JPH063324A - Electrochemical gas sensor - Google Patents
Electrochemical gas sensorInfo
- Publication number
- JPH063324A JPH063324A JP4159522A JP15952292A JPH063324A JP H063324 A JPH063324 A JP H063324A JP 4159522 A JP4159522 A JP 4159522A JP 15952292 A JP15952292 A JP 15952292A JP H063324 A JPH063324 A JP H063324A
- Authority
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- Japan
- Prior art keywords
- water
- gas
- housing
- internal space
- sensor element
- 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.)
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- Measuring Oxygen Concentration In Cells (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電気化学式ガスセンサ
に関し、例えば大気中等における窒素酸化物、あるいは
火災時における一酸化炭素の検知に有用な電気化学式ガ
スセンサに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrochemical gas sensor, and more particularly to an electrochemical gas sensor useful for detecting nitrogen oxides in the atmosphere or carbon monoxide in a fire.
【０００２】[0002]
【従来の技術】電気化学的な酸化還元反応を利用して、
雰囲気中の特定のガス、たとえば、炭酸ガス、一酸化炭
素、水素、アルコール、窒素酸化物等の検知対象ガスを
検知する電気化学式ガスセンサがこれまで数多く提案さ
れている。ここで、電気化学式ガスセンサを構成する公
知のセンサ素子１０を示す図４及び図５に基づいて説明
すると、このセンサ素子１０は、特開昭６４−８８３５
４号公報に開示されている如く、絶縁基板１００に作用
極７０と対極９０が向かい合うように形成され、この対
極９０と作用極７０の隣に参照極８０が並べられ、さら
に、含水状態で電解質と化する高分子の固体電解質膜１
１０でこれらの電極群を被覆しており、上記作用極７０
と対極９０間に電圧を印加すると、検知対象ガスが上記
作用極７０上で酸化反応あるいは還元反応を起こし、こ
の反応にともなって生成されたイオンが含水状態に保持
された固体電解質膜１１０中を移動して対極９０で還元
反応あるいは酸化反応を起こす。この電気化学的な酸化
還元反応によって、対極９０−作用極７０間を流れる電
流値をセンサ素子１０に接続した電流計等の外部機器で
測定すると、検知対象ガスを検知できるものである。2. Description of the Related Art Utilizing an electrochemical redox reaction,
A large number of electrochemical gas sensors have been proposed so far, which detect a specific gas in the atmosphere, for example, carbon dioxide, carbon monoxide, hydrogen, alcohol, nitrogen oxides or the like. Here, the known sensor element 10 constituting the electrochemical gas sensor will be described with reference to FIGS. 4 and 5, and this sensor element 10 is disclosed in JP-A-64-8835.
As disclosed in Japanese Unexamined Patent Publication No. 4 (1998), a working electrode 70 and a counter electrode 90 are formed on an insulating substrate 100 so as to face each other, a reference electrode 80 is arranged next to the counter electrode 90 and the working electrode 70, and further, an electrolyte in a water-containing state. Polymer electrolyte membrane 1
These electrode groups are covered with 10 and the working electrode 70
When a voltage is applied between the counter electrode 90 and the counter electrode 90, the gas to be detected causes an oxidation reaction or a reduction reaction on the working electrode 70, and the ions generated by this reaction pass through the solid electrolyte membrane 110 held in a water-containing state. It moves and causes a reduction reaction or an oxidation reaction at the counter electrode 90. By measuring the current value flowing between the counter electrode 90 and the working electrode 70 by an external device such as an ammeter connected to the sensor element 10 by this electrochemical redox reaction, the gas to be detected can be detected.
【０００３】このセンサ素子１０を用いた電気化学式ガ
スセンサの一例を示す図３に基づいて説明すると、この
電気化学式ガスセンサは内部空間３５を有するハウジン
グ３０と、ハウジング３０に付設された貯水槽４０と外
部から検知対象ガスを内部空間３５に導入する通気口３
４と、上記のハウジング３０と貯水槽４０を分断する隔
壁２０に形成された、内部空間３５と貯水槽４０とが連
通する連絡口３６を備え、さらに上記のハウジング３０
の内部空間３５に上述のセンサ素子１０を収容して構成
されている。Referring to FIG. 3 showing an example of an electrochemical gas sensor using the sensor element 10, this electrochemical gas sensor has a housing 30 having an internal space 35, a water tank 40 attached to the housing 30, and an external unit. Vent 3 for introducing the detection target gas into the internal space 35
4 and a communication port 36 formed in the partition wall 20 that divides the housing 30 and the water storage tank 40 from each other, the communication space 36 communicating with the internal space 35 and the water storage tank 40.
The sensor element 10 is housed in the internal space 35 of the above.
【０００４】しかし、上記のような電気化学式ガスセン
サは、通気口３４から、センサ素子１０を収容する内部
空間３５に導入された検知対象ガスが、内部空間３５に
留まらずに連絡口３６を通過して貯水槽４０の気相部４
５に拡散する結果、内部空間３５内のガスが希釈される
ので、実存するガス濃度に相当して流れるはずの電流値
に比べて、センサ素子１０に生ずる電気化学反応に伴っ
て流れる電流値は低下し、その結果、検知が遅延する点
に問題がある。However, in the electrochemical gas sensor as described above, the gas to be detected introduced from the vent hole 34 into the internal space 35 accommodating the sensor element 10 passes through the communication port 36 without remaining in the internal space 35. Gas phase part 4 of the water tank 40
As a result of diffusing into 5, the gas in the internal space 35 is diluted, so that the current value flowing with the electrochemical reaction occurring in the sensor element 10 is smaller than the current value that should flow corresponding to the existing gas concentration. However, there is a problem in that the detection is delayed as a result.
