JP3514001B2 - Oxygen sensor element - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an oxygen sensor element used for combustion control of an internal combustion engine for an automobile.

[0002]

2. Description of the Related Art Conventionally, for example, an oxygen concentration electromotive force type gas detector using a ZrO ₂ solid electrolyte has been used as a gas detector for detecting the oxygen concentration in exhaust gas discharged from an automobile internal combustion engine. It is known and has been put to practical use. An example of the gas detector is an oxygen concentration detector having the structure shown in FIG.

The oxygen concentration detector 9 is provided with an oxygen sensor element 90 at its tip. The oxygen sensor element 90
As shown in FIGS. 11 and 12, the outer electrode 131 and the inner electrode 132 are provided on both surfaces of the solid electrolyte 13, and the electrode protection layer 8 covering the outer electrode 131. Further, the oxygen sensor element 90 is a bottomed cylindrical body, and the heater 5 is inserted into the inner cavity 15 thereof. In addition, the outer electrode 13
1, the inner electrode 132 is made of platinum. Also,
The electrode protection layer 8 is made of a porous material, and its surface 80 has a large number of pores.

The oxygen sensor element 90 is covered by a housing 96 as shown in FIG. Further, the oxygen concentration detector 9 is attached to the exhaust path of the internal combustion engine for automobiles by a flange 97 provided on the housing 96. In the oxygen sensor element 90, a sensor output is generated between the outer electrode 131 and the inner charge side 132 when the exhaust gas reaches the outer electrode 131 through the pores of the electrode protection layer 8.

By the way, the exhaust gas contains unburned gas components and residual oxygen.
By causing the platinum constituting 31 to react by the catalytic action to bring it into an equilibrium state, it is possible to obtain a sensor output having sharp characteristics. Therefore, the responsiveness of the oxygen sensor element 90 can be improved by promoting the above reaction.

The outer electrode 1 is used to promote the above reaction.
It is important to properly limit the flow rate of exhaust gas reaching 31. In order to limit the flow rate, the electrode protection layer 8 needs to be a dense layer having a low porosity and a small average pore diameter.

The dense electrode protective layer 8 as described above can be generally formed by a method called plasma spraying. Since the electrode protective layer 8 formed by the plasma spraying is appropriately porous, the outer electrode 131 made of platinum is used.
Good adhesion with. Further, the plasma spraying is also excellent in that it is easy to control the distribution of pores in the electrode protection layer 8 and the thickness of the electrode protection layer 8 to be formed.

However, as shown in FIG. 12, such an electrode protective layer 8 has the above-mentioned effect, but under certain practical conditions, the entire surface 80 is covered with poisonous substances 79 derived from exhaust gas. The diffusion of exhaust gas to the outer electrode 131 may be hindered. As a result,
Various problems such as a decrease in sensor output of the oxygen sensor element 90 and a decrease in responsiveness occur. The poisonous substances 79
Is an oil component such as P, Ca, Zn, Si, and K, N
It is composed of fine particles composed of gasoline mixed components such as a and Pb, filmy glass, and the like.

Furthermore, in recent years, as the fuel consumption of internal combustion engines has been improved and the performance thereof has been improved, the chances of the gas detector being used in a higher temperature atmosphere have increased, and the amount of poisonous substances in the exhaust gas has also increased. There is.

In a high temperature atmosphere, the poisoning substances attached to the surface may cause a chemical reaction with each other or may melt. The above-described poisoning substances that have undergone a chemical reaction and melted may form a dense glass-like adhered coating having no air permeability on the surface of the electrode protective layer due to the subsequent decrease in the ambient temperature of the gas detector. In this case, the glass-like adhered coating greatly hinders the exhaust gas from reaching the electrode, and a normal sensor output cannot be obtained.

In these oxygen sensor elements, the sensor output may change over time,
Therefore, it is impossible to accurately measure the air-fuel ratio of the internal combustion engine for automobiles. From the above, it can be said that the durability of the oxygen sensor element is not so high.

In order to solve the above problems, an improvement has been proposed in which a poisoning substance trap layer is provided in the oxygen sensor element to prevent clogging of the electrode protective layer. That is, there has been proposed a method of forming a poisoning substance trap layer having a constant pore diameter, thickness and porosity on the surface of the electrode protective layer of the oxygen sensor element by using alumina or the like (Japanese Patent Laid-Open No. 6-1746).
No. 83).

