METHOD OF OPERATING AN AIR-FUEL RATIO SENSOR

Abstract: An air-fuel ratio sensor installed in exhaust gas emitted by an internal combustion engine for detecting from the exhaust composition on the air-fuel ratio in the engine becoming equal to a stoichiometric air-fuel ratio. The sensor comprises a solid electrolytic layer of zirconia (10), a pair of electrodes (20, 30) formed on both sides of the electrolytic layer, and a cover (70) provided over the electrolytic layer to enclose one of the electrodes, with a diffusion room formed between the cover and the electrolytic layer and with a gas diffusion hole (5) formed to communicate the diffusion room with the outside of the sensor. The electrode (20) in the diffusion room works as a positive electrode, while another electrode (30) works as a negative electrode to conduct a current (Ip) between these electrodes so as to control the oxygen concentration in the diffusion room as a reference oxygen concentration. The fact that the air-fuel ratio has become equal to the stoichiometric air-fuel ratio is detected from a voltage (Eo) appearing between the electrodes.

Description: AIR-FUEL RATIO SENSOR USED TO CONTROL AN INTERNAL COMBUSTION ENGINE The present invention relates to an air-fuel ratio sensor for detecting the air-fuel ratio in an automobile engine becoming equal to the stoichiometric air-fuel ratio on the basis of the composition of exhaust emission of the engine, and more particularly to an air-fuel ratio sensor for use in controlling án automobile engine, wherein the oxygen concentration in a diffuser provided within the sensor is controlled so that it is used as a reference of measurement and the fact that the air-fuel ratio has become equal to the stoichiometric air-fuel ratio is detected from the electromotive force generated in re response to the difference between the oxygen concentration in the exhaust emission and in the diffuser. In order to detect that the air-fuel ratio in the automobile engine has become equal to the stoichiometric air-fuel ratio (with the excess air factor A=1) on the basis of the composition of exhaust emission, there have been used conventionally an oxygen sensor incorporating a pair of platinum electrodes having catalytic action and a solid electrolyte of zirconia. This type of oxygen sensor is arranged to have one platinum electrode exposed to the exhaust emission and another electrode to the atmosphere, and the state of A=1 is detected by the "atmospheric reference method", in which an electromotive force is produced in response to the difference between the oxygen partial pressure in the exhaust gas and that of the atmosphere. However, this oxygen sensor on the basis of the atmospheric reference method is complex and bulky in structure, and hence it is costly. To cope with these problems there has been proposed an oxygen sensor, wherein the sensor is totally exposed to the exhaust emission, with one electrode made of noncatalytic gold and another electrode of platinum. However, the gold electrode is not durable (reliable) enough to withstand a severe operating environment of the oxygen sensor, and the realization of this sensor is unpracticable. Another oxygen sensor proposed is that wherein the sensor is totally exposed to the exhaust gas with one platinum electrode being exposed to the exhaust gas, while the reference oxygen concentration is created at another platinum electrode by utilization of the oxygen pumping phenomenon. The oxygen pumping is referred to as the conveyance of oxygen from a positive electrode to a negative electrode, both attached to a solid electrolyte, through the conduction of a current for moving oxygen ions from the negative to positive electrodes across the solid electrolyte. Japanese Patent Apptication Laid-open Publication No. 69690/77 discloses the oxygen sensor utilizing the oxygen pumping phenomenon, wherein the sensor comprises a solid electrolyte of zirconia and a reference oxygen room formed in the electorlyte, with the provision of a diffusion hole for diffusing oxygen into the room. The sensor is designed to operate to evacuate oxygen from the reference oxygen room by the oxygen pumping phenomenon and the oxygen concentration in the sensor environment is measured from the amount of oxygen introduced through the diffusion hole in response to the reduction of oxygen in the reference oxygen room. Japanese Patene Laid-open Publication No. 69690/77, discloses nothing about the concept of detecting the state of A=l. Japanese Patent Laid-open Publication No. 30681/80 discloses an oxygen sensor comprising two solid electrolytic cells of zirconia laminated together with a reference oxygen room and an evacuation