JP2545050B2 - Oxygen sensor element - Google Patents
Oxygen sensor elementInfo
- Publication number
- JP2545050B2 JP2545050B2 JP7152138A JP15213895A JP2545050B2 JP 2545050 B2 JP2545050 B2 JP 2545050B2 JP 7152138 A JP7152138 A JP 7152138A JP 15213895 A JP15213895 A JP 15213895A JP 2545050 B2 JP2545050 B2 JP 2545050B2
- Authority
- JP
- Japan
- Prior art keywords
- lead
- contact
- oxygen sensor
- sensor element
- external terminal
- 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.)
- Expired - Lifetime
Links
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- Measuring Oxygen Concentration In Cells (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は各種燃焼機器の酸素濃度
を検知するための酸素センサ素子、特に内燃機関からの
排ガスを浄化するために利用される空燃比制御用の酸素
センサ素子に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxygen sensor element for detecting the oxygen concentration of various combustion equipment, and more particularly to an oxygen sensor element for controlling the air-fuel ratio used for purifying exhaust gas from an internal combustion engine.
【０００２】[0002]
【従来技術及び課題】空燃比制御用酸素センサ素子は、
酸素イオン伝導性の固体電解質体とその内外面に備えら
れる一対の電極（基準電極、測定電極）とからなり、両
電極間に生じた電位差に基づく信号を外部（制御回路な
ど）に出力して酸素濃度を検知するのが一般的である。
そして、エンジン系ノイズによる影響を防止するため、
測定電極（外側電極）と外部端子とを固体電解質体の外
面側に備えられたリ―ドによって導通するようにしたも
のが知られている（特開昭61−146209）。2. Description of the Related Art An oxygen sensor element for air-fuel ratio control is
It consists of an oxygen ion conductive solid electrolyte and a pair of electrodes (reference electrode, measurement electrode) provided on its inner and outer surfaces, and outputs a signal based on the potential difference between both electrodes to the outside (control circuit, etc.). It is common to detect the oxygen concentration.
And to prevent the influence of engine system noise,
There is known one in which a measuring electrode (outer electrode) and an external terminal are electrically connected by a lead provided on the outer surface side of a solid electrolyte body (JP-A-61-146209).
【０００３】しかし、この種の酸素センサ素子にあって
は、リ―ドと外部端子との接続部位においては耐久性の
見地から白金が使用され、しかも外部端子との係合接続
によってもその導通性を確実に維持するために、その接
続部位はリ―ドの中でもその存在面積が非常に大とな
る。そのため、貴重な資源である白金を多量に消費せざ
るを得ず、また素子コスト増大の一因ともなる。However, in this type of oxygen sensor element, platinum is used at the connecting portion between the lead and the external terminal from the standpoint of durability, and the conduction is achieved even by the engaging connection with the external terminal. In order to maintain the reliability, the connecting area has a very large area in the lead. Therefore, platinum, which is a valuable resource, must be consumed in large amounts, which also contributes to an increase in device cost.
【０００４】本発明はかかる課題を解決すること、即ち
リ―ドと外部端子との導通性を損うことなく、資源の有
効利用かつ廉価な酸素センサ素子を開発することを目的
とする。It is an object of the present invention to solve such a problem, that is, to develop an oxygen sensor element which uses resources efficiently and is inexpensive without impairing the electrical continuity between the lead and the external terminal.
【０００５】[0005]
【課題解決の手段】本発明者はこうした見地に鑑み鋭意
研究を重ねた結果、本発明を完成するに至ったものであ
り、本発明は上述の課題を下記手段によって解決する。The inventors of the present invention have completed the present invention as a result of earnest studies in view of such viewpoints, and the present invention solves the above problems by the following means.
【０００６】（１）固体電解質体の一面側に基準電極、
他面側に測定電極を備え、測定電極が被測定ガスに接触
される酸素センサ素子において、固体電解質体の他面側
に測定電極と外部端子とを接続するリードを備え、前記
リードが前記被測定ガスに接触する部分について白金
（Ｐｔ）からなり、前記被測定ガスに接触しない部分に
ついて白金（Ｐｔ）及びパラジウム（Ｐｄ）の混合物か
らなり、該混合物におけるＰｔとＰｄの重量比が、０．
２≦Ｐｄ／Ｐｔ≦９であり、前記外部端子と前記リード
との接続部位において、前記リードが前記個体電解質体
の外周に沿って環状であり、かつリード材料の存在部と
リード材料の不存在部とが円周方向において交互に分布
して位置すると共に、隣接する各存在部が相互に連通し
て環状外部端子に対する当接面を成すパターンで形成さ
れることを特徴とする酸素センサ素子。(1) A reference electrode on one surface side of the solid electrolyte body,
In the oxygen sensor element having the measurement electrode on the other surface side, the measurement electrode being in contact with the gas to be measured, a lead connecting the measurement electrode and the external terminal is provided on the other surface side of the solid electrolyte body, and the lead is the The portion that comes into contact with the measurement gas is made of platinum (Pt), and the portion that does not come into contact with the measurement gas is made of a mixture of platinum (Pt) and palladium (Pd), and the weight ratio of Pt and Pd in the mixture is 0.
