JP3518706B2 - Manufacturing method of gas sensor element - Google Patents

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a working electrode, a solid electrolyte layer, a reference electrode (those having three or more are hereinafter also simply referred to as a "gas detector"), and a ceramic plate having a heater (hereinafter, "gas detector"). The present invention relates to a gas sensor element having a novel structure consisting of a "heater substrate"). For more information,
The present invention relates to a method for manufacturing a gas sensor element having a structure in which a heater substrate and a solid electrolyte layer are bonded to each other via a reference electrode or a working electrode. Further, when the electrode used for bonding is a reference electrode, the gap generated between the heater substrate and the solid electrolyte layer when bonded as described above was sealed with a gas impermeable substance.
The present invention relates to a method for manufacturing a gas sensor element .

2. Description of the Related Art Conventionally, measurement of the concentration of inorganic gases such as carbon dioxide, nitrogen oxides and sulfur oxides in the atmosphere in various fields has been used for data such as combustion control and environmental measurement. For the measurement of such inorganic gas, various analysis methods such as infrared absorption method, ultraviolet absorption method or chemiluminescence method have been mainly adopted, but the problem that the device is large, expensive and maintenance is required has been pointed out. Was there.
For these devices, a solid electrolyte type gas sensor element that utilizes a change in electromotive force of a solid electrolyte has been proposed as a small, simple and inexpensive gas sensor element. The sensor element is generally composed of an ion-conducting solid electrolyte layer, a reference electrode made of an electron-conducting substance, a metal salt having dissociation equilibrium with a gas to be detected (hereinafter also simply referred to as "metal salt"), and an electron-conducting substance. Is composed of a working electrode. FIG. 2 is a sectional view of a conventional typical gas sensor element. In this gas sensor element, a pair of electrodes 6 and 8 are formed on both surfaces of a solid electrolyte layer 7 which is a cation conductor, and a metal salt 9 having dissociation equilibrium with a gas to be detected is formed on one of the electrodes 8. It is the structure provided. When the concentration of the gas to be detected changes, the solid electrolyte layer 7
Since the electromotive force generated between the electrodes 6 and 8 formed on both sides of the electrode changes, the electromotive force change is measured by the voltmeter 5, and the correlation between the electromotive force created in advance and the concentration of the detected gas is measured. It is intended to know the concentration of the gas to be detected by using a calibration curve indicating The gas sensor element is used after being heated to 300 to 700 ° C., which is a temperature required for the solid electrolyte layer 7 to exhibit a certain ionic conductivity or more. The heating for this may be performed by side heat from the outside of the sensor element, but in consideration of downsizing of the gas sensor element, it was necessary to attach a heater substrate capable of self-heating.

However, in order to attach the heater substrate to the gas detecting portion, the adhesive layer 4 using an inorganic adhesive or the like is required, so that the heat conduction from the heater substrate to the gas detecting portion is required. There was a problem that the stabilization time of the initial electromotive force of the gas sensor element immediately after the application of the heater voltage was prolonged due to the inhibition and the manufacturing process was complicated. Further, by providing the adhesive layer 4, when heating and non-heating are repeated, there is a possibility that problems such as peeling may occur due to the difference in the coefficient of thermal expansion of the material used. Therefore, it has been desired to develop a gas sensor element integrated with a heater substrate, which has a structure excellent in heat conduction from the heater substrate to the gas detection unit, and which can reduce the size of parts and simplify the process.