The oxygen sensor element can capture a poisonous substance in the poisoning substance trap layer. Therefore, the electrode protection layer is not clogged. Further, by forming the poisonous substance trap layer as a porous body having a large average pore diameter and increasing the thickness thereof, it is possible to prevent the formation of a glassy adhered coating film on the surface of the poisonous substance trap layer. Further, the conduction of exhaust gas in the poisonous substance trap layer can be reliably ensured. Therefore, the poisoning substance trap layer has an effect of significantly improving the durability of the oxygen sensor element.

The poisonous substance trap layer as described above is
For example, it can be formed by the following method. The heat resistant particles are mixed with an inorganic binder, a dispersant and water to prepare a slurry, and the slurry is attached to the surface of the electrode protective layer by dipping or spraying. After that, the poisoning substance trap layer can be formed by baking the slurry at 500 to 900 ° C.

[0015]

However, the poisonous substance trap layer is formed by binding a large number of particles with an inorganic binder. Therefore, the bond between particles is weak. Therefore, when the oxygen sensor element having the poisoning substance trap layer is used for a long time under a severe use condition such as a high temperature atmosphere, the poisoning substance trap layer peels off,
The electrode protective layer is exposed. In this case, the electrode protection layer may be clogged, and the normal sensor output of the oxygen sensor element may not be obtained.

The poisonous substance trapping layer is very porous. Therefore, the gas diffusion suppression function (described above,
Only the electrode protective layer bears "to appropriately limit the flow rate of the exhaust gas reaching the electrode"). For this reason,
In the above oxygen sensor element, an electrode protective layer is provided on the surface of the electrode.
Further, a poisoning substance trap layer is provided on the surface of the electrode protective layer. Therefore, there is also a problem that the manufacturing cost becomes high.

In view of the above problems, the present invention aims to provide an oxygen sensor element which can secure a stable sensor output only with an electrode protection layer without using a poisoning substance trap layer.

[0018]

The present invention provides an oxygen sensor element comprising a solid electrolyte and a pair of electrodes arranged on the solid electrolyte, at least one of the electrodes having an electrode protective layer covering the surface thereof. In the oxygen sensor element, the electrode protective layer is made of a porous body formed by plasma spraying and has a surface roughness of 50 μm or more in ten-point average roughness.

First, the operation of the present invention will be described below. The surface of the electrode protective layer is a concavo-convex surface having a surface roughness within the specific range and having a large number of concaves and convexes (see FIG. 2 described later). The electrode protective layer is a porous body and has a large number of pores on its surface.

As a result, even when a poisonous substance adheres to the surface of the electrode protective layer, the poisonous substance adhered by the convex portion and the concave portion is divided, and the poisonous substance does not adhere to the intermediate portion between the two. Almost never. Therefore, it is possible to prevent the poisoning substance from covering the entire surface of the electrode protection layer.

Further, the pores in the middle portion of the poisoned substance which is divided in the electrode protective layer serve as a ventilation passage for the exhaust gas, and the exhaust gas can be guided to the outer electrode. Therefore, according to the present invention, it is possible to provide an oxygen sensor element capable of ensuring a stable sensor output only by the electrode protection layer without using the poisoning substance trapping layer.

The surface roughness of the electrode protective layer is defined by the ten-point average roughness. What is the above ten-point average roughness?
Assume an arbitrary curve that is parallel to the average surface position at the reference length and does not cross the profile curve. The length a between this curve and the apex of the convex portion (measured from the highest to the fifth convex portion), the length b between this line and the deepest point of the concave portion (the deepest to fifth concave portion) Measure). The value obtained by subtracting the average value of 5 b from the average value of 5 a thus obtained is the ten-point average roughness (J
According to IS standard JIS B 0601-1982).
The cross-sectional curve indicates the contour of the uneven surface of the electrode protection layer.

