JPS6117950A - Formation of electrode in detecting part of oxygen sensor - Google Patents
Formation of electrode in detecting part of oxygen sensorInfo
- Publication number
- JPS6117950A JPS6117950A JP59138597A JP13859784A JPS6117950A JP S6117950 A JPS6117950 A JP S6117950A JP 59138597 A JP59138597 A JP 59138597A JP 13859784 A JP13859784 A JP 13859784A JP S6117950 A JPS6117950 A JP S6117950A
- Authority
- JP
- Japan
- Prior art keywords
- oxygen sensor
- solid electrolyte
- noble metal
- layer
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
- G01N27/4075—Composition or fabrication of the electrodes and coatings thereon, e.g. catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Measuring Oxygen Concentration In Cells (AREA)
Abstract
Description
【発明の詳細な説明】 (発明の属する技術分野) 本発明は酸素センサ検出部の電極形成法に関する。[Detailed description of the invention] (Technical field to which the invention pertains) The present invention relates to a method for forming electrodes of an oxygen sensor detection section.
(従来技術とその問題点) ・
従来は、未焼成の酸素イオン伝導性固体電解質(以下固
体電解質という)成形体又は仮焼体に白金ベーストを塗
布し、白金ベーストを焼き付けて電極を形成していた。(Prior art and its problems) - Conventionally, electrodes were formed by applying platinum base to an unfired oxygen ion conductive solid electrolyte (hereinafter referred to as solid electrolyte) compact or calcined body, and then baking the platinum base. Ta.
この電極形成法によって得られた酸素センサは寿命が長
いという長所はあるが9反面抵抗が高いという欠点があ
る。The oxygen sensor obtained by this electrode formation method has the advantage of long life, but has the disadvantage of high resistance.
上記欠点に対し固体電解質の焼結体にガラス分を含有し
た白金ベーストを低温で焼き付けて電極とするものが試
みられたが、ガラス分を含有させると酸素イオンの拡散
を妨げるという欠点が生じる。更に固体電解質の焼結体
−ヒに直接白金メッキを施し、抵抗の小さい酸素センサ
が提案されているが、この方法では電極厚みが薄く、焼
結体との密着性が弱いため電極が剥離し易く酸素センサ
の寿命が短いという欠点がある。To address the above drawbacks, attempts have been made to make electrodes by baking a glass-containing platinum base into a solid electrolyte sintered body at low temperatures, but the drawback is that the inclusion of glass impedes the diffusion of oxygen ions. Furthermore, a low-resistance oxygen sensor has been proposed in which a solid electrolyte sintered body is directly plated with platinum, but with this method, the electrodes are thin and the adhesion to the sintered body is weak, resulting in the electrodes peeling off. The disadvantage is that the oxygen sensor is easily used and the life of the oxygen sensor is short.
(発明の目的)
本発明はかかる欠点のない酸素センサ検出部の電極形成
法を提供することを目的とするものである。(Object of the Invention) An object of the present invention is to provide a method for forming electrodes of an oxygen sensor detecting section without such drawbacks.
(問題点を解決するための手段)
本発明者らは上記の欠点に鑑み種々検討した結果、未焼
成の固体電解質成形体又は仮焼体に貴金属ベーストを塗
布したのち焼成して貴金属ベーストを焼き付け、その後
その土面に触媒活性な金属層を設けたところ上記欠点の
ない酸素センサを得ることができた。(Means for Solving the Problems) The inventors of the present invention have conducted various studies in view of the above-mentioned shortcomings, and have found that a noble metal base is applied to an unfired solid electrolyte molded body or a calcined body, and then fired to bake the precious metal base. Then, when a catalytically active metal layer was provided on the soil surface, an oxygen sensor without the above-mentioned drawbacks could be obtained.