【０００５】[0005]
【発明が解決しようとする課題】したがって、この発明
の課題は、ハウジングと隔壁を介してこのハウジングに
付設された貯水槽を有し、上記ハウジングは検知対象ガ
スを導入する通気口と外部から導入された検知対象ガス
が拡散する内部空間を有し、上記ハウジングの内部空間
にはセンサ素子が収容され、上記隔壁には内部空間と貯
水槽を連通する連絡口が形成され、上記センサ素子は、
互いに対設された作用極と対極及びこの作用極と対極を
被覆する、含水状態で電解質となる固体電解質膜とを備
えた電気化学式ガスセンサにおいて、センサ素子を収容
した内部空間内の検知対象ガスの希釈化を防いで検知す
る応答時間を短縮する点にある。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to have a housing and a water storage tank attached to the housing through a partition wall, and the housing is provided with a ventilation port for introducing a gas to be detected and an external introduction. The detection target gas has an internal space in which the gas is diffused, a sensor element is accommodated in the internal space of the housing, a communication port that connects the internal space and a water tank is formed in the partition wall, and the sensor element is
In an electrochemical gas sensor having a working electrode and a counter electrode which are opposite to each other and a solid electrolyte membrane which coats the working electrode and the counter electrode, and which becomes an electrolyte in a water-containing state, the detection target gas in the internal space containing the sensor element The point is to prevent dilution and shorten the response time for detection.
【０００６】[0006]
【課題を解決するための手段】本発明の請求項１に係る
電気化学式ガスセンサは、（１）ハウジング３０と隔壁
２０を介してこのハウジング３０に付設された貯水槽４
０を有し、（２）上記ハウジング３０は検知対象ガスを
導入する通気口３４と外部から導入された検知対象ガス
が拡散する内部空間３５を有し、（３）上記ハウジング
３０の内部空間３５にはセンサ素子１０が収容され、
（４）上記隔壁２０には内部空間３５と貯水槽４０を連
通する連絡口３６が形成され、（５）上記センサ素子１
０は、互いに対設された作用極７０と対極９０及びこの
作用極７０と対極９０を被覆する、含水状態で電解質と
なる固体電解質膜１１０とから構成され、さらに（６）
一端が上記連絡口３６を塞ぎ、且つ他端が貯水槽４０内
の水相部４６に浸る、含水すると気密性が生じる、吸水
性の幕５０を備えたことを特徴とする。The electrochemical gas sensor according to claim 1 of the present invention is (1) a water tank 4 attached to the housing 30 through the housing 30 and the partition wall 20.
0, (2) the housing 30 has a vent hole 34 for introducing the gas to be detected and an internal space 35 in which the gas to be detected introduced from the outside is diffused, and (3) the internal space 35 of the housing 30. The sensor element 10 is housed in
(4) The partition wall 20 is formed with a communication port 36 that communicates the internal space 35 with the water storage tank 40. (5) The sensor element 1
Reference numeral 0 is composed of a working electrode 70 and a counter electrode 90 opposite to each other, and a solid electrolyte membrane 110 which covers the working electrode 70 and the counter electrode 90 and serves as an electrolyte in a water-containing state, and further (6)
It is characterized in that it is provided with a water-absorbing curtain 50, one end of which closes the communication port 36, and the other end of which dips into the water phase portion 46 in the water storage tank 40, and which causes airtightness when it contains water.
【０００７】本発明の請求項２に係る電気化学式ガスセ
ンサは、（１）上記幕５０を基準にして、貯水槽４０内
の水相部４６の反対側に連絡口３６を塞ぐ通気性と水密
性の多孔質層６０を備えたことを特徴とする。The electrochemical gas sensor according to claim 2 of the present invention is: (1) With the curtain 50 as a reference, the ventilation and water-tightness of the communication port 36 in the water tank 40 opposite to the water phase portion 46. The porous layer 60 is provided.
【０００８】[0008]
【作用】本発明の請求項１に係る電気化学式ガスセンサ
を構成するセンサ素子１０は、ハウジング３０の内部空
間３５に収容することによって、雰囲気中の汚染物質か
ら保護される。このハウジング３０は雰囲気中の検知対
象ガスを内部空間３５に導入する通気口３４を有するの
で、雰囲気中に検知対象ガスが発生すると通気口３４か
ら検知対象ガスが内部空間３５に入る。内部空間３５と
貯水槽４０とを連通する隔壁２０の連絡口３６は、他端
が貯水槽４０内の水相部４６に浸る、含水すると気密性
が生じる、吸水性の幕５０の一端で閉塞されているの
で、内部空間３５の水蒸気が未飽和状態にある場合、幕
５０の他端から吸い上げられた水に起因して飽水状態に
保持された一端から水が蒸発し、連絡口３６を通過し
て、内部空間３５内に拡散する。そして、内部空間３５
内の水蒸気が内部空間３５に収容されたセンサ素子１０
の固体電解質膜１１０に水添して固体電解質膜１１０を
含水状態に保持するとともに、通気口３４から導入され
る検知対象ガスが発生したときには、連絡口３６を塞ぐ
幕５０の一端の飽水状態によって生じる気密性のため
に、内部空間３５内に導入された検知対象ガスは連絡口
３６を通過して貯水槽４０内の水相部４６に拡散するの
を阻止し、その結果、内部空間３５内の検知対象ガスの
希釈を阻止する。すなわち、内部空間３５内に導入され
た検知対象ガスの濃度の低下が阻止される。The sensor element 10 constituting the electrochemical gas sensor according to claim 1 of the present invention is protected from contaminants in the atmosphere by being housed in the internal space 35 of the housing 30. Since the housing 30 has the ventilation port 34 for introducing the detection target gas in the atmosphere into the internal space 35, when the detection target gas is generated in the atmosphere, the detection target gas enters the internal space 35 through the ventilation port 34. The communication port 36 of the partition wall 20 that communicates the internal space 35 and the water storage tank 40 is closed at one end of a water-absorbing screen 50 in which the other end is immersed in the water phase portion 46 in the water storage tank 40 and airtightness occurs when water is contained. Therefore, when the water vapor in the internal space 35 is in an unsaturated state, water is evaporated from one end held in a saturated state due to the water sucked from the other end of the curtain 50, and the communication port 36 is closed. It passes through and diffuses into the internal space 35. And the internal space 35
The sensor element 10 in which the water vapor inside is stored in the internal space 35
The solid electrolyte membrane 110 is hydrogenated to keep the solid electrolyte membrane 110 in a water-containing state, and when a gas to be detected introduced from the vent 34 is generated, a saturated state of one end of the screen 50 that closes the communication port 36 is generated. Due to the airtightness caused by the gas, the gas to be detected introduced into the internal space 35 is prevented from passing through the communication port 36 and diffusing into the water phase portion 46 in the water storage tank 40, and as a result, the internal space 35. The dilution of the gas to be detected inside is prevented. That is, the decrease in the concentration of the gas to be detected introduced into the internal space 35 is prevented.