2 ≦ Pd / Pt ≦ 9, the lead is annular along the outer periphery of the solid electrolyte body at the connection portion between the external terminal and the lead, and the lead material existing portion and the lead material absent. The oxygen sensor element is characterized in that the parts and the parts are alternately distributed in the circumferential direction, and adjacent existing parts are formed in a pattern that communicates with each other and forms a contact surface for the annular external terminal.
【０００７】なお、環状とは断面が円の他に四角形等の
多角形の場合も含む。また、Ｐｄ／Ｐｔ比は０．３〜３
とすることが好ましい。The term "annular" includes the case where the cross section is not only a circle but also a polygon such as a quadrangle. Further, the Pd / Pt ratio is 0.3 to 3
It is preferable that
【０００８】[0008]
【好適な実施態様及び作用】素子形状ないしは固体電解
質体形状は先端が閉塞され後端が開口している限り、袋
状、板状または管状など種々の形状でよく、あるいは絶
縁物基材に固体電解質体等の素子の各要素を結合させて
前記と同様の形状になるものでも良い。固体電解質材料
としては例えばＺｒＯ2 に安定化剤としてＹ2 Ｏ3 、Ｃ
ａＯ等を添加したものを用いるとよい。基準電極及び測
定電極（層状）はともに多孔質とされ、Ｐｔまたは２％
程度以下のＲｈを含有するＰｔ等の貴金属を用いてもよ
い。[Preferable Embodiments and Functions] The element shape or the solid electrolyte shape may be various shapes such as a bag shape, a plate shape or a tubular shape, as long as the front end is closed and the rear end is open, or a solid material is used as an insulating base material. It is also possible to combine elements of an element such as an electrolyte body to form a shape similar to the above. The solid electrolyte material may be, for example, ZrO 2 and Y 2 O 3 or C as a stabilizer.
It is preferable to use one to which aO or the like is added. Both the reference electrode and the measurement electrode (layered) are made porous, and Pt or 2%
A noble metal such as Pt containing Rh of about the same or less may be used.
【０００９】リ―ドは測定電極と外部端子との導通のた
めに固体電解質体の他面側（測定電極の位置する側）に
備えられるものである。酸素センサのハウジングを介す
ることなく外部と導通させ、エンジンノイズの悪影響を
回避できる。リ―ドは、その先端を測定電極の後端部に
接続すると共に、その後端を外部端子に接続するとよ
い。後端部以外については周方向（板状固体電解質体の
場合、「側方向」という。以下同じ）に係る幅少くとも
0.3mm、厚み１〜50μｍで直線状に形成するとよい。導
通に最小限必要な量で存在させればよいからである。な
お、測定電極との接続は、係合ではなく通常融着によっ
てなされるので、その導通性は接続面積が小さくても比
較的確実である。The lead is provided on the other surface side of the solid electrolyte body (the side on which the measurement electrode is located) for electrical connection between the measurement electrode and the external terminal. The oxygen sensor is electrically connected to the outside without passing through the housing of the oxygen sensor, and the adverse effect of engine noise can be avoided. The lead may have its tip connected to the rear end of the measurement electrode and its rear end connected to an external terminal. At least the width related to the circumferential direction (in the case of a plate-shaped solid electrolyte body, referred to as “side direction”; the same applies hereinafter) except for the rear end portion
It may be formed in a linear shape with a thickness of 0.3 mm and a thickness of 1 to 50 μm. This is because it is sufficient to make it exist in the minimum necessary amount for conduction. Since the connection with the measurement electrode is usually made by fusion rather than engagement, the conductivity is relatively reliable even if the connection area is small.