hole for evacuating oxygen from the room being formed between the cells, wherein the oxygen concentration in the reference oxygen room-is controlled constantly and the environmental oxygen concentration is measured with respect to the reference. This sensor is for merely measuring the oxygen concentration in the atmosphere, and the publication describes nothing about the concept of detecting the state of A=1. Japanese Patent Laid-open Publication No. 111441/82 discloses an oxygen sensor having two cells, one use for oxygen pumping and the other for detecting the oxygen concentration in the atmosphere at the transitional point of a generated electromotive force. The device is designed to make variable the transitional point of electromotive force, and is not directed to detection of the state of X=1. In addition, this sensor has a complex laminated structure as in the case of Japanese Patent Laid-open Publication No. 30681/80. Japanese Patent Laid-open Publication No. 154450/80 discloses an oxygen sensor using two solid electrolytic cells of zirconia, one used for controlling oxygen pumping and the other for measurement. This sensor is designed to control, by introduction or evacuation, the oxygen partial pressure at a reference electrode located at the center of the laminated cells through the application of a voltage or current to the pump cell, so that the x is measured from the electromotive force of the detection cell. This method cannot avoid a complex structure due to the laminated cells, and the hermetic structure for the reference electrode conceivably causes the peeling of electrode or breakage of element due to a rising pressure when oxygen is introduced. Moreover, the porous electrode pressed between the layers will have a decreased surface area of gaseous domain where the electrode is in contact with oxygen molecules, resulting in a fallen catalytic activity, and a transitional output characteris- tic will hardly be attained. In addition, the solid electrolyte of zirconia used for the pump cell needs to be a porous sintered material, and its difficulty in control ling the manufacturing process suggests rather inferiour productivity. Japanese Patent Laid-open Publication Nos. 16419/79 and 156856/80 disclose oxygen sensors using a single cell working for both oxygen pumping and detection. In these sensors, a cell is placed on a substrate with a voltage or current applied to the cell so as to control the oxygen partial pressure in the vicinity of the electrode on the side in contact with the substrate, and the state of A=1 is detected from the electromotive force of the cell. This method also-employs a hermetic structure for the electrode interface, posing possibly problems of peeling electrode, broken element and falling catalytic activity as in the case of Japanese Patent Laid-open Publication No. 154450/80. An object of the present invention is to provide an air-fuel ratio sensor for use in controlling an internal combustion engine, with the intention of overcoming the foregoing prior art problems, wherein the sensor, which is totally exposed to the exhaust gas, is provided therein with a diffusion room in which the oxygen concentration is controlled by utilization of the oxygen pumping phenomenon, and the air-fuel ratio of the engine becoming the stoichiometric air-fuel ratio is detected from the generated electromotive force. The air-fuel ratio sensor according to the present invention comprises a solid state electrolytic layer of zirconia, a pair of electrodes formed on both sides of the electrolytic layer, a cover provided over the electrolytic layer to enclose one of the electrode with a diffusion room being formed between the electrolytic¯layer, and a gas diffusion hole for communicating the diffusion room with the outside of the sensor. A current is conducted between the positive electrode inside the diffusion room and the negative electrode provided outside so as to control the oxygen concentration in the diffusion room, and the fact that the air-fuel ratio has become the stoichiometric airfuel ratio is detected from the voltage between both electrodes produced in response to the difference between the oxygen concentration at the electrode in the diffusion room and that at another electrode exposed to the exhaust gas. The result of detection is used to control the airfuel ratio of the automobile engine. In this invention, the air-fuel sensor has a diffusion room provided around one of electrodes, which one is exposed to oxygen of reference concentration having a large surface area of gaseous domain so as to prevent its catalytic activity from falling, and a gas diffusion hole for preventing the peeling of electrode