JP5938298B2 - Gas sensor element, gas sensor and manufacturing method thereof - Google Patents

Description

  The present invention relates to a gas sensor element that detects the concentration of a gas to be detected, a gas sensor, and a method for manufacturing the gas sensor element.

As a gas sensor for detecting an oxygen concentration in an exhaust gas of an automobile or the like, a gas sensor that extends in an axial direction and has a substantially cylindrical gas sensor element that is inserted and held inside a cylindrical metal shell is known. (Patent Document 1). This gas sensor element has a cylindrical solid electrolyte body and inner and outer electrodes formed on the inner and outer surfaces of the solid electrolyte body, respectively.
Among these, the inner electrode is formed by electroless plating of a noble metal such as platinum on the inner surface of the solid electrolyte body, and it is preferable from the viewpoint of cost to form the inner electrode only in a necessary portion functioning as an electrode. For this reason, a technique has been developed in which a mask jig is mounted on the inner surface of a solid electrolyte body to perform plating, and a portion that does not require plating is masked (Patent Document 2). The inner electrode formed in this way has an inner detection portion that is located on the front end side and formed over the entire circumference, and a narrow inner lead portion that extends from the inner detection portion toward the rear end. Therefore, the electrode material can be reduced as compared with the case where the inner electrode is formed on the entire inner surface of the solid electrolyte body.

JP 2012-26789 A (FIG. 2) JP 2011-247621 A

By the way, when the narrow inner lead portion is provided from the inner detection portion of the inner electrode, the rear end edge of the inner detection portion extends in the circumferential direction, while the inner lead portion extends in the axial direction, and the rear end edge of the inner detection portion. The angle formed by the connection point at which the tangent line and the contour line of the inner lead portion are connected is a right angle. When such a gas sensor element is subjected to a thermal cycle in which the gas sensor element is rapidly cooled from a high temperature to 100 ° C. or less, there is a problem that the inner electrode is easily peeled from the vicinity of the connection point. This is thought to be due to stress concentration at the connection point as an edge.
In general, the outer surface of the solid electrolyte body is roughened to prevent the protective layer for protecting the outer electrode from poisoning and the like from peeling off from the solid electrolyte body. High and difficult to peel. On the other hand, the inner surface of the solid electrolyte body does not form a protective layer unlike the outer surface, so it is not roughened. Furthermore, in order to insert and remove the press pin when molding the solid electrolyte body cylinder It has a mirror surface reflecting the surface of the pin, and the inner electrode has low adhesion and is easy to peel off. In addition, since the compressive stress generally acts on the plating film, the outer electrode on the outer surface of the solid electrolyte body is difficult to peel off even when subjected to a thermal cycle, whereas the inner electrode accelerates peeling when subjected to the thermal cycle. Tend to be.
Therefore, the present invention can reduce the electrode material of the inner electrode by making the inner lead portion narrower in the radial direction than the inner detection portion, and can reduce the electrode material of the gas sensor element, the gas sensor, and the gas sensor element in which the inner electrode is difficult to peel off even when subjected to a thermal cycle. The purpose is to provide a manufacturing method.

In order to solve the above problems, a gas sensor element of the present invention includes a solid electrolyte body formed in a bottomed cylindrical shape extending in the axial direction and having a closed tip, and a plating layer provided on an inner peripheral surface of the solid electrolyte body an inner electrode made of, a gas sensor element having an outer electrode provided on the outer peripheral surface of the solid electrolyte body, the inner electrode includes an inner detection portion located distally, after the inner sensing unit One inner lead portion extending toward the end side and narrower in the circumferential direction than the inner detection portion, and the inner detection portion is formed on the inner surface of the solid electrolyte body over the entire circumferential direction. are, through the connection point with the contour of the inner lead and the rear edge of the inner detection unit is connected, the contour of the inner lead portion, the tangent of the rear edge of the inner detection unit, and The angle formed on the outside in the circumferential direction of the inner lead Obtuse der is, the rear edge of the inner detection portion with distance from the connection point that is under stood toward the tip.
According to this gas sensor element, since the inner lead portion is narrower in the radial direction than the inner detection portion, the electrode material of the inner electrode can be reduced. And since the angle formed by the contour line of the inner lead part and the tangent of the rear edge of the inner detection part (the angle formed on the outer side in the circumferential direction of the inner lead part) is an obtuse angle, stress concentration at the connection point is reduced, Even if the gas sensor element is subjected to a cooling cycle in which the gas sensor element is rapidly cooled from a high temperature to 100 ° C. or less, the inner electrode is difficult to peel from the vicinity of the connection point. In particular, the inner surface of the solid electrolyte body is a mirror surface, the adhesion of the inner electrode is low, and the plating film generally has a compressive stress, and therefore the inner electrode tends to peel off. By making the obtuse angle, peeling of the inner electrode can be suppressed.