The inventors of the present invention have solved the above problems, and have conducted extensive research on a gas sensor element having excellent heat conduction and capable of simplifying the manufacturing process. As a result, by removing the adhesive layer 4 and directly joining the heater substrate and the solid electrolyte layer 7 with the electrode 6, heat conduction from the heater substrate to the gas detection portion becomes efficient, and as a result, the initial electromotive force is stabilized. As a result, it has become possible to shorten the process time, further simplify the manufacturing process, and propose the present invention. That is,
The present invention provides an adhesive conductive paste or an adhesive conductive paste on one surface of a solid electrolyte layer and on one surface of a ceramic plate on which a heater is formed, on which a heater is not formed.
Apply a mixture of electro-deposition paste and metal salt,
The quality layer and the ceramic plate are laminated and fired.
And the adhesive conductive paste or the adhesive conductive
Mix the paste and metal salt with the reference or working electrode.
Gas to bond the solid electrolyte layer and the ceramic plate
And a method of manufacturing a sensor element. Also, in the solid electrolyte layer
Ceramic plate with heater formed on one side and one side
On one of the surfaces of the
Mixing electric paste or adhesive conductive paste with metal salt
The solid electrolyte layer and the ceramic plate
By bonding and firing
Mixture of paste or adhesive conductive paste and metal salt
As the reference electrode or working electrode, and the solid electrolyte layer and the ceramic
The solid electrolyte layer and the ceramic plate.
Apply a gas impermeable substance to the side surface of the bonded plate
After firing, gas is generated in the gap between the solid electrolyte layer and the ceramic plate.
A method of manufacturing a gas sensor element that is sealed with an impermeable substance.
is there.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below in detail with reference to the accompanying drawings, but the present invention is not particularly limited to these accompanying drawings. FIG. 1 shows the gas obtained by the present invention .
It is sectional drawing which shows the typical aspect of a sensor element . The present invention
In the gas sensor element obtained in 1., electrodes 6 and 8 made of an electronically conductive substance are formed on both surfaces of a solid electrolyte layer 7, and a metal salt 9 having dissociation equilibrium with the gas to be detected is further formed on the electrode 8. . The electrode 8 and the metal salt 9 formed on one surface of the solid electrolyte 7 constitute a working electrode, and the electrode 6 formed on the other surface thereof constitutes a reference electrode. Then, one surface of the solid electrolyte 7 and the surface of the heater substrate formed by forming the heater 2 on the ceramic plate 3 on which the heater is not formed are directly bonded via the working electrode or the reference electrode. In the present invention, as the solid electrolyte substance forming the solid electrolyte layer 7, a substance having ion conductivity and being solid under the use condition is generally used. For example, Na _{1 + X} Z having ionic conductivity of sodium, lithium, etc.
r ₂ Si _X P _3-X O ₁₂ (where 0 ≦ x ≦ 3) (hereinafter, also referred to as NASICON), β-Al ₂
O ₃ , β-Ga ₂ O ₃ , Li _16-2y Zn _y (GeO ₄ ) ₄ (provided 0 ≦ y <8) (hereinafter, referred to as a silicon (LISIC)
ON)), Li ₄ GeO ₄ .Li ₃ VO _4, etc. are preferably used. Although the thickness of the solid electrolyte layer 7 is not particularly limited, it is generally adopted in the range of 0.2 to 1.5 mm. As the electron conductive substance forming the electrodes 6 and 8 in the present invention, known materials are used without particular limitation. For example, noble metals such as platinum, gold, silver, palladium, rhodium and oxides thereof, and the general formula La _1-z Sr _z BO ₃ (where B represents an element selected from Co, Cu, Fe and Ni) , Z represents a number of 0.01 to 0.5), and a composite composition in which the noble metal or the noble metal oxide and the perovskite oxide are mixed. Of these, noble metals such as platinum, gold, silver, palladium, rhodium, etc., particularly platinum and gold are preferably used. The thickness of the electrodes 6 and 8 is not particularly limited, but is generally within the range of 2 to 20 μm. In the present invention,
The metal salt 9 can be used without any limitation as long as it has dissociation equilibrium with the gas to be detected. Particularly, carbonates of alkali metals such as Na, Li and K, carbonates of alkaline earth metals such as Ca, Mg and Ba, carbonates of Bi, Ag, La and Cu, or N
Sulfates and nitrates of alkali metals such as a, Li and K and alkaline earth metals such as Ca, Mg and Ba can be used.
These metal salts can be selected according to the type of gas to be detected. For example, when the gas to be detected is carbon dioxide, carbonate is used, when it is sulfur oxide, sulfate is used, and when it is nitrogen oxide, nitrate is used. In the present invention, the electrode 8 and the metal salt 9 formed on one surface of the solid electrolytic layer 7 constitute a working electrode, and the electrode 6 formed on the other surface thereof constitutes a reference electrode. The electrode 8 and the metal salt 9 forming the working electrode are
As shown in FIG. 1, it may exist as a separate layer, or as shown in FIG. 3 described later, a metal salt may be dispersed in the electrode to form a mixed working electrode 10 having one layer.
The heater substrate used heretofore can be used without any limitation. In general, a heater in which a metal or metal oxide paste is applied and fired on the semix plate 3 is provided and a direct current or an alternating current is applied to the heater from a power source is preferably used. As the ceramics plate 3, conventionally known ones can be used without limitation, but generally, ceramics plates such as alumina, mullite, aluminum nitride and glass are preferably used. As the heater material, conventionally known resistors are used without limitation, but generally, metals such as platinum, gold, rhodium and palladium, or metal oxides such as ruthenium oxide are preferably used. The ceramic plate 3 efficiently conducts the heat of the heater to the solid electrolyte layer,
It is preferable that the thickness is not too thick, and a thickness in the range of 0.2 to 1.0 mm is generally used.
In the gas sensor element obtained in the present invention, one surface of the solid electrolyte 7 and the surface of the heater substrate formed by forming the heater 2 on the ceramic substrate 3 on which the heater is not formed are
It is directly bonded via a working electrode or a reference electrode.
Therefore, the working electrode or reference electrode used for joining the solid electrolyte layer and the heater substrate needs to have both electron conductivity and adhesiveness. In this case, the formed working electrode or reference electrode itself may have adhesiveness, or may exhibit adhesiveness when the working electrode or reference electrode is formed. In general,