When the surface roughness is less than 50 μm in terms of ten-point average roughness, the space between the convex portions and the concave portions on the surface is filled, and the entire surface of the electrode protective layer is covered with poisonous substances to protect the electrode. The passage of exhaust gases through the formation may be impeded. This problem is particularly noticeable when the usage time is long (when the usage time is relatively short, the amount of poisonous substances deposited is small and the entire surface of the electrode protective layer may not be covered). Further, the lower limit of the ten-point average roughness is more preferably 80 μm or more. On the other hand, when the surface roughness exceeds 200 μm in terms of ten-point average roughness, manufacturing may be substantially difficult.

Further, it is preferable that, on the above-mentioned surface, there are five or more protrusions for a measurement length of 1 mm. When the number of the convex portions is less than 5, the portion not covered with the poisonous substance (for example, the intermediate portion 25 shown in FIG. 3) is small, and exhaust gas sufficient to obtain the sensor output cannot pass through. There is a risk. In this case, the response speed of the oxygen sensor element and the magnitude of the sensor output may be adversely affected.

Next, the electrode protection layer is formed by plasma spraying particles. The electrode protective layer formed by the plasma spraying has good adhesion to the electrode. Furthermore,
The distribution of pores and the thickness of the electrode protective layer to be formed can be easily controlled. Therefore, it is a very excellent method for forming an electrode protective layer that satisfies various required conditions (surface roughness, thickness, porosity).

For example, in the above plasma spraying, the surface roughness of the electrode protective layer can be adjusted by changing the particle size of the sprayed particles. For example, the surface roughness can be further increased by using particles having a large particle size.

The surface roughness can also be adjusted by adjusting the spraying conditions. That is, the plasma spraying is, for example, to generate an arc between the electrodes in the plasma gun and supply a gas from the rear of the arc to generate a high temperature and high speed plasma jet. The powder to be sprayed is put into the flame of this plasma jet and melted. The molten powder is made to collide with and adhere to the base material to form a film on the surface of the base material. At this time, the surface roughness can be adjusted by, for example, intentionally adding a pulsation to the powder supply, intentionally vibrating the spray gun, or changing the moving speed of the spray gun.

It is also possible to use two types of the particles to be sprayed. That is, the one different particle and the other particles melting point than the particles (e.g., for a MgO · Al ₂ O ₃ spinel ZrO _2, etc.). As a result, the semi-molten particles can be nonuniformly attached to each other via the molten particles. Also in this method, the surface roughness can be adjusted.

Particles sprayed by the plasma spraying are not only MgO ₂ .Al ₂ O ₃ spinel but also Al.
It is preferably composed of one or more kinds of heat resistant particles selected from the group consisting of ₂ O ₃ , ZrO ₂ , CaO mullite and the like.
These particles do not change during use at high temperature and can form a stable electrode protective layer.

Next, the thickness of the electrode protective layer is 80 to 5
It is preferably 00 μm. If the thickness is less than 80 μm, the thinnest part of the electrode protection layer is 30 μm.
Since it is less than m, the effect as the electrode protective layer may not be sufficiently exhibited.

On the other hand, when the thickness is more than 500 μm, the diffusion time of the exhaust gas (the time required for the exhaust gas to pass through the electrode protection layer) becomes long because the electrode protection layer is too thick, and the response speed of the oxygen sensor element and the The output may be adversely affected.

Next, the electrode protective layer has a porosity of 6
It is preferably -40%. When the porosity is less than 6%, continuity is lost due to a large number of pores formed on the surface of the electrode protective layer, exhaust gas cannot reach the electrode, and sensor output cannot be obtained. There is a risk.

On the other hand, when it exceeds 40%, the electrode protective layer is too porous, so that the flow rate of the exhaust gas cannot be suppressed (gas diffusion suppressing function). Further, the adhesive force between the electrode protective layer and the electrode becomes weak, and the electrode protective layer may peel off during use of the oxygen sensor element.

Next, the average pore diameter of the electrode protective layer is
It is preferably 0.05 to 0.5 μm. If the average pore diameter is less than 0.05 μm, the electrode protective layer is too dense, and a sufficient amount of exhaust gas cannot reach the electrode, which may adversely affect the response speed and output of the oxygen sensor element. . In particular, this problem becomes remarkable when the electrode protective layer becomes thick. On the other hand, when the thickness exceeds 0.5 μm, the above-mentioned electrode protective layer is too porous, so that it may not be possible to suppress the flow rate of exhaust gas (gas diffusion suppressing function). In addition, poisonous substances with a particularly small particle size may pass through the electrode protective layer and adhere to the electrodes.

