Solid electrolyte sensors

Figure 1. Schematic of oxygen sensor solid electrolyte galvanic cell...

Naj -alumina Stillwell (1926) oxygen sensor Solid electrolyte. 

Inchemical sensors, solid electrolytes functionastransducersbyprovidingarelationship between chemical species and electrons, so that an electrical signal corresponding to the concentration of a particular chemical species is produced. This signal can be either a voltage or current, depending on the configuration in which the solid electrolyte is used. 

The major part of the volumes consists of a careful description of basic sensors in Chapters 7-13. They include liquid electrolyte sensors, solid electrolyte sensors, electronic conductivity and capacitance sensors, field effect sensors, calorimetric sensors, optochemical sensors, and mass sensitive sensors. 

Active enzymes were encapsulated into a sol-gel matrix for the first time in 1990 719 About 60 different types of hybrid bioceramic materials with inotganic matrices made from silicon, titanium, and zirconium oxides Ti02-cellulose composites etc. were described. Recentiy, bioceramic sensors, solid electrolytes, electrochemical biosensors, etc. have been surveyed in a review. The moderate temperatures and mild hydrolytic and polymerization conditions in sol-gel reactions of alkoxides make it possible to trap proteins during matrix formation. This prevent proteins denaturation. The high stability of the trapped biomolecules, the inertness, the large specific surface, the porosity, and the optical transparency of the matrix facilitate use of sol-gel immobilization. The principal approaches ate considered below. 

Parameter Severinghaus electrode Conductivity sensor Solid electrolyte sensor NDIR sensor... 

In the ceramics field many of the new advanced ceramic oxides have a specially prepared mixture of cations which determines the crystal structure, through the relative sizes of the cations and oxygen ions, and the physical properties through the choice of cations and tlreh oxidation states. These include, for example, solid electrolytes and electrodes for sensors and fuel cells, fenites and garnets for magnetic systems, zirconates and titanates for piezoelectric materials, as well as ceramic superconductors and a number of other substances... 

Yamazoe, N. and Miura, N. (1999) Gas sensors using solid electrolytes, MRS Bull. 24(6), 37... 

FIGURE 13.52 (a) Solid electrolyte and (b) arrangement of the zirconia sensor. 

Progress in the development of solid electrolytes is also being achieved from advances in several other fields of technology such as fuel and electrolysis cells, thermoelectric converters, electrochromic devices, and sensors for many chemical and physical quantities. 

Today, the term solid electrolyte or fast ionic conductor or, sometimes, superionic conductor is used to describe solid materials whose conductivity is wholly due to ionic displacement. Mixed conductors exhibit both ionic and electronic conductivity. Solid electrolytes range from hard, refractory materials, such as 8 mol% Y2C>3-stabilized Zr02(YSZ) or sodium fT-AbCb (NaAluOn), to soft proton-exchange polymeric membranes such as Du Pont s Nafion and include compounds that are stoichiometric (Agl), non-stoichiometric (sodium J3"-A12C>3) or doped (YSZ). The preparation, properties, and some applications of solid electrolytes have been discussed in a number of books2 5 and reviews.6,7 The main commercial application of solid electrolytes is in gas sensors.8,9 Another emerging application is in solid oxide fuel cells.4,5,1, n... 

When a solid electrolyte component is interfaced with two electronically conducting (e.g. metal) films (electrodes) a solid electrolyte galvanic cell is formed (Fig. 3.3). Cells of this type with YSZ solid electrolyte are used as oxygen sensors.8 The potential difference U R that develops spontaneously between the two electrodes (W and R designate working and reference electrode, respectively) is given by ... 

T. Arakawa, A. Saito, and J. Shiokawa, Surface study of a Ag electrode on a solid electrolyte used as oxygen sensor, Applications of Surface Science 16, 365-372 (1983). 

W. Gopel, and H.-D. Wiemhofer, Electrode kinetics and interface analysis of solid electrolytes for fuel cells and sensors, Ber. Buns. Phys. Chem. 94, 981-987 (1990). 