The electrodes are preferably formed using an adhesive conductive paste having both adhesiveness and conductivity. As the adhesive conductive paste, a composition comprising the above-mentioned electron conductive substance, adhesive, organic polymer compound and organic solvent can be preferably used. As the adhesive material, glass frit or metal oxide is preferably used. As the glass frit, known ones can be used without any limitation, and for example, borosilicate glass, barium glass, silicate glass, lead glass, alkali silicate glass and the like are preferable. Further, as the metal oxide, Al ₂ O ₃ , Bi ₂ O ₃ , PbO, CdO, ZnO,
BaO, CaO and the like are preferably used. As the organic polymer compound, known compounds can be used without any limitation, but generally, acrylic resins such as acrylic acid esters and methacrylic acid esters, butyral resins such as polyvinyl butyral, ethyl cellulose, acetyl cellulose,
Cellulose derivatives such as methyl cellulose can be mentioned. As the organic solvent, any organic solvent capable of dissolving the above organic polymer compound can be used without any limitation. For example, aliphatic hydrocarbons such as n-hexane and n-pentane; aromatics such as toluene and xylene. Group hydrocarbons;
Alcohols such as methyl alcohol and cyclohexyl alcohol; glycols such as ethylene glycol and propylene glycol; ketones such as cyclohexanone and isophorone; glycol derivatives such as terpineol, butyl carbitol acetate and ethylene glycol monomethyl ether; acetic acid ester, acetic acid Examples thereof include esters such as isopropyl. The amount of adhesive compounded is
It is preferably in the range of 3 to 20 parts by weight with respect to 100 parts by weight of the electron conductive material. The compounding amount of the organic polymer compound is in the range of 1 to 10 parts by weight with respect to 100 parts by weight of the electron conductive substance, and the organic solvent is in the range of 5 to 30 parts by weight with respect to 100 parts by weight of the electron conductive substance. Is preferred. The adhesive conductive paste is applied to the solid electrolyte layer or the ceramic plate. As a coating method, a known method can be adopted, and examples thereof include brush coating, a dispenser, and various printing methods. Among these, it is preferable to use a printing method such as a screen printing method or an offset printing method because the electrodes can be formed with high accuracy. An electrode is formed by baking after applying the adhesive conductive paste. 1 and 3 show a mode in which the solid electrolyte layer 7 and the ceramic plate 3 are joined via the electrode 6 which can serve as a reference electrode, the mixed working electrode 10 may be formed as a working electrode as described above. In that case,
A gas sensor element in which the solid electrolyte layer 7 and the ceramic plate 3 are joined via the mixed working electrode 10 is also possible. In the present invention, when the solid electrolyte layer 7 and the ceramic plate 3 are joined via the reference electrode, the reference electrode in the gap between the solid electrolyte layer 7 and the ceramic plate 3 does not come into contact with the outside air as shown in FIG. As described above, the gas sensor element of the aspect in which the gas impermeable layer 11 is formed by sealing the gap between the solid electrolyte layer 7 and the ceramic plate 3 with the gas impermeable substance is suitable. As the gas-impermeable substance, conventionally known substances can be used without any limitation as long as they do not pass the gas to be detected or a contaminant gas such as water vapor. Generally, glass, ceramics, metal and the like can be mentioned, but glass and ceramics are preferable, and glass is more preferable in terms of operability. When using the gas sensor element obtained in the present invention, in order to prevent malfunctions due to the influence of miscellaneous gases contained in the gas to be detected, for example, organic gases such as toluene, ethyl acetate, and ethanol, to remove the organic gas. You may use the filter of. As the filter, known filters can be used without any limitation. Gas obtained by the present invention
The sensor element is manufactured by the following manufacturing method. First, the solid electrolyte layer 7 can be manufactured by a known method. As a typical production method, powder of a solid electrolyte substance, a powder obtained by adding a molding aid to the powder, and a powder obtained by adding a binder to the powder and then granulating the powder are subjected to 1000 to 1300.
A method of sintering at 5 ° C. for 5 to 30 hours, a powder of a solid electrolyte substance is kneaded with a binder made of an organic polymer compound, a plasticizer and a solvent to form a paste, and a green sheet is prepared by a doctor blade method or the like. 1000 to 1300
A method of sintering at 5 ° C. for 5 to 30 hours, a method of laminating a solid electrolyte substance on a substrate using a thin film forming method such as vacuum deposition, a sputtering method, and the like are suitably used. As the above-mentioned molding aid, binder, plasticizer and solvent, known materials can be used without any limitation. Generally, polyvinyl alcohol, polyethylene glycol, as a molding aid,
Ethyl cellulose, polyvinyl methyl ether, hydroxypropyl cellulose and the like, as the binder ethyl cellulose, polyvinyl butyral, abietic acid resin, polyvinyl alcohol and the like, as the plasticizer polyethylene glycol, polyalkylene glycol, phthalic acid ester and the like, as the solvent Toluene, methyl ethyl ketone, etc. are used. The following method can be preferably used for forming the electrode on the one surface of the solid electrolyte layer.
The adhesive conductive paste or the mixture of the adhesive conductive paste and the metal salt is applied to one surface of the solid electrolyte layer 7 by a method such as brush painting, dispenser or printing. Then
Dry the paste at 100-200 ° C. for 0.5-1 hour,
Baking is performed at 500 to 1000 ° C. for 0.5 to 2 hours. To bond the heater substrate to the solid electrolyte layer 7, an adhesive conductive paste or a mixture of the adhesive conductive paste and a metal salt was applied to one surface of the solid electrolyte layer 7 or the surface of the ceramic plate 3 on which the heater 2 was not formed. After that, the solid electrolyte layer 7
And the heater substrate, and then proceed as above.
U When the layer of the metal salt 9 is formed as a layer different from the electrode layer, a method of dropping and impregnating a solution or suspension of the metal salt on the electrode 8 as shown in FIG. 1, or A paste prepared by mixing an organic polymer compound or an organic solvent used in the preparation of the adhesive conductive paste with a metal salt is applied onto the electrode by a method such as screen printing or brush coating,
Generally used is a method of firing at a temperature below the temperature at which the metal salt is not decomposed, preferably above the melting temperature. The method for forming the gas impermeable layer 11 is not particularly limited,
Generally, the powder of the gas-impermeable substance described above is dispersed in an organic solvent in which an organic polymer compound is dissolved to form a paste,
A method of pouring into the gap between the solid electrolyte layer 7 and the ceramic plate 3 and firing at 500 to 800 ° C. for 0.5 to 2 hours is preferably used. Further, after applying the adhesive conductive paste of the reference electrode used for joining the solid electrolyte layer and the heater substrate, after applying the gas impermeable substance paste in a donut shape around it and joining the solid electrolyte layer and the heater substrate The method of firing under the above conditions is also suitable.