本発明は未焼成の固体電解質成形体又は仮焼体に貴金属
ベーストを塗布1−たのち焼成して貴金属ベーストを焼
き付け、その後その上面に触媒活性な金属層を設ける酸
素センサ検出部の電極形成法に関する。The present invention is a method for forming electrodes of an oxygen sensor detection part, in which a noble metal base is coated on an unfired solid electrolyte molded body or a calcined body, and then the noble metal base is baked, and a catalytically active metal layer is then formed on the upper surface of the noble metal base. Regarding.
詳し7くは未焼成の固体電解質成形体又は仮焼体に貴金
属ベーストを塗布し、固体電解質の層に貴金属ベースト
をじみと1せ、貴金属の蒸発しない温度で焼成すること
によって第2図に示すよう碌固体電解質1の層に貴金属
2を入り込ませた状態にする。さらにこの貴金属20層
上に触媒活性な金属層を設けて第1図に示すように貴金
属20層上に金属の粒子3を密着させ電極を形成する。In detail, as shown in Fig. 2, a noble metal base is applied to an unfired solid electrolyte molded body or a calcined body, the noble metal base is soaked in the solid electrolyte layer, and fired at a temperature at which the precious metal does not evaporate. A noble metal 2 is introduced into a layer of a strong solid electrolyte 1. Further, a catalytically active metal layer is provided on the 20 layers of noble metal, and as shown in FIG. 1, metal particles 3 are closely attached to the 20 layers of noble metal to form an electrode.
上記のように貴金属の層−ヒに金属の粒子を密着させれ
ば第2図に示す構造のものより電極となる部分の表面積
が大きく、さらに金属の粒子を密着させるのに比較的低
温で焼き付けるか又はメッキを施すので触媒活性な電極
が形成されるため第2図に示す構造のものよりも低抵抗
のものを得ることができ本発明の目的が達成される。If metal particles are brought into close contact with the noble metal layer as described above, the surface area of the part that will become an electrode will be larger than that of the structure shown in Figure 2, and furthermore, in order to bring the metal particles into close contact, baking is performed at a relatively low temperature. Since a catalytically active electrode is formed by applying plating or plating, a structure having a lower resistance than that shown in FIG. 2 can be obtained, thereby achieving the object of the present invention.
なお本発明において、触媒活性な金属層は1例えば白金
、ロジウム、パラジウム等の金属又はそれらの合金の塩
化物水溶液を塗布し、触媒活性を失なわない温度(白金
の場合は1200℃以下。In the present invention, the catalytically active metal layer is formed by coating an aqueous chloride solution of a metal such as platinum, rhodium, palladium, or an alloy thereof at a temperature that does not cause loss of catalytic activity (1200° C. or less in the case of platinum).
ロジウムの場合は1300℃以下、パラジウムの場合は
1000℃以下)で焼き付けるか、上記の金属又は合金
のメッキを施して設ける。In the case of rhodium, it is baked at 1300 degrees Celsius or less, in the case of palladium it is baked at 1000 degrees Celsius or less), or it is provided by plating with the above metal or alloy.
金属又は合金のメッキを施す場合は必要に応じ焼き付け
を行なうものとする。If metal or alloy plating is applied, baking shall be performed as necessary.
(実施例) 以下本発明の詳細な説明する。(Example) The present invention will be explained in detail below.
実施例1 イツトリアで安定化したジルコニアを内径8mm。Example 1 Zirconia stabilized with Ittria, inner diameter 8mm.
肉厚1閣、長さ100mmに成形した袋管状成形物を1
100℃で1時間焼成し1袋管状仮焼物を得た。1 bag tubular molded product with a wall thickness of 1 mm and a length of 100 mm
The product was fired at 100° C. for 1 hour to obtain one bag of tubular calcined product.
次に前記の袋管状仮焼物の内外表面に白金ベーストを塗
布し、1560℃にて1時間焼成して白金の層を形成し
た。このときの白金の層の面積は1 cm”とした。さ
らに前記の白金の層−Eに塩化白金酸水溶液を塗布し、
800℃で1時間焼成して白金の粒子を密着させ、酸素
センサ検出部の電極を形成した。Next, a platinum base coat was applied to the inner and outer surfaces of the bag-tube-shaped calcined product and baked at 1560° C. for 1 hour to form a platinum layer. The area of the platinum layer at this time was 1 cm''.Furthermore, a chloroplatinic acid aqueous solution was applied to the platinum layer-E.