Next, another oxygen sensor element according to the present invention will be described. The oxygen sensor element comprises a solid electrolyte and a pair of electrodes arranged on the solid electrolyte, and at least one of the electrodes has an electrode protective layer covering the surface thereof. The layer is composed of a first electrode protection layer and a second electrode protection layer, and further, the first electrode protection layer is formed on the electrode, and the second electrode protection layer is formed on the first electrode protection layer. The second electrode protective layer has a surface roughness of 50 μm or more in terms of ten-point average roughness, and the first electrode protective layer is denser than the second electrode protective layer. It is a characteristic oxygen sensor element.

When the surface roughness of the second electrode protective layer is within the above specified range, when a poisonous substance adheres to the surface thereof, the adhered substance is divided between the convex portion and the concave portion, and the convex portion A portion where the poisonous substance hardly adheres is formed in the intermediate portion between the portion and the concave portion (see FIG. 5 described later). Therefore,
It is possible to prevent the poisoning substance from covering the entire surface of the second electrode protection layer.

Usually, when the electrode protective layer is particularly porous, poisonous substances may pass through the electrode protective layer and deteriorate the electrode. Further, the adhesive force between the electrode protective layer and the electrode becomes weak, and the electrode protective layer may peel off. However, since the first electrode protective layer is denser than the second electrode protective layer, the poisonous substances passing through the second electrode protective layer are trapped in the first electrode protective layer. Therefore, the deterioration of the electrode due to the poisonous substance hardly occurs.

Since the first electrode protective layer is dense,
The adhesive force between the electrode and the first electrode protection layer is so strong that peeling of the first electrode protection layer does not occur. Furthermore, since the adhesive force between the second electrode protective layer and the first electrode protective layer is both formed by plasma spraying, a strong adhesive force is generated between them due to mechanical meshing. Therefore, the peeling of the second electrode protective layer does not occur.

Further, by providing the relatively dense first electrode protective layer with the gas diffusion suppressing function, the second electrode protective layer can have only the film thickness necessary for exhibiting the function of cutting off the deposit. . Therefore, the thickness of the second electrode protection layer can be reduced.

The surface roughness of the second electrode protective layer is preferably 50 μm or more in terms of ten-point average roughness for the same reason as described for the electrode protective layer consisting of one layer. In addition, the number of protrusions on the uneven surface is a measurement length of 1 mm
It is preferably 5 or more. The thickness of the electrode protective layer is preferably 80 to 500 μm.

Further, the second electrode protective layer can give priority to the function of separating the adhered substances, and therefore exerts its effect more, so that the average pore diameter thereof is preferably 0.1 to 0.5 μm. . The porosity of the second electrode protective layer is also preferably 10 to 40%.

Next, the average pore diameter of the first electrode protective layer is preferably 0.05 to 0.2 μm. If the average pore diameter is less than 0.05 μm, the first electrode protective layer is too dense and a sufficient amount of exhaust gas cannot reach the electrode, which may affect the responsiveness and output of the oxygen sensor element. May have an adverse effect.

On the other hand, when it is larger than 0.2 μm, when the second electrode protective layer is particularly porous, and when the first electrode protective layer is thin, the poisonous substances passing through the second electrode protective layer are trapped. Cannot be done, and the electrodes may deteriorate. In addition, the first electrode protective layer becomes porous, the gas diffusion suppressing function is deteriorated, and the effect of reducing the thickness of the entire electrode protective layer may not be exhibited.

The porosity of the first electrode protective layer is 6 to
It is preferably 20%. If the porosity is less than 6%, the continuity of pores may be lost, exhaust gas may not reach the electrode, and sensor output may not be obtained. On the other hand, when the porosity is larger than 20%, the first electrode protective layer becomes porous, the gas diffusion suppressing function is deteriorated, and the effect of reducing the thickness of the entire electrode protective layer may not be exhibited. is there. Further, when the second electrode protection layer is porous and the thickness of the first electrode is thin, poisonous substances that have passed through the second electrode protection layer cannot be captured, which may deteriorate the electrode.

