Biopotential Electrodes Material from M. ODonnell, U. Mich. and Webster 1.

0 Introduction - Biopotential Electrodes

One of the most common biomedical sensors is simply an electrode to measure and record potentials and currents in the body. This seems to be a very simple function, but in fact an electrode recording biopotentials is actually a transducer, converting ionic currents in the body into electronic currents in the electrode. This transduction function greatly complicates electrode design. To understand how such electrodes work, we first must discuss some of the basic properties of an electrode-electrolyte interface.

1.1

Electrode-Electrolyte Interface

The electrode-electrolyte interface is illustrated below. The electrode only has one type of charge carrier (electron), whereas the electrolyte has two types of charge carriers (cation and anion). The direction of current flow is noted in the figure. For charge to cross the interface, something must happen at the interface since there are no free electrons in the electrolyte and there are no cations or anions in the electrode.

At the interface, charge is exchanged through chemical reactions, which can be generally represented as: C C n+ + neA m- A + mewhere n is the valence of C and m is the valence of A. Note this equation assumes that the electrode contains some atoms of the same material as the cation and that this material in the electrode at the interface can become oxidized to from a cation and one or more free electrons. Similarly, an anion coming to the electrode-electrolyte interface can be oxidized to a neutral atom, giving off one or more free electrons to the electrode.
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To better understand this interaction, consider what happens when we place a piece of metal into a solution containing ions of that metal. These ions are cations, and the solution must have an equal number of anions to insure electrical neutrality of the solution. Initially the cation reaction above goes predominately to the left or right depending on the concentration of cations in solution and the equilibrium conditions for that particular reaction. The local concentration of cations in the solution at the interface changes, which affects the anion concentration as well. The net result is that charge neutrality is not maintained, and the electrolyte surrounding the metal is at a different electric potential from the rest of the solution. This is true even when no current flows across the interface. A potential difference know as the half-cell potential is determined by the metal involved, the concentration of its ions in solution, and the temperature. The standard half cell potential, E0, is the potential for 1M concentration solution at 25 C when no current flows across the interface. This potential cant be measured in the lab since two electrodes are needed to make this measurement (i.e., induce a current). To avoid this problem, electrochemists have adopted the convention that the standard half cell potential is the potential difference between a particular electrode in 1M solution to a hydrogen electrode in 1M solution. The hydrogen electrode is based on the reaction H 2 2H 2H + + 2e where H2 gas bubbled over a platinum electrode is the source of hydrogen molecules.

1.2

Polarization

In normal operation, the potential difference from the standard half-cell potential (i.e., half-cell potential) is determined primarily by temperature and ionic activity of the electrolyte. Ionic activity can be defined as the availability of an ionic species to enter into reaction. This process is often characterized by the reaction rate k. The reaction rate for a process overcoming an energy barrier G is k = e - G/RT where R is the natural gas constant and T is the temperature in K. For an electrodeelectrolyte interface, the energy barrier describes ionic dissociation across the interface. The electrical energy associated with this energy barrier is simply the product of free charge and the electrical potential (i.e., half-cell potential). Therefore, the energy barrier G is related to the potential as G = qV = n F E where n is the valence of the relevant ion, E is the potential change across the interface, and F is the Faraday constant. Using these two equations, the reaction rate related to the electrical potential difference across the interface (i.e., half-cell potential) RT E = ln(k) nF This is the famous Nernst equation of electrochemistry.

The Nernst equation can help analyze the electrode-electrolyte interaction. Consider a biopotential electrode system described by the general oxidation-reduction reaction A + B C + D + ne where n electrons are transferred. The reaction rate for this reaction is simply related to the ratio of the activities of the products to the activities of the reactants, leading to the general equation for the potential across the interface: RT a C a D E = E ln( ) nF aA a B
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where the as are the appropriate activities. Similar expressions can be found for electrolyte-electrolyte interfaces. When a circuit is constructed which allows current to flow across an electrodeelectrolyte interface, the observed half-cell potential is often altered. The difference between the observed half-cell potential for a particular circuit and the standard half cell potential is known as the overpotential. Three basic mechanisms contribute to the overpotential: ohmic, concentration, and activation. The ohmic overpotential is the voltage drop across the electrolyte itself due to the finite resistivity of the solution. These ohmic losses need not be linear with current this is especially true in low concentration electrolytes. Overall, this is usually not a big voltage in high concentration solutions. The concentration overpotential results from changes in ionic concentration near the electrode-electrolyte interface when current flows. With excess charge due to a finite current, oxidation-reduction reaction rates at the interface change, altering the equilibrium concentration of ions - this changes the half-cell potential. Charge transfer in the oxidation-reduction reaction at the interface is not entirely reversible. For metal ions to be oxidized, they must overcome an energy barrier. If the direction of current flow is one way, then either oxidation or reduction dominates, and the height of the barrier changes. This energy difference produces a voltage between the electrode and the electrolyte, known as the activation overpotential.