【００１０】リードの材質については、酸素センサとし
ての使用時において、被測定ガス（例えば排ガス）に接
触する部分（接触部）はＰｔからなり、被測定ガスに接
触しない部分（非接触部）はＰｔ及びＰｄの混合物（但
し重量比で０．２≦Ｐｄ／Ｐｔ≦９）からなるものとし
なければならない。導通性及び耐久性のために必要なＰ
ｔ材料を必要最小限とし、資源的に貴重なＰｔの有効利
用を図るためである。接触部において、Ｐｔ１００ｗｔ
％が好ましいが、他の責金属Ｒｈ、Ａｕ、Ａｇ等の他、
不可避の不純物を計１０ｗｔ％以下含有してもよい。非
接触部において、Ｐｔ及びＰｄの混合物の重量比は０．
２≦Ｐｄ／Ｐｔ≦９にする。下限未満ではＰｔ使用量の
実質的な削減にならず、一方上限を越えると使用時にお
いてリードの剥離を生じ易くなるためである。好ましく
は０．３≦Ｐｄ／Ｐｔ≦３である。ここにＰｄ／Ｐｔ比
３以下では、所定のテスト後も剥離が全く生じない。し
かもＰｄ／Ｐｔ比０．３以上では十分にＰｔを節約する
ことができる。つまりこの範囲内であれば、双方の長所
を同時に満足することができる。接触部についてＰｄ、
Ｐｔの混合物からなる材料を用いることは不適である。
酸素センサ使用時においてＰｄが被測定ガス（特に高温
の排ガス）によって容易に昇華するためである。なお、
リードの非接触部についても他の貴金属、不可避の不純
物を計１０ｗｔ％以下含有してもよい。Regarding the material of the lead, when it is used as an oxygen sensor, the portion (contact portion) that comes into contact with the gas to be measured (exhaust gas) is made of Pt, and the portion that does not come into contact with the gas to be measured (non-contact portion). It must consist of a mixture of Pt and Pd, with a weight ratio of 0.2 ≦ Pd / Pt ≦ 9. P required for conductivity and durability
This is to minimize the amount of t material and to effectively use Pt, which is valuable in terms of resources. At the contact part, Pt100wt
% Is preferable, but in addition to other responsible metals Rh, Au, Ag, etc.,
Inevitable impurities may be contained in a total amount of 10 wt% or less. In the non-contact part, the weight ratio of the mixture of Pt and Pd was 0.
2 ≦ Pd / Pt ≦ 9. This is because if the amount is less than the lower limit, the amount of Pt used is not substantially reduced, while if it exceeds the upper limit, peeling of the leads tends to occur during use. Preferably 0.3 ≦ Pd / Pt ≦ 3. If the Pd / Pt ratio is 3 or less, peeling does not occur even after a predetermined test. Moreover, if the Pd / Pt ratio is 0.3 or more, Pt can be sufficiently saved. That is, within this range, both advantages can be satisfied at the same time. About contact part Pd,
It is unsuitable to use a material consisting of a mixture of Pt.
This is because Pd easily sublimes due to the gas to be measured (especially high temperature exhaust gas) when the oxygen sensor is used. In addition,
The non-contact portion of the lead may also contain other noble metal and inevitable impurities in a total amount of 10 wt% or less.
【００１１】個体電解質体の他面側に測定電極と外部端
子とを接続するリードパターンは帯状に形成されてい
る。On the other surface side of the solid electrolyte body, a lead pattern for connecting the measuring electrode and the external terminal is formed in a strip shape.