【０００９】本発明の請求項２に係る電気化学式ガスセ
ンサは、上記幕５０を基準にして、水相部４６の反対側
に設けられた連絡口３６を塞ぐ多孔質層６０は通気性と
水密性を有するので、貯水槽４０内の水相部４６から蒸
発した水蒸気は多孔質層６０を通過して連絡口３６を通
り、内部空間３５内に拡散するが、貯水槽４０内の水相
部４６の水が液体の状態で多孔質層６０を通過して連絡
口３６を通り、内部空間３５内に入るのを阻止する。つ
まり、センサ素子１０が過度の水濡れから保護され、そ
れに伴って起こるセンサ素子１０の出力異常を防止す
る。In the electrochemical gas sensor according to the second aspect of the present invention, the porous layer 60 for closing the communication port 36 provided on the opposite side of the water phase portion 46 with respect to the curtain 50 is gas-permeable and water-tight. Therefore, the water vapor evaporated from the water phase portion 46 in the water storage tank 40 passes through the porous layer 60, the communication port 36, and diffuses into the internal space 35. It prevents the water in the liquid state from passing through the porous layer 60, the communication port 36 and the inside space 35. That is, the sensor element 10 is protected from excessive water wetting, and the output abnormality of the sensor element 10 that accompanies it is prevented.
【００１０】[0010]
【実施例】以下、本発明を実施例に係る図面に基づいて
詳しく説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference to the drawings according to the embodiments.
【００１１】図１に示すとおり、本発明の電気化学式ガ
スセンサは、ハウジング３０を有する。このハウジング
３０は内部空間３５を有し、かつ、隔壁２０を介してハ
ウジング３０の下方には貯水槽４０が形成されている。
ハウジング３０と貯水槽４０全体の形状は、直方体であ
るが、特に問わない。ハウジング３０と貯水槽４０全体
の材質は、例えばアクリル樹脂等の種々の樹脂を用いる
ことができる。このハウジング３０の上方には内部空間
３５に連通する検知対象ガスを導入する通気口３４及び
隔壁２０には貯水槽４０とハウジング３０を連通する連
絡口３６が設けられている。As shown in FIG. 1, the electrochemical gas sensor of the present invention has a housing 30. The housing 30 has an internal space 35, and a water tank 40 is formed below the housing 30 via the partition wall 20.
The overall shape of the housing 30 and the water storage tank 40 is a rectangular parallelepiped, but is not particularly limited. Various resins such as acrylic resin can be used for the materials of the housing 30 and the water storage tank 40 as a whole. Above the housing 30, a vent hole 34 for introducing a detection target gas communicating with the internal space 35 and a communication port 36 for communicating the water tank 40 with the housing 30 are provided in the partition wall 20.
【００１２】さらに、本発明に係る電気化学式ガスセン
サは、上記ハウジング３０の内部空間３５に収容された
センサ素子１０を有する。このセンサ素子１０は、絶縁
基板１００に作用極７０と対極９０が向かい合うように
形成されている。この絶縁基板１００には、アルミナ、
窒化アルミ、シリコン等のセラミックス製基板やエポキ
シ樹脂、フェノール樹脂等の樹脂製基板が使用される。
また、作用極７０と対極９０は、例えば白金電極を用い
る。この対極９０あるいは作用極７０の隣に参照極８０
が並べられている。参照極８０には、例えば金電極を用
いる。電極形成には、真空蒸着やスパッタリング等通常
の薄膜形成手段が利用される。さらに、対極９０、作用
極７０及び参照極８０の電極群を被覆する固体電解質膜
１１０が設けられている。この固体電解質膜１１０は、
含水すると、電解質となる性質を持っている。固体電解
質膜１１０としては、パーフルオロスルホネートポリマ
ー等からなる高分子化合物、あるいは無機化合物が用い
られる。パーフルオロスルホネートポリマーからなる固
体電解質膜は、溶融状態で絶縁基板１００上に塗布する
等の手段で形成できる。作用極７０に一定の電位をかけ
ると、検知対象ガスが上記作用極７０上で酸化反応ある
いは還元反応がおこり、この時生成されたイオンが高分
子の固体電解質膜１１０中を移動して対極９０で還元反
応あるいは酸化反応がおこる。この電気化学的な酸化還
元反応によって、対極９０−作用極７０間を流れる電流
値で検知対象ガスを検知し、センサ素子１０が応答す
る。つまり、センサ素子１０は外部で検知対象ガスが発
生し、ハウジング３０の内部空間３５の検知対象ガス濃
度がある一定のレベル以上になると、直ちに応答する。
ハウジング３０に収容されたセンサ素子１０の作用極７
０、対極９０、参照極８０の一端を端子５とし、この端
子５はハウジング３０の外側に露出し、電流計などの外
部機器の接続に用いられる。Further, the electrochemical gas sensor according to the present invention has the sensor element 10 housed in the internal space 35 of the housing 30. The sensor element 10 is formed on the insulating substrate 100 so that the working electrode 70 and the counter electrode 90 face each other. Alumina,
A ceramic substrate such as aluminum nitride or silicon, or a resin substrate such as epoxy resin or phenol resin is used.