The thickness of the first electrode protective layer is 30 to
It is preferably 200 μm. The thickness is 30 μm
If it is less than the above range, the effect as an electrode protective layer may not be exhibited when the second electrode protective layer is porous. On the other hand, if the thickness is greater than 200 μm, the dense first electrode protective layer may be too thick, which may hinder gas diffusion.

The first electrode protective layer is made of MgO.A.
In addition to l ₂ O ₃ spinel, Al ₂ O ₃ , ZrO ₂ , CaO
It is preferably composed of one or more heat-resistant particles selected from the group such as mullite. These particles do not change during use at high temperature, and thus a stable first electrode protective layer can be formed.

[0047]

DETAILED DESCRIPTION OF THE INVENTION

First Exemplary Embodiment An oxygen sensor element according to an exemplary embodiment of the present invention will be described with reference to FIGS. As shown in FIG. 1, the oxygen sensor element 1 of the present embodiment comprises a solid electrolyte 13 and the solid electrolyte 1
3 is provided with an outer electrode 131 and an inner electrode 132, and has an electrode protection layer 2 covering the outer electrode 131.

As shown in FIG. 2, the electrode protection layer 2 is
It is composed of a porous body formed by plasma spraying MgO.Al ₂ O ₃ spinel having an average particle size of 50 μm,
The surface roughness is 100 μm in ten-point average roughness. Further, the electrode protection layer 2 has a large number of pores on its surface 20. The porosity is 15% and the average pore size is 0.15 μm. The film thickness is 200
μm. In the figure, reference numeral 5 is a heater (see FIG. 10).

Next, the function and effect of this example will be described. The surface 20 of the electrode protection layer 2 is an uneven surface having the above-mentioned specific surface roughness and having a large number of concave portions 24 and convex portions 23 as shown in FIG. As a result, as shown in FIG. 3, even when the poisoning substance 79 adheres to the surface 20 of the electrode protection layer 2, the poisoning substance 79 adhered by the convex portions 23 and the concave portions 24 is divided, and an intermediate portion between them is formed. Part 25
The poisonous substance 79 hardly adheres to.

Therefore, it is possible to prevent the poisoning substance 79 from covering the entire surface 20 of the electrode protection layer 2. Further, the pores present in the intermediate portion 25 of the electrode protection layer 2 serve as a ventilation path for the exhaust gas and can guide the exhaust gas to the outer electrode 131.

Therefore, according to this example, it is possible to provide an oxygen sensor element which can secure a stable sensor output only by the electrode protection layer without providing the poisonous substance trapping layer.

Embodiment 2 As shown in Table 1, this embodiment measures the durability of poisoning and the initial response of the oxygen sensor element. First,
Each of the samples 1 to 21 used for the above measurement is the same oxygen sensor element as in the first embodiment. However, each sample has different surface roughness, average pore diameter, porosity, and thickness of the electrode protective layer.

The poisoning durability was judged by the rate of change in responsiveness of each of the samples 1 to 21 before and after the accelerated poisoning durability test. That is, the sample whose rate of change is less than 5% is ◎, 5%
The results are shown in Table 1 with the samples of 10% or more and less than 10%, the samples of 10% or more and less than 20% as Δ, and the samples of 20% or more as x.

Next, the accelerated poisoning durability test will be described. Each of the samples 1 to 21 was assembled in an oxygen concentration detector (see FIG. 10) and installed in the exhaust path of a 2000 cc in-line 4-cylinder engine with a fuel injection device. Then, the condition of idling the engine for 30 minutes and then driving the engine at 4000 rpm for 30 minutes was continuously repeated. The temperature of the exhaust gas at this time was 500 to 700 ° C. The fuel used to drive the engine was unleaded gasoline to which 5% by weight of engine oil and detergent was added. The duration of the above test is 100 hours.

A method of measuring the response change rate will be described. The oxygen concentration detectors to which the samples 1 to 21 were attached were installed in the exhaust path of a 2000 cc in-line 6-cylinder engine with a fuel injection device. Using unleaded gasoline as fuel, the engine was driven at a rotation speed of 1100 rpm.