These three polarization mechanisms add, yielding the overpotential of an electrode: Vp = Vr + Vc + Va where Vr is the ohmic overpotential, Vc is the concentration overpotential, and Va is the activation overpotential. Note that overpotentials impede current flow across the interface. The example on the following page illustrates how overpotentials play a part in electrode-electrolyte systems.

1.3

Polarizable and Nonpolarizable Electrodes

There are two basic types of biopotential electrodes. Perfectly polarizable electrodes do not allow conduction current to flow across a electrode-electrolyte interface when a current is applied. The current across the interface for this electrode, therefore, must be a displacement current (i.e., electric field coupled). Perfectly nonpolarizable electrodes allow conduction current to flow across the interface with no energy exchange (i.e., there are no overpotentials for this type of electrode). In practice, neither of these ideal configurations can be produced, but there are several electrode types that can approach the ideal. In this course we will only be interested in systems approaching the nonpolarizable ideal. This means we must investigate electrodes minimizing the overpotential, such as the silver/silver chloride ones. The structure of silver/silver chloride (Ag/AgCl) electrode is illustrated in the figure below. A silver metal base with attached insulated lead wire is coated with a layer of the ionic compound AgCl. (Silver chloride is only very slightly soluble in water, so it remains stable.) The electrode is then immersed in an electrolyte bath in which the principle anion of the electrolyte is Cl-. For the best results, the electrolyte solution should also be saturated with AgCl so there is little chance for any of the surface film on the electrode to dissolve. Cl- is an attractive anion for electrode applications with mammals since these animals (including humans) have an excess of chloride ions in solution. The electrode-electrolyte interaction is described by the reaction Ag Ag + + e Ag + + Cl - AgCl (precipitate)

Silver ions on the electrode surface oxidize to silver ions in solution at the interface. These ions combine with Cl- already in solution to form the ionic compound AgCl. Silver chloride is only very slightly soluble in water, so most of it precipitates out of solution onto the silver electrode and contributes to a silver chloride deposit.

The precipitation rate, and rate of returning to solution, is described by the constant Ks, know as the solubility product. Under equilibrium conditions the product of the ionic activities of the Ag+ and Cl- ions must equal the solubility product: a Ag + x a Cl- = K s As noted above, in biological fluids the concentration of Cl- is relatively high, which gives it an activity slightly less than unity. The solubility product for AgCl, however, is on the order of 10-10. This means when a Ag/AgCl electrode is in contact with biological fluids, the activity of the Ag+ ion must be very low and of the same order as the solubility product. This means the half-cell potential can be approximated as RT E = E0 + ln(a Ag + ) nF Or, using the definition of the solubility product RT K E = E0 + ln( s ) nF a ClRT RT ln(K s ) ln(a Cl- ) nF nF The first two terms on the right side of this last expression are constants - only the third is related to ionic activity. In biological systems, the large chlorine ion concentration makes its activity fairly constant. This means that the half-cell potential for this electrode is quite stable for biological systems. One method to fabricate Ag-AgCl electrodes is illustrated in the example below. The ammeter is included in this circuit to monitor the reaction rate, since the reaction rate is proportional to the current. When the switch is closed, the silver oxidation reaction with concomitant silver chloride precipitation occur and the current jumps to its maximal value. As the thickness of the deposited AgCl layer increases, the reaction rate decreases and the current drops. This process continues, and the current approaches zero asymptotically. E = E0 +
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An alternate process uses sintering to form pellet electrodes, as shown in the figure on the next page. The electrode consists of an Ag lead wire surrounded by a sintered Ag/AgCl cylinder. It is formed by placing the cleaned wire in a die filled with a mixture of powdered Ag and AgCl. The die is compressed into a pellet, and baked at 400 C for several hours.

1.4

Electrode Behavior and Circuit Models

The current-voltage relation across an electrode-electrolyte interface is often nonlinear, especially for high current densities. In this course we will only consider low current densities, and consequently the electrode-electrolyte interface can be modeled as a linear system with an equivalent circuit composed exclusively of linear components (i.e., voltage/current sources, resistors, capacitors and inductors). The terminal characteristics of an electrode have both resistive and reactive components. Over most frequencies, the response can be modeled as a series resistance and capacitance. However, this simple model does not adequately describe the response at low frequencies. To avoid this problem, we can convert the series RC to a parallel RC with a purely resistive impedance at low frequencies. This equivalent circuit is shown in the figure below. In this circuit Rd and Cd represent the resistance (i.e., conduction currents) and the capacitance (i.e., displacement currents) respectively resulting from the double-layer of ionic charge at the electrode-electrolyte interface. The resistance Rs is the series resistance associated with equivalent losses in the electrolyte itself.

The frequency dependence of the impedance of this equivalent circuit is presented below. In this figure the impedance of a silver/silver chloride electrode is contrasted with that of a pure silver electrode. Note the strikingly different performance at low frequencies. The AgCl layer produces an almost perfectly nonpolarizable electrode providing a strong conduction current path with nearly constant impedance over a large frequency range.

Finally, the Ag/AcCl electrode is nearly the best for all possibilities for biological electrode systems. For example, the frequency dependence of the impedance of a nickeland carbon-loaded silicone rubber is presented in the figure below. Note the high DC impedance and the low cutoff frequency compared to the Ag/AcCl electrode. In practice, nearly all macroscopic electrodes used for biomedical applications are Ag/AcCl.

