JP6576054B2 - Constant potential electrolytic gas sensor - Google Patents

Constant potential electrolytic gas sensor Download PDF

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JP6576054B2
JP6576054B2 JP2015044703A JP2015044703A JP6576054B2 JP 6576054 B2 JP6576054 B2 JP 6576054B2 JP 2015044703 A JP2015044703 A JP 2015044703A JP 2015044703 A JP2015044703 A JP 2015044703A JP 6576054 B2 JP6576054 B2 JP 6576054B2
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克典 近藤
克典 近藤
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New Cosmos Electric Co Ltd
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Description

本発明は、ガスを検知するガス電極として被検知ガスを電気化学反応させる反応極、前記反応極に対する対極および前記反応極の電位を制御する参照極を、電解槽に収容した電解液に接触するように備えた定電位電解式ガスセンサに関する。   In the present invention, a reaction electrode for electrochemically reacting a gas to be detected as a gas electrode for detecting gas, a counter electrode with respect to the reaction electrode, and a reference electrode for controlling the potential of the reaction electrode are brought into contact with an electrolytic solution accommodated in an electrolytic cell. The present invention relates to a constant potential electrolysis gas sensor.

従来の定電位電解式ガスセンサは、電極を電解液が密に収容される電解槽の電解液収容部内に臨んで設けて構成してあり、例えば電極としては、ガスを検知するガス電極として被検知ガスを電気化学反応させる反応極、当該反応極に対する対極、反応極の電位を制御する参照極の3電極を設けてあり、また、これらが接触自在な電解液を収容した電解槽と、各電極の電位を設定するポテンシオスタット回路等を接続してある。前記3電極の材料としては撥水性を有するガス透過性の多孔質PTFE膜に白金や金、パラジウム等の貴金属触媒等を塗布したものが、電解液としては、硫酸やリン酸等の酸性水溶液等が用いられていた。   A conventional constant potential electrolytic gas sensor is configured such that an electrode is provided facing an electrolytic solution storage part of an electrolytic cell in which an electrolytic solution is densely stored. For example, an electrode is detected as a gas electrode that detects gas. There are provided three electrodes: a reaction electrode for electrochemically reacting gas, a counter electrode for the reaction electrode, and a reference electrode for controlling the potential of the reaction electrode. A potentiostat circuit for setting the potential is connected. As the material of the three electrodes, a gas-permeable porous PTFE film having water repellency is coated with a noble metal catalyst such as platinum, gold, palladium, etc. As an electrolyte, an acidic aqueous solution such as sulfuric acid or phosphoric acid is used. Was used.

また、定電位電解式ガスセンサは、周囲の環境変化に対して反応極の電位を制御して一定に維持することによって、反応極と対極との間に周囲の環境変化に相当する電流を生じさせる。そして、反応極の電位が変化せず、またガス種によって酸化還元電位が異なることを利用することにより、ポテンシオスタット回路の設定電位によってはガスの選択的な検知が可能になる。また、ガス電極に用いる触媒を変えることで、目的とするガスに対して高い選択性を持たすことができる。   In addition, the constant potential electrolytic gas sensor generates a current corresponding to the change in the surrounding environment between the reaction electrode and the counter electrode by controlling the potential of the reaction electrode to be constant with respect to the change in the surrounding environment. . Then, by utilizing the fact that the potential of the reaction electrode does not change and the oxidation-reduction potential varies depending on the gas type, it becomes possible to selectively detect the gas depending on the set potential of the potentiostat circuit. Further, by changing the catalyst used for the gas electrode, it is possible to have high selectivity for the target gas.

尚、本発明における従来技術となる上述した定電位電解式ガスセンサは、一般的な技術であるため、特許文献等の従来技術文献は示さない。   Note that the above-described constant potential electrolytic gas sensor, which is a conventional technique in the present invention, is a general technique, and therefore does not show any prior art documents such as patent documents.

このような定電位電解式ガスセンサにおいて、各ガス電極における電極反応等で発生した気泡や、急激な加圧状態における空気の侵入、また急激な温度変化に伴い電解液中に溶解していた空気が発生した場合、これら気泡や空気が各ガス電極の表面に付着して大きく成長すれば、その部分における電極反応が不安定となり、センサの出力値が安定しなくなる虞があった。   In such a constant potential electrolytic gas sensor, air bubbles generated by electrode reactions at each gas electrode, air intrusion in a sudden pressurization state, and air dissolved in the electrolyte solution due to a sudden temperature change If generated, if these bubbles or air adhere to the surface of each gas electrode and grow large, the electrode reaction at that portion becomes unstable, and the output value of the sensor may not be stable.

従って、本発明の目的は、出力値の安定した定電位電解式ガスセンサを提供することにある。   Accordingly, an object of the present invention is to provide a constant potential electrolytic gas sensor having a stable output value.

上記目的を達成するための本発明に係る定電位電解式ガスセンサは、ガスを検知するガス電極として被検知ガスを電気化学反応させる反応極、前記反応極に対する対極および前記反応極の電位を制御する参照極を、電解槽に収容した電解液に接触するように備えた定電位電解式ガスセンサであって、その第一特徴構成は、電解液を収容する電解液収容部に電解液を吸水して保持する複数の保水部材が、前記反応極および前記参照極の間に、前記反応極の側および前記参照極の側に分かれて配設してあり、これらの保水部材を、前記反応極および前記参照極に対して各別に押圧する押え部材を設け、前記押え部材は、弾性変形可能な芯部材と、当該芯部材の両端に配設した有孔の板状部材と、を備えた点にある。 In order to achieve the above object, a constant potential electrolytic gas sensor according to the present invention controls a reaction electrode for electrochemically reacting a gas to be detected as a gas electrode for detecting gas, a counter electrode for the reaction electrode, and a potential of the reaction electrode. A constant potential electrolytic gas sensor provided with a reference electrode in contact with an electrolytic solution accommodated in an electrolytic cell, the first characteristic configuration is that the electrolytic solution is absorbed in an electrolytic solution accommodating portion that accommodates the electrolytic solution. A plurality of water retaining members to be held are arranged between the reaction electrode and the reference electrode, separately on the reaction electrode side and the reference electrode side, and these water retention members are connected to the reaction electrode and the reference electrode. A presser member that presses the reference electrode separately is provided , and the presser member includes an elastically deformable core member and perforated plate-like members disposed at both ends of the core member. .

