JP2003149194A - Controlled potential electrolytic gas sensor and gas detector - Google Patents
Controlled potential electrolytic gas sensor and gas detectorInfo
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- JP2003149194A JP2003149194A JP2001343034A JP2001343034A JP2003149194A JP 2003149194 A JP2003149194 A JP 2003149194A JP 2001343034 A JP2001343034 A JP 2001343034A JP 2001343034 A JP2001343034 A JP 2001343034A JP 2003149194 A JP2003149194 A JP 2003149194A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、定電位電解式ガス
センサおよびガス検知装置に関する。TECHNICAL FIELD The present invention relates to a potentiostatic electrolytic gas sensor and a gas detection device.
【０００２】[0002]
【従来の技術】例えば、二酸化硫黄ガス、ホスフィンガ
スなどのガスを検知するためのガス検知装置に用いられ
るセンサとして、定電位電解式ガスセンサが知られてい
る。2. Description of the Related Art For example, a potentiostatic electrolytic gas sensor is known as a sensor used in a gas detection device for detecting gases such as sulfur dioxide gas and phosphine gas.
【０００３】定電位電解式ガスセンサの或る種のものと
しては、例えば電解液を収容するための電解液収容用空
間を形成し、ガス透過性を有する多孔質シートによって
塞がれる２つの開口を有するセルと、一方の多孔質シー
トの表面に設けられ、被検知ガスを電気分解させるため
の作用極と、他方の多孔質シートに設けられ、作用極に
対する対極、当該他方多孔質シートに対極と分離して設
けられ、作用極の電位を制御するための参照極とを備え
てなるものが広く用いられている。As a kind of potentiostatic electrolysis gas sensor, for example, an electrolytic solution storage space for storing an electrolytic solution is formed, and two openings closed by a porous sheet having gas permeability are provided. A cell having, and a working electrode provided on the surface of one porous sheet, for electrolyzing the gas to be detected, and provided on the other porous sheet, a counter electrode for the working electrode, a counter electrode for the other porous sheet. The one provided separately and provided with a reference electrode for controlling the potential of the working electrode is widely used.
【０００４】このような構成の定電位電解式ガスセンサ
は、作用極、対極および参照極が電解液に浸された状態
において、当該作用極において被検知ガスが電気分解さ
れることにより、この作用極および対極に生じる電気化
学反応に起因して発生する電解電流値の大きさと、被検
知ガス濃度とが比例関係にあることを利用し、電解電流
値を測定することによって被検知ガス濃度を検知するも
のである。In the potentiostatic electrolysis gas sensor having such a structure, when the working electrode, the counter electrode and the reference electrode are immersed in the electrolytic solution, the working gas is electrolyzed and the working electrode is electrolyzed. Also, by utilizing the fact that the magnitude of the electrolysis current value generated due to the electrochemical reaction occurring on the counter electrode and the concentration of the gas to be detected are in proportion to each other, the concentration of the gas to be detected can be detected by measuring the electrolysis current value. It is a thing.
【０００５】しかしながら、電解液として一般に用いら
れている硫酸水溶液は、高湿度環境下においては水分を
吸収することによって低濃度化し、一方、低湿度環境下
においては水分を放出することによって高濃度化すると
いう湿度依存性を有しているが、作用極として金薄膜層
よりなる電極が用いられる場合には、この湿度依存性に
基づく電解液の濃度変化によって定電位電解式ガスセン
サのガス濃度検知性能が大きく変化してしまう、という
問題がある。However, the sulfuric acid aqueous solution generally used as an electrolytic solution has a low concentration by absorbing water in a high humidity environment, while it has a high concentration by releasing water in a low humidity environment. However, when an electrode composed of a gold thin film layer is used as the working electrode, the gas concentration detection performance of the potentiostatic electrolysis gas sensor depends on the concentration change of the electrolytic solution based on this humidity dependency. There is a problem that changes greatly.
【０００６】[0006]
【発明が解決しようとする課題】本発明は以上のような
事情に基づいてなされたものであって、その目的は、信
頼性の高いガス検知を行うことのできる定電位電解式ガ
スセンサおよびガス検知装置を提供することにある。SUMMARY OF THE INVENTION The present invention has been made under the circumstances described above, and an object thereof is a potentiostatic electrolytic gas sensor capable of highly reliable gas detection and gas detection. To provide a device.