or the destruction of element that would otherwise occur due to a rising pressure in the diffusion room. The air-fuel sensor according to this invention can be fabricated by the thick-film process, that realizes miniaturization and cost reduction for the air-fuel sensor. The air fuel sensor of the type having a diffusion room and setting up the reference oxygen concentration in the diffusion room utilizing the oxygen pumping phenomenon introduces oxygen from the outside of the sensor, resulting in a slightly lower oxygen concentration at the exterior electrode than the oxygen concentration of the exhaust gas. This causes the sensor to respond to the oxygen concentration of the exhaust gas slightly higher than the point of stoichiometric air-fuel ratio, and in order to minimize this error, the current contributing to the oxygen pumping phenomenon needs to be reduced. The sensor provides on its electrode terminals an electromotive force arising in response to the difference between the oxygen concentration inside the diffusion room and outside the sensor, and this terminal voltage includes a voltage drop which is the product of the oxygen pumping current by the impedance of the zir conia electrolytic layer. The impedance of the zirconia electrolyte varies depending on the temperature, and the oxygen pumping current needs to be reduced also for. minimizing the effect of the impedance variation on the electrode terminal voltage. On the other hand, carbon monoxide in the exhaust gas diffuses into the diffusion room through the diffusion hole, causing the carbon monoxide to react with oxygen to produce carbon dioxide, that is a reversible reaction, and when the exhaust gas is rich, the quantity of oxygen contributing to the above reaction increases, resulting in a fall in the oxygen concentration in the diffusion room if less amount of oxygen is introduced by oxygen pumping, thus, in a less difference of oxygen concentration from that outside the sensor, that eventually results in a decreased sensor output. On this account, the oxygen pumping current needs to be set appropriately. The magnitude of current depends on the sectional area of the diffusion hole which prevents the deterioration or breakage of the device by the rising pressure in the diffusion room due to the introduction of oxygen. The inventors of this invention have confirmed through the experiment that by the provision of a diffusion hole with a sectional area about 1/100 or less the electrode area, the above-mentioned error in detecting the stoichiometric air-fuel ratio can be reduced, the effect of voltage drop across the zirconia layer can be minimized, and a fall in the electromotive force in a rich domain can be reduçedthereby providing practically satisfactory sensor characteristics. The pressure rise in the diffusion room was found fairly sustainable. These and other object5 and advantages of the present invention will become more apparent from the following description and drawings, in which: Fig. 1 is an illustration showing the principle of the air-fuel ratio sensor according to this invention used to control the internal combustion engine; Fig. 2 is a graph showing the current dependency of the output characteristics of the air-fuel ratio sensor; Fig. 3 is a graph showing the temperature dependency of the output characteristics of the air-fuel ratio sensor; Fig. 4 is a graph showing the effect of the magnitude of the constant current on the output of the air-fuel ratio sensor; Fig. 5 is a graph showing the experimental results of the prototype sensor; Figs. 6a and 6b are diagrams showing the shape of the gas diffusion hole provided in the prototype sensor; ; Fig. 7 is a diagram used to explain the fabricat ing process for the air-fuel ratio sensor; Fig. 8 is a graph showing the static charac terists of the prototype sensor; Fig. 9 is a graph showing the dynamic charac teristics of the prototype sensor; Fig. 10 is an illustration showing the principle of the practical air-fuel ratio sensor incorporating a heater; and Fig. 11 is a graph used to explain the effect of the size of the gas diffusion hole. The principle arrangement of the air-fuel ratio sensor according to this invention is shown in Fig. 1. The arrangement includes a solid electrolyte of zirconia (ZrO2), a platinum electrode 2 working as a positive electrode of the sensor, a platinum electrode 3 working as a negative electrode of the sensor, a diffusion room 4, a gas diffusion hole 5, a constant current source 6, and terminals 7 and 8 connected to the electrodes 2 and 3, respectively. - In the arrangement of Fig. 1, the voltage e between the terminals 7 and 8 is expressed as a function of the electromotive