  The present invention is not limited to the inner electrode formed with two connection points (that is, the connection points are connected to the contour lines on both sides in the circumferential direction of the inner lead portion), and one connection point is formed. It may be applied to the inner electrode. When there is one connection point, the contour line of the inner lead portion on the side where the connection point is not formed indicates a form in which the contour line is connected to the contour line of the inner detection portion. In addition, in the case of the inner electrode formed with two connection points, the corners are obtuse at the connection points on one side, not limited to those having obtuse angles at the connection points on both sides. Also good.

  Even in the case where the inner lead portion bleeds and a waviness or a minute waveform occurs in the contour line, in the present invention, linear approximation is performed and the above definition is applied. Further, the contour line of the inner lead portion may be a straight line parallel to the axial direction, or inclined toward the rear end side in the axial direction (more specifically, the width of the inner lead portion toward the rear end side). It may be narrower).

  Furthermore, in the present invention, when the contour line of the inner lead part is a straight line parallel to the axial direction, the width of the inner lead part can be reduced at any position, and the amount of electrode material used in the inner lead part Can be reduced.

Furthermore, in the present invention, before Kisotogawa electrode includes an outer sensing portion located on the distal end side extends toward the rear end side from the outer detection unit, and the width from the outer sensing portion in the circumferential direction narrow outer lead portions The outer side detection unit is provided over a part of the circumferential direction on the outer surface of the solid electrolyte body provided on the side opposite to the inner surface of the solid electrolyte body on which the inner lead portion is formed. It is characterized by. Thereby, the usage-amount of electrode material can be reduced also in an outer electrode.

Further, the present invention is characterized in that the rear end edge of the outer side detection unit is formed on the front side of the rear end edge of the inner side detection unit. Thereby, an outer side and an inner side electrode can oppose reliably, and the specific gas component in to-be-measured gas can be measured favorably.
In addition, the rear end edge of the inner side detection unit means the front end side of the rear end edges when the rear end edge is not perpendicular to the axial direction. Further, the rear end edge of the outer side detection unit means the rear end side of the rear end edge when the rear end edge is not perpendicular to the axial direction.

The method for producing a gas sensor element of the present invention includes a nucleation step of attaching nuclei to an inner surface of a bottomed cylindrical solid electrolyte body extending in an axial direction, and a plating solution in which the nuclei act as a catalyst. A plating process for depositing a metal in a liquid on the inner surface of the solid electrolyte body, and a method for producing a gas sensor element, wherein an inner electrode made of the metal is formed on the inner surface of the solid electrolyte body, Prior to the plating step, a mask jig mounting step for mounting a mask jig on a mask portion different from a planned electrode portion on which the inner electrode is to be formed on the inner surface of the solid electrolyte body, and the planned electrode portion and a said plating step of depositing said metal, the mask jig, which has a slit extending along the axial direction, falls toward the leading edge from the cut portion Ri has a cylindrical shape with a mask outer surface in contact with the mask portion when wearing the mask jig to the mask portion, and, in the mask outer surface, a distal end of the mask jig and contour of the cut portion The angle formed on the outer side in the circumferential direction of the cut portion formed by the contour line of the cut portion and the tangent line of the tip edge is an obtuse angle through the connection point to which the edge is connected, and in the mask jig mounting step, The mask jig is inserted inside the solid electrolyte body while elastically deforming the mask jig in a direction in which the diameter of the mask jig is reduced, and the outer surface of the mask is moved by the elastic restoring force of the mask jig. Contact the mask portion.
According to this method of manufacturing a gas sensor element, the mask jig has a cut portion extending along the axial direction, and thus the inner electrode to be formed is provided with a lead portion narrower than the detection portion. . Therefore, the electrode material for the inner electrode can be reduced. In the mask jig, the angle formed by the contour line of the cut portion and the tangent line of the tip edge (the angle formed on the outer side in the circumferential direction of the cut portion) is an obtuse angle. The angle formed by the line and the tangent line of the rear end edge of the detection portion (the angle formed on the outer side in the circumferential direction of the lead portion) is an obtuse angle. As a result, stress concentration at the connection point is reduced, and even when the gas sensor element is subjected to a thermal cycle in which the gas sensor element is rapidly cooled from a high temperature to 100 ° C. or less, the inner electrode is difficult to peel off from the vicinity of the connection point. In particular, the inner surface of the solid electrolyte body is a mirror surface, the adhesion of the inner electrode is low, and the plating film generally has a compressive stress, and therefore the inner electrode tends to peel off. By making the obtuse angle, peeling of the inner electrode can be suppressed.

  According to the present invention, the inner lead portion is narrower in the radial direction than the inner detection portion, so that the electrode material of the inner electrode can be reduced, and a gas sensor element in which the inner electrode is not easily peeled even when subjected to a thermal cycle can be obtained.