本構成によれば、保水部材を反応極および参照極に接するように配設することができるため、保水部材が保持する電解液を、反応極および参照極に接触させることができる。また、保水部材を反応極および参照極に対して各別に押圧する押え部材を設けることにより、保水部材を反応極および参照極に対して確実に密着させることができる。そのため、これらガス電極の表面に気泡が生じ難くなり、当該ガス電極における電極反応が安定に行われる。従って、本構成であれば出力値の安定したセンサとなる。   According to this configuration, since the water retention member can be disposed so as to be in contact with the reaction electrode and the reference electrode, the electrolytic solution retained by the water retention member can be brought into contact with the reaction electrode and the reference electrode. In addition, by providing a pressing member that presses the water retention member against the reaction electrode and the reference electrode, the water retention member can be securely adhered to the reaction electrode and the reference electrode. Therefore, bubbles are hardly generated on the surfaces of these gas electrodes, and the electrode reaction in the gas electrodes is stably performed. Therefore, with this configuration, the sensor has a stable output value.

また、保水部材を押え部材によって押圧できるため、保水部材を反応極および参照極の間に配設し易くなってセンサの組み立て作業効率が向上する。
本構成によれば、反応極および参照極の間の寸法や保水部材の厚さに応じて、芯部材はその弾性力によってある程度、芯部材が収縮する方向に弾性変形することができる。この場合、芯部材は弾性変形可能であるため収縮する方向とは逆の反発力が発生する。この反発力が、芯部材の両端に配設した板状部材を介して、保水部材を反応極および参照極に対して各別に押圧する押圧力となる。
また、板状部材を設けることで、押え部材が保水部材と面接触して押圧力を保水部材のより広い範囲に伝達することができる。さらに板状部材を有孔とすることで、電解液が板状部材の孔を介して保水部材に吸収され易くなる。
Further, since the water retaining member can be pressed by the pressing member, the water retaining member can be easily disposed between the reaction electrode and the reference electrode, and the assembly work efficiency of the sensor is improved.
According to this structure, according to the dimension between the reaction electrode and the reference electrode and the thickness of the water retaining member, the core member can be elastically deformed in a direction in which the core member contracts to some extent by its elastic force. In this case, since the core member is elastically deformable, a repulsive force opposite to the contracting direction is generated. This repulsive force becomes a pressing force that presses the water retaining member against the reaction electrode and the reference electrode separately via the plate-like members disposed at both ends of the core member.
Further, by providing the plate-like member, the pressing member can be brought into surface contact with the water retaining member and the pressing force can be transmitted to a wider range of the water retaining member. Furthermore, by making the plate-like member perforated, the electrolytic solution is easily absorbed by the water retention member through the hole of the plate-like member.

本発明に係る定電位電解式ガスセンサの第二特徴構成は、前記保水部材は、前記押え部材による押圧力によってその厚みが変動する点にある。   A second characteristic configuration of the constant potential electrolytic gas sensor according to the present invention is that the thickness of the water retaining member varies depending on the pressing force of the pressing member.

本構成によれば、保水部材は、押え部材による押圧力によって最適な厚みに変動して、各ガス電極や押え部材に負荷をかけることなく、反応極および参照極に確実に密着させることができる。また、センサの筐体や押え部材に製造の寸法誤差があったとしても、保水部材が押え部材による押圧力によって最適な厚みに変動して、当該寸法誤差を吸収することができる。   According to this configuration, the water retaining member can be brought into an optimum thickness by the pressing force of the pressing member, and can be reliably brought into close contact with the reaction electrode and the reference electrode without applying a load to each gas electrode and the pressing member. . Further, even if there is a manufacturing dimensional error in the sensor casing or the pressing member, the water retaining member is changed to an optimum thickness by the pressing force by the pressing member, and the dimensional error can be absorbed.

本発明に係る定電位電解式ガスセンサの第三特徴構成は、前記電解槽の側方に開口してガスを導入するガス導入部を備え、前記芯部材を、前記ガス導入部に対応する位置となるように前記押え部材を配設した点にある。 A third characteristic configuration of the constant potential electrolytic gas sensor according to the present invention includes a gas introduction part that opens to a side of the electrolytic cell and introduces gas, and the core member is positioned at a position corresponding to the gas introduction part. Thus, the presser member is disposed.

本構成によれば、押え部材が保水部材を押圧する際、板状部材が平坦であれば芯部材に対応する位置が最も押圧力が強いと考えられる。そのため、芯部材に対応する位置において保水部材は反応極に対して最も確実に密着している。ガス導入部からはサンプリングしたガスが導入されてくるため、本構成のように、芯部材がガス導入部に対応する位置となるように押え部材を配設することで、保水部材が反応極に対して最も確実に密着している位置と、ガス導入部とを一致させることができる。そのため、反応極における電極反応を、気泡の影響を受けることが殆ど無い状態で確実に行うことができる。   According to this configuration, when the pressing member presses the water retaining member, the position corresponding to the core member is considered to have the strongest pressing force if the plate-like member is flat. For this reason, the water retention member is most closely attached to the reaction electrode at a position corresponding to the core member. Since the sampled gas is introduced from the gas introduction part, the water retaining member is attached to the reaction electrode by arranging the holding member so that the core member is positioned corresponding to the gas introduction part as in this configuration. On the other hand, it is possible to make the gas introduction part coincide with the position that is most reliably in close contact with the gas introduction part. Therefore, the electrode reaction at the reaction electrode can be reliably performed in a state where the reaction is hardly affected by bubbles.

本発明に係る定電位電解式ガスセンサの第四特徴構成は、前記保水部材を、前記反応極および前記参照極の全面を覆うように配設した点にある。 A fourth characteristic configuration of the constant potential electrolytic gas sensor according to the present invention is that the water retaining member is disposed so as to cover the entire surface of the reaction electrode and the reference electrode.

本構成によれば、保水部材によって反応極および参照極の全面においてこれらガス電極の表面に気泡を生じ難くすることができるため、より出力値の安定したセンサとすることができる。   According to this configuration, it is possible to make it difficult for bubbles to be generated on the surface of the gas electrode on the entire surface of the reaction electrode and the reference electrode by the water retaining member, so that a sensor with a more stable output value can be obtained.

