JP5988485B2 - Electrochemical gas sensor - Google Patents

Electrochemical gas sensor Download PDF

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JP5988485B2
JP5988485B2 JP2012184914A JP2012184914A JP5988485B2 JP 5988485 B2 JP5988485 B2 JP 5988485B2 JP 2012184914 A JP2012184914 A JP 2012184914A JP 2012184914 A JP2012184914 A JP 2012184914A JP 5988485 B2 JP5988485 B2 JP 5988485B2
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electrode
cell container
working electrode
hydrophobic porous
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達也 米倉
達也 米倉
良治 青
良治 青
晃 赤松
晃 赤松
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Riken Keiki KK
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Description

本発明は、通気性隔膜に作用極が電解液に接液してガスを検出する電気化学式センサのエア抜き構造に関する。   The present invention relates to an air vent structure of an electrochemical sensor in which a working electrode is in contact with an electrolyte solution on a gas permeable membrane to detect gas.

電気化学式ガスセンサは、電解液を容器に密封した構造を採用しているため、気温などの変化により容器の内圧が変動するという問題がある。   Since the electrochemical gas sensor employs a structure in which an electrolytic solution is sealed in a container, there is a problem that the internal pressure of the container fluctuates due to a change in temperature or the like.

このような問題を解消するため特許文献１に見られるようにセンサを構成する電解液と電極との間を疎水性多孔質材で連絡し、疎水性多孔質材を介してセンサ内の流体圧を電極から逃がすようにしたのも提案されている。
しかしながら電極がセンサの上部側に位置する姿勢でしか機能しないという問題がある。 In order to solve such a problem, as shown in Patent Document 1, the electrolyte and the electrode constituting the sensor are connected by a hydrophobic porous material, and the fluid pressure in the sensor is passed through the hydrophobic porous material. It has also been proposed to escape from the electrode.
However, there is a problem that the electrode functions only in a posture positioned on the upper side of the sensor.

カナダ特許第2255472号明細書Canadian Patent No. 2255472

本発明はこのような問題に鑑みてなされたものであって、その目的とするところはセル容器の姿勢にかかわりなくセル容器の圧力を大気圧に維持できる電気化学式ガスセンサを提供することである。   The present invention has been made in view of such problems, and an object of the present invention is to provide an electrochemical gas sensor capable of maintaining the pressure of the cell container at atmospheric pressure regardless of the attitude of the cell container.

このような課題を達成するために本発明は、電解液を収容するセル容器の外気と連通する窓に作用極が液密に配置されている電気化学的ガスセンサにおいて、前記作用極は、疎水性多孔質膜に周縁部を残すように電極形成材料の電極層を形成して構成され、作用極の疎水性多孔質膜の電極層が存在しない周縁領域に接する領域と前記電解液を横切る帯状領域と、前記セル容器の底部の略全面に対向する広さの幅広部とを有する疎水性多孔質材からなるエア抜き片が配置されている。
In order to achieve such a problem, the present invention provides an electrochemical gas sensor in which a working electrode is disposed in a liquid-tight manner in a window communicating with the outside air of a cell container that contains an electrolytic solution. An electrode layer made of an electrode forming material is formed so as to leave a peripheral portion on the porous membrane, and a region in contact with the peripheral region where the electrode layer of the hydrophobic porous membrane of the working electrode does not exist and a belt-shaped region crossing the electrolyte solution And an air bleeding piece made of a hydrophobic porous material having a wide portion facing the substantially entire surface of the bottom portion of the cell container.

容器の相対向する面にほぼ周縁部に位置する領域を帯状領域で接続されたエア抜き片が配置されているので、セル容器内の空間がエア抜き片を介して外気に接続されるから、姿勢にかかわりなくセル容器内の圧力を大気圧に維持することができる。   Since the air vent piece connected to the opposite surfaces of the container by the belt-like region is located in the region located almost at the periphery, the space in the cell container is connected to the outside air through the air vent piece, Regardless of the posture, the pressure in the cell container can be maintained at atmospheric pressure.