【００１２】外部端子とリードとの接続部位において
は、前記リードは環状であり、既述の通りリードはリー
ド材料の存在部とその不存在部とが円周方向において交
互に位置すると共に、隣接する各存在部が相互に連通す
るパターンとする。導通性を確保しつつ、責重なリード
材料の使用量をできるだけ抑えかつ環状外部端子に対す
る当接面を十分に確保するためである。外部端子との接
続に係るリードの後端部のパターンは、周方向に沿って
形成させる。外部端子との接触面積を大としその係合接
続によっても導通性を維持するためである。リードの後
端部は格子状ないしは網目状パターンでリード材料を存
在させるとよい。パターン外周面積が従来パターンと同
様の大きさであるため、リード材料の使用量が従来のも
のに比して低減されたにも拘らず、仮に外部端子との係
合状態が偏った場合であっても、その導通性を確実に維
持できる。パターン要素の幅は０．１ｍｍ以上にすると
よい。０．１ｍｍ未満では導通信頼性が乏しくなるから
である。好ましくは０．３ｍｍ以上である。隣接するパ
ターン要素間の離間長さは５ｍｍ以下にするとよい。ま
た、パターン外周面積に対してリード材料の存在部に係
る面積を５０％以上にするとよい。５０％未満ではパタ
ーン要素間の導通信頼性が乏しくなる。好ましくは６０
％以上である。ここでパターン外周面積とは、この種の
リードの後端部における従来パターンの外周面積に相当
し、これを基準とする。例えばリードの後端部が周方向
に帯状に存在する場合、その帯状リード部の外周面積が
基準となる。At the connecting portion between the external terminal and the lead, the lead is annular, and as described above, the lead has the lead material existing portion and the lead material non-existing portion alternately located in the circumferential direction and is adjacent to each other. It is assumed that the existing units are connected to each other. This is because while ensuring electrical continuity, the amount of responsible lead material used is suppressed as much as possible and a sufficient contact surface for the annular external terminal is ensured. The pattern of the rear end portion of the lead relating to the connection with the external terminal is formed along the circumferential direction. This is because the contact area with the external terminal is increased and the conductivity is maintained even by the engagement connection. At the rear end of the lead, the lead material may be present in a lattice or mesh pattern. Since the outer peripheral area of the pattern is the same size as the conventional pattern, the amount of lead material used was reduced compared to the conventional pattern, but the engagement state with the external terminals was biased. However, the conductivity can be surely maintained. The width of the pattern element is preferably 0.1 mm or more. This is because if it is less than 0.1 mm, conduction reliability becomes poor. It is preferably 0.3 mm or more. The distance between adjacent pattern elements is preferably 5 mm or less. Further, it is preferable that the area related to the existing portion of the lead material is 50% or more of the peripheral area of the pattern. If it is less than 50%, the reliability of conduction between pattern elements becomes poor. Preferably 60
% Or more. Here, the pattern outer peripheral area corresponds to the outer peripheral area of the conventional pattern at the rear end portion of this type of lead, and is used as a reference. For example, when the rear end portion of the lead exists in a strip shape in the circumferential direction, the outer peripheral area of the strip-shaped lead portion serves as a reference.
【００１３】こうしたリ―ドの固体電解質体への形成
は、電気メッキ、化学メッキ等のメッキ処理の他、気相
析着法例えばスパッタリング、蒸着など種々の手段によ
って行なうことができる。特に、リ―ド材料としての金
属ペ―ストをスクリ―ン印刷または転写印刷によって被
着させるとよい。酸素センサの製造は、各構成要素を段
階的に被着形成する方法の他、各構成要素を積層して一
体焼成に供する、いわゆる積層印刷法によって行なって
もよい（特開昭62−222159参照）。得られた酸素センサ
は例えば特開昭63−3252に開示されたような構成とな
る。The lead can be formed on the solid electrolyte body by various means such as electroplating, chemical plating and the like, as well as vapor deposition method such as sputtering and vapor deposition. In particular, a metal paste as a lead material is preferably applied by screen printing or transfer printing. The oxygen sensor may be manufactured by a so-called laminated printing method in which each constituent element is laminated and subjected to integral firing in addition to a method of forming each constituent element in a stepwise manner (see JP-A-62-222159). ). The obtained oxygen sensor has a structure as disclosed in, for example, JP-A-63-3252.
【００１４】[0014]
【実施例】以下、本発明の実施例を図面に基づいて説明
する。Embodiments of the present invention will be described below with reference to the drawings.
【００１５】第１図は第１実施例を示したものであり、
１は略円筒状とされた固体電解質体であり、先方より試
験管状部１ａ、拡径部１ｂ及び同径部１ｃを有する。試
験管状部１ａはセンサ検出部に略対応し、拡径部１ｂは
絶縁体を介してセンサハウジングへの保持に供され、同
径部１ｃ後端においてリ―ド２と外部端子３（第４、５
図）とが実際に接続されて導通が図られることになる。
リ―ド２は試験管状部１ａ後端から拡径部１ｂを経て同
径部１ｃ後端に至るまで固体電解質体１の外面形状に沿
って直線的に後方へ帯状に延びている（幅２mm）。FIG. 1 shows a first embodiment,
Reference numeral 1 is a solid electrolyte body having a substantially cylindrical shape, and has a test tubular portion 1a, a diameter-enlarged portion 1b, and an equal-diameter portion 1c from the front side. The test tubular portion 1a substantially corresponds to the sensor detection portion, the expanded diameter portion 1b is used for holding in the sensor housing through an insulator, and the lead 2 and the external terminal 3 (fourth portion) are provided at the rear end of the same diameter portion 1c. 5,
(Fig.) And are actually connected to achieve conduction.