The platinum particles were baked at 800° C. for 1 hour to make them adhere to each other, thereby forming the electrode of the oxygen sensor detection section.
実施例2
実施例1の塩化白金酸水溶液の代わりに無電解白金メッ
キを施した以外は実施例1と同様の方法にて酸素センサ
検出部の電極を形成した。Example 2 The electrode of the oxygen sensor detection part was formed in the same manner as in Example 1, except that electroless platinum plating was applied instead of the chloroplatinic acid aqueous solution in Example 1.
実施例3
実施例1で得た袋管状仮焼物の内外表面に形成1〜だ白
金の層上に塩化ロジウム酸水溶液を塗布し。Example 3 A chlorinated rhodic acid aqueous solution was applied on the platinum layer formed on the inner and outer surfaces of the bag-tubular calcined product obtained in Example 1.
900℃で1時間焼成してロジウムの粒子を密着させ、
酸素センサ検出部の電極を形成j−た。Baked at 900℃ for 1 hour to make the rhodium particles adhere,
The electrodes of the oxygen sensor detection section were formed.
実施例4
実施例1で得た袋管状仮焼物の内外表面に形成した白金
の層上に塩化パラジウム酸水溶液を塗布り、700℃で
1時間焼成してパラジウムの粒子を密着させ、酸素セン
サ検出部の電極を形成した。Example 4 A chloropalladium acid aqueous solution was applied on the platinum layer formed on the inner and outer surfaces of the bag-tubular calcined product obtained in Example 1, and baked at 700°C for 1 hour to make the palladium particles adhere to each other, allowing oxygen sensor detection. electrodes were formed.
□各実施例で得られた酸素センサ検出部の電極について
観察したところ、第1図に示す如く電極は固体電解質の
焼結体に強固に密着され剥離に対し何ら問題がないこと
を確認l−た。□ When we observed the electrodes of the oxygen sensor detection part obtained in each example, we confirmed that the electrodes were firmly adhered to the sintered body of the solid electrolyte and there was no problem with peeling off, as shown in Figure 1. Ta.
次に本発明の実施例になる酸素センサ検出部の電極を形
成した酸素センサと従来の酸素センサの内周側に空気を
流1〜.外周側に11)[)mの酸素を含む窒素ガスを
流l〜起電力を発生させ、そ17て酸素センサ温度を種
々変え、電圧降下法により抵抗を測定(7た。その結果
を第3図に示す。第3図かられかるように本発明の実施
例になる酸素センサ検出部の電極を形成した酸素センサ
は従来の酸素センサに比較し低抵抗であることがわかる
。Next, air is flowed through the inner circumferential sides of the oxygen sensor forming the electrode of the oxygen sensor detection part according to the embodiment of the present invention and the conventional oxygen sensor. Flow 11) m of nitrogen gas containing oxygen on the outer circumferential side to generate an electromotive force, then vary the oxygen sensor temperature and measure the resistance by the voltage drop method (7). As shown in Fig. 3, it can be seen that the oxygen sensor in which the electrode of the oxygen sensor detecting section according to the embodiment of the present invention is formed has a lower resistance than the conventional oxygen sensor.
なお実施例でメッキは白金を施した例で示したがロジウ
ムメッキおよびバラジウムメツギを施しても同様の効果
が得られる。In the examples, platinum plating is used, but the same effect can be obtained by using rhodium plating or palladium plating.