It is sectional drawing which cut | disconnected the gas sensor which concerns on the 1st Embodiment of this invention in the surface which follows an axial direction. It is a perspective view which shows the structure of the inner side electrode of the gas sensor element which concerns on 1st Embodiment, and an outer side electrode. It is a partial expansion perspective view of the edge vicinity of the connection point of an inner side lead part and an inner side detection part. It is a side view of an inner side electrode and an outer side electrode. It is a side view which shows the case where the rear end edge of an inner side detection part is a curve. It is a figure which shows the structure of a mask jig | tool. It is process drawing which shows the manufacturing method of the gas sensor element using a mask jig | tool. It is a perspective view which shows the structure of the inner side electrode of the gas sensor element which concerns on 2nd Embodiment. It is a side view of the inner side electrode which concerns on 2nd Embodiment. It is a figure which shows the structure of the mask jig | tool which concerns on 2nd Embodiment. It is a side view which shows the structure of the inner side electrode of the gas sensor element which concerns on 3rd Embodiment.

Hereinafter, embodiments of the present invention will be described.
FIG. 1 shows a cross-sectional structure in which a gas sensor 100 having a gas sensor element 3 according to a first embodiment of the present invention is cut along a plane along the axis O direction. In this embodiment, the gas sensor 100 is an oxygen sensor that is inserted into an exhaust pipe of an automobile and has a tip exposed to the exhaust gas to detect the oxygen concentration in the exhaust gas. The gas sensor element 3 is a known oxygen sensor element that constitutes an oxygen concentration cell in which a pair of electrodes are laminated on an oxygen ion conductive solid electrolyte body and outputs a detection value corresponding to the amount of oxygen.
In addition, let the lower side of FIG. 1 be the front end side of the gas sensor 100, and let the upper side of FIG.

The gas sensor 100 is assembled so that a substantially cylindrical (hollow shaft-shaped) gas sensor element (in this example, an oxygen sensor element) 3 having a closed tip is inserted and held inside a cylindrical metal fitting body (main metal fitting) 20. It has been. The sensor element 3 includes a cylindrical solid electrolyte body 3s having a tapered diameter toward the tip, an inner electrode 50 (see FIG. 2) and an outer electrode respectively formed on the inner and outer peripheral surfaces of the solid electrolyte body. 450 (see FIG. 2). Further, a round bar heater 15 is inserted into the hollow portion of the gas sensor element 3 so as to raise the temperature of the solid electrolyte body 3s to the activation temperature.
A cylindrical outer tube 40 that holds lead wires and terminals (described later) provided on the rear end side of the gas sensor element 3 and covers the rear end portion of the sensor element 3 is joined to the rear end portion of the metal fitting body 20. ing. Further, an insulating and cylindrical separator 121 is caulked and fixed inside the outer cylinder 40 on the rear end side of the gas sensor element 3. On the other hand, the detection part at the tip of the gas sensor element 3 is covered with a protector 7. The male screw part 20d of the metal fitting body 20 of the gas sensor 100 manufactured in this way is attached to a screw hole such as an exhaust pipe, so that the detection part at the tip of the gas sensor element 3 is exposed in the exhaust pipe and the gas to be detected (exhaust gas) Gas). A polygonal flange 20c for engaging a hexagon wrench or the like is provided near the center of the metal fitting body 20, and the step between the flange 20c and the male thread 20d is attached to the exhaust pipe. A gasket 14 is inserted to prevent the gas from leaking when it is blown.

A flange portion 3 a is provided at the center side of the gas sensor element 3, and a step portion that is reduced in diameter is provided on the inner peripheral surface near the tip of the metal fitting body 20. In addition, a cylindrical ceramic holder 5 is disposed on the surface facing the rear end of the step portion via a washer 12. The gas sensor element 3 is inserted inside the metal fitting body 20 and the ceramic holder 5, and the flange 3 a of the gas sensor element 3 is in contact with the ceramic holder 5 through the washer 13 from the rear end side.
Furthermore, a cylindrical talc powder 6 and a cylindrical ceramic sleeve 10 are arranged in the radial gap between the gas sensor element 3 and the metal fitting body 20 on the rear end side of the flange 3a. And the ceramic sleeve 10 is pressed to the front end side by arranging the metal ring 30 on the rear end side of the ceramic sleeve 10 and bending the rear end portion of the metal fitting body 20 inward to form the crimped portion 20a. Thereby, the talc ring 6 is crushed and the ceramic sleeve 10 and the talc powder 6 are caulked and fixed, and the gap between the gas sensor element 3 and the metal fitting body 20 is sealed.

The separator 121 disposed on the rear end side of the gas sensor element 3 is provided with insertion holes (four in this example), and two of the insertion holes are plate-like base portions of the inner terminal fitting 71 and the outer terminal fitting 91, respectively. 74 and 94 are inserted and fixed. Connector portions 75 and 95 are formed at the rear ends of the plate-like base portions 74 and 94, respectively, and lead wires 41 and 41 are crimped to the connector portions 75 and 95, respectively. Further, a heater lead wire 43 (only one is shown in FIG. 1) drawn from the heater 15 is inserted into two insertion holes (heater lead holes) (not shown) of the separator 121.
A cylindrical grommet 131 is caulked and fixed inside the outer cylinder 40 on the rear end side of the separator 121, and two lead wires 41 and two heater lead wires 43 are respectively inserted from the four insertion holes of the grommet 131. Has been pulled out.
A through hole 131 a is formed at the center of the grommet 131 and communicates with the internal space of the gas sensor element 3. A water-repellent ventilation filter 140 is interposed in the through-hole 131a of the grommet 131 so that the reference gas (atmosphere) is introduced into the internal space of the gas sensor element 3 without passing outside water.