The lead 2 linearly extends rearward in a strip shape along the outer surface shape of the solid electrolyte body 1 from the rear end of the test tubular portion 1a to the rear end of the same diameter portion 1c through the enlarged diameter portion 1b (width 2 mm. ).
【００１６】本例にあっては、被測定ガスと接触するお
それがある拡径部１ｂにおいてリ―ドはＰｔ材料からな
り、また接触するおそれがない同径部１ｃにおいてＰｄ
／Ｐｔ（１／３）混合材料からなる。ここで、本例のよ
うなセンサ素子の場合、使用時に被測定ガスが接触する
部分は通常、試験管状部１ａ、及び拡径部１ｂのうち試
験管状部１ａ寄りの部分が該当する。拡径部１ｂ及び同
径部１ｃ後端の夫々において周方向全域に夫々軸方向幅
３mm、５mmをもってリ―ド２が存在している。これによ
って、リ―ド（検出機能をも発揮し得る拡径部１ｂに係
るものを除く）２について、貴重なＰｔ使用量を従来リ
―ドに比して25％低減できる。In this example, the lead is made of a Pt material in the expanded diameter portion 1b which may come into contact with the gas to be measured, and the lead Pd in the expanded diameter portion 1c which has no possibility of contact.
/ Pt (1/3) mixed material. Here, in the case of the sensor element as in the present example, the portion in contact with the gas to be measured during use usually corresponds to the portion of the test tubular portion 1a and the enlarged diameter portion 1b near the test tubular portion 1a. Leads 2 having an axial width of 3 mm and 5 mm are present in the entire circumferential direction at the enlarged diameter portion 1b and the rear end of the same diameter portion 1c, respectively. As a result, the amount of precious Pt used in the lead 2 (excluding the portion related to the expanded diameter portion 1b that can also exhibit the detection function) 2 can be reduced by 25% compared to the conventional lead.
【００１７】第２図は、第２実施例を示したものであ
り、本例にあっては、同径部１ｃ後端（リ―ドと外部端
子との接続部位となる）において、リ―ド２は環状（２
ａ・２ｂ）であり、リ―ド材料の存在部２ａと共にその
不存在部２ｂが存在している。従って、その不存在部２
ｂの面積分だけ、従来リ―ドの比してリ―ド材料（Ｐ
ｔ）が少なくなっている。ここでは、周方向に沿って延
びて外周面積に係る二条の周方向パタ―ン要素は軸方向
幅 0.7mm、またこの周方向パタ―ン要素を軸方向におい
て導通する軸方向パタ―ン要素は幅 0.6mmである。これ
によって、従来リ―ドに比してリ―ド材料の使用量を30
％低減できる。なお、縮径部１ｄは外部端子３（第４、
５図）と固体電解質体１との係合を確実にするためのも
のである。FIG. 2 shows a second embodiment. In this embodiment, a lead is formed at the rear end of the same diameter portion 1c (which is a connection portion between the lead and the external terminal). Do 2 is circular (2
a.2b), and the nonexistent portion 2b exists together with the existing portion 2a of the lead material. Therefore, the absence portion 2
Compared to the conventional lead, the lead material (P
t) is low. Here, the two circumferential pattern elements extending along the circumferential direction and related to the outer peripheral area have an axial width of 0.7 mm, and the axial pattern elements that connect the circumferential pattern elements in the axial direction are The width is 0.6 mm. This will reduce the amount of lead material used to 30% compared to conventional leads.
%. In addition, the reduced diameter portion 1d is provided with the external terminal 3 (fourth,
This is for ensuring the engagement between the solid electrolyte body 1 (Fig. 5).
【００１８】従って、外部端子３とリード２との接続部
において、外部端子３は、個体電解質体１の形状に応じ
て第４、５図のように環状体に形成することが好まし
く、そして本発明の第２の手段のように前記接続部位に
おいて、リード２が環状体（２ａ・２ｂ）であれば、環
状体同士であるので外部端子３とリード２との密着性が
増して導通性が向上する。Therefore, at the connecting portion between the external terminal 3 and the lead 2, the external terminal 3 is preferably formed into an annular body as shown in FIGS. 4 and 5 according to the shape of the solid electrolyte body 1. If the lead 2 is an annular body (2a, 2b) at the connecting portion as in the second means of the invention, since the two are annular bodies, the adhesion between the external terminal 3 and the lead 2 is increased and the electrical continuity is improved. improves.