Further, for the working electrode 70 and the counter electrode 90, for example, platinum electrodes are used. Next to the counter electrode 90 or the working electrode 70, a reference electrode 80
Are lined up. For the reference electrode 80, for example, a gold electrode is used. For forming the electrodes, ordinary thin film forming means such as vacuum deposition or sputtering is used. Furthermore, a solid electrolyte membrane 110 that covers the electrode group of the counter electrode 90, the working electrode 70, and the reference electrode 80 is provided. This solid electrolyte membrane 110 is
It has the property of becoming an electrolyte when it contains water. As the solid electrolyte membrane 110, a polymer compound such as a perfluorosulfonate polymer or an inorganic compound is used. The solid electrolyte membrane made of a perfluorosulfonate polymer can be formed by means such as coating on the insulating substrate 100 in a molten state. When a constant potential is applied to the working electrode 70, the gas to be detected undergoes an oxidation reaction or a reduction reaction on the working electrode 70, and the ions generated at this time move in the polymer solid electrolyte membrane 110 to move the counter electrode 90. Causes a reduction reaction or an oxidation reaction. By this electrochemical redox reaction, the gas to be detected is detected by the current value flowing between the counter electrode 90 and the working electrode 70, and the sensor element 10 responds. That is, the sensor element 10 immediately responds when the gas to be detected is generated outside and the concentration of the gas to be detected in the internal space 35 of the housing 30 becomes higher than a certain level.
Working electrode 7 of sensor element 10 housed in housing 30
0, the counter electrode 90, and one end of the reference electrode 80 are terminals 5, and the terminals 5 are exposed to the outside of the housing 30 and used for connecting an external device such as an ammeter.
【００１３】本発明の電気化学式ガスセンサは、さらに
上記幕５０を有する。この幕５０は吸水性を有し、含水
すると気密性が生じる材質であって、例えば濾紙や布な
どが用いられる。この幕５０は垂直片５５とこの垂直片
５５の上端から水平に延びた水平片５６からなり、垂直
片５５の下端を貯水槽４０内の水相部４６に浸し、水平
片５６を隔壁２０の下面に添接させるとともに、この水
平片５６の先端で連絡口３６を塞いで配置することによ
り、含水すると気密性が生じる、吸水性の幕５０が一端
で上記連絡口３６を塞ぎ、且つ他端が貯水槽４０内の水
相部４６に浸っている。すなわち、貯水槽４０内の水相
部４６に浸水する幕５０の垂直片５５の下端から吸い上
げられた水は水平片５６を伝わって他端を飽水状態にす
る。したがって、上記連絡口３６は飽水状態に保持され
た幕５０で塞がれ、内部空間３５と貯水槽４０内の水相
部４６間の通気性は失う。The electrochemical gas sensor of the present invention further includes the curtain 50. The curtain 50 is a material that absorbs water and exhibits airtightness when it contains water. For example, filter paper or cloth is used. The curtain 50 is composed of a vertical piece 55 and a horizontal piece 56 extending horizontally from the upper end of the vertical piece 55. The lower end of the vertical piece 55 is dipped in the water phase portion 46 in the water tank 40, and the horizontal piece 56 is attached to the partition wall 20. By arranging the horizontal piece 56 so that it is attached to the lower surface and the communication port 36 is closed by the tip of the horizontal piece 56, airtightness occurs when water is contained. A water-absorbing screen 50 closes the communication port 36 at one end and the other end. Are immersed in the water phase portion 46 in the water tank 40. That is, the water sucked up from the lower end of the vertical piece 55 of the curtain 50 that floods the water phase portion 46 in the water storage tank 40 is transmitted through the horizontal piece 56 and the other end is saturated. Therefore, the communication port 36 is closed by the curtain 50 kept in a saturated state, and the air permeability between the internal space 35 and the water phase portion 46 in the water storage tank 40 is lost.
【００１４】以下、本発明の電気化学式ガスセンサの機
能について述べる。まず、雰囲気中に検知対象ガスが発
生すると通気口３４から検知対象ガスが内部空間３５に
入る。検知対象ガスが内部空間３５内に拡散し、そのう
ちに連絡口３６に達するが、連絡口３６を塞ぐ幕５０の
一端の飽水状態によって生じる気密性のために貯水槽４
０内の水相部４６に拡散するのを阻止する。つまり、検
知対象ガスは内部空間３５内のみで拡散し、内部空間３
５内に導入された検知対象ガスの希釈化が阻止される。
センサ素子１０は、検知対象ガス濃度が内部空間３５内
である一定のレベル以上になると、直ちに応答するので
応答時間を短縮することができる。センサ素子１０から
の応答があると、端子５を通じて外部機器がそれに応じ
て作動する。The function of the electrochemical gas sensor of the present invention will be described below. First, when the gas to be detected is generated in the atmosphere, the gas to be detected enters the internal space 35 through the ventilation port 34. The gas to be detected diffuses into the internal space 35 and reaches the communication port 36, but due to the airtightness caused by the saturated state of one end of the screen 50 that closes the communication port 36, the water tank 4
It is prevented from diffusing into the water phase portion 46 within 0. That is, the gas to be detected diffuses only in the internal space 35, and the internal space 3
Dilution of the gas to be detected introduced into 5 is prevented.
The sensor element 10 responds immediately when the concentration of the gas to be detected exceeds a certain level in the internal space 35, so that the response time can be shortened. When there is a response from the sensor element 10, the external device operates accordingly through the terminal 5.