The gas sensor element obtained by the present invention adheres the electron conductive material formed for the electrode without using the adhesive layer used for joining the conventional heater substrate and the gas detecting portion. Since it is intended to be used as a layer as well, the efficiency of heat conduction from the heater substrate to the gas detection part will be improved, and the stabilization time of the initial electromotive force of the gas sensor element immediately after applying the heater voltage is shortened. It becomes possible to do. In addition, the method for manufacturing the gas sensor element can reduce the size of the component parts and simplify the process, and has great industrial significance. By removing the conventionally used adhesive layer, when heating and non-heating are repeated, it is expected that the occurrence of problems such as peeling due to the difference in the coefficient of thermal expansion of the member being used can be reduced. Furthermore, by sealing the gap between the heater substrate and the solid electrolyte layer with a gas impermeable substance, the gas sensor element is stable for a long period of time even when exposed to a high humidity atmosphere or a high concentration of undesired gas. The electromotive force is shown.

[Function] In a gas sensor element that requires heating, since the efficiency of heat conduction from the heater substrate to the gas detection unit is directly connected to the power consumption of the heater, effective heat conduction is an important factor for reducing power consumption. Become. To achieve this, joining by material having excellent thermal conductivity, but shortening the distance between the heater substrate and the gas detecting portion is considered, in the present invention
In the obtained gas sensor element, it is considered that the distance can be shortened by removing the adhesive layer, and effective heat conduction can be achieved by directly joining the electrodes with excellent heat conductivity. Generally, the stabilization time of the initial electromotive force of the solid electrolyte type gas sensor element is considered to depend on the thermal stabilization time of the gas sensor element after application of the heater voltage, and is obtained by the present invention.
It is considered that the heat stabilization time of the gas sensor element is shortened by the efficient heat conduction from the heater substrate to the gas detection portion, and thus the stabilization time of the initial electromotive force is also shortened. The mode in which the gap between the heater substrate and the solid electrolyte layer is sealed with a gas impermeable layer is considered to have made the above-described action more effective by eliminating the air having the worst thermal conductivity. To be