本発明の定電位電解式ガスセンサを示す概略図である。It is the schematic which shows the constant potential electrolytic gas sensor of this invention. 押え部材の概略図である。It is the schematic of a pressing member. 開口装着部材を示す概略図である。It is the schematic which shows an opening mounting member. 被検知ガスとして酸素ガス(21vol%)を検知したときにおいて、気泡の影響の有無を調べたグラフである。It is the graph which investigated the presence or absence of the influence of a bubble, when oxygen gas (21 vol%) was detected as to-be-detected gas.

以下、本発明の実施形態を図面に基づいて説明する。
図1に示すように、定電位電解式ガスセンサXは、ガスを検知するガス電極10として被検知ガスを電気化学反応させる反応極11、当該反応極11に対する対極12、反応極11の電位を制御する参照極13を、電解槽30に収容した電解液20に接触するように備えている。この定電位電解式ガスセンサXは、電解槽30の側方に開口してガスを導入するガス導入部32と、電解槽30の側方に開口してガスを排出するガス排出部33と、を備えている。
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
As shown in FIG. 1, the constant potential electrolytic gas sensor X controls a reaction electrode 11 that causes a gas to be detected to electrochemically react as a gas electrode 10 that detects gas, a counter electrode 12 with respect to the reaction electrode 11, and a potential of the reaction electrode 11. The reference electrode 13 is provided so as to be in contact with the electrolytic solution 20 accommodated in the electrolytic cell 30. The constant potential electrolytic gas sensor X includes a gas introduction part 32 that opens to the side of the electrolytic cell 30 and introduces gas, and a gas discharge part 33 that opens to the side of the electrolytic cell 30 and discharges gas. I have.

反応極11、対極12及び参照極13は、撥水性を有する多孔質のガス透過膜14の表面に、公知の電極材料より作製したペーストを塗布・焼成して形成してある。ガス透過膜14は、例えば疎水性でガスを透過する性質を有するものであればどのような膜でもよく、例えば耐薬品性を有する多孔質PTFE(ポリテトラフルオロエチレン)膜などを使用することができる。反応極11と参照極13とは対向して配置してあり、また、ガス排出部33の側から順に対極12および参照極13を配設してある。反応極11と参照極13との間の空間が電解液20を収容する電解液収容部31となる。電解液20は硫酸やリン酸等の酸性水溶液等を使用することができるが、これらに限定されるものではない。被検知ガスはガス導入部32よりセンサの内部に導入され、反応極11上で反応する。   The reaction electrode 11, the counter electrode 12, and the reference electrode 13 are formed by applying and baking a paste made of a known electrode material on the surface of a porous gas permeable film 14 having water repellency. The gas permeable membrane 14 may be any membrane as long as it is hydrophobic and has a property of transmitting gas. For example, a porous PTFE (polytetrafluoroethylene) membrane having chemical resistance may be used. it can. The reaction electrode 11 and the reference electrode 13 are arranged to face each other, and the counter electrode 12 and the reference electrode 13 are arranged in this order from the gas discharge part 33 side. A space between the reaction electrode 11 and the reference electrode 13 serves as an electrolyte solution storage unit 31 that stores the electrolyte solution 20. The electrolytic solution 20 may be an acidic aqueous solution such as sulfuric acid or phosphoric acid, but is not limited thereto. The gas to be detected is introduced into the sensor from the gas introduction part 32 and reacts on the reaction electrode 11.

それぞれのガス電極10、ガス透過膜14、溶存酸素遮断膜41、干渉ガス遮断膜42、Oリング15aおよびガスケット15bは電解槽30の蓋部材16によって固定される。溶存酸素遮断膜41は、電解液20に溶存する酸素(溶存酸素)を遮断するために、反応極11における電解液20の側に設けてある。また、干渉ガス遮断膜42は、干渉ガスを遮断するため対極12および参照極13の間に設けてある。
反応極11、対極12及び参照極13は、触媒および疎水性樹脂を含むガス拡散電極からなり、触媒としては、白金(Pt)、金(Au)、ルテニウム(Ru)、酸化ルテニウム(RuO2)、パラジウム(Pd)、白金担持カーボン(Pt/C)などが好適に用いられ、疎水性樹脂としては多孔質PTFE膜などが好適に用いられる。
Each gas electrode 10, gas permeable membrane 14, dissolved oxygen barrier film 41, interference gas barrier film 42, O-ring 15 a and gasket 15 b are fixed by the lid member 16 of the electrolytic cell 30. The dissolved oxygen blocking film 41 is provided on the reaction electrode 11 on the side of the electrolytic solution 20 in order to block oxygen dissolved in the electrolytic solution 20 (dissolved oxygen). Further, the interference gas blocking film 42 is provided between the counter electrode 12 and the reference electrode 13 in order to block interference gas.
The reaction electrode 11, the counter electrode 12, and the reference electrode 13 are composed of a gas diffusion electrode containing a catalyst and a hydrophobic resin. Examples of the catalyst include platinum (Pt), gold (Au), ruthenium (Ru), ruthenium oxide (RuO2), Palladium (Pd), platinum-supported carbon (Pt / C) and the like are preferably used, and a porous PTFE membrane and the like are preferably used as the hydrophobic resin.

電解槽30の一端には、0.5〜1mm程度の小径とした内圧調整孔17が形成されている。内圧調整孔17における電解液収容部31の側には、多孔質シート18が配設してある。電解液収容部31は、小径の流路31aを介して大径の二つの収容部31bを有する態様とする。当該流路31aを2〜4mm程度の小径とした場合、電解液20の表面張力で電解液20が一方の収容部31bから他方の収容部31bに逆流し難くなる。筐体を構成する電解槽30および蓋部材16は、耐食性を有する合成樹脂、例えば硬質塩化ビニル或いはニッケル合金等の金属で構成すればよい。   An internal pressure adjusting hole 17 having a small diameter of about 0.5 to 1 mm is formed at one end of the electrolytic cell 30. A porous sheet 18 is disposed on the internal pressure adjusting hole 17 on the side of the electrolytic solution containing portion 31. The electrolyte storage unit 31 has two large-diameter storage units 31b through a small-diameter channel 31a. When the flow path 31a has a small diameter of about 2 to 4 mm, the electrolytic solution 20 is less likely to flow backward from one housing portion 31b to the other housing portion 31b due to the surface tension of the electrolytic solution 20. The electrolytic cell 30 and the lid member 16 constituting the housing may be made of a synthetic resin having corrosion resistance, for example, a metal such as hard vinyl chloride or nickel alloy.