force E generated between the electrodes by the difference of oxygen partial pressure at both electrodes, the resistance r of the solid zirconia electrolyte, and the current Ip flowing from the current source 6 through the sensor, as follows. e = E + r Ip .......... (1) The electromotive force E is expressed by the Nernst's equation in terms of the oxygen partial pressure P1 at the three-phase interface of the negative electrode, i.e., a surface where the electrode, exhaust gas and zirconia are in contact with one another, the oxygen partial pressure P2 in the diffusion room 4, as follows. EMI10.1 where F is the Faraday constant, T is the absolute temperature, and R is the gas constant. The air-fuel ratio sensor according to this invention, which is totally exposed to the exhaust gas, provides and equal value for the P1 and P2 unless oxygen pumping takes place and, therefore, the electromotive force E is zero. On this account, the constant current source 6 is used to control the oxygen concentration in the diffusion room 4. When a constant current I is conducted from the positive p platinum electrode 2 to the negative platinum electrode 3, oxygen at the three-phase interface of the negative platinum electrode 3 and zirconia electrolyte 1 is ionized and attracted by the positive electrode, where ionized oxygen is oxidized by the platinum electrode 2 and restored to oxygen molecules. Namely, oxygen molecules at the negative electrode interface are injected into the diffusion room by the current excitation. The amount of oxygen molecules injected is determined by the value of the constant current Ip. The value of the current Ip does not always need to be constant. Due to the presence of oxygen and carbon monoxide flowing through the gas diffusion hole 5 into the diffusion room 4, the following well known reaction takes place in the diffusion room 4 as in the case of the reaction on the negative electrode. CO + 2 t CO2 (3) In the exhaust gas of the automobile engine, carbon monoxide is more inquantity than oxygen in a rich region where the excess air factor X is smaller than 1, and carbon monoxide is less than oxygen in a lean region where X is larger than or equal to 1.. Accordingly, in the rich region, oxygen is consumed by the reaction shown by Equation (3), and the diffusion room 4 needs to be supplied with much oxygen from the negative electrode through the conduction of the constant current Ip. Consequently, the positive electrode becomes to have a high oxygen concentration, while the negativ electrode interface approaches a state of oxyger deficiency due to the catalytic action of the platinum electrode, resulting in a higher electromotive force E. Conversely, in the lean region, oxygen is excessive and carbon monoxide is deficient at the negative electrode, resulting in a less difference of oxygen concentration in the diffusion room 4 and on the negative electrode interface, and the electromotive force given by Equation (1) is substantially zero. As a result, the state of Azl can be detected by injecting oxygen from the negative electrode to the diffusion room 4. Fig. 2 shows the output characteristics of the air-fuel ratio sensor according to this invention. As mentioned previously, the amount of oxygen injected into the diffusion room 4 is proportional to the value of the constant current Ip. Accordingly, an increased Ip causes the oxygen deficiency at the three-phase interface of the negative electrode to occur on the lean side, and the stepwise transition of electromotive force occurs notexactly at the excess air factor of X=l, but at a point shifted toward the lean region side. Therefore, it is necessary to choose the best value of Ip for preventing the shift of the transition point. Fig. 3 shows an example of the thermal characteristics of the inventive air-fuel ratio sensor. On the graph, temperature Temp 1 is lower than Temp 2, and the reason why the output voltage is higher at the lower temperature Temp 1 is that the zirconia electrolyte has increasing impedance as the temperature falls, and thus e ¯e voltage drop also increases by the influence of the ¯eCrrent Ip and the ohmic loss excessive voltage. To prevent the increased voltage drop, the current Ip must be made small. Fig. 4 shows the sensor output characteristics resulting from different values of the constant current Ip. On the graph, current Ip3 is larger than Ip4. The constant current Ip3 gives satisfactory output charac teristics throughout the excess air factor A, while the constant current Ip4 provides the lower output voltage as the value of X decreases. The reason of this phenomenon is that the amount of carbon monoxide in the exhaust gas increases in