  On the other hand, a cylindrical protector 7 is fitted on the distal end side of the metal fitting body 20, and the distal end side of the gas sensor element 3 protruding from the metal fitting body 20 is covered with the protector 7. The protector 7 is configured by attaching a bottomed cylindrical metal (for example, stainless steel, etc.) double outer protector 7b and an inner protector 7a having a plurality of holes (not shown) by welding or the like.

  Next, the configuration of the outer electrode 450 and the inner electrode 50 will be described with reference to FIGS. As shown in FIG. 2, the inner electrode 50 is formed on the inner peripheral surface of the solid electrolyte body 3 s and is located on the front end side and formed over the entire circumference in the circumferential direction. And is formed in a part in the circumferential direction and has a narrow inner lead part 52 narrower in the radial direction than the inner detection part 51, and extends with the same width as the inner lead part 52 on the rear end side from the inner lead part 52. The inner terminal connecting portion 53 is integrally provided. In this example, the inner side detector 51 is also formed on the bottom of the inner peripheral surface of the solid electrolyte body 3s. Further, the inner terminal connecting portion 53 may be wider than the inner lead portion 52, or may be formed over the entire circumference.

  On the other hand, the outer electrode 450 is formed on the outer peripheral surface of the solid electrolyte body 3s, is located on the front end side and is formed over a part of the circumferential direction, and extends from the outer detector 451 toward the rear end. An elongated outer lead portion 452 that is formed in a part in the circumferential direction and narrower in the radial direction than the outer detection portion 451, and an outer terminal connection portion 453 that extends to the rear end side of the outer lead portion 452 with the same width as the outer lead portion 452. Are integrated. In this example, the outer side detector 451 is also partially formed at the bottom of the inner peripheral surface of the solid electrolyte body 3s. Further, the outer terminal connection portion 453 may be wider than the outer lead portion 452, or may be formed over the entire circumference in the circumferential direction.

This inner side detection unit 51 is exposed to a reference gas atmosphere introduced into the internal space of the gas sensor element 3. On the other hand, the outer electrode 450 formed on the outer surface of the gas sensor element 3 is exposed to the gas to be detected, and the inner electrode 50 (the inner detection unit 51) and the outer electrode 450 (the outer detection unit 451) through the solid electrolyte body 3s. Gas is detected between the two.
The inner terminal connecting portion 53 is electrically connected to the inner terminal fitting 71 inserted in the opening of the solid electrolyte body 3s, and the detection output of the gas sensor element 3 is taken out from the inner terminal fitting 71 to the outside. The outer terminal connection portion 453 is electrically connected to the outer terminal fitting 91 fitted in the solid electrolyte body 3s, and the detection output of the gas sensor element 3 is taken out from the inner terminal fitting 91 to the outside.

Here, as shown in FIG. 3, the contour line g of the inner lead portion 52 passing through the connection point C where the contour line g of the inner lead portion 52 and the rear edge 51e of the inner detection portion 51 are connected, and the inner detection. An angle θ formed on the outer side in the circumferential direction of the inner lead portion 52 formed by the tangent t of the rear end edge 51e of the portion 51 is an obtuse angle. When the angle θ is an obtuse angle (θ> 90 degrees), stress concentration on the edge C of the joint is reduced, so that the inner side of the gas sensor element is subjected to a thermal cycle in which the gas sensor element is rapidly cooled from a high temperature to 100 ° C. or less. It becomes difficult for the electrode 50 to peel from the vicinity of the connection point C.
In particular, the inner surface of the solid electrolyte body 3s is a mirror surface reflecting the surface of the pin in order to insert and remove the press pin when molding the cylindrical body of the solid electrolyte body 3s, and the adhesion of the inner electrode 50 is reduced. It is advantageous that θ> 90 degrees. Furthermore, since compressive stress generally acts on the plating film, it tends to facilitate the peeling of the inner electrode 50, so that θ> 90 degrees is advantageous.

In the example of FIG. 3, the outline g of the inner lead portion 52 is a straight line parallel to the direction of the axis O, and the rear edge 51e of the inner detection portion 51 is on the same plane S1. Here, the surface S1 is inclined with respect to the horizontal. Therefore, as shown in FIG. 4, the contour line g and the tangent line t are both linear, and the angle formed between the contour line g and the tangent line t that does not pass through the junction C is equal to θ. As shown in FIG. 5, considering the case where the contour line g and the tangent line t are not linear, such as when the rear end edge 51e of the inner side detection unit 51 falls toward the front end as the distance from the edge C of the joint portion increases, As the contour line g and the tangent line t, those passing through the connection point C are adopted.
If the contour line g of the inner lead portion 52 is a straight line parallel to the direction of the axis O, the inner lead portion 52 can be narrowed at any position, and the amount of electrode material used in the inner lead portion 52 can be reduced. Can be reduced.