The stability of ceramic materials at high temperatures has made them useful as furnace liners and has led to interest in ceramic automobile engines, which could endure overheating. Currently, a typical automobile contains about 35 kg of ceramic materials such as spark plugs, pressure and vibration sensors, brake linings, catalytic converters, and thermal and electrical insulation. Some fuel cells make use of a porous solid electrolyte such as zirconia, Zr02, that contains a small amount of calcium oxide. It is an electronic insulator, and so electrons do not flow through it, but oxide ions do. 

When analyzing hot gases for their hydrogen snlfide content, for instance, a solid electrolyte sensor consisting of the galvanic cell... 

A similar device with Nasicon solid electrolyte Na3Sc(P04)3 is used when analyzing the concentration of nitrogen oxides in air. The electrochemical system in this sensor can be formnlated as... 

Doped zirconium dioxide is the solid electrolyte in lambda sensors (oxygen sensors used in the field of environmental protection). 

Electrochemical cells where ions dissipate through a solid electrolyte are mainly used for measuring oxygen concentrations. The most common sensors based on this principle are the A-probe for monitoring combustion engines in motor vehi-... 

Besides these potentiometric sensors there are also amperometric sensors using the principle of ion conductive solid electrolytes. In addition to the heating voltage those sensors are also equipped with a second voltage supply, inducing a current, which varies depending on the concentration of the test gas. Fig. 3.19 shows a schematic view of these so-called saturating current probe. 

Kaneyasu, J. Otsuka, K. Setoguchi, Y. Sonoda, S. Nakahara, T. Aso, I. Naka-gaichi, N. A carbon dioxide gas sensor based on solid electrolyte for air quality control. Sensors and Actuators B, 66 (2000) 1-3, p. 56-58. 

A key factor in the possible applications of oxide ion conductors is that, for use as an electrolyte, their electronic transport number should be as low as possible. While the stabilised zirconias have an oxide ion transport number of unity in a wide range of atmospheres and oxygen partial pressures, the BijOj-based materials are easily reduced at low oxygen partial pressures. This leads to the generation of electrons, from the reaction 20 Oj + 4e, and hence to a significant electronic transport number. Thus, although BijOj-based materials are the best oxide ion conductors, they cannot be used as the solid electrolyte in, for example, fuel cell or sensor applications. Similar, but less marked, effects occur with ceria-based materials, due to the tendency of Ce ions to become reduced to Ce +. 

Electrochemical cells are of two types power cells and sensors. In an ideal power cell, the ionic current through the electrolyte inside the cell matches an electronic current through an external load. The solid electrolyte is in the form of a membrane of thickness L and area A that separates electronically the two electrodes of the cell. Any internal electronic current across the electrolyte reduces the power output. The internal resistance to the ionic current is... 

In the early part of this century, many types of solid electrolyte had already been reported. High conductivity was found in a number of metal halides. One of the first applications of solid electrolytes was to measure the thermodynamic properties of solid compounds at high temperatures. Katayama (1908) and Kiukkola and Wagner (1957) made extensive measurements of free enthalpy changes of chemical reactions at higher temperatures. Similar potentiometric measurements of solid electrolyte cells are still made in the context of electrochemical sensors which are one of the most important technical applications for solid electrolytes. 

Different types of sensor based on solid electrolytes have been developed following a report by Kiukkola and Wagner (1957). These sensors are based on one of two principles (a) the chemical potential difference across the solid electrolyte (potentiometric sensor), or (b) the charge passed through the electrolyte (amperometric sensor). In the following galvanic cell,... 

Generally, in solid electrolytes, ionic conductivity is predominant (( = 1) only over a limited chemical potential. The electrolytic conductivity domain is an important factor limiting the application of solid electrolytes in electrochemical sensors. 

The most thoroughly developed sensor based on a solid electrolyte is the oxygen sensor using a stabilised zirconia electrolyte. This type of sensor is one of the most successful commercial sensors to date. They are widely used in industry, especially in the analysis of exhaust gases from combustion engines. The following configuration is used in the Oj sensors ... 

To reduce the working temperature for solid electrolyte oxygen sensors, fluoride electrolytes have been proposed. Such sensors are composed of the following cell (Sibert, Fouletier and Vilminot, 1983),... 

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