In this state, the gas response time, that is, when switching to the excess air ratio λ = 0.9 to 1.1,
It measured about the time until the output of each said sample 1-21 changed to 0.6V-0.3V. Then, the response measurement was performed before and after the accelerated poisoning durability test. Response time t1 before the test, response time t after the test
2, and the value obtained by {(t2-t1) / t1} × 100 was taken as the response change rate.

The initial responsiveness is shown in Table 1 when the responsiveness measurement result is less than 150 ms, ◯, 150 to 200 ms is Δ, and 200 ms is x.

As shown in Table 1, the electrode protective layer has a surface roughness of 50 to 200 μm, a thickness of 80 to 500 μm, an average pore diameter of 0.05 to 0.40 μm, and a porosity of 6 to 40%. In this case, it was found that the oxygen sensor element has excellent poisoning durability and initial response.

[0059]

[Table 1]

Embodiment 3 As shown in FIGS. 4 to 7, this embodiment relates to an oxygen sensor element having an electrode protective layer having a two-layer structure. Figure 4,
As shown in FIG. 5, the electrode protective layer 3 in the oxygen sensor element 19 of this example is composed of the first electrode protective layer 31 and the second electrode protective layer 3.
2 has a two-layer structure. The second electrode protective layer 3
The second surface 30 is an uneven surface, and the concave portions 34 and the convex portions 33 are alternately formed.

Table 2 shows the surface roughness, the average pore diameter, the porosity, and the thickness of the first electrode protective layer 31 and the second electrode protective layer 32, which are based on the ten-point average roughness. Others are the same as those in the first embodiment.

In the oxygen sensor element 19 of this example, as shown in FIG. 6, the second electrode protective layer 32 has the surface 30 thereof.
Has the above-mentioned specific surface roughness and has a large number of projections 33 and recesses 3.
4 and. As a result, even when the poisonous substance 79 adheres to the surface 30, the adhering substance 79 is divided by the convex portion 33 and the concave portion 34. Therefore, the poisoning substance 79 does not adhere to the intermediate portion 35 between the convex portion 33 and the concave portion 34. Therefore, the poison 79 may be the second electrode protection layer 3.
It is possible to prevent the entire second surface 30 from being covered.

The first electrode protective layer 31 has a smaller average pore diameter and porosity than the second electrode protective layer 32, that is, is dense. Particularly, a poisonous substance having a small particle size may pass through the second electrode protection layer 32, but in this example,
The poisoning substance can be trapped by the first electrode protection layer 31.

Since the first electrode protection layer 31 and the second electrode protection layer 32 are both formed by plasma spraying, they are firmly joined by mechanical meshing. Others have the same effects as those of the first embodiment.

Next, the poisoning durability of the oxygen sensor element of this example will be described in comparison with the oxygen sensor element of the conventional example (see FIGS. 11 and 12). An oxygen sensor element 19 according to this example and an oxygen sensor element 90 according to a conventional example are prepared. The oxygen sensor element according to the conventional example has an electrode protective layer having a small surface roughness (30 μm). Then, the rate of change in responsiveness before and after the acceleration poisoning durability test of both oxygen sensor elements was determined by the same method as in the second embodiment.
It was measured. The result is shown in FIG. 7.

According to the figure, in the oxygen sensor element according to the present invention, the responsiveness change rate does not change even when the duration of the durability test reaches 200 hours. However, it was found that the oxygen sensor element according to the conventional example had a responsiveness change rate that consistently increased immediately after the start of the durability test, and the sensor output changed with time.

[0067]

[Table 2]

Fourth Embodiment As shown in FIGS. 8 and 9, this embodiment is various oxygen sensor elements having an electrode protective layer according to the present invention. First, FIG. 8 shows a laminated oxygen sensor element 3. The oxygen sensor element 3 is provided with an inner electrode 332 and an outer electrode 331 on both surfaces of the solid electrolyte 33, and has an electrode protection layer 4 covering the outer electrode 331. In addition, the solid electrolyte 33
A forming plate 45 for forming the air introducing duct 451 is disposed below the. Further, below the forming plate 45, a heater portion 46 having a heating element 461 built therein is provided.