a rich region, that results in more carbon monoxide diffusing into the diffusion room, and a lack of injected oxygen necessary for the reaction of Equation (3) causes the oxygen concentrations at the positive electrode and negative electrode three-phase interfaces to become close, thus resulting in a falling electromotive force. As described above, the air-fuel ratio sensor has a problem of output transient shift toward the lean side with respect to the point of X=l and a problem of output reduction with the increase in the amount of dif fusing carbon monoxide in a rich region, all largely depending on the value of the constant current and the size of the gas diffusion hole. The oxygen concentration is con trolled by injecting oxygen from the negative electrode into the diffusion room, and the shape of gas diffusion hole relates to the problem of deterioration and desctuction of the device due to a rising pressure in the diffusion room. In view of these matters, the inventors of this invention have fabricated experimental air-fuel ratio sensors S1 and S2 with different diameters of gas diffusion hole, and confirmed the above-mentioned facts. Fig. 5 shows the result of the experiment. The shift of the detected value of X caused by the excitation current increases progressively as the current increases. The reason is that an increased current causes an increased oxygen injection into the diffusion room, resulting in a state of exygen deficiency on the negative electrode three-phase interface occurring at a point leaner than A=1, and consequently the value of X at which the sensor electromotive force makes a transition is also shifted to the lean side, as explained in connection with Fig. 2. Therefore, in order to minimize the shift of X at the output transition point, the value of constant current Ip must be made as small as possible. Making the Ip small is also favorable to prevent the increase of voltage drop caused by the increased impedance in the lower temperature range as shown in Fig. 3. The fact that Ip can be made small allows the gas diffusion hole to have a smaller diameter, that favors the miniaturization of the air-fuel ratio sensor. However, if the excitation current Ip is made extremely small, the oxygen injection into the diffision room 4 decreases, resulting disadvantageously in a falling output in a rich region due to the increased diffusion of carbon monoxide, as mentioned in connection with Fig. 4. The dashed line sections on the graph show the characteristics of this region, and the comparison of hole diameters, i.e., 0.12 mm for sensor S1 and 0.03 mm for sensor S2, indicates that the sensor S2 with the smaller diameter of gas diffusion hole can detect the point of A=1 more accurately. The aforementioned problem of deterioration and destruction of the device due to increased pressure in the diffuser, that would result from a smaller diameter of the gas diffusion hole, was examined for the sensor and it was confirmed that the maximum stress a in the laminated body of the sensor was so small as to be free from that problem. In conclusion, it was confirmed experimentally that the practically satisfactory sensor characteristics can be attained by setting the sectional area of the gas diffusion hole to about 1/100 or less the area of the negative electrode, although it depends on the length of the hole. Figs. 6a and 6b are a set of diagrams illustrating shape of the gas diffusion hole formed in the protype sensor, Fig. 6a showing the horizontal cross-section, Fig. 6b showing the longitudinal cross-section. Fig. 7 is a diagram used to explain the fabricating process for the air-fuel ratio sensor according to this invention. The diameter of the gas diffusion hole 5 is so small to be drilled or punched, and therefore it is formed in a lateral groove in the sensor cell as shown in Fig. 6b. The actual fatricating process for the sensor structure shown in Figs. 6a and 6b will be described briefly with reference to Fig. 7. First, on both sides of a green sheet of zirconia 10, platinum pastes 20 and 30 are printed so that electrodes with a thickness of about 10 pm are formed. Next, a carbon-inclusive organic binder 70 is printed at both ends of the platinum electrode 20, and ceramics 60 and 60' well adherent to the green sheet 10 are printed on the outside of the binder 70. The ceramics 60 and 60' may be of the same material as of the green sheet 10. Organic binder 70 is further printed over the ceramics 60' and platinum paste 20 so as to form diffusion hole and diffusion room. Then, it is overlaid by a green sheet cover member 10', that is heat pressed at about 2000C. In a state of rising temperature follow- * ing the heat