【０００７】[0007]
【課題を解決するための手段】本発明の定電位電解式ガ
スセンサは、硫酸水溶液よりなる電解液を用いる定電位
電解式ガスセンサにおいて、ガス透過膜の一面に、比表
面積が４〜１６ｍ2 ／ｇの金粒子を焼結して得られる金
焼結体層が形成されてなるガス拡散電極を備えることを
特徴とする。The potentiostatic electrolysis gas sensor of the present invention is a potentiostatic electrolysis gas sensor using an electrolytic solution composed of an aqueous solution of sulfuric acid, and has a specific surface area of 4 to 16 m 2 / g on one surface of a gas permeable membrane. And a gas diffusion electrode formed with a gold sintered body layer obtained by sintering the gold particles.
【０００８】本発明の定電位電解式ガスセンサにおいて
は、被検知ガスが二酸化硫黄ガスまたはホスフィンガス
である。In the potentiostatic electrolysis gas sensor of the present invention, the gas to be detected is sulfur dioxide gas or phosphine gas.
【０００９】本発明のガス検知装置は、上記の定電位電
解式ガスセンサを備えていることを特徴とする。The gas detector of the present invention is characterized by including the above-mentioned potentiostatic electrolysis gas sensor.
【００１０】[0010]
【作用】本発明の定電位電解式ガスセンサによれば、特
定の比表面積を有する金粒子よりなる金焼結体層が形成
されてなるガス拡散電極が設けられており、このガス拡
散電極が作用極として作用するため、電解液である硫酸
水溶液の湿度依存性に基づく濃度変化によってガス濃度
検知性能が変化することが抑制されることから、信頼性
の高いガス検知を行うことができる。According to the potentiostatic electrolysis type gas sensor of the present invention, the gas diffusion electrode formed by forming the gold sintered body layer made of gold particles having a specific specific surface area is provided. Since it acts as a pole, the gas concentration detection performance is suppressed from changing due to the concentration change based on the humidity dependency of the sulfuric acid aqueous solution as the electrolytic solution, so that highly reliable gas detection can be performed.
【００１１】[0011]
【発明の実施の形態】以下、本発明の実施の形態につい
て詳細に説明する。図１は、本発明のガス検知装置の構
成の一例を示す説明図である。このガス検知装置は、定
置型であって検知対象のガス（被検知ガス）を導入する
ためのガス導入口１１Ａおよびガス排出口１１Ｂを有す
るガス用セル１１と、当該ガス用セル１１に連結された
定電位電解式ガスセンサ２０と、当該定電位電解式ガス
センサ２０を作動させるための制御部（図示せず）とに
より構成されている。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. FIG. 1 is an explanatory diagram showing an example of the configuration of the gas detection device of the present invention. This gas detection device is a stationary type and has a gas cell 11 having a gas inlet 11A and a gas outlet 11B for introducing a gas to be detected (gas to be detected), and is connected to the gas cell 11. The constant potential electrolysis gas sensor 20 and a control unit (not shown) for operating the constant potential electrolysis gas sensor 20.
【００１２】定電位電解式ガスセンサ２０は、硫酸水溶
液よりなる電解液を収容するための電解液収容空間２１
Ａを形成し、外方に伸びる円筒状の連結用部材２２が設
けられた第１の開口２３と、当該第１の開口２３と対向
する位置に設けられた円状の第２の開口２４とを有す
る、例えばポリカーボネート、塩化ビニルなどよりなる
の電解液用セル２１を備えてなり、当該電解液用セル２
１の第１の開口２３に適合する大きさを有し、この第１
の開口２３を塞ぐよう設けられた、電解液を透過させな
い第１のガス透過膜３１と、当該第１のガス透過膜３１
の電解液収容空間２１Ａに臨む表面に形成された、被検
知ガスを電気分解させるための作用極４０と、第２の開
口２４に適合する大きさを有し、この第２の開口２４を
塞ぐよう設けられた、電解液を透過させない第２のガス
透過膜３２と、当該第２のガス透過膜３２の電解液収容
空間２１Ａに臨む表面に形成された、作用極４０に対す
る対極３５およびこの対極３５と分離して設けられた作
用極４０の電位を制御するための参照極３６とを備えて
なるものである。この図の例において、２１Ｂは、電解
液用セル２１内部の圧力を調整するための開口である。The potentiostatic electrolysis gas sensor 20 is provided with an electrolytic solution containing space 21 for containing an electrolytic solution composed of a sulfuric acid aqueous solution.