Next, FIG. 9 shows a limiting current type oxygen sensor element 18. In the oxygen sensor element 18, the inner electrodes 13 arranged on both sides of the solid electrolyte 13 having a bottomed cylindrical body are used.
2. It has an outer electrode 133 and an electrode protection layer 2 that covers the outer electrode 133. The outer electrode 133 is provided in a strip shape on the surface of the solid electrolyte 13. Others are the same as those in the first embodiment. Further, the oxygen sensor elements 3 and 18 also have the same effects as those of the first embodiment.

[0070]

As described above, according to the present invention, it is possible to provide an oxygen sensor element which can secure a stable sensor output only by the electrode protection layer without using the poisoning substance trap layer.

[Brief description of drawings]

FIG. 1 is an explanatory cross-sectional view of an oxygen sensor element according to a first embodiment.

FIG. 2 is a cross-sectional view of an electrode protective layer of an oxygen sensor element according to the first embodiment.

FIG. 3 is a cross-sectional view of an electrode protective layer with a poisoning substance of an oxygen sensor element according to the first embodiment.

FIG. 4 is an explanatory cross-sectional view of an oxygen sensor element according to the third embodiment.

FIG. 5 is a sectional view of an electrode protective layer of an oxygen sensor element according to the third embodiment.

FIG. 6 is a cross-sectional view of an electrode protective layer with a poisoning substance of an oxygen sensor element according to a third embodiment.

FIG. 7 is a graph showing the relationship between the response change rate of the oxygen sensor element and the duration of the poisoning durability test in the third embodiment.

FIG. 8 is an explanatory cross-sectional view of an oxygen sensor element according to the fourth embodiment.

FIG. 9 is an explanatory cross-sectional view of another oxygen sensor element according to the fourth embodiment.

FIG. 10 is a partially cutaway sectional view of an oxygen concentration detector in a conventional example.

FIG. 11 is a cross-sectional explanatory view of an oxygen sensor element in a conventional example.

FIG. 12 is a cross-sectional view of an electrode protective layer with a poisonous substance attached to an oxygen sensor element in a conventional example.

[Explanation of symbols]

1, 18, 19, 3. ． ． Oxygen sensor element, 13, 33. ． ． Solid electrolyte, 131, 331. ． ． Outer electrode, 132,332. ． ． Inner electrode, 2,4. ． ． Electrode protection layer, 31. ． ． First electrode protective layer, 32. ． ． Second electrode protective layer,

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasumichi Hotta 1-1, Showa-cho, Kariya city, Aichi Prefecture, Nippon Denso Co., Ltd. (72) Naoto Miwa 1-1-1, Showa-cho, Kariya city, Aichi prefecture Nippon Denso Co., Ltd. (56) Reference JP-A-7-333191 (JP, A) JP-A-6-174683 (JP, A) JP-A-2-276956 (JP, A) JP-A-7-110315 (JP, A) JP-A-2-222831 (JP, A) JP-A 1-274057 (JP, A) JP-A 2-85756 (JP, A) JP-A 8-128988 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G01N 27/409 G01N 27/41

Claims (5)

(57) [Claims] 1. An oxygen sensor element comprising a solid electrolyte and a pair of electrodes disposed on the solid electrolyte, wherein at least one of the electrodes has an electrode protection layer covering the surface thereof. Is a porous body formed by plasma spraying, and has a surface roughness of 10-point average roughness of 50.
An oxygen sensor element having a thickness of at least μm. 2. The electrode protective layer according to claim 1, wherein
The porosity is 6 to 40%, and the average pore diameter is 0.
An oxygen sensor element having a thickness of 05 to 0.5 μm. 3. An oxygen sensor element comprising a solid electrolyte and a pair of electrodes arranged on the solid electrolyte, wherein at least one of the electrodes has an electrode protection layer covering the surface thereof. Is composed of a first electrode protection layer and a second electrode protection layer, wherein the first electrode protection layer is formed on the electrode, and the second electrode protection layer is formed on the first electrode protection layer. The second electrode protective layer has a surface roughness of 50 μm or more in ten-point average roughness, and the first electrode protective layer is denser than the second electrode protective layer. Oxygen sensor element. 4. The oxygen sensor according to claim 3, wherein the second electrode protective layer has a porosity of 6 to 40% and an average pore diameter of 0.05 to 0.5 μm. element. 5. The method according to any one of claims 1 to 4,
An oxygen sensor element, wherein the ten-point average roughness is 200 μm or less.