1.5

Electrode-Skin Interface and Motion Artifacts

In coupling a Ag/AgCl electrode to the skin, a transparent gel containing Cl- as the principal ion is used to maintain good contact. The interface between the electrode and the gel is an electrode-electrolyte interface of the type described above. However, the interface between the electrolyte and the skin is quite different, as illustrated below.

There are three primary layers in the skin. The outermost layer, or epidermis, plays the most important role in the electrode-skin interface. It is a constantly changing layer, the

outer surface of which consists of dead material on the skins surface with different electrical characteristics from live tissue. The deeper layers of skin contain the vascular and nervous components of the skin as well as the sweat glands, ducts, and hair follicles. These layers are similar to others in the body, and with the exception of the sweat glands, can be modeled as equivalent to the electrical characteristics of the rest of the viscera. Given this anatomy, a general equivalent circuit describing the characteristics of both the electrode-electrolyte interaction and the connection to the skin can be developed, as illustrated in the figure below.

The resistance Rs represents interface losses within the gel/epidermis interface. The epidermis can be considered a semipermeable membrane to ions, so a potential Ese, given by the Nernst equation, can be developed if there is a difference in ionic concentrations across this membrane. This layer also behaves as a parallel RC circuit, where the skin impedance reduces from approximately 200 k at 1 Hz to 200 at 1 MHz. The dermis and subcutaneous layer under it behave in general as pure resistances. They generate negligible DC potentials. To reduce the influence of Ese, Re and Ce on the connection, the outer layer of the epidermis is often removed by abrasion . Finally, the electrical characteristics of the sweat glands most also be taken into account for a complete model of a skin electrode. The fluid secreted by sweat glands contains Na+, K+, and Cl- ions, the concentrations of which differ from those in extracellular fluid. This produces a potential between the lumen of

the sweat duct and the dermis and subcutaneous layers. There is also a parallel RpCp combination with this potential representing the wall of the sweat gland and duct. When a polarizable electrode is in contact with an electrolyte, space charge forms in two layers at the interface to produce the half-cell potential and a capacitive reactance for current flow. If the electrode is moved so that the space charge distribution is altered, then there is momentary change of the half-cell potential until equilibrium is reestablished. If an electrode pair is in an electrolyte and one moves with respect to the other, a potential difference appears between the two electrodes during this movement. This potential is a motion artifact associated with a polarizable electrode and can be a serious interference source in recording biopotentials. From the equivalent circuit, there are two potential sources of motion artifact: Ehe and Ese. To minimize these effects, the polarizability of the electrode-skin interface must be reduced. The best way to do this is to insure good contact between the electrode and the inner layers of the epidermis, meaning that something must be done to the skin surface (i.e., abrasion) to minimize polarization.

1.6

Recording Electrodes for Biomedical Applications

One of the most frequently used biopotential electrodes is the metal plate electrode, as illustrated in the figure below. In this figure, several configurations are presented. The most common for skin-surface recording is the snap electrode, illustrated in panel (c). It consists of a relatively large disk of plastic foam material with a silver plated disk on one side attached to a silver platted snap on the other side. A lead wire with the female portion of the snap is then snapped onto the electrode and used to connect the assembly to the monitoring apparatus. The silver plated disk serves as the electrode and should be coated with an AgCl layer. A layer of electrolyte gel covers the disk. The electrode side of the foam is covered with an adhesive material compatible with the skin.

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A modification of the metal-plate electrode requiring no straps or adhesives is the suction electrode illustrated below. Electrolyte gel is placed over the contacting surface of the electrode, the bulb is squeezed, and the electrode is then placed on the body, usually on the chest wall for electrocardiography. Because these electrodes can irritate the skin, they are only used for quick contact recordings, such as in an emergency setting.

To minimize motion artifacts, floating electrodes are often used. The figure below presents an example of one of these devices. The actual electrode is recessed in a cavity so that it doesnt come into contact with the skin itself. Instead, the electrode is surrounded by electrolyte gel in the cavity. The cavity does not move with respect to the metal disk, so it doesnt produce any mechanical movement of the space charge layer between the electrode and gel. As long as there is good contact across the skin line, motion artifacts are greatly reduced with this design.

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One other common electrode type for body-surface recording is the flexible electrode illustrated in the figure below. The idea of this electrode is to conform better to the nonplanar body surface. Such flexible electrodes are most important in recording biopotentials on infants and young children who do not have large, flat areas on the skin surface for contact with conventional electrodes.

The electrode configurations presented above represent a subset of recording and stimulating electrodes used throughout medicine and biomedical research. The final few sections of Chapter 5 in the book present a number of examples of internal electrodes, electrode arrays, microelectrodes (e.g., electrodes used in MEMS devices), and actuator electrodes (i.e., stimulator electrodes). These devices are beyond the scope of this course but they function using exactly the same principles as the simple Ag/AgCl electrode systems presented above for surface recording of biopotentials.

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