A first opening 23 that forms A and is provided with a cylindrical connecting member 22 that extends outward, and a circular second opening 24 that is provided at a position facing the first opening 23. And an electrolytic solution cell 21 made of, for example, polycarbonate or vinyl chloride.
The first opening 23 has a size that fits in the first opening 23.
And a first gas permeable film 31 that does not allow the electrolyte solution to pass therethrough and is provided so as to close the opening 23 of the first gas permeable film 31.
Of the working electrode 40 for electrolyzing the gas to be detected, which is formed on the surface facing the electrolytic solution containing space 21A, and has a size matching the second opening 24, and closes the second opening 24. The second gas permeable membrane 32 that does not allow the electrolyte to permeate therethrough, and the counter electrode 35 for the working electrode 40 and the counter electrode formed on the surface of the second gas permeable membrane 32 facing the electrolyte solution containing space 21A. 35 and a reference electrode 36 for controlling the potential of a working electrode 40 provided separately. In the example of this figure, 21B is an opening for adjusting the pressure inside the electrolytic solution cell 21.
【００１３】このガス検知装置においては、作用極４０
および対極３５は、例えばポテンショスタット回路３９
に接続されており、このポテンショスタット回路３９に
は、抵抗Ｒを介して参照極３６も接続されている。In this gas detector, the working electrode 40
And the counter electrode 35 is, for example, a potentiostat circuit 39.
The reference electrode 36 is also connected to the potentiostat circuit 39 via the resistor R.
【００１４】そして、この定電位電解式ガスセンサ２０
においては、作用極４０は、金粒子を焼結して得られる
金焼結体層よりなるガス拡散電極であり、この金焼結体
層の比表面積は、４〜１６ｍ2 ／ｇ、好ましくは６〜１
２ｍ2 ／ｇである。The constant potential electrolysis gas sensor 20
In the above, the working electrode 40 is a gas diffusion electrode composed of a gold sintered body layer obtained by sintering gold particles, and the specific surface area of this gold sintered body layer is 4 to 16 m 2 / g, preferably 6-1
It is 2 m 2 / g.
【００１５】金焼結体層の比表面積が４ｍ2 ／ｇ未満で
ある場合には、多孔質シートに対する付着強度が低下す
るため、ガス拡散電極として用いることができず、一
方、金焼結体層の比表面積が１６ｍ2 ／ｇを超える場合
には、空気中出力（ベース電流）が増大したり、被検知
ガス以外のガスの干渉影響を受けやすくなるため、正確
なガス検知を行うことができなくなる。When the specific surface area of the gold sintered body layer is less than 4 m 2 / g, it cannot be used as a gas diffusion electrode because the adhesion strength to the porous sheet is lowered, while the gold sintered body is not used. If the specific surface area of the layer exceeds 16 m 2 / g, the in-air output (base current) increases and the influence of gases other than the gas to be detected is likely to occur, so accurate gas detection can be performed. become unable.
【００１６】ガス拡散電極を構成する金焼結体層の厚み
は、通常、５０〜１５０μｍである。The thickness of the gold sintered body layer constituting the gas diffusion electrode is usually 50 to 150 μm.