  Further, as shown in FIG. 2, the outer side detection unit 451 is circumferentially arranged on the outer surface of the solid electrolyte body 3s provided on the side opposite to the inner surface of the solid electrolyte body 3s where the inner lead portion 52 is formed. It is provided over a part of. Thereby, also in the outer side electrode 450, the usage-amount of an electrode material can be reduced. In addition, the rear end edge of the outer detection unit 451 is formed on the front end side of the rear end edge of the inner detection unit 51. Thereby, the specific gas component in gas to be measured can be measured favorably.

Next, with reference to FIG. 6, FIG. 7, the manufacturing method of the gas sensor element which concerns on embodiment of this invention is demonstrated.
FIG. 6A is a perspective view showing a configuration of a mask jig 60 used when the inner electrode 50 is formed on the inner surface of the solid electrolyte body 3s. The mask jig 60 is a member that is mounted on the inner surface of the solid electrolyte body 3s and masks a portion (mask portion) that does not need to form an inner electrode as a non-plated portion.
The mask jig 60 has a parallel cut portion 60c along the axis O direction. The mask outer surface 60s in contact with the mask portion forms an arc in a cross section cut in a direction (radial direction) orthogonal to the axis O direction. The leading edge 60e of the mask jig 60 is slanted at an angle with respect to the radial direction, and the leading edge 60e falls from the cut portion 60c toward the leading edge 60t (see side view 6B). ). Although the material of the mask jig | tool 60 is not specifically limited, For example, resin (for example, polypropylene, polyethylene, PET) which has elasticity can be used. Further, the mask jig 60 can be elastically deformed in the direction in which the diameter expands and contracts.
On the other hand, the rear end portion 60h of the mask jig 60 expands in a tapered shape from the mask outer surface 60s, and a flange portion 60f extends radially outward from the rear end portion 60h.

Further, the angle θ formed by the outline 60g of the notch 60c and the tangent tx of the tip edge 60e passes through the connection point D where the outline 60g of the notch 60c and the tip edge 60e of the mask jig 60 are connected. It is. Therefore, as will be described later, when the inner electrode 50 is formed using this mask jig, the inner lead portion 52 and the inner terminal connection portion 53 are plated on the cut portion 60c, and the inner detection portion is located on the tip side from the mask jig 60. 51 is plated. The angle θ of the mask jig 60 is the angle θ formed by the connection point D where the contour line g of the inner lead portion 52 and the tangent t of the rear end edge 51e of the inner detection portion 51 are connected (see FIG. 3). ).
In this embodiment, since the mask jig 60 falls from the cut portion 60c toward the tip edge 60t, the tip edge 60t tapered when the mask jig 60 is inserted into the inner surface of the solid electrolyte body 3s. This has an advantage that the mask jig 60 can be easily inserted.

Next, a method for manufacturing a gas sensor element using the mask jig 60 will be described.
First, the outer electrode 450 is formed on the outer surface of the solid electrolyte body 3s before the mask jig 60 is mounted using a known method (for example, see Japanese Patent Application Laid-Open No. 2007-248123).
Next, in the nucleation step, nuclei are attached to the inner surface of the solid electrolyte body 3s (see Patent Document 2). Specifically, a chloroplatinic acid aqueous solution (for example, platinum concentration; 0.5 g / L) is injected into the internal space of the solid electrolyte body 3s using a liquid injection device. The injection amount at this time may be adjusted so that the liquid level becomes the rear end edge of the terminal connection portion 53. Next, the aqueous solution of chloroplatinic acid is heated to form a coating film of the aqueous solution of chloroplatinic acid on the inner surface of the solid electrolyte body 3s. Thereafter, the chloroplatinic acid aqueous solution injected into the internal space of the solid electrolyte body 3s is discharged to the outside of the solid electrolyte body 3s using the liquid injection device.
Next, an aqueous hydrazine solution (for example, concentration: 5% by mass) is injected into the internal space of the solid electrolyte body 3s using the liquid injection device. Thereafter, the injected hydrazine aqueous solution is heated and left at 75 ° C. for 30 minutes. Thereby, platinum nuclei can be deposited on the inner surface of the solid electrolyte body 3s. Thereafter, the hydrazine aqueous solution injected into the internal space of the solid electrolyte body 3s is discharged to the outside of the solid electrolyte body 3s using the liquid injection device.