【００１５】図２に示すとおり、本発明の電気化学式ガ
スセンサは、さらに上記幕５０を基準にして、水相部４
６の反対側に設けられた連絡口３６を塞ぐ、多孔質層６
０を備える。この多孔質層６０は通気性と水密性を有す
る。この多孔質層６０の一例をあげると、ポリフッ化エ
チレン系繊維の不織布が用いられる。また、多孔質層６
０は先にあげたポリフッ化エチレンの一種であるテトラ
フルオロエチレン（以下ＴＦＥと略す）モノマーを用い
たプラズマケミカルベーパーディポジット（プラズマＣ
ＶＤ）により、濾紙や布の表面にＴＦＥの重合体を形成
したものを使用してもよい。この多孔質層６０は、上記
幕５０の垂直片５５の下端から吸い上げられ、水平片５
６を伝わって他端に達した水が液体状態で多孔質層６０
を通過して連絡口３６を通り、内部空間３５内に入るの
を阻止する。内部空間３５内に入るのを阻止する理由
は、多孔質層６０が水密性を有するからである。また、
内部空間３５内が未飽和状態のときは貯水槽４０内の水
相部４６から上記幕５０の垂直片５５の下端から吸い上
げられ、水平片５６を伝わって他端に達した水が蒸発
し、蒸気が多孔質層６０を通過して連絡口３６を通り、
内部空間３５内に蒸気を拡散させる。内部空間３５内に
蒸気が入り拡散する理由は、多孔質層６０が通気性を有
するからである。したがって、内部空間３５内に収容さ
れているセンサ素子１０が過度の水濡れから保護され、
それに伴って起こるセンサ素子１０の破壊や出力異常を
防止する。As shown in FIG. 2, the electrochemical gas sensor of the present invention further includes the water phase portion 4 based on the curtain 50.
6, the porous layer 6 that closes the communication port 36 provided on the opposite side
Equipped with 0. The porous layer 60 has air permeability and watertightness. As an example of the porous layer 60, a non-woven fabric of polyfluorinated ethylene fiber is used. In addition, the porous layer 6
0 is a plasma chemical vapor deposit (plasma C) using tetrafluoroethylene (hereinafter abbreviated as TFE) monomer, which is one of the above-mentioned polyfluoroethylenes.
According to VD), a filter paper or cloth on which a TFE polymer is formed may be used. The porous layer 60 is sucked up from the lower end of the vertical piece 55 of the curtain 50, and
6, the water reaching the other end of the porous layer 60 in a liquid state
To pass through the communication port 36 and enter the interior space 35. The reason why the porous layer 60 is prevented from entering the interior space 35 is that the porous layer 60 is watertight. Also,
When the interior space 35 is in an unsaturated state, water that has been sucked up from the lower end of the vertical piece 55 of the curtain 50 from the water phase portion 46 in the water storage tank 40 and has reached the other end through the horizontal piece 56 evaporates, The vapor passes through the porous layer 60 and the communication port 36,
The vapor is diffused in the internal space 35. The reason why the vapor enters and diffuses in the internal space 35 is that the porous layer 60 has air permeability. Therefore, the sensor element 10 housed in the internal space 35 is protected from excessive wetting,
The destruction of the sensor element 10 and the output abnormality that accompany it are prevented.
【００１６】[0016]
【発明の効果】この発明の電気化学式ガスセンサによる
と、長期の使用や保管によって貯水槽の水が蒸発し、そ
れによって応答時間が遅れていたのを防ぐことができ、
また検知するガス種には制限なく利用することができ
る。According to the electrochemical gas sensor of the present invention, it is possible to prevent the water in the water storage tank from evaporating due to long-term use and storage, and thereby delaying the response time.
Further, the gas type to be detected can be used without limitation.
【図１】本発明の請求項１の実施例に係る電気化学式ガ
スセンサの断面図である。FIG. 1 is a sectional view of an electrochemical gas sensor according to an embodiment of claim 1 of the present invention.
【図２】本発明の請求項２の実施例に係る電気化学式ガ
スセンサの断面図である。FIG. 2 is a sectional view of an electrochemical gas sensor according to a second embodiment of the present invention.
【図３】本発明の従来例に係る電気化学式ガスセンサの
断面図である。FIG. 3 is a sectional view of an electrochemical gas sensor according to a conventional example of the present invention.
【図４】本発明に係る電気化学式ガスセンサ素子の平面
図である。FIG. 4 is a plan view of an electrochemical gas sensor element according to the present invention.
【図５】図４に係る電気化学式ガスセンサ素子をＸ−Ｙ
で切った断面図である。FIG. 5 shows an electrochemical gas sensor element according to FIG.
It is sectional drawing cut by.