pressing process, the organic binder 70 is burnt, and rooms for the gas diffusion hole and diffusion room are left. Finally, through the baking process at 15000C, the air-fuel ratio sensor as shown in Figs. 6a and 6b is completed. Figs. 8 and 9 show the output characteristics and response characteristics, respectively, of the airfuel ratio sensor fabricated as illustrated in Figs. 6a and 6b and Fig. 7. The device makes an output transition at the excess air factor of A=1 with little hydteresis. The device is responsive, showing the dynamic characteristics comparable with that of the currently available oxygen sensors. A shortcoming of air-fuel ratio sensors, including the one according to this invention, utilizing the oxygen pump phenomenon is that they do not operate in the low temperature range. On this account, the sensor needs to be heated up to the operable temperature range above 5000C when it is used. Fig. 10 shows, as an example, the air-fuel ratio sensor incorporating a heater. This heaters fabricated by the thick film process technology, and it is provided on both sides thereof with an insulation layer made of, for example, alumina so as to be insulated from the zirconia layer. The inventors of this invention have examined the influence of the size of the gas diffusion hole on the detection accuracy of the stoichiometric air-fuel ratio. Fig. 11 shows the result. On the graph, the value of X detected by a test sample which does not spoil the output in a rich region is plotted on the ordinate against the ratio of the electrode area to the sectional area of the gas diffusion hole. Examination was conducted using tens of test samples in different combinations of parametric dimensions, i.e., the area of electrode ranging 3-200 mm, the depth of diffusion room ranging 0.002-3 mm, and the length of gas diffusion hole ranging 0.1-7 mm. It was found that the values of X detected by these samples, i.e., the values of A at the transition of the sensor output, distribute within the hatched area of the graph. There was a trend of characteristics that the shorter the length of the gas diffusion hole, the larger was the amount of shift of detected X toward the lean side. Conceivably, the reason is a large amount of carbon monoxide diffusing into the diffusion room through the short gas diffusion hole. As can be seen from the graph, in order for a test sample to have an offset of X detection within few percent, the ratio of the electrode area to the sectional area of the diffusion hole must be at least 100. While particular embodiments of the invention have been shown and described, it will be obvious to those skilled in the art that various changes and modifications may be made without departing from the present invention in its broader aspects.

Claims: CLAIMS: 1. An air-fuel ratio sensor installed in exhaust gas emitted by an internal combustion engine for detecting from the exhaust gas composition that the air-fuel ratio in said engine has become a stoichiometric airfuel ratio, said sensor comprising: a solid electrolytic layer of zirconia (10); a pair of electrodes (20, 30) formed on both sides of said solid electrolytic layer; and a cover (70) provided on said solid electrolytic layer to enclose one of said electrodes, a diffusion room being formed between said cover and said solid electrolytic layer, and a gas diffusion hole for communicating said diffusion room.with the outside of said sensor, wherein a current (Ip) is conducted between the electrode (20) in said diffusion room as a positive electrode and another electrode (30) as a negative electrode so as to control the oxygen concentration in said diffusion room as a reference oxygen concentration, and fact that the air-fuel ratio has become equal to the stoichiometric air-fuel ratio is detected from a voltage (Eo) generated. between said electrodes. 2. A sensor according to claim 1, wherein the oxygen concentration at said positive electrode in said diffusion room is controlled by the constant current excitation method. 3. A sensor according to claim 2, wherein said gas diffusion hole has a sectional area 1/100 or less the area of said negative electrode. 4. A sensor according to claim 3, wherein said gas diffusion hole has a shape of a groove and is located between said cover and said solid electrolytic layer. 5. A sensor according to claim 4, wherein said gas diffusion hole and said diffusion room are formed using an organic binder. 6. A sensor according to claim 5, wherein said sensor incorporates a heater.

Inventors: MIKI, MASAYUKI, SASAYAMA, TAKAO, SUZUKI, SEIKOH, SUZUKI, TOSHITAKA
Applicants: HITACHI, LTD.
Application year: 1984
Main classification: G01N27
IPC codes: G01N27