EXAMPLES The present invention will be described with reference to the following examples in order to specifically describe the present invention, but the present invention is not limited to these examples. Example 1, Comparative Example 1 A carbon dioxide sensor having a structure as shown in FIG.
Then, a carbon dioxide sensor as shown in FIG. 2 was produced in Comparative Example 1. The solid electrolyte layer 7 has a diameter of 4 mm and a thickness of 0.5 mm by uniaxially molding NASICON powder obtained by adding 5% by weight of polyvinyl alcohol as a binder and granulating with a spray dryer, and then sintering at 1200 ° C. for 12 hours. A disc-shaped chip was prepared. Further, the heater substrate was screen-printed in a corrugated pattern with a commercially available platinum paste on a ceramic plate 3 (thickness: 0.6 mm) made of alumina.
It was formed by drying at 00 ° C. for 1 hour and baking at 1000 ° C. for 1 hour. In the case of Example 1, a commercially available gold paste was screen-printed on one surface of the solid electrolyte layer described above,
An electrode 8 was formed by drying at 0 ° C for 1 hour, and a paste containing terpineol in which ethyl cellulose was dissolved and containing 5% by weight of lithium carbonate powder was screen-printed thereon and dried at 100 ° C for 1 hour. By doing so, a layer of metal salt 9 was formed. Then, a mixture of 9 parts by weight of borosilicate glass with 100 parts by weight of gold powder was mixed with 6 parts by weight of ethyl cellulose and 10 parts by weight of terpineol on the surface of the solid electrolyte layer on which the electrode 8 was not formed. It is melted into a paste to form a paste, which is printed, and before the paste is dried, the surfaces of the ceramic plate 3 on which the heater 2 is not formed are stuck together,
The electrode 6 was formed by drying at 6 ° C. for 1 hour. Finally,
A gas sensor element was produced by firing at 650 ° C. for 1 hour. In the case of Comparative Example 1, a commercially available gold paste was screen-printed on both sides of the solid electrolyte layer, and the step of drying at 100 ° C. for 1 hour was repeated on each side to form an electrode 6,
8 was formed. A layer of the metal salt 9 was formed on the electrode 8 by screen-printing the lithium carbonate paste used in Example 1 and drying at 100 ° C. for 1 hour. Finally, the gas detection part was produced by baking at 650 degreeC for 1 hour. After that, a commercially available glass paste is screen-printed on the electrode 6 as the adhesive layer 4, the surfaces of the ceramic plate 3 on which the heater 2 is not formed are pasted before the paste is dried, and the ceramic plate 3 is dried at 100 ° C. for 1 hour and 650 ° C. A gas sensor element was produced by baking for 30 minutes. The gas sensor element was heated to 450 ° C. by applying a DC voltage from the power source 1 to the heater 2. A platinum wire was taken out from the electrodes 6 and 8, and the electromotive force generated between both electrodes was measured with a voltmeter 5. The carbon dioxide gas sensitivity is evaluated by measuring the change in electromotive force when the gas sensor element is heated and left in 350 ppm which is almost equal to the carbon dioxide concentration in the atmosphere, and then the carbon dioxide concentration in the atmosphere is changed to 700, 1000 and 2000 ppm. I went there. The results are shown in Table 1, and it is found that the gas sensor element manufactured according to Example 1 is good in both electromotive force value and sensitivity as compared with the conventional gas sensor element manufactured according to Comparative Example 1. It was

[Table 1] The initial electromotive force stabilization was evaluated by leaving the gas sensor elements of Example 1 and Comparative Example 1 in a carbon dioxide concentration of 350 ppm.
At the same time, after applying the heater voltage, the time until the electromotive force of the sensor element reached within 3% of the final stable value was measured. The results are shown in Table 2, and the gas sensor element of Comparative Example 1 required 53 minutes, whereas Example 1
The gas sensor element of showed a stable electromotive force in 25 minutes. From the above, it has been clarified that the gas sensor element obtained in the present invention is superior in initial electromotive force stability as compared with the conventional gas sensor element.