電解液収容部31には、電解液20を吸水して保持する保水部材37を配設することが可能である。   A water retention member 37 that absorbs and holds the electrolytic solution 20 can be disposed in the electrolytic solution storage unit 31.

このような定電位電解式ガスセンサXは、被検知ガスの反応によって反応極11上で生じた電子に基づく電流を検知自在な電流測定部と、反応極11の電位制御自在な電位制御部とを備えたガス検知回路(図外)に接続して、ガス検知装置として用いられる。本発明の定電位電解式ガスセンサXは、例えば酸素ガスや、シラン、ホスフィン、ゲルマン、アルシン、ジボランなどの水素化物ガスの検知や、一酸化炭素、硫化水素等の毒性ガスの検知に用いられる。本実施形態では、被検知ガスとして酸素ガスを検知する場合について説明する。   Such a constant potential electrolytic gas sensor X includes a current measuring unit capable of detecting a current based on electrons generated on the reaction electrode 11 due to a reaction of the gas to be detected, and a potential control unit capable of controlling the potential of the reaction electrode 11. It is used as a gas detection device by connecting to a gas detection circuit (not shown). The constant potential electrolytic gas sensor X of the present invention is used for detecting oxygen gas, hydride gas such as silane, phosphine, germane, arsine and diborane, and detecting toxic gas such as carbon monoxide and hydrogen sulfide. In the present embodiment, a case where oxygen gas is detected as the gas to be detected will be described.

(保水部材)
本実施形態では、反応極11および参照極13の間に、複数の保水部材37を、反応極11の側および参照極13の側に分かれて配設する。このとき、これらの保水部材37を、反応極11および参照極13に対して各別に押圧する押え部材50を設ける(図1,2)。押え部材50が保水部材37を反応極11および参照極13に対して各別に押圧する押圧力は、押え部材50の材質や形状によって設定することができる。
(Water retaining material)
In the present embodiment, a plurality of water retaining members 37 are separately disposed between the reaction electrode 11 and the reference electrode 13 between the reaction electrode 11 and the reference electrode 13. At this time, the holding member 50 which presses these water retention members 37 separately with respect to the reaction electrode 11 and the reference electrode 13 is provided (FIGS. 1 and 2). The pressing force with which the pressing member 50 presses the water retaining member 37 against the reaction electrode 11 and the reference electrode 13 can be set according to the material and shape of the pressing member 50.

本構成では、当該保水部材37を反応極11および参照極13に接するように配設することができるため、保水部材37が保持する電解液20を、反応極11および参照極13に接触させることができる。また、保水部材37を反応極11および参照極13に対して各別に押圧する押え部材50を設けることにより、保水部材37を反応極11および参照極13に対して確実に密着させることができる。そのため、これらガス電極10の表面に気泡が生じ難くなり、当該ガス電極10における電極反応が安定に行われる。従って、本構成であれば出力値の安定したセンサとなる。   In this configuration, since the water retaining member 37 can be disposed so as to be in contact with the reaction electrode 11 and the reference electrode 13, the electrolytic solution 20 held by the water retaining member 37 is brought into contact with the reaction electrode 11 and the reference electrode 13. Can do. In addition, by providing the holding members 50 that press the water retaining member 37 against the reaction electrode 11 and the reference electrode 13 separately, the water retaining member 37 can be securely adhered to the reaction electrode 11 and the reference electrode 13. For this reason, bubbles are hardly generated on the surfaces of the gas electrodes 10, and the electrode reaction in the gas electrodes 10 is stably performed. Therefore, with this configuration, the sensor has a stable output value.

また、保水部材37を押え部材50によって押圧できるため、保水部材37を反応極11および参照極13の間に配設し易くなってセンサの組み立て作業効率が向上する。   Further, since the water retaining member 37 can be pressed by the pressing member 50, the water retaining member 37 can be easily disposed between the reaction electrode 11 and the reference electrode 13, and the assembly work efficiency of the sensor is improved.

保水部材37は、押え部材50による押圧力によってその厚みが変動するように構成すればよい。本構成においても、保水部材37は、電解液20を保持できる吸水性の部材とすればよく、保水性の繊維(例えばガラス繊維、セラミックス繊維など)、吸水性の高分子等、特に限定されることなく使用することができる。   What is necessary is just to comprise the water retention member 37 so that the thickness may be fluctuate | varied with the pressing force by the pressing member 50. FIG. Also in this configuration, the water retaining member 37 may be a water absorbing member that can hold the electrolytic solution 20, and is particularly limited to a water retaining fiber (for example, glass fiber, ceramic fiber, etc.), a water absorbing polymer, and the like. Can be used without

これにより、保水部材37は、押え部材50による押圧力によって最適な厚みに変動して、各ガス電極10や押え部材50に負荷をかけることなく、反応極11および参照極13に確実に密着させることができる。また、センサの筐体や押え部材50に製造の寸法誤差があったとしても、保水部材37が押え部材50による押圧力によって最適な厚みに変動して、当該寸法誤差を吸収することができる。   As a result, the water retaining member 37 is changed to an optimum thickness by the pressing force of the pressing member 50, and is reliably brought into close contact with the reaction electrode 11 and the reference electrode 13 without applying a load to each gas electrode 10 or the pressing member 50. be able to. Further, even if there is a manufacturing dimensional error in the sensor housing or the pressing member 50, the water retaining member 37 is changed to an optimum thickness by the pressing force by the pressing member 50, and the dimensional error can be absorbed.

また、保水部材37は、反応極11および参照極13の全面を覆うように配設すればよい。   The water retaining member 37 may be disposed so as to cover the entire surface of the reaction electrode 11 and the reference electrode 13.

これにより、保水部材37によって反応極11および参照極13の全面においてこれらガス電極10の表面に気泡を生じ難くすることができるため、より出力値の安定したセンサとすることができる。   Thereby, since it is possible to make it difficult for bubbles to be generated on the surfaces of the gas electrodes 10 on the entire surface of the reaction electrode 11 and the reference electrode 13 by the water retaining member 37, a sensor with a more stable output value can be obtained.

押え部材50は、弾性変形可能な芯部材51と、当該芯部材51の両端に配設した有孔の板状部材52と、を備えるように構成してある。押え部材50は、耐薬品性を有する硬質塩化ビニル等の樹脂によって作製することができるが、これに限定されるものではない。このような樹脂で製造することで、芯部材51を弾性変形可能に構成することができる。   The pressing member 50 is configured to include an elastically deformable core member 51 and perforated plate-like members 52 disposed at both ends of the core member 51. The pressing member 50 can be made of a resin such as hard vinyl chloride having chemical resistance, but is not limited to this. By manufacturing with such resin, the core member 51 can be configured to be elastically deformable.