５ 端子 １０ センサ素子 ２０ 隔壁 ３０ ハウジング ３４ 通気口 ３５ 内部空間 ３６ 連絡口 ４０ 貯水槽 ４５ 気相部 ４６ 水相部 ５０ 幕 ５５ 垂直片 ５６ 水平片 ６０ 多孔質層 ７０ 作用極 ８０ 参照極 ９０ 対極 １００ 絶縁基板 １１０ 固体電解質膜 5 terminal 10 sensor element 20 partition wall 30 housing 34 vent hole 35 internal space 36 communication port 40 water reservoir 45 gas phase portion 46 water phase portion 50 curtain 55 vertical piece 56 horizontal piece 60 porous layer 70 working electrode 80 reference electrode 90 counter electrode 100 Insulating substrate 110 Solid electrolyte membrane
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成４年９月２日[Submission date] September 2, 1992
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項１[Name of item to be corrected] Claim 1
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００２[Name of item to be corrected] 0002
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００２】電気化学的な酸化還元反応を利用して、雰
囲気中の特定のガス、たとえば、炭酸ガス、一酸化炭
素、水素、アルコール、窒素酸化物等の検知対象ガスを
検知する電気化学式ガスセンサがこれまで数多く提案さ
れている。ここで、電気化学式ガスセンサを構成する公
知のセンサ素子１０を示す図４及び図５に基づいて説明
すると、このセンサ素子１０は、特開昭６４−８８３５
４号公報に開示されている如く、絶縁基板１００に作用
極７０と対極９０が向かい合うように形成され、この対
極９０と作用極７０の隣に参照極８０が並べられ、さら
に、含水状態に保持される固体電解質膜１１０でこれら
の電極群を被覆しており、上記作用極７０と対極９０間
に電圧を印加すると、検知対象ガスが上記作用極７０上
で酸化反応あるいは還元反応を起こし、この反応にとも
なって生成されたイオンが含水状態に保持された固体電
解質膜１１０中を移動して対極９０で還元反応あるいは
酸化反応を起こす。この電気化学的な酸化還元反応によ
って、対極９０−作用極７０間を流れる電流値をセンサ
素子１０に接続した電流計等の外部機器で測定すると、
検知対象ガスを検知できるものである。An electrochemical gas sensor for detecting a specific gas in an atmosphere, for example, a gas to be detected such as carbon dioxide gas, carbon monoxide, hydrogen, alcohol, and nitrogen oxide by utilizing an electrochemical redox reaction is known. Many have been proposed so far. Here, the known sensor element 10 constituting the electrochemical gas sensor will be described with reference to FIGS. 4 and 5, and this sensor element 10 is disclosed in JP-A-64-8835.
As disclosed in Japanese Patent Publication No. 4, the working electrode 70 and the counter electrode 90 are formed on the insulating substrate 100 so as to face each other, and the reference electrode 80 is arranged next to the counter electrode 90 and the working electrode 70, and is further kept in a water-containing state. These electrode groups are covered with a solid electrolyte membrane 110 to be detected. When a voltage is applied between the working electrode 70 and the counter electrode 90, the gas to be detected causes an oxidation reaction or a reduction reaction on the working electrode 70. The ions generated by the reaction move in the solid electrolyte membrane 110 held in a water-containing state and cause a reduction reaction or an oxidation reaction at the counter electrode 90. When the value of the current flowing between the counter electrode 90 and the working electrode 70 is measured by an external device such as an ammeter connected to the sensor element 10 by this electrochemical redox reaction,
The gas to be detected can be detected.
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００４[Correction target item name] 0004
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００４】しかし、上記のような電気化学式ガスセン
サは、通気口３４から、センサ素子１０を収容する内部
空間３５に導入された検知対象ガスが、内部空間３５に
留まらずに連絡口３６を通過して貯水槽４０の気相部４
５に拡散する結果、内部空間３５内のガスが希釈される
ため、実存するガス濃度に達するまでの時間が長くな
る。したがって、センサ素子１０に生ずる電気化学反応
に伴って流れる電流値は、内部空間３５のガス濃度に相
当した電流値を示し、実存するガス濃度に相当した電流
値になるのには、長く時間がかかり、その結果、検知が
遅延する点に問題がある。However, in the electrochemical gas sensor as described above, the gas to be detected introduced from the vent hole 34 into the internal space 35 accommodating the sensor element 10 passes through the communication port 36 without remaining in the internal space 35. Gas phase part 4 of the water tank 40
As a result of diffusing to 5, the gas in the internal space 35 is diluted.
Therefore, it takes a long time to reach the existing gas concentration.
It Therefore, the electrochemical reaction occurring in the sensor element 10
The value of the current flowing with the
Indicates the applied current value, the current corresponding to the existing gas concentration
It takes a long time to reach the value, and as a result, there is a problem in that detection is delayed.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００５[Name of item to be corrected] 0005
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００５】したがって、この発明の課題は、ハウジン
グと隔壁を介してこのハウジングに付設された貯水槽を
有し、上記ハウジングは検知対象ガスを導入する通気口
と外部から導入された検知対象ガスが拡散する内部空間
を有し、上記ハウジングの内部空間にはセンサ素子が収
容され、上記隔壁には内部空間と貯水槽を連通する連絡
口が形成され、上記センサ素子は、互いに対設された作
用極と対極及びこの作用極と対極を被覆する、含水状態
に保持される固体電解質膜とを備えた電気化学式ガスセ
ンサにおいて、センサ素子を収容した内部空間内の検知
対象ガスの希釈化を防いで検知する応答時間を短縮する
点にある。Therefore, an object of the present invention is to provide a housing and a water storage tank attached to the housing through a partition wall, and the housing has a vent for introducing the gas to be detected and a gas to be detected introduced from the outside. The housing has a diffusing internal space, a sensor element is housed in the housing, a communication port is formed in the partition wall to connect the internal space and a water tank, and the sensor elements are arranged opposite to each other. Hydrous state covering the pole and the counter electrode and this working electrode and the counter electrode
In the electrochemical gas sensor provided with the solid electrolyte membrane held by , the detection time is shortened by preventing dilution of the gas to be detected in the internal space containing the sensor element.
【手続補正５】[Procedure Amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００６[Correction target item name] 0006
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００６】本発明の請求項１に係る電気化学式ガスセ
ンサは、（１）ハウジング３０と隔壁２０を介してこの
ハウジング３０に付設された貯水槽４０を有し、（２）
上記ハウジング３０は検知対象ガスを導入する通気口３
４と外部から導入された検知対象ガスが拡散する内部空
間３５を有し、（３）上記ハウジング３０の内部空間３
５にはセンサ素子１０が収容され、（４）上記隔壁２０
には内部空間３５と貯水槽４０を連通する連絡口３６が
形成され、（５）上記センサ素子１０は、互いに対設さ
れた作用極７０と対極９０及びこの作用極７０と対極９
０を被覆する、含水状態に保持される固体電解質膜１１
０とから構成され、さらに（６）一端が上記連絡口３６
を塞ぎ、且つ他端が貯水槽４０内の水相部４６に浸る、
含水すると気密性が生じる、吸水性の幕５０を備えたこ
とを特徴とする。The electrochemical gas sensor according to claim 1 of the present invention comprises (1) a housing 30 and a water tank 40 attached to the housing 30 through a partition wall 20, (2)
The housing 30 has a vent hole 3 through which the gas to be detected is introduced.