[Table 2] Further, as a result of manufacturing 100 gas sensor elements of each of Example 1 and Comparative Example 1, the time for manufacturing the gas sensor element of Example 1 is about 80% of the time for manufacturing the gas sensor element of Comparative Example 1. From the above, it was found that the method of manufacturing the gas sensor element of Example 1 has a simplified process as compared with the conventional manufacturing method. Example 2 A carbon dioxide sensor element as shown in FIG. 3 was produced. The same solid electrolyte layer 7 and heater substrate as in Example 1 were used. Apply a commercially available gold paste on one side of the solid electrolyte layer.
Add 0% by weight of lithium carbonate, mix, adjust viscosity with thinner, paste-form, screen print,
The mixed working electrode 10 was formed by drying at 100 ° C. for 1 hour. On the other side, a mixture of 8 parts by weight of borosilicate glass and 4 parts by weight of ZnO was mixed with 100 parts by weight of gold powder, and 6 parts by weight of ethyl cellulose was dissolved in 15 parts by weight of terpineol. The paste was formed, screen-printed, the surfaces of the ceramic plate 3 on which the heater 2 was not formed were adhered before the paste was dried, and the paste was dried at 100 ° C. for 1 hour to form the electrode 6. Then, it baked at 650 degreeC for 1 hour. Further, the glass powder was made into a paste with terpineol in which 3% by weight of ethyl cellulose was dissolved, and the paste was applied from the side surface with a brush so that the paste would penetrate into the gap formed between the solid electrolyte layer 7 and the ceramic plate 3. A gas sensor element having the gas impermeable layer 11 formed was produced by drying at 1 ° C. for 1 hour and baking at 650 ° C. for 30 minutes. The gas sensor element was evaluated in the same manner as in Example 1, and the results are also shown in Table 1. It was found that the gas sensor element manufactured according to Example 2 was excellent in both electromotive force value and sensitivity as compared with the conventional gas sensor element manufactured according to Comparative Example 1. Furthermore, the initial electromotive force stabilization was evaluated in the same manner as in Example 1, and the results are also shown in Table 2. The electromotive force stabilization time of the gas sensor element of Example 2 was 23 minutes, which was sufficiently early.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a typical aspect of a gas sensor element of the present invention.

FIG. 2 is a cross-sectional view of a conventional representative gas sensor element.

FIG. 3 is a cross-sectional view showing another aspect of the gas sensor element of the present invention.

[Explanation of symbols]

1 power supply 2 heater 3 Ceramics plate 4 Adhesive layer 5 Voltmeter 6, 8 electrodes 7 Solid electrolyte layer 9 metal salts 10 Mixed working electrode 11 Gas impermeable layer

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) G01N 27/41 G01N 27/416 G01N 27/406

Claims (2)

(57) [Claims] 1. An adhesive conductive paste or an adhesive agent is provided on either one surface of a solid electrolyte layer or a ceramic plate having a heater formed on one surface thereof on which no heater is formed .
Apply a mixture of conductive paste and metal salt to
The degradation layer and the ceramics plate are laminated and fired.
The adhesive conductive paste or adhesive conductive
Electrolytic paste and metal salt mixture as reference or working electrode
And a method for manufacturing a gas sensor element, in which a solid electrolyte layer and a ceramics plate are joined together . 2. An adhesive conductive paste or adhesive property is provided on either one surface of the solid electrolyte layer or a surface of a ceramic plate having a heater formed on one surface thereof on which no heater is formed .
Apply a mixture of conductive paste and metal salt to
The degradation layer and the ceramics plate are laminated and fired.
The adhesive conductive paste or adhesive conductive
Electrolytic paste and metal salt mixture as reference or working electrode
Then, the solid electrolyte layer and the ceramic plate are bonded together , and then the side surface of the bonded body of the solid electrolyte layer and the ceramic plate
, A gas impermeable substance is applied and baked to form a solid electrolyte layer.
The gap between the ceramic plate and the ceramic plate with a gas impermeable substance
A method for manufacturing a gas sensor element.