【００１９】第３図は第３実施例を示したものであり、
いわば第１実施例と第２実施例とを組合せたものに相当
する。即ち、第２実施例に係るリ―ド２について、拡径
部１ｂ中央より先方部と後方部に区分けし、被測定ガス
に接触するおそれがある先方部においてはＰｔ材料、接
触するおそれがない後方部においてはＰｄ／Ｐｔ（１／
３）混合材料をもってリ―ド２を構成させたものであ
る。これによって、Ｐｔ使用量を従来リ―ドに比して47
％低減できる。FIG. 3 shows a third embodiment,
In a sense, it corresponds to a combination of the first embodiment and the second embodiment. That is, the lead 2 according to the second embodiment is divided into a front portion and a rear portion from the center of the expanded diameter portion 1b, and there is no possibility of contact with the Pt material in the front portion that may come into contact with the gas to be measured. In the rear part, Pd / Pt (1 /
3) The lead 2 is made of a mixed material. As a result, the amount of Pt used is 47 compared with the conventional lead.
%.
【００２０】なお、第４、５図に外部端子３の例を示し
ておく。An example of the external terminal 3 is shown in FIGS.
【００２１】[0021]
【製造例】前記実施例に係る酸素センサ素子は、例えば
次のようにして製造される。まず、部分安定化ジルコニ
ア（ＰＳＺ）からなる所定形状の固体電解質体を用意す
る（例えば特開昭54−4913参照）。[Manufacturing Example] The oxygen sensor element according to the above embodiment is manufactured, for example, as follows. First, a solid electrolytic body having a predetermined shape made of partially stabilized zirconia (PSZ) (e.g. see Japanese Open Sho 54-4913).
【００２２】(1) 実施例１について：固体電解質体の所
定表面にＰｔペ―ストまたはＰｄ／Ｐｔペ―ストを刷毛
塗布する。なお、使用材料は次の通り。 (a) Ｐｄ／Ｐｔペ―スト：Ｐｄ／Ｐｔ＝ 0.3 Ｐｄ：石福金属（株）製、ＭＢタイプとＲＡタイプとを
ＭＢ／ＲＡ＝２の割合で混合。 Ｐｔ：田中マッセイ（株）製、ＣＡタイプ。 溶剤：ブチルカルビト―ル (b) Ｐｔペ―スト：石福金属（株）製、ＭタイプとＳタ
イプとをＭ／Ｓ＝２の割合で混合。(1) Regarding Example 1: Pt paste or Pd / Pt paste was brush-applied to a predetermined surface of the solid electrolyte body. The materials used are as follows. (a) Pd / Pt paste: Pd / Pt = 0.3 Pd: manufactured by Ishifuku Metal Co., Ltd., MB type and RA type are mixed at a ratio of MB / RA = 2. Pt: CA type manufactured by Tanaka Massey Co., Ltd. Solvent: Butyl carbitol (b) Pt paste: made by Ishifuku Metal Co., Ltd., M type and S type were mixed at a ratio of M / S = 2.
【００２３】(2) 実施例２、３について：固体電解質体
の所定表面にＰｔまたはＰｄ／Ｐｔペ―ストを転写印刷
する。なお、使用材料は次の通り。 (a) Ｐｄ／Ｐｔペ―スト：Ｐｄ／Ｐｔ＝ 0.3 Ｐｄ：三井金属（株）製、真球状粉末。 Ｐｔペースト：田中マッセイ（株）製、ＣＡタイプ粉
末。溶剤：ブチルカルビトール (b) Ｐｔペ―スト：田中マッセイ（株）製、真球状粉
末。(2) Regarding Examples 2 and 3: Pt or Pd / Pt paste is transfer-printed on a predetermined surface of the solid electrolyte body. The materials used are as follows. (a) Pd / Pt paste: Pd / Pt = 0.3 Pd: Mitsui Kinzoku Co., Ltd. true spherical powder. Pt paste : CA type powder manufactured by Tanaka Massey Co., Ltd.
End . Solvent: Butyl carbitol (b) Pt paste: True spherical powder manufactured by Tanaka Massey Co., Ltd.
【００２４】[0024]
【試験例】上記実施例の酸素センサ素子を用いて応答性
及び導通性について、センサ制御時における周波数［H
z］を測定することにより評価した。なお、比較例とし
てリ―ド材料がパタ―ン外周面全域に存在するもの（他
の構成は実施例と同一）及びリ―ドがすべての部位にお
いてＰｔ単一材料からなるものを採用した。[Test Example] The oxygen sensor element of the above example was used to measure the response and conductivity at the frequency [H
It was evaluated by measuring [z]. As comparative examples, one in which the lead material is present on the entire outer peripheral surface of the pattern (other configurations are the same as those in the example) and one in which the lead is made of a single Pt material in all parts are adopted.