4 and an internal space 35 in which the gas to be detected introduced from the outside diffuses, and (3) the internal space 3 of the housing 30.
5, the sensor element 10 is housed, and (4) the partition wall 20.
A communication port 36 that communicates the internal space 35 and the water storage tank 40 is formed therein. (5) In the sensor element 10, the working electrode 70 and the counter electrode 90 and the working electrode 70 and the counter electrode 9 that are provided opposite to each other are formed.
Solid electrolyte membrane 11 which covers 0 and is kept in a water-containing state
0, and (6) one end has the communication port 36.
And the other end is immersed in the water phase portion 46 in the water storage tank 40,
It is characterized in that it is provided with a water-absorbing curtain 50 which becomes airtight when it contains water.
【手続補正６】[Procedure correction 6]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１１[Correction target item name] 0011
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１１】図１に示すとおり、本発明の電気化学式ガ
スセンサは、ハウジング３０を有する。このハウジング
３０は内部空間３５を有し、かつ、隔壁２０を介してハ
ウジング３０の下方には貯水槽４０が形成されている。
ハウジング３０と貯水槽４０全体の形状は、直方体であ
るが、特に問わない。ハウジング３０と貯水槽４０全体
の材質は、例えばアクリル樹脂等の種々の樹脂やＳＵＳ
などの金属を用いることができる。このハウジング３０
の上方には内部空間３５に連通する検知対象ガスを導入
する通気口３４及び隔壁２０には貯水槽４０とハウジン
グ３０を連通する連絡口３６が設けられている。As shown in FIG. 1, the electrochemical gas sensor of the present invention has a housing 30. The housing 30 has an internal space 35, and a water tank 40 is formed below the housing 30 via the partition wall 20.
The overall shape of the housing 30 and the water storage tank 40 is a rectangular parallelepiped, but is not particularly limited. The housing 30 and the water tank 40 are made of various materials such as acrylic resin and SUS.
Metals such as can be used. This housing 30
A ventilation port 34 communicating with the internal space 35 for introducing the gas to be detected and a communication port 36 for communicating the water tank 40 with the housing 30 are provided in the partition wall 20.
【手続補正７】[Procedure Amendment 7]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１２[Correction target item name] 0012
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１２】さらに、本発明に係る電気化学式ガスセン
サは、上記ハウジング３０の内部空間３５に収容された
センサ素子１０を有する。このセンサ素子１０は、絶縁
基板１００に作用極７０と対極９０が向かい合うように
形成されている。この絶縁基板１００には、アルミナ、
窒化アルミ、シリコン等のセラミックス製基板やエポキ
シ樹脂、フェノール樹脂等の樹脂製基板が使用される。
また、作用極７０と対極９０は、例えば白金電極を用い
る。この対極９０あるいは作用極７０の隣に参照極８０
が並べられている。参照極８０には、例えば金電極を用
いる。電極形成には、真空蒸着やスパッタリング等通常
の薄膜形成手段が利用される。さらに、対極９０、作用
極７０及び参照極８０の電極群を被覆する固体電解質膜
１１０が設けられている。この固体電解質膜１１０は、
含水すると、電解質となる性質を持っている。固体電解
質膜１１０としては、パーフルオロスルホネートポリマ
ー等からなる高分子化合物、あるいは無機化合物が用い
られる。パーフルオロスルホネートポリマーからなる固
体電解質膜は、溶融状態で絶縁基板１００上に塗布する
等の手段で形成できる。作用極７０に一定の電位をかけ
ると、検知対象ガスが上記作用極７０上で酸化反応ある
いは還元反応がおこり、この時生成されたイオンが固体
電解質膜１１０中を移動して対極９０で還元反応あるい
は酸化反応がおこる。この電気化学的な酸化還元反応に
よって、対極９０−作用極７０間を流れる電流値で検知
対象ガスを検知し、センサ素子１０が応答する。つま
り、センサ素子１０は外部で検知対象ガスが発生し、ハ
ウジング３０の内部空間３５に検知対象ガスが流入する
とその濃度に応じた出力が得られる。ハウジング３０に
収容されたセンサ素子１０の作用極７０、対極９０、参
照極８０の一端を端子５とし、この端子５はハウジング
３０の外側に露出し、電流計などの外部機器の接続に用
いられる。Further, the electrochemical gas sensor according to the present invention has the sensor element 10 housed in the internal space 35 of the housing 30. The sensor element 10 is formed on the insulating substrate 100 so that the working electrode 70 and the counter electrode 90 face each other. Alumina,
A ceramic substrate such as aluminum nitride or silicon, or a resin substrate such as epoxy resin or phenol resin is used.
Further, for the working electrode 70 and the counter electrode 90, for example, platinum electrodes are used. Next to the counter electrode 90 or the working electrode 70, a reference electrode 80
Are lined up. For the reference electrode 80, for example, a gold electrode is used. For forming the electrodes, ordinary thin film forming means such as vacuum deposition or sputtering is used. Furthermore, a solid electrolyte membrane 110 that covers the electrode group of the counter electrode 90, the working electrode 70, and the reference electrode 80 is provided. This solid electrolyte membrane 110 is
It has the property of becoming an electrolyte when it contains water. As the solid electrolyte membrane 110, a polymer compound such as a perfluorosulfonate polymer or an inorganic compound is used. The solid electrolyte membrane made of a perfluorosulfonate polymer can be formed by means such as coating on the insulating substrate 100 in a molten state. When a constant potential is applied to the working electrode 70, the gas to be detected undergoes an oxidation reaction or a reduction reaction on the working electrode 70, and the ions generated at this time are solid.