本構成であれば、反応極11および参照極13の間の寸法や保水部材37の厚さに応じて、芯部材51はその弾性力によってある程度、芯部材51が収縮する方向に弾性変形することができる。この場合、芯部材51は弾性変形可能であるため収縮する方向とは逆の反発力が発生する。この反発力が、芯部材51の両端に配設した板状部材52を介して、保水部材37を反応極11および参照極13に対して各別に押圧する押圧力となる。   With this configuration, the core member 51 is elastically deformed in a direction in which the core member 51 contracts to some extent by the elastic force according to the dimension between the reaction electrode 11 and the reference electrode 13 and the thickness of the water retaining member 37. Can do. In this case, since the core member 51 is elastically deformable, a repulsive force opposite to the contracting direction is generated. This repulsive force becomes a pressing force that presses the water retaining member 37 against the reaction electrode 11 and the reference electrode 13 separately via the plate-like members 52 disposed at both ends of the core member 51.

本実施形態では、板状部材52に四つの板状部材開口部52aを設けてあるが、これに限定されるものではない。板状部材開口部52aの数は、電解液20の表面張力や、保水部材37の吸水性等を勘案して適宜設定すればよい。   In the present embodiment, four plate member openings 52a are provided in the plate member 52, but the present invention is not limited to this. The number of the plate-like member openings 52a may be appropriately set in consideration of the surface tension of the electrolytic solution 20, the water absorption of the water retaining member 37, and the like.

このように板状部材52を設けることで、押え部材50が保水部材37と面接触して押圧力を保水部材37のより広い範囲に伝達することができる。また、板状部材52を有孔とすることで、電解液20が板状部材開口部52aを介して保水部材37に吸収され易くなる。   By providing the plate-like member 52 in this manner, the pressing member 50 can be brought into surface contact with the water retaining member 37 and the pressing force can be transmitted to a wider range of the water retaining member 37. Further, by making the plate-like member 52 perforated, the electrolytic solution 20 is easily absorbed by the water retaining member 37 through the plate-like member opening 52a.

また、芯部材51を弾性変形可能に構成するため、芯部材51をバネ材で構成してもよい。   Further, in order to configure the core member 51 so as to be elastically deformable, the core member 51 may be configured with a spring material.

押え部材50は、芯部材51が、ガス導入部32に対応する位置となるように配設するのがよい。   The pressing member 50 is preferably arranged so that the core member 51 is at a position corresponding to the gas introduction part 32.

押え部材50が保水部材37を押圧する際、板状部材52が平坦であれば芯部材51に対応する位置が最も押圧力が強いと考えられる。そのため、芯部材51に対応する位置において保水部材37は反応極11に対して最も確実に密着している。ガス導入部32からはサンプリングしたガスが導入されてくるため、本構成のように、芯部材51がガス導入部32に対応する位置となるように押え部材50を配設することで、保水部材37が反応極11に対して最も確実に密着している位置と、ガス導入部32とを一致させることができる。そのため、反応極11における電極反応を、気泡の影響を受けることが殆ど無い状態で確実に行うことができる。   When the pressing member 50 presses the water retaining member 37, if the plate-like member 52 is flat, the position corresponding to the core member 51 is considered to have the strongest pressing force. Therefore, the water retaining member 37 is most securely in contact with the reaction electrode 11 at a position corresponding to the core member 51. Since the sampled gas is introduced from the gas introduction part 32, the holding member 50 is disposed so that the core member 51 is located at a position corresponding to the gas introduction part 32 as in this configuration, so that the water retention member The position where 37 is in most reliable contact with the reaction electrode 11 can be matched with the gas introduction part 32. Therefore, the electrode reaction at the reaction electrode 11 can be reliably performed in a state where the reaction is hardly affected by bubbles.

(開口装着部材)
ガス導入部32およびガス排出部33の少なくとも何れか一方には、金属酸化物により作製してピンホール34aを形成してある筒部材34を、樹脂製の弾性部材35に圧入した開口装着部材36を備えてある(図3)。
(Opening mounting member)
At least one of the gas introduction part 32 and the gas discharge part 33 is an opening mounting member 36 in which a cylindrical member 34 made of metal oxide and formed with a pinhole 34a is press-fitted into an elastic member 35 made of resin. (FIG. 3).

開口装着部材36はガス導入部32およびガス排出部33の少なくとも何れか一方に備えればよく、本実施形態ではガス導入部32およびガス排出部33の両方に設けた場合について説明する。開口装着部材36は、筐体を構成する蓋部材16に形成した貫通孔16aに挿入して当該蓋部材16に固定してある。   The opening mounting member 36 may be provided in at least one of the gas introduction part 32 and the gas discharge part 33. In the present embodiment, the case where the opening attachment member 36 is provided in both the gas introduction part 32 and the gas discharge part 33 will be described. The opening mounting member 36 is inserted into a through hole 16 a formed in the lid member 16 constituting the housing and fixed to the lid member 16.

本実施形態の開口装着部材36は、筒部材34が貫く柱状部36aと、当該柱状部36aの一端側に設けた板状部36bと、当該柱状部36aの他端側に設けた返し部36cと、を備える。板状部36bによって開口装着部材36を筐体(蓋部材16)と面接触させて確実に固定することができる。また、返し部36cによって開口装着部材36が筐体(蓋部材16)に形成した貫通孔16aから抜け落ちるのを防止することができる。開口装着部材36は、当該貫通孔16aに対して圧入するように挿入すればよい。   The opening mounting member 36 of the present embodiment includes a columnar part 36a through which the cylindrical member 34 penetrates, a plate-like part 36b provided on one end side of the columnar part 36a, and a return part 36c provided on the other end side of the columnar part 36a. And comprising. The opening mounting member 36 can be brought into surface contact with the housing (lid member 16) by the plate-like portion 36b and can be fixed securely. Moreover, it is possible to prevent the opening mounting member 36 from falling out of the through hole 16a formed in the housing (the lid member 16) by the return portion 36c. What is necessary is just to insert the opening mounting member 36 so that it may press-fit with respect to the said through-hole 16a.