【００２５】その結果、本実施例の酸素センサ素子は比
較例のものに比して電極材料としての貴金属材料が30％
低減されているにも拘らず、比較例と同等の優れた応答
性、即ち 1.3［Hz］を示した。なお、導通性について
も、実用上全く問題を生じないものであった。As a result, the oxygen sensor element of this example contained 30% of noble metal material as the electrode material as compared with that of the comparative example.
Despite being reduced, it showed excellent responsiveness equivalent to that of the comparative example, that is, 1.3 [Hz]. Regarding the conductivity, there was no problem in practical use.
【００２６】[0026]
【効果】以上の如く本発明（請求項１）によれば、第１
に貴重かつ高価なＰｔ使用量を大幅に低減できるので、
資源の有効利用を図り、かつ廉価な酸素センサ素子を提
供することができる。しかも、このＰｔ使用量低減にも
拘らず、導通性、応答性及び接着性を安定に維持できる
ので酸素センサ分野において極めて有用である。第２
に、外部端子とリードとの接続部位を特定のパターンと
することにより、接続の不安定化を招くことなくＰｔ使
用量をさらに節約できる。また、請求項２によれば一層
高いパターン効果が得られる。 As described above, according to the present invention (Claim 1) , the first
Since the amount of precious and expensive Pt used can be greatly reduced,
It is possible to effectively use resources and provide an inexpensive oxygen sensor element. Moreover, the conductivity, responsiveness and adhesiveness can be stably maintained in spite of this reduction in the amount of Pt used, which is extremely useful in the field of oxygen sensors. Second
In addition, the connection part between the external terminal and the lead should have a specific pattern.
Use Pt without causing instability of the connection.
Further dose savings. Further, according to claim 2,
A high pattern effect can be obtained.
【００２７】[0027]
【図１】本発明の第１実施例に係る酸素センサ素子のリ
―ド状態を示す正面図。FIG. 1 is a front view showing a lead state of an oxygen sensor element according to a first embodiment of the present invention.
【図２】第２実施例に係る酸素センサ素子のリ―ド状態
を示す正面図。FIG. 2 is a front view showing a lead state of an oxygen sensor element according to a second embodiment.
【図３】第３実施例に係る酸素センサ素子のリ―ド状態
を示す正面図。FIG. 3 is a front view showing a lead state of an oxygen sensor element according to a third embodiment.
【図４】本発明の実施例に係るリ―ドとの接続に供され
る外部端子の一例を示した図であって、その斜視図。FIG. 4 is a perspective view showing an example of an external terminal used for connection with a lead according to an embodiment of the present invention.
【図５】本発明の実施例に係るリ―ドとの接続に供され
る外部端子の一例を示した図であって、そのリ―ド接続
部位に係る断面図。FIG. 5 is a diagram showing an example of an external terminal used for connection with a lead according to an embodiment of the present invention, and a cross-sectional view of the lead connection portion.