Next, as shown in FIG. 7A, the process proceeds to the mask jig mounting step, and when the mask jig 60 is inserted from the rear end opening of the solid electrolyte body 3s, the rear end portion 60h of the mask jig 60 becomes the solid electrolyte. It is possible to position the insertion depth of the mask jig 60 by closely adhering to the reverse taper surface of the rear end opening of the body 3s and engaging the front surface of the flange portion 60f with the rear end surface of the solid electrolyte body 3s. .
Since the curvature radius of the mask outer surface 60s before being mounted on the solid electrolyte body 3s is larger than the curvature radius of the mask portion (that is, the inner peripheral surface of the solid electrolyte body 3s), the diameter of the mask jig 60 is reduced. The mask jig 60 is inserted into the solid electrolyte body 3s while being elastically deformed to reduce the diameter. In the solid electrolyte body 3 s, the mask outer surface 60 s comes into contact with the mask portion by the elastic restoring force of the mask jig 60. Therefore, no gap is generated between the mask portion and the mask outer surface 60s, and it is possible to prevent unnecessary plating from being applied to the mask portion due to the plating solution flowing into the gap in the subsequent plating step.

Next, as shown in FIG. 7 (b), the process proceeds to a plating step, and a plating solution 80 in which nuclei deposited on the inner surface of the solid electrolyte body 3s act as a catalyst is used. ) Is deposited on the planned electrode portion (the planned detection portion 51x, the planned lead portion 52x, and the planned terminal connection portion 53x) on the inner surface of the solid electrolyte body 3s. Specifically, the plating solution 80 is injected into the internal space of the solid electrolyte body 3 s using the liquid injection device 81. At this time, the injection amount of the plating solution 80 may be adjusted so that the liquid level L becomes the rear edge of the terminal connection scheduled portion 53x. For example, a composition prepared by mixing a platinum complex salt aqueous solution (platinum concentration: 15 g / L) and a hydrazine aqueous solution (concentration: 85 mass%) can be used as the plating solution 80.
Next, the plating solution 80 injected into the internal space of the solid electrolyte body 3s is heated and then left for a predetermined time. Thereby, the platinum in the plating solution 80 can be deposited on the inner surface (the electrode planned portion) of the solid electrolyte body 3s. Thereafter, using the liquid injection device 81, the plating solution 80 injected into the internal space of the solid electrolyte body 3s is discharged to the outside of the solid electrolyte body 3s.
Therefore, when the inner electrode 50 is formed using the mask jig 60, the lead portion 52 and the terminal connection portion 53 are plated on the planned lead portion 52x and the planned terminal connection portion 53x located in the cut portion 60c, respectively. Moreover, the detection part 51 is formed in the detection scheduled part 51x located in the front end side from the mask jig | tool 60. FIG. Since the above-described angle θ of the mask jig 60 is the angle θ formed by the connection point C between the lead portion 52 and the detection portion 51 (see FIG. 3), the stress concentration at the connection point C is reduced, and the gas sensor element. The above-described effect that the inner electrode 50 becomes difficult to peel off from the vicinity of the connection portion even when the battery is subjected to the cooling / heating cycle.

Next, the process proceeds to a mask jig removing step, and the mask jig 60 is removed from the plated solid electrolyte body 3s. Since the mask jig 60 is only fixed to the mask portion in the solid electrolyte body 3s by its own elastic restoring force, it can be easily removed.
Thereafter, the process proceeds to a reduction treatment step, and the plated solid electrolyte body 3s is heat-treated in a reducing atmosphere at 750 ° C., for example. Accordingly, oxygen adsorbed on the surface of the inner electrode (platinum plating) can be removed, and the inner electrode (platinum plating) can be baked on the inner surface of the solid electrolyte body 3s to give predetermined characteristics. In this way, the gas sensor element 3 is completed.
Further, the gas sensor element 3 can be assembled to the gas sensor 100 (see FIG. 1) by a known assembling method (for example, see Japanese Patent Application Laid-Open No. 2004-053425).

Next, a gas sensor element according to a second embodiment of the present invention will be described with reference to FIGS. Since the gas sensor element according to the second embodiment is the same as the gas sensor element according to the first embodiment except that the configuration of the inner electrode 150 is different, illustration and description of the same parts are omitted.
As shown in FIG. 8 and FIG. 9, the inner electrode 150 is formed on the inner peripheral surface of the solid electrolyte body 3 s and is located on the tip side and formed over the entire circumference in the circumferential direction. An elongated lead part 152 that extends toward the end and is formed in a part in the circumferential direction and narrower in the radial direction than the detection part 151, and is formed wider than the lead part 152 positioned on the rear end side from the lead part 152. And a terminal connecting portion 153.
Here, the outline g of the lead portion 152 has a letter C shape extending in the radial direction toward the distal end side, and the rear end edge 151e of the detection portion 151 is on the same horizontal plane S2. Therefore, also in the second embodiment, the contour line g of the lead portion 152 and the detection portion 151 pass through the connection point C where the contour line g of the lead portion 152 and the tangent t of the rear end edge 151e of the detection portion 151 are connected. The angle θ formed by the tangent t of the rear end edge 151e of 151 is an obtuse angle. For this reason, even when the gas sensor element is subjected to a thermal cycle, the stress concentration on the edge C of the joint portion is reduced, and the inner electrode 150 is difficult to peel from the vicinity of the connection portion, as in the first embodiment. .