筒部材34を構成する金属酸化物は、例えばアルミナ、ジルコニア等のセラミックスが挙げられるが、これらに限定されるものではない。筒部材の長寸は0.5〜6.0mmであり、好ましくは1.5〜5.5mmとするのがよい。また、ピンホール34aの孔径が8〜200μmであり、好ましくは12〜125μmとするのがよい。   Examples of the metal oxide constituting the cylindrical member 34 include, but are not limited to, ceramics such as alumina and zirconia. The long dimension of the cylindrical member is 0.5 to 6.0 mm, preferably 1.5 to 5.5 mm. Moreover, the hole diameter of the pinhole 34a is 8-200 micrometers, Preferably it is 12-125 micrometers.

筒部材34の形状は円柱状とするのがよいが、これに限定されるものではなく、角柱状等の態様であってもよい。   The shape of the cylindrical member 34 is preferably a columnar shape, but is not limited thereto, and may be an aspect such as a prismatic shape.

弾性部材35は、弾性を有する材料、例えばパッキンに使用されるゴム状の弾性材料、熱可塑性エラストマー等、によって形成すればよい。弾性部材35に筒部材34の外径よりも小さい孔径の貫通孔35aを形成しておき、当該貫通孔35aに筒部材34を圧入する。   The elastic member 35 may be formed of a material having elasticity, for example, a rubber-like elastic material used for packing, a thermoplastic elastomer, or the like. A through hole 35a having a smaller diameter than the outer diameter of the cylindrical member 34 is formed in the elastic member 35, and the cylindrical member 34 is press-fitted into the through hole 35a.

筒部材34に設けるピンホール34aは、一つでもよいし、複数設けてもよい。ピンホール34aの数については、センサ内に導入したい被検知ガスの量に応じて適宜設定すればよい。本実施形態では、それぞれの筒部材34に、一つのピンホール34aが形成してある場合について説明する。   One or more pinholes 34a may be provided in the cylindrical member 34. What is necessary is just to set suitably about the number of the pinholes 34a according to the quantity of to-be-detected gas to introduce | transduce into a sensor. In the present embodiment, a case where one pinhole 34a is formed in each cylindrical member 34 will be described.

(結露・圧力緩和膜)
開口装着部材36を蓋部材16に形成した貫通孔16aに挿入した状態で、開口装着部材36を両側から覆うように、結露を防ぐ結露・圧力緩和膜40を配設する。即ち、結露・圧力緩和膜40は、ガス導入部32およびガス排出部33を覆うように配設してある。本実施形態では結露・圧力緩和膜40はガス導入部32およびガス排出部33の両方を覆う態様であるが、結露・圧力緩和膜40はガス導入部32およびガス排出部33において、少なくともガス導入部32を覆う態様であればよい。
(Condensation / pressure relief membrane)
In a state where the opening mounting member 36 is inserted into the through hole 16 a formed in the lid member 16, a dew condensation / pressure relaxation film 40 for preventing condensation is disposed so as to cover the opening mounting member 36 from both sides. That is, the dew condensation / pressure relaxation film 40 is disposed so as to cover the gas introduction part 32 and the gas discharge part 33. In this embodiment, the dew condensation / pressure relaxation film 40 covers both the gas introduction part 32 and the gas discharge part 33. However, the dew condensation / pressure relaxation film 40 is at least a gas introduction in the gas introduction part 32 and the gas discharge part 33. Any mode that covers the portion 32 may be used.

結露・圧力緩和膜40は、ガスを透過して液体を透過しない性質を有するものであればどのような膜でもよく、多孔質PTFE膜などを使用することができる。   The dew condensation / pressure relaxation film 40 may be any film as long as it has a property of permeating gas but not liquid, and a porous PTFE film or the like can be used.

本実施形態の結露・圧力緩和膜40は厚さ0.2mm程度で、その特性は、例えば透気度がガーレー値で200〜700程度、空孔率が35〜45%、WEP(水の侵入圧力)が196kPa以上、好ましくは500kPaとするのがよい。   The dew condensation / pressure relief film 40 of this embodiment has a thickness of about 0.2 mm, and its characteristics are, for example, an air permeability of about 200 to 700 in terms of Gurley value, a porosity of 35 to 45%, and WEP (water intrusion). The pressure) is 196 kPa or more, preferably 500 kPa.

また、本実施形態では、透気度の異なる二枚の結露・圧力緩和膜40のセットを、ガス導入部32およびガス排出部33において、少なくともガス導入部32に配設する場合について説明する。   Further, in the present embodiment, a case will be described in which a set of two dew condensation / pressure relaxation films 40 having different air permeability is disposed at least in the gas introduction part 32 in the gas introduction part 32 and the gas discharge part 33.

結露・圧力緩和膜40は、単層の膜としてもよいし、透気度が同じ二枚の膜を重ねて構成してもよいし、透気度の異なる二枚の膜を重ねて構成してもよい。
例えば結露・圧力緩和膜40を二枚重ねにして少なくともガス導入部32に配設する場合、上述した透気度およびWEPを有する膜を二枚としてもよいし、一方の膜を上述した透気度およびWEPを有する膜とし、他方の膜を上述した透気度およびWEPより低い値の膜としてもよい。当該他方の膜は、一方の膜を押えて密着させることができ、さらに反応極11から電解液20が漏出するのを防止できるもの(例えば撥水性を有する態様)であればよい。二枚重ねにした場合の二枚の膜の配設順序としては、適宜設定してもよいが、例えばガス導入部32であれば、反応極11、他方の膜、一方の膜、筒部材34(ピンホール34a)のようにすることができる。このように二枚重ねとした結露・圧力緩和膜40を、開口装着部材36の外側および内側にそれぞれ配設(図1)してもよいし、外側および内側の何れか一方のみに配設してもよいが、何れか一方のみに配設する場合は外側に配設するのが好ましい。
The dew condensation / pressure relaxation film 40 may be a single layer film, may be formed by stacking two films having the same air permeability, or may be formed by stacking two films having different air permeability. May be.
For example, in the case where two dew condensation / pressure relaxation films 40 are stacked and disposed in at least the gas introduction part 32, the above-described air permeability and WEP film may be two sheets, or one film may have the above air permeability and A film having WEP may be used, and the other film may be a film having a lower value than the above-described air permeability and WEP. The other film may be any film (for example, having water repellency) that can press and adhere one film and prevent the electrolyte solution 20 from leaking from the reaction electrode 11. For example, in the case of the gas introduction part 32, the reaction electrode 11, the other film, the one film, and the cylindrical member 34 (pin) Hole 34a) can be used. The two layers of the dew condensation / pressure relaxation film 40 may be disposed on the outer side and the inner side of the opening mounting member 36 (FIG. 1), or may be disposed only on either the outer side or the inner side. Although it is good, when arrange | positioning only in any one, disposing outside is preferable.