After moving through the electrolyte membrane 110 , a reduction reaction or an oxidation reaction occurs at the counter electrode 90. By this electrochemical redox reaction, the gas to be detected is detected by the current value flowing between the counter electrode 90 and the working electrode 70, and the sensor element 10 responds. That is, the detection target gas is generated outside the sensor element 10, and the detection target gas flows into the internal space 35 of the housing 30.
And an output corresponding to the concentration is obtained. One end of the working electrode 70, the counter electrode 90, and the reference electrode 80 of the sensor element 10 housed in the housing 30 is used as a terminal 5. The terminal 5 is exposed to the outside of the housing 30 and is used for connecting an external device such as an ammeter. .
【手続補正８】[Procedure Amendment 8]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１４[Correction target item name] 0014
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１４】以下、本発明の電気化学式ガスセンサの機
能について述べる。まず、雰囲気中に検知対象ガスが発
生すると通気口３４から検知対象ガスが内部空間３５に
入る。検知対象ガスが内部空間３５内に拡散し、そのう
ちに連絡口３６に達するが、連絡口３６を塞ぐ幕５０の
一端の飽水状態によって生じる気密性のために貯水槽４
０内の水相部４６に拡散するのを阻止する。つまり、検
知対象ガスは内部空間３５内のみで拡散し、内部空間３
５内に導入された検知対象ガスの希釈化が阻止される。
連絡口３６により検知対象ガスが希釈されると、検知対
象ガス濃度に応じた出力を得るセンサ素子１０は、外部
のガス濃度に達する時間が長くなることから応答が遅れ
るが、幕５０があるのでガスの希釈がなく、応答時間を
短縮することができる。センサ素子１０からの応答があ
ると、端子５を通じて外部機器がそれに応じて作動す
る。The function of the electrochemical gas sensor of the present invention will be described below. First, when the gas to be detected is generated in the atmosphere, the gas to be detected enters the internal space 35 through the ventilation port 34. The gas to be detected diffuses into the internal space 35 and reaches the communication port 36, but due to the airtightness caused by the saturated state of one end of the screen 50 that closes the communication port 36, the water tank 4
It is prevented from diffusing into the water phase portion 46 within 0. That is, the gas to be detected diffuses only in the internal space 35, and the internal space 3
Dilution of the gas to be detected introduced into 5 is prevented.
When the gas to be detected is diluted by the communication port 36,
The sensor element 10 that obtains an output according to the elephant gas concentration is external
Response is delayed because it takes longer to reach the gas concentration of
However, since there is a curtain 50, there is no gas dilution, and the response time is
It can be shortened. When there is a response from the sensor element 10, the external device operates accordingly through the terminal 5.
Claims (2)
このハウジング３０に付設された貯水槽４０を有し、
（２）上記ハウジング３０は検知対象ガスを導入する通
気口３４と外部から導入された検知対象ガスが拡散する
内部空間３５を有し、（３）上記ハウジング３０の内部
空間３５にはセンサ素子１０が収容され、（４）上記隔
壁２０には内部空間３５と貯水槽４０を連通する連絡口
３６が形成され、（５）上記センサ素子１０は、互いに
対設された作用極７０と対極９０及びこの作用極７０と
対極９０を被覆する、含水状態で電解質となる固体電解
質膜１１０とから構成され、さらに（６）一端が上記連
絡口３６を塞ぎ、且つ他端が貯水槽４０内の水相部４６
に浸る、含水すると気密性が生じる、吸水性の幕５０を
備えたことを特徴とする電気化学式ガスセンサ。1. A housing 30 and a water storage tank 40 attached to the housing 30 through a partition wall 20,
(2) The housing 30 has a vent hole 34 for introducing the detection target gas and an internal space 35 in which the detection target gas introduced from the outside diffuses. (3) The sensor element 10 is provided in the internal space 35 of the housing 30. (4) A communication port 36 is formed in the partition wall 20 to connect the internal space 35 and the water tank 40, and (5) the sensor element 10 includes a working electrode 70 and a counter electrode 90 which are arranged opposite to each other. The working electrode 70 and the counter electrode 90 are covered with a solid electrolyte membrane 110 which becomes an electrolyte in a water-containing state, and (6) one end closes the communication port 36 and the other end has a water phase in the water storage tank 40. Part 46
An electrochemical gas sensor comprising a water-absorbing curtain 50 which is airtight when immersed in water or contains water.
０内の水相部４６の反対側に連絡口３６を塞ぐ通気性と
水密性の多孔質層６０を備えたことを特徴とする請求項
１記載の電気化学式ガスセンサ。(1) The water tank 4 with the curtain 50 as a reference
2. The electrochemical gas sensor according to claim 1, further comprising a gas-permeable and water-tight porous layer 60 that closes the communication port 36 on the side opposite to the water phase portion 46 in 0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04159522A JP3100764B2 (en) | 1992-06-18 | 1992-06-18 | Electrochemical gas sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04159522A JP3100764B2 (en) | 1992-06-18 | 1992-06-18 | Electrochemical gas sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH063324A true JPH063324A (en) | 1994-01-11 |
| JP3100764B2 JP3100764B2 (en) | 2000-10-23 |
Family
ID=15695608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04159522A Expired - Fee Related JP3100764B2 (en) | 1992-06-18 | 1992-06-18 | Electrochemical gas sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3100764B2 (en) |
-
1992
- 1992-06-18 JP JP04159522A patent/JP3100764B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3100764B2 (en) | 2000-10-23 |
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