(発明の効果)
本発明は未焼成の固体電解質成形体又は仮焼体に貴金属
ベーストを塗布したのち焼成1〜て貴金属ベーストを焼
き付け、その後その上面に触媒活性な金属層を設けるの
で、固体電解質との密着性が良く、長期にわたって剥離
等の心配がなく、シかも従来の酸素センサよりも抵抗の
低い酸素センサ6一
検出部の電極を形成することができる。(Effects of the Invention) The present invention applies a noble metal base to an unfired solid electrolyte molded body or a calcined body, and then bakes the noble metal base through firing 1, and then provides a catalytically active metal layer on the top surface. It is possible to form the electrode of the oxygen sensor 6-detecting part which has good adhesion with the oxygen sensor 6 and has good adhesion with the oxygen sensor 6 without worrying about peeling over a long period of time, and which has a lower resistance than the conventional oxygen sensor.
第1図は本発明の実施例になる酸素センサ検出部の電極
を形成した酸素センサの拡大断面図、第2図は従来の酸
素センサの拡大断面図および第3図は本発明の実施例に
なる酸素センサ検出部の電極を形成した酸素センサと従
来の酸素センサの温度と抵抗との関係を示すグラフであ
る。
符号の説明
1、固体電解質 2.貴金属
3、 金属の粒子
第10 算20
某3図
1戊 (C)
逼11 1KX/θ’(K−’ン
手続補正書(自発)
昭和59年8 月278
1、事件の表示
昭和59年特許願第138597号
2、発明の名称
酸素センサ検出部の電極形成法
3、補正をする者
事件との関係 特許出願人
名 称 (445) 日立化成工業株式会社4、代 理
人
5、補正の対象
図面の第3図
6、補正の内容
革 3 B
埴11(”C)FIG. 1 is an enlarged sectional view of an oxygen sensor in which an electrode of an oxygen sensor detection part is formed according to an embodiment of the present invention, FIG. 2 is an enlarged sectional view of a conventional oxygen sensor, and FIG. 3 is an embodiment of the present invention. 2 is a graph showing the relationship between temperature and resistance of an oxygen sensor in which an electrode of an oxygen sensor detection section is formed and a conventional oxygen sensor. Explanation of symbols 1. Solid electrolyte 2. Precious Metals 3, Metal Particles No. 10 Calculation 20 Certain 3 Figure 1 戊 (C) 〼 11 1K Application No. 138597 2, Name of the invention: Electrode formation method for oxygen sensor detection section 3, Relationship with the case of the person making the amendment Name of patent applicant (445) Hitachi Chemical Co., Ltd. 4, Agent 5, Drawings subject to amendment Figure 3 6, Contents of correction 3 B Hani 11 ("C)
Claims (1)
焼体に貴金属ベーストを塗布したのち焼成して貴金属ベ
ーストを焼き付け,その後その上面に触媒活性な金属層
を設けることを特徴とする酸素センサ検出部の電極形成
法。1. An oxygen sensor detection unit characterized in that a noble metal base is applied to an unfired oxygen ion conductive solid electrolyte molded body or a calcined body, and then fired to bake the noble metal base, and then a catalytically active metal layer is provided on the top surface. electrode formation method.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59138597A JPS6117950A (en) | 1984-07-04 | 1984-07-04 | Formation of electrode in detecting part of oxygen sensor |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59138597A JPS6117950A (en) | 1984-07-04 | 1984-07-04 | Formation of electrode in detecting part of oxygen sensor |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS6117950A true JPS6117950A (en) | 1986-01-25 |
Family
ID=15225807
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP59138597A Pending JPS6117950A (en) | 1984-07-04 | 1984-07-04 | Formation of electrode in detecting part of oxygen sensor |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6117950A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0598339A1 (en) * | 1992-11-17 | 1994-05-25 | Hoechst Aktiengesellschaft | Acrylic fibres with an improved dispersibility in viscous matrixes, and method of making fibre reinforced composites |
-
1984
- 1984-07-04 JP JP59138597A patent/JPS6117950A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0598339A1 (en) * | 1992-11-17 | 1994-05-25 | Hoechst Aktiengesellschaft | Acrylic fibres with an improved dispersibility in viscous matrixes, and method of making fibre reinforced composites |
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