(溶存酸素遮断膜)
上述した溶存酸素遮断膜41は、電解液20に溶存する酸素(溶存酸素)を遮断するために、反応極11における電解液20の側に設けてある。溶存酸素遮断膜41は、反応極11における電解液20の側の全面に設けるとよい。
(Dissolved oxygen barrier membrane)
The dissolved oxygen blocking film 41 described above is provided on the side of the electrolytic solution 20 in the reaction electrode 11 in order to block oxygen dissolved in the electrolytic solution 20 (dissolved oxygen). The dissolved oxygen blocking film 41 is preferably provided on the entire surface of the reaction electrode 11 on the side of the electrolytic solution 20.

溶存酸素遮断膜41は、イオン導電性および透水性を有し、かつ酸素ガスを透過させないイオン交換膜を使用すればよい。具体的には、溶存酸素遮断膜41は、ナフィオン(登録商標:デュポン社製)、アシプレックス(登録商標:旭化成社製)、フレミオン(登録商標:旭硝子社製)などを使用することができるが、これに限定されるものではない。例えば、ナフィオンはプロトン伝導性および透水性を有し、かつ耐酸化性に優れている。   The dissolved oxygen blocking film 41 may be an ion exchange membrane that has ionic conductivity and water permeability and does not allow oxygen gas to permeate. Specifically, Nafion (registered trademark: manufactured by DuPont), Aciplex (registered trademark: manufactured by Asahi Kasei Co., Ltd.), Flemion (registered trademark: manufactured by Asahi Glass Co., Ltd.) and the like can be used as the dissolved oxygen barrier film 41. However, the present invention is not limited to this. For example, Nafion has proton conductivity and water permeability and is excellent in oxidation resistance.

溶存酸素遮断膜41はイオン導電性および透水性を有するため、H+およびH2O分子は、電解液20の側から溶存酸素遮断膜41を介して反応極11に移動することができるため、定電位電解式ガスセンサXにおける電極反応の場を反応極11の表面とすることができる。 Since the dissolved oxygen barrier film 41 has ionic conductivity and water permeability, H + and H 2 O molecules can move to the reaction electrode 11 through the dissolved oxygen barrier film 41 from the electrolyte solution 20 side. The electrode reaction field in the constant potential electrolytic gas sensor X can be the surface of the reaction electrode 11.

溶存酸素遮断膜41は、反応極11に熱圧着させることができる。溶存酸素を遮断するには、反応極11に溶存酸素遮断膜41を構成する成分を含有する溶液を塗布し乾燥させた状態でも効果はあるが、更に溶存酸素遮断膜41を熱圧着させるように形成することで、より効果的となる。   The dissolved oxygen blocking film 41 can be thermocompression bonded to the reaction electrode 11. In order to block dissolved oxygen, there is an effect even when a solution containing a component constituting the dissolved oxygen blocking film 41 is applied to the reaction electrode 11 and dried, but the dissolved oxygen blocking film 41 is further thermocompression bonded. By forming, it becomes more effective.

具体的には、当該熱圧着は、反応極11の表面に溶存酸素遮断膜41を構成する成分を含有する溶液を塗布し(塗布工程)、当該溶液を塗布し乾燥させた後、リード線を反応極11に載置した状態で溶存酸素遮断膜41を積層し、溶存酸素遮断膜41を積層(積層工程)した後、120〜140℃、好ましくは130℃、1〜4MPaで熱圧着(熱圧着工程)したものである。   Specifically, in the thermocompression bonding, a solution containing components constituting the dissolved oxygen blocking film 41 is applied to the surface of the reaction electrode 11 (application process), the solution is applied and dried, and then the lead wire is applied. After the dissolved oxygen blocking film 41 is stacked in a state of being placed on the reaction electrode 11 and the dissolved oxygen blocking film 41 is stacked (stacking step), it is thermocompression-bonded at 120 to 140 ° C., preferably 130 ° C. and 1 to 4 MPa (thermal). Crimping process).

溶存酸素遮断膜41をナフィオンとした場合、反応極11の表面にナフィオン溶液を塗布する(塗布工程)。ナフィオン溶液の濃度は5〜20wt%で、溶媒は低級アルコールと純水(15〜34%)の混合物、または、純水とすればよい。   When the dissolved oxygen blocking film 41 is Nafion, a Nafion solution is applied to the surface of the reaction electrode 11 (application process). The concentration of the Nafion solution is 5 to 20 wt%, and the solvent may be a mixture of lower alcohol and pure water (15 to 34%) or pure water.

このようにリード線を反応極11に載置した状態でナフィオンを積層することにより、リード線および反応極11との集電を確実にすることができる。   Thus, by stacking Nafion with the lead wire placed on the reaction electrode 11, current collection between the lead wire and the reaction electrode 11 can be ensured.

(干渉ガス遮断膜)
上述した干渉ガス遮断膜42は、干渉ガスを遮断するため対極12および参照極13の間に設けてある。干渉ガスは、サンプリングガス中に被検知ガスと共存し、被検知ガス検知の指示値に影響を及ぼす気体のことをいう。干渉ガス遮断膜42は、例えばイオン導電性および透水性を有し、かつ干渉ガスを透過させないイオン交換膜を使用すればよいがこのような膜に限定されず、PET、PP、PE等の膜も使用することができる。具体的には上述したナフィオン等を使用することができるが、これに限定されるものではない。
(Interference gas barrier film)
The interference gas blocking film 42 described above is provided between the counter electrode 12 and the reference electrode 13 in order to block interference gas. The interference gas is a gas that coexists with the gas to be detected in the sampling gas and affects the detected gas detection value. The interference gas blocking film 42 may be, for example, an ion exchange film having ion conductivity and water permeability and not allowing interference gas to pass therethrough, but is not limited to such a film, and is a film such as PET, PP, PE, etc. Can also be used. Specifically, Nafion etc. mentioned above can be used, but it is not limited to this.