本発明の電気化学式ガスセンサの一実施例を示す断面図である。It is sectional drawing which shows one Example of the electrochemical gas sensor of this invention. エア抜き片の一実施例を示す正面図と使用時の形態を示す斜視図である。It is a front view which shows one Example of an air bleeding piece, and a perspective view which shows the form at the time of use. 図（ａ）〜（ｃ）は、それぞれエア抜き片の一実施例を示す図と、作用極の一実施例を電極層側から見た図である。Drawing (a)-(c) is a figure showing one example of an air bleeding piece, and a figure which looked at one example of a working electrode from the electrode layer side, respectively. 本発明に適したエア抜き片の他の実施例を示す図である。It is a figure which shows the other Example of the air bleeding piece suitable for this invention.

そこで以下に本発明の詳細を図示した実施例に基づいて説明する。
本発明の一実施例を定電位電解式ガス検出器に例を採って示すものであって、セル容器１は、底部１ａに後述するエア抜き片２の位置決め孔２ａに係合する突起１ｂを有し、足３ａにより電解液を貯蔵する空間４を確保し、上面に対極５、及び参照極６を収容する面３ｂを有し、また電解液を貯蔵する空間４の電解液を含水紙７に補給する貫通孔３ｃが穿設された電極受け材３が収容されている。 Therefore, details of the present invention will be described below based on the illustrated embodiment.
One embodiment of the present invention is shown by taking a constant potential electrolytic gas detector as an example, and a cell container 1 has a protrusion 1b that engages with a positioning hole 2a of an air bleeding piece 2 to be described later on a bottom 1a. A space 4 for storing the electrolyte solution by the legs 3a, a surface 3b for accommodating the counter electrode 5 and the reference electrode 6 on the upper surface, and the electrolyte solution in the space 4 for storing the electrolyte solution in the water-containing paper 7 An electrode receiving member 3 having a through-hole 3c for replenishing it is accommodated.

対極５、及び参照極６の上面には電解液を吸液保持する含水紙７、Ｏリング８を介してエア抜き片２のリング状部２ｂ、作用極９が積層配置され、リング状の両面接着板１０を介して上蓋１１が嵌合されている。   On the upper surface of the counter electrode 5 and the reference electrode 6, a water-containing paper 7 that absorbs and holds the electrolyte solution, a ring-shaped portion 2 b of the air bleeding piece 2 via an O-ring 8, and a working electrode 9 are laminated and disposed. An upper lid 11 is fitted through the adhesive plate 10.

上蓋１１には空気取入口１１ａが設けられていてここにフィルタ材１２が配置されている。
なお、図中符号１３は対極５、及び参照極６に導通するリードアッセンブリで、接着材１４を介してセル容器１の底部１ａに配置固定されている。 The upper lid 11 is provided with an air intake port 11a, and a filter material 12 is disposed here.
In the figure, reference numeral 13 denotes a lead assembly that conducts to the counter electrode 5 and the reference electrode 6, and is arranged and fixed to the bottom 1 a of the cell container 1 via an adhesive 14.

作用極９は、周知の如く図３（ｃ）に示したように疎水性多孔質膜９１の電解液側にその周縁部９２を残すように被検ガスを酸化、還元するのに適した電極形成材料、例えば酸化白金（ＰｔＯ）や、酸化ルテリウム（ＲｕＯ2）等の金属の微粉末とフッ素樹脂粉末を混合したものを、塗布、焼結したり、また反応性スパッタリング等により電極層９３を作り付けて構成されている。   As is well known, the working electrode 9 is an electrode suitable for oxidizing and reducing the test gas so as to leave the peripheral edge 92 on the electrolyte side of the hydrophobic porous membrane 91 as shown in FIG. Forming material, for example, a mixture of fine metal powder such as platinum oxide (PtO) or ruthelium oxide (RuO2) and fluororesin powder is applied, sintered, or electrode layer 93 is formed by reactive sputtering or the like. Configured.