FIG. 10A is a perspective view showing the configuration of the mask jig 62 used when forming the inner electrode 150 on the inner surface of the solid electrolyte body 3s. The mask jig 62 is also a member that is mounted on the inner surface of the solid electrolyte body 3s and masks a portion (mask portion) that does not need to form the inner electrode as a non-plated portion.
The mask jig 62 has a cut portion 62c along the axis O direction. The mask outer surface 62s in contact with the mask portion forms an arc in a cross section cut in a direction (radial direction) orthogonal to the axis O direction. The leading edge 62e of the mask jig 62 is parallel to the radial direction.
On the other hand, the rear end portion 62h of the mask jig 62 has a diameter larger than that of the mask outer surface 62s, and a flange portion 62f extends radially outward from the rear end portion 62h.
Further, the rear end side of the cut portion 62c further expands stepwise in the radial direction to form a widened portion 62d. For this reason, when the cut portion 62c is plated, the terminal connection portion 153 wider than the lead portion 152 can be formed in the widened portion 62d on the rear end side from the stepped portion.

As shown in FIG. 10 (b), the notch 62c has a square shape that expands in the radial direction toward the tip. For this reason, although the tip edge 62e is horizontal, the contour line 62g of the notch 62c passes through the edge D of the joint between the notch 62c and the tip edge 62e of the mask jig 62, and the tip edge. The angle θ formed with the tangent tx of 62e becomes an obtuse angle. Therefore, when the inner electrode 150 is formed using the mask jig 62, the lead portion 152 is plated on the cut portion 62 c, and the detection portion 151 is plated on the tip side from the mask jig 62.
Accordingly, when the inner peripheral surface of the solid electrolyte body 3 s on which the mask jig 62 is mounted is plated in the same manner as in FIG. 7, the above-described angle θ of the mask jig 62 causes the contour line g of the lead portion 152 and the detection portion 151 to follow. Since the angle θ is formed with the tangent t of the edge 151e (see FIG. 8), the stress concentration on the edge C of the joint is reduced, and the inner electrode 150 is in the vicinity of the connection even if the gas sensor element is subjected to a thermal cycle. The above-described effect that it becomes difficult to peel off from the substrate similarly occurs.

Next, a gas sensor element according to a third embodiment of the present invention will be described with reference to FIG. Since the gas sensor element according to the third embodiment is the same as the gas sensor element according to the first embodiment except that the configuration of the inner electrode 250 is different, illustration and description of the same parts are omitted.
As shown in FIG. 11, the inner electrode 250 is formed on the inner peripheral surface of the solid electrolyte body 3s, is located on the front end side and is formed over the entire circumference, and extends from the detection unit 251 toward the rear end. And an elongated lead portion 252 that is formed in a part in the circumferential direction and narrower in the radial direction than the detection portion 251, and a terminal connection portion (not shown) located on the rear end side from the lead portion 252 are integrally formed. Have. The terminal connection portion has the same shape as that of the first embodiment.
Here, the outline g of the lead part 252 is a straight line parallel to the direction of the axis O, and the rear end edge 251e of the detection part 251 extends horizontally. On the other hand, the end edge (corner) of the joint portion between the lead portion 252 and the detection portion 251 is slanted. Accordingly, if it is considered that the oblique portion is included in the detection unit 251, the boundary portion between the oblique portion and the lead portion 252 becomes the connection point C1, passes through the connection point C1, and the outline g1 of the lead portion 152 and the detection portion. An angle θ <b> 1 formed with a tangent t <b> 2 (= the oblique portion) of the rear end edge of 251 is an obtuse angle. On the other hand, assuming that the oblique portion is included in the lead portion 252, the boundary portion between the oblique portion and the detection portion 251 becomes the connection point C2, passes through the connection point C2, and the outline g2 of the lead portion 152 (= the oblique portion). ) And the tangent t1 of the rear edge 251e of the detection unit 251 is an obtuse angle. In this way, since the angles θ1 and θ2 are obtuse in any case, even if the gas sensor element is subjected to a thermal cycle, the stress concentration on the edge C1 or C2 of the joint portion is reduced, and the inner electrode 250 is near the connection portion. As in the first embodiment, it is difficult to peel off the film.

  It goes without saying that the present invention is not limited to the above-described embodiment, but extends to various modifications and equivalents included in the spirit and scope of the present invention. For example, the shape of the inner electrode is not limited to the above.

The gas sensor element 3 was manufactured by changing the angle θ of the inner electrode 50 of FIG. 3 by changing the cut-off angle of the leading edge 60e of the mask jig 60 of FIG. As the solid electrolyte body, ZrO _{2 in} which Yb ₂ 0 ₃ was dissolved was used, and the inner electrode 50 and the outer electrode were each formed by electroless plating of Pt having a thickness of 1 μm. And this gas sensor element 3 was assembled | attached and the gas sensor 100 shown in FIG. 1 was obtained.
The gas sensor 100 was repeatedly heated and cooled for a predetermined time in the cooling cycle shown in FIG. 12, the gas sensor element 3 was cut after the test, and the peeling state of the connection point C of the inner electrode 50 was observed with an electron microscope. The cooling cycle is a total of 1/30 cycle in which heating is stopped from 100 ° C. or lower for 15 minutes and the maximum temperature reached 650 ° C. or higher, then heating is stopped and air cooling is performed for 15 minutes to set the minimum temperature to 100 ° C. or lower. Was repeated.
The obtained results are shown in Table 1. In addition, (circle) of a table | surface shows no peeling and x shows peeling.

