limits, that bridges the gap between electrolytic capacitors and rechargeable batteries. It typically stores 10 to 100 times more energy per unit volume or mass than electrolytic capacitors, can accept and deliver charge much faster than batteries, and tolerates many more charge and discharge cycles than rechargeable batteries.

Film capacitor Electrical capacitor with an insulating plastic film as the dielectric

Film capacitors, plastic film capacitors, film dielectric capacitors, or polymer film capacitors, generically called film caps as well as power film capacitors, are electrical capacitors with an insulating plastic film as the dielectric, sometimes combined with paper as carrier of the electrodes.

Pseudocapacitance

Pseudocapacitance is the electrochemical storage of electricity in an electrochemical capacitor (Pseudocapacitor). This faradaic charge transfer originates by a very fast sequence of reversible faradaic redox, electrosorption or intercalation processes on the surface of suitable electrodes. Pseudocapacitance is accompanied by an electron charge-transfer between electrolyte and electrode coming from a de-solvated and adsorbed ion. One electron per charge unit is involved. The adsorbed ion has no chemical reaction with the atoms of the electrode since only a charge-transfer takes place.

Double-layer capacitance is the important characteristic of the electrical double layer which appears, for example, at the interface between a conductive electrode and an adjacent liquid electrolyte. At this boundary two layers of charge with opposing polarity form, one at the surface of the electrode, and one in the electrolyte. These two layers, electrons on the electrode and ions in the electrolyte, are typically separated by a single layer of solvent molecules that adhere to the surface of the electrode and act like a dielectric in a conventional capacitor. The amount of electric charge stored in double-layer capacitor depends on the applied voltage. The unit of capacitance is the farad.

SAL electrolytic capacitor Capacitor with high capacitance in a small package

SAL electrolytic capacitors are a form of capacitor developed for high capacitance in a small package, with a long and robust service life. They are aluminum electrolytic capacitors with anodic oxidized aluminum oxide as dielectric and with the semiconducting solid manganese dioxide as electrolyte. They are made of etched and formed aluminum anodes, which are folded for the dipped pearl types or wound into a roll for the axial style. The solid manganese dioxide electrolyte is formed onto this roll in a pyrolytic process, similar to that for solid tantalum capacitors.

Aluminum electrolytic capacitor Type of capacitor

Aluminium capacitors are polarized electrolytic capacitors whose anode electrode (+) is made of a pure aluminum foil with an etched surface. The aluminum forms a very thin insulating layer of aluminium oxide by anodization that acts as the dielectric of the capacitor. A non-solid electrolyte covers the rough surface of the oxide layer, serving in principle as the second electrode (cathode) (-) of the capacitor. A second aluminum foil called “cathode foil” contacts the electrolyte and serves as the electrical connection to the negative terminal of the capacitor.

References

  1. "Archived copy" (PDF). Archived from the original (PDF) on 2014-11-27. Retrieved 2015-03-22.{{cite web}}: CS1 maint: archived copy as title (link)
  2. "Archived copy" (PDF). ocw.mit.edu. Archived from the original (PDF) on 13 February 2015. Retrieved 13 January 2022.{{cite web}}: CS1 maint: archived copy as title (link)