Ａ…酸素センサ １…固体電解質体 ２…リ―ド ２ａ…存在部 ２ｂ…不存在部 ３…外部端子 A ... Oxygen sensor 1 ... Solid electrolyte body 2 ... Lead 2a ... Existence part 2b ... Absence part 3 ... External terminal
フロントページの続き (56)参考文献 特開 昭63−3251（ＪＰ，Ａ) 特開 昭58−221159（ＪＰ，Ａ) 特開 昭60−108747（ＪＰ，Ａ) 特開 昭57−175251（ＪＰ，Ａ) 特開 昭61−243354（ＪＰ，Ａ) 実開 平１−93562（ＪＰ，Ｕ)Continuation of the front page (56) Reference JP-A-63-3251 (JP, A) JP-A-58-221159 (JP, A) JP-A-60-108747 (JP, A) JP-A-57-175251 (JP , A) JP-A-61-243354 (JP, A) Actual Kaihei 1-93562 (JP, U)
Claims (2)
に測定電極を備え、測定電極が被測定ガスに接触される
酸素センサ素子において、 固体電解質体の他面側に測定電極と外部端子とを接続す
る帯状のリードを備え、 前記リードが前記被測定ガスに接触する部分について白
金（Ｐｔ）からなり、前記被測定ガスに接触しない部分
について白金（Ｐｔ）及びパラジウム（Ｐｄ）の混合物
からなり、該混合物におけるＰｔとＰｄの重量比が、
０．２≦Ｐｄ／Ｐｔ≦９であり、 前記外部端子と前記リードとの接続部位において、前記
リードが前記個体電解質体の外周に沿って環状の部分を
有し、かつリード材料の存在部とリード材料の不存在部
とが円周方向において交互に分布して位置すると共に隣
接する各存在部が相互に連通して環状外部端子に対する
当接面を成すパターンで形成されることを特徴とする酸
素センサ素子。 1. An oxygen sensor element in which a reference electrode is provided on one surface side of a solid electrolyte body and a measurement electrode is provided on the other surface side, and the measurement electrode is in contact with a gas to be measured, the measurement electrode being provided on the other surface side of the solid electrolyte body. A strip-shaped lead that connects to an external terminal is provided, and a portion of the lead that comes into contact with the measurement gas is made of platinum (Pt), and a portion that does not come into contact with the measurement gas is made of platinum (Pt) and palladium (Pd). And a weight ratio of Pt and Pd in the mixture is
Ri 0.2 ≦ Pd / Pt ≦ 9 der in connection portion between the external terminal and the lead, the
The reeds form an annular portion along the outer periphery of the solid electrolyte body.
Yes, with lead material and without lead material
And are alternately distributed in the circumferential direction and
The existing parts that contact each other communicate with each other and
An acid characterized by being formed in a pattern forming the contact surface
Elementary sensor element.
上であり、かつパターン外周面積に対してリード材料の
存在部に係る面積が５０％以上であることを特徴とする
請求項１に記載の酸素センサ素子。 2. The minimum width of the pattern element is 0.5 mm or less.
And the lead material
The area related to the existing portion is 50% or more
The oxygen sensor element according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7152138A JP2545050B2 (en) | 1995-05-26 | 1995-05-26 | Oxygen sensor element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7152138A JP2545050B2 (en) | 1995-05-26 | 1995-05-26 | Oxygen sensor element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07306177A JPH07306177A (en) | 1995-11-21 |
| JP2545050B2 true JP2545050B2 (en) | 1996-10-16 |
Family
ID=15533881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7152138A Expired - Lifetime JP2545050B2 (en) | 1995-05-26 | 1995-05-26 | Oxygen sensor element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2545050B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1195602A1 (en) | 1997-11-20 | 2002-04-10 | Denso Corporation | Oxygen sensor with the heater element contacting the inner surface of the closed end tubular solid electrolyte |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11153571A (en) * | 1997-11-20 | 1999-06-08 | Denso Corp | Oxygen sensor element |
| JP2008281584A (en) * | 2008-08-25 | 2008-11-20 | Denso Corp | Oxygen sensor element |
| JP2008286810A (en) * | 2008-08-25 | 2008-11-27 | Denso Corp | Oxygen sensor element |
| JP5931603B2 (en) * | 2011-07-07 | 2016-06-08 | 日本特殊陶業株式会社 | Gas sensor |
| JP5770773B2 (en) * | 2012-05-24 | 2015-08-26 | 日本特殊陶業株式会社 | Gas sensor |
| JP5905342B2 (en) * | 2012-06-19 | 2016-04-20 | 日本特殊陶業株式会社 | Gas sensor and manufacturing method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3112739A1 (en) * | 1981-03-31 | 1982-10-07 | Bosch Gmbh Robert | Electrode of stable structure for solid-state electrolytes for electrochemical applications, and use of such an electrode in electrochemical sensors for determining the oxygen content in gases |
| JPS58221159A (en) * | 1982-06-15 | 1983-12-22 | ハネウェル・インコーポレーテッド | Detector for partial pressure of oxygen |
| US4479868A (en) * | 1983-10-21 | 1984-10-30 | Westinghouse Electric Corp. | Gas measuring probe |
| JPS61243354A (en) * | 1985-04-20 | 1986-10-29 | Toyota Central Res & Dev Lab Inc | Oxygen sensor |
| JP2514000B2 (en) * | 1986-06-24 | 1996-07-10 | 日本特殊陶業株式会社 | Oxygen sensor |
-
1995
- 1995-05-26 JP JP7152138A patent/JP2545050B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1195602A1 (en) | 1997-11-20 | 2002-04-10 | Denso Corporation | Oxygen sensor with the heater element contacting the inner surface of the closed end tubular solid electrolyte |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07306177A (en) | 1995-11-21 |
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