参照極13および干渉ガス遮断膜42には、それぞれ細孔13a,42aを形成し、当該細孔13a,42aを介して電解液20が対極12の側に流通するように構成してある。このとき、電解液20を吸水して保持する保水部材37を、対極12および干渉ガス遮断膜42の間に配設するとよい。細孔13a,42aの孔径は約2mm程度とすればよい。   The reference electrode 13 and the interference gas blocking film 42 are formed with pores 13a and 42a, respectively, and the electrolytic solution 20 is circulated to the counter electrode 12 through the pores 13a and 42a. At this time, a water retaining member 37 that absorbs and holds the electrolytic solution 20 may be disposed between the counter electrode 12 and the interference gas blocking film 42. The diameter of the pores 13a and 42a may be about 2 mm.

本発明の定電位電解式ガスセンサXおよび従来の定電位電解式ガスセンサ(比較例)において、それぞれの性能の比較を行った。本発明の定電位電解式ガスセンサXは保水部材37および押え部材50を備え、従来の定電位電解式ガスセンサは保水部材37および押え部材50を備えない態様とした。本発明の定電位電解式ガスセンサXは二つのセンサを使用し、被検知ガスとして酸素ガス(21vol%)を検知したときにおいて、気泡の影響の有無を調べた。結果を図4に示した。   The performance of each of the controlled potential electrolytic gas sensor X of the present invention and the conventional controlled potential electrolytic gas sensor (comparative example) was compared. The constant potential electrolytic gas sensor X of the present invention includes the water retaining member 37 and the holding member 50, and the conventional constant potential electrolytic gas sensor does not include the water retaining member 37 and the pressing member 50. The constant potential electrolytic gas sensor X of the present invention used two sensors, and when oxygen gas (21 vol%) was detected as the gas to be detected, the presence or absence of the influence of bubbles was examined. The results are shown in FIG.

この結果、従来の定電位電解式ガスセンサにおいて、100日以上の長期に亘るセンシングでは、対極の表面に気泡が発生する場合があり、酸素ガスを検知したときの指示値が安定しない場合があった。一方、本発明の定電位電解式ガスセンサXでは、酸素ガスを検知したときの指示値は安定しており、ガス電極10の表面に気泡が生じ難く、また、発生したとしても保水材中に分散され、気泡固まりとして残存しないため、対極を始めとする各ガス電極10に対して気泡による直接的な影響は認められなかった。   As a result, in a conventional constant potential electrolytic gas sensor, in sensing over a long period of 100 days or more, bubbles may be generated on the surface of the counter electrode, and the indicated value when oxygen gas is detected may not be stable. . On the other hand, in the controlled potential electrolysis gas sensor X of the present invention, the indicated value when oxygen gas is detected is stable, bubbles are not easily generated on the surface of the gas electrode 10, and even if they are generated, they are dispersed in the water retaining material. In addition, since it does not remain as a bubble mass, no direct influence of the bubbles was observed on each gas electrode 10 including the counter electrode.

本発明は、ガスを検知するガス電極として被検知ガスを電気化学反応させる反応極、前記反応極に対する対極および前記反応極の電位を制御する参照極を、電解槽に収容した電解液に接触するように備えた定電位電解式ガスセンサに利用できる。   In the present invention, a reaction electrode for electrochemically reacting a gas to be detected as a gas electrode for detecting gas, a counter electrode with respect to the reaction electrode, and a reference electrode for controlling the potential of the reaction electrode are brought into contact with an electrolytic solution accommodated in an electrolytic cell. It can utilize for the constant potential electrolytic gas sensor provided.

X 定電位電解式ガスセンサ
10 ガス電極
11 反応極
12 対極
13 参照極
20 電解液
30 電解槽
31 電解液収容部
37 保水部材
50 押え部材
51 芯部材
52 板状部材
X Constant Potential Electrolytic Gas Sensor 10 Gas Electrode 11 Reaction Electrode 12 Counter Electrode 13 Reference Electrode 20 Electrolytic Solution 30 Electrolytic Tank 31 Electrolyte Storage Unit 37 Water Retaining Member 50 Pressing Member 51 Core Member 52 Plate Member

Claims (4)

ガスを検知するガス電極として被検知ガスを電気化学反応させる反応極、前記反応極に対する対極および前記反応極の電位を制御する参照極を、電解槽に収容した電解液に接触するように備えた定電位電解式ガスセンサであって、
電解液を収容する電解液収容部に電解液を吸水して保持する複数の保水部材が、前記反応極および前記参照極の間に、前記反応極の側および前記参照極の側に分かれて配設してあり、これらの保水部材を、前記反応極および前記参照極に対して各別に押圧する押え部材を設け
前記押え部材は、弾性変形可能な芯部材と、当該芯部材の両端に配設した有孔の板状部材と、を備えた定電位電解式ガスセンサ。
As a gas electrode for detecting gas, a reaction electrode for electrochemically reacting a gas to be detected, a counter electrode for the reaction electrode, and a reference electrode for controlling the potential of the reaction electrode were provided so as to come into contact with an electrolytic solution contained in an electrolytic cell. A constant potential electrolytic gas sensor,
A plurality of water retaining members that absorb and hold the electrolyte solution in an electrolyte solution storage portion that stores the electrolyte solution are separately arranged between the reaction electrode and the reference electrode on the reaction electrode side and the reference electrode side. A presser member that presses these water retaining members against the reaction electrode and the reference electrode separately ,
The presser member is a potentiostatic gas sensor including an elastically deformable core member and perforated plate-like members disposed at both ends of the core member .
前記保水部材は、前記押え部材による押圧力によってその厚みが変動する請求項1に記載の定電位電解式ガスセンサ。   The constant potential electrolytic gas sensor according to claim 1, wherein the thickness of the water retaining member varies depending on the pressing force of the pressing member. 前記電解槽の側方に開口してガスを導入するガス導入部を備え、
前記芯部材が、前記ガス導入部に対応する位置となるように前記押え部材を配設してある請求項1または2に記載の定電位電解式ガスセンサ。
A gas introduction part that opens to the side of the electrolytic cell and introduces gas;
The constant potential electrolytic gas sensor according to claim 1 or 2 , wherein the pressing member is disposed so that the core member is located at a position corresponding to the gas introduction portion.
前記保水部材は、前記反応極および前記参照極の全面を覆うように配設してある請求項1〜の何れか一項に記載の定電位電解式ガスセンサ。 The constant-potential electrolysis gas sensor according to any one of claims 1 to 3 , wherein the water retention member is disposed so as to cover the entire surface of the reaction electrode and the reference electrode.
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