図３（ａ）は、エア抜き片２の実施例を示すものであって、作用極９の電極層９３が形成されていない周縁部９２に接するサイズの環状部２ｂと、これに連続する帯状領域２ｃと、セル容器１の底部１ａの可及的に広い面積、好ましくは全面を覆う幅広領域２ｄとで構成されている。   FIG. 3A shows an embodiment of the air bleeding piece 2, and an annular portion 2 b having a size in contact with the peripheral edge portion 92 where the electrode layer 93 of the working electrode 9 is not formed, and a continuous belt-like shape. The region 2c and a wide region 2d covering the largest possible area, preferably the entire surface, of the bottom 1a of the cell container 1 are configured.

そして図２（ｂ）に示すように環状部２ｂと幅広領域２ｄが相対向するように帯状領域２ｃとの境界で折曲げて、幅広領域２ｄの位置決め孔２ａをセル容器１の底部１ａの突起１ｂに嵌合させ、また環状部２ｂを作用極９の電極層９３が形成されていない周縁部９２と対向するようにセットされる。   Then, as shown in FIG. 2 (b), the positioning hole 2a of the wide region 2d is bent at the boundary between the annular region 2b and the wide region 2d so that the wide region 2d faces each other, and the protrusion of the bottom portion 1a of the cell container 1 is formed. The annular portion 2b is set so as to face the peripheral portion 92 where the electrode layer 93 of the working electrode 9 is not formed.

これによりセル容器１の天地に位置する環状部２ｂ、幅広領域２ｄが電解液中の帯状領域２ｃを介して連通する。
またエア抜き片２のセル容器１の開口１ｂの側を環状部２ｂとして形成することにより、作用極９の周縁部９２をセル容器１の上蓋１１とＯリング８とで均一に圧接して電解液の漏れを確実に防止することができる。 Thereby, the annular part 2b and the wide area | region 2d located in the top and bottom of the cell container 1 are connected via the strip | belt-shaped area | region 2c in electrolyte solution.
Further, by forming the air bleed piece 2 on the side of the opening 1b of the cell container 1 as an annular part 2b, the peripheral part 92 of the working electrode 9 is uniformly pressed by the upper lid 11 and the O-ring 8 of the cell container 1 to perform electrolysis Liquid leakage can be reliably prevented.

この実施例において、被検ガスが作用極９に到達すると、周知のように含水紙７の電解液を介してガス濃度に応じて対極５との間で電流が流れ濃度信号として検出される。   In this embodiment, when the test gas reaches the working electrode 9, a current flows between the counter electrode 5 according to the gas concentration through the electrolytic solution of the water-containing paper 7 and is detected as a concentration signal.

一方、外気温の変化によりセル容器１の内圧が上昇すると、セル容器１内の空気はエア抜き片２を構成する疎水性多孔質膜の細孔を介してリング状部２ｂに移動し、さらにこれに圧接している作用極７の疎水性多孔質膜９１の電極層９３が形成されていない領域、つまり周縁部９２に移動してセル容器１の外に抜ける。   On the other hand, when the internal pressure of the cell container 1 rises due to a change in the outside air temperature, the air in the cell container 1 moves to the ring-shaped part 2b through the pores of the hydrophobic porous membrane constituting the air vent piece 2, and It moves to the region where the electrode layer 93 of the hydrophobic porous membrane 91 of the working electrode 7 in pressure contact is not formed, that is, the peripheral edge portion 92, and comes out of the cell container 1.

反対にセル容器１の内圧が低下すると疎水性多孔質膜９１の電極層９３が形成されていない周縁部９２のエアがエア抜き片２のリング状部２ｂに移動しセル容器１内に進入する。
このような作用によりセル容器１の空気と外気が相互に移動してセル容器１の内外の圧力が均等なる。 On the contrary, when the internal pressure of the cell container 1 decreases, the air in the peripheral portion 92 where the electrode layer 93 of the hydrophobic porous membrane 91 is not formed moves to the ring-shaped portion 2 b of the air bleeding piece 2 and enters the cell container 1. .
By such an action, the air in the cell container 1 and the outside air move to each other, and the pressure inside and outside the cell container 1 becomes equal.