  As is clear from Table 1, in Examples 1 to 3 where the angle θ is an obtuse angle, the inner electrode did not peel from the solid electrolyte body at the connection point C even when the cooling cycle was repeated for 300 hours or more. On the other hand, in the case of the comparative example in which the angle θ is an acute angle (90 degrees), the connection point C peeled off when the cooling / heating cycle was repeated for 300 hours or more.

3 Gas sensor element 3s Solid electrolyte body 20 Metal shell 50, 150, 250 Inner electrode 51, 151, 251 Inner detection part 51e, 151e, 251e Rear edge 52, 152, 252 Inner lead part 60, 62 Mask treatment Tool 60s, 62s Mask outer surface 60c, 62c Notch 60e, 62e Edge edge of mask jig 60g, 62g Outline of notch 80 Plating solution 100 Gas sensor 450 Outside electrode 451 Outside detector 452 Outside lead C, C1, C2 connection Point D Connection point g, g2 Contour line of lead part passing through edge of joint part t, t2 Tangent line of rear end edge of detection part passing through edge part of joint part θ, θ1, θ2 Contour line of lead part and detection part The angle between the tangent line of the rear edge and the angle between the contour line of the notch and the tangent line of the leading edge of the mask jig. O Axial direction

Claims (6)

A solid electrolyte body formed in a bottomed cylindrical shape extending in the axial direction and closed at the tip, an inner electrode made of a plating layer provided on the inner surface of the solid electrolyte body, and provided on the outer surface of the solid electrolyte body A gas sensor element having an outer electrode formed,
The inner electrode has an inner detection portion located on the front end side, and one inner lead portion extending from the inner detection portion toward the rear end side and narrower in the circumferential direction than the inner detection portion,
The inner detector is formed over the entire circumferential direction on the inner surface of the solid electrolyte body,
The inner side formed by the contour line of the inner lead part and the tangent line of the rear end edge of the inner detection part passing through a connection point where the contour line of the inner lead part and the rear edge of the inner detection part are connected. Ri corner obtuse der possible in the circumferential direction outwardly of the lead portion,
The trailing edge sensor element under standing toward the tip that the inner sensing portion with distance from the connection point.   The gas sensor element according to claim 1, wherein an outline of the lead portion is a straight line parallel to the axial direction. Before Kisotogawa electrode has an outer sensing portion located on the distal end side extends toward the rear end side from the outer sensing portion, and said width than the outer sensing portion in the circumferential direction narrow outer lead portion,
The outer detection section is provided over a part in the circumferential direction on the outer surface of the solid electrolyte body provided on the opposite side to the inner surface of the solid electrolyte body on which the inner lead portion is formed. The gas sensor element according to claim 1 or 2.   The gas sensor element according to claim 3, wherein a rear end edge of the outer side detection unit is formed on a front end side with respect to a rear end edge of the inner side detection unit. A gas sensor comprising a sensing element that detects a specific gas in a gas to be measured, and a metal shell that holds the gas sensor element,
A gas sensor comprising the gas sensor element according to claim 1 as the detection element. A nucleation step of attaching nuclei to the inner surface of a bottomed cylindrical solid electrolyte body extending in the axial direction;
Using a plating solution in which the nucleus acts as a catalyst, a plating step of depositing a metal in the plating solution on the inner surface of the solid electrolyte body,
A gas sensor element manufacturing method for forming an inner electrode made of the metal on the inner surface of the solid electrolyte body,
Prior to the plating step, a mask jig mounting step of mounting a mask jig on a mask portion different from an electrode planned portion that is to form the inner electrode on the inner surface of the solid electrolyte body,
The plating step of depositing the metal on the planned electrode portion, and
The mask jig has a cut portion extending along the axial direction, and falls from the cut portion toward a leading edge, and when the mask jig is attached to the mask portion, It has a cylindrical shape with the mask outer surface in contact,
In addition, the cut portion formed by the contour line of the cut portion and the tangent line of the tip edge passes through a connection point where the contour line of the cut portion and the tip edge of the mask jig are connected on the outer surface of the mask. The angle that can be made outside in the circumferential direction is an obtuse angle,
In the mask jig mounting step,
The mask jig is inserted inside the solid electrolyte body while elastically deforming the mask jig in a direction in which the diameter of the mask jig is reduced, and the outer surface of the mask is moved by the elastic restoring force of the mask jig. A method for manufacturing a gas sensor element to be brought into contact with the mask portion.

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