言うまでもなく、エア抜き片２の環状部２ｂと幅広領域２ｄとが天地に位置すると共に、セル容器１の天地の周縁部にも位置するため、いずれかの部分がセル容器１内の空気に接する。したがって、たとえセル容器１の底部１ａが上部となっても幅広領域２ｄが空気に接触し、帯状部２ｃを介して作用極側に移動し作用極９の周縁部９２から外部に抜ける。これにより姿勢にかかわりなくセル容器１の圧力は外気と均一に調整される。   Needless to say, since the annular portion 2b and the wide region 2d of the air bleeding piece 2 are positioned on the top and the peripheral edge of the top of the cell container 1, either portion is in contact with the air in the cell container 1. . Therefore, even if the bottom portion 1a of the cell container 1 is the upper portion, the wide region 2d comes into contact with air, moves to the working electrode side through the strip-shaped portion 2c, and comes out from the peripheral portion 92 of the working electrode 9 to the outside. Thereby, the pressure of the cell container 1 is adjusted uniformly with the outside air regardless of the posture.

なお上述の実施例においては、エア抜き片２を作用極９と別体に構成しているが、図４に示したように帯状部２ｃ’の一端に作用極を構成するのに適した円状部２ｂ’を、また他端にセル容器の底部に対向する広さの幅広部２ｄ’を形成するようにを疎水性多孔質材を切り抜き、円状部にその周縁部９２’を残すように電極層９３’を形成しても同様の作用を奏することは明らかである   In the above-described embodiment, the air bleeding piece 2 is configured separately from the working electrode 9, but as shown in FIG. The hydrophobic porous material is cut out so as to form a wide portion 2d 'having a width opposite to the bottom of the cell container at the other end, and the peripheral portion 92' is left in the circular portion. It is clear that the same effect can be obtained even if the electrode layer 93 'is formed on

１ セル容器 ２ エア抜き片 ８ パッキング ６ 押さえ蓋 ７ 含水紙 ９ 作用極 ９１ 疎水性多孔質材 ９２ 周縁部 ９３ 電極層 DESCRIPTION OF SYMBOLS 1 Cell container 2 Air bleeding piece 8 Packing 6 Holding lid 7 Water-containing paper 9 Working electrode 91 Hydrophobic porous material 92 Peripheral part 93 Electrode layer

Claims (2)

電解液を収容するセル容器の外気と連通する窓に作用極が液密に配置されている電気化学的ガスセンサにおいて、前記作用極は、疎水性多孔質膜に周縁部を残すように電極形成材料の電極層を形成して構成され、作用極の疎水性多孔質膜の電極層が存在しない周縁領域に接する領域と前記電解液を横切る帯状領域と、前記セル容器の底部の略全面に対向する広さの幅広部とを有する疎水性多孔質材からなるエア抜き片が配置されている電気化学式ガスセンサ。   In an electrochemical gas sensor in which a working electrode is disposed in a liquid-tight manner in a window communicating with the outside air of a cell container that stores an electrolyte solution, the working electrode has an electrode-forming material so that a peripheral portion is left in the hydrophobic porous membrane. The electrode layer of the hydrophobic porous membrane of the working electrode is in contact with the peripheral region where the electrode layer does not exist, the belt-like region across the electrolyte solution, and the substantially entire bottom of the cell container. An electrochemical gas sensor in which an air bleeding piece made of a hydrophobic porous material having a wide portion is arranged. 前記エア抜き片の前記作用極の電極層に対向する側は、前記作用極を構成する疎水性多孔質膜の前記電極層が存在しない領域に対応するように環状に形成されている請求項１に記載の電気化学式ガスセンサ。   The side of the air bleeding piece facing the electrode layer of the working electrode is formed in an annular shape so as to correspond to a region where the electrode layer of the hydrophobic porous film constituting the working electrode does not exist. The electrochemical gas sensor according to 1.
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