【００１７】このような金焼結体層は、例えば最大粒子
径が４５μｍ以下の金粒子と、例えばフッ素樹脂などの
適宜の樹脂バインダーとを、例えば「金粒子：樹脂バイ
ンダ」の質量比が５：１〜２０：１となる割合で混合し
た混合材料によってガス透過膜用材料の表面に混合材料
層を形成し、この混合材料層を、例えば温度３２０℃で
焼結処理する手法により製造することができる。In such a gold sintered body layer, for example, gold particles having a maximum particle diameter of 45 μm or less and an appropriate resin binder such as a fluororesin, for example, the mass ratio of “gold particles: resin binder” is 5 A mixed material layer is formed on the surface of the material for a gas permeable membrane by a mixed material mixed in a ratio of 1: 1 to 20: 1, and the mixed material layer is produced by, for example, a sintering treatment at a temperature of 320 ° C. You can
【００１８】金粒子として最大粒子径が４５μｍ以下の
ものを用いることにより、特定の範囲の比表面積を有す
る金焼結体層を確実に形成することができるという利点
がある。By using gold particles having a maximum particle diameter of 45 μm or less, there is an advantage that a gold sintered body layer having a specific surface area within a specific range can be reliably formed.
【００１９】対極３５としては、例えば白金、金、銀、
銅、ルテニウム、酸化ルテニウムまたはそれらの混合物
などの電極用材料金属よりなる、通常、５０〜１５０μ
ｍの厚みを有する金属層よりなる電極を用いることがで
きる。また、参照極３６としては、例えば白金、金、
銀、銅、ルテニウム、酸化ルテニウムまたはそれらの混
合物などの電極用材料金属よりなる、通常、５０〜１５
０μｍの厚みを有する金属層よりなる電極を用いること
ができる。As the counter electrode 35, for example, platinum, gold, silver,
The electrode material metal such as copper, ruthenium, ruthenium oxide or a mixture thereof, usually 50 to 150 μm
An electrode made of a metal layer having a thickness of m can be used. Further, as the reference electrode 36, for example, platinum, gold,
The electrode material metal such as silver, copper, ruthenium, ruthenium oxide or a mixture thereof, usually 50 to 15
An electrode made of a metal layer having a thickness of 0 μm can be used.
【００２０】このような対極３５および参照極３６を構
成する金属層は、例えば（１）最大粒子径が４５μｍ以
下の電極用材料金属の粒子と、例えばフッ素樹脂などの
適宜の樹脂バインダーとを混合した混合材料によってガ
ス透過膜用材料の表面に混合材料層を形成し、この混合
材料層を焼結処理する手法、（２）真空蒸着法によって
ガス透過膜用材料の表面に電極用材料金属の薄膜を形成
する手法などにより形成することができる。The metal layers forming the counter electrode 35 and the reference electrode 36 are, for example, (1) particles of a metal for electrodes having a maximum particle diameter of 45 μm or less and a suitable resin binder such as a fluororesin. A mixed material layer is formed on the surface of the material for gas permeable membrane by the mixed material, and the mixed material layer is sintered. (2) The material for electrode is formed on the surface of the material for gas permeable membrane by the vacuum deposition method. It can be formed by a method of forming a thin film.
【００２１】第１のガス透過膜３１としては、通常、５
０〜３００μｍの厚みを有する、例えばポリテトラフル
オロエチレン樹脂（ＰＴＦＥ樹脂）製などの多孔質シー
トを用いることができる。この多孔質シートは、気孔が
均一に分散した状態であって、気孔率が２０〜７０％、
平均気孔径が０．１〜１．０μｍであることが好まし
い。The first gas permeable film 31 is usually 5
A porous sheet having a thickness of 0 to 300 μm and made of, for example, polytetrafluoroethylene resin (PTFE resin) can be used. This porous sheet is in a state where pores are uniformly dispersed, and has a porosity of 20 to 70%,
The average pore diameter is preferably 0.1 to 1.0 μm.
【００２２】また、第２のガス透過膜３２としては、第
１のガス透過膜３１と同様の構成の多孔質シートを用い
ることができる。As the second gas permeable film 32, a porous sheet having the same structure as the first gas permeable film 31 can be used.
【００２３】このような構成を有するガス検知装置は、
電解液用セル２１の電解液収容空間２１Ａ内に、少なく
とも作用極４０、対極３５および参照極３６が浸された
状態となる適宜の量の電解液が収容されることによって
ガス検知動作が可能となるものであり、そのガス検知動
作中においてはポテンショスタット回路３９により作用
極４０と、参照極３６との間の電位が一定に保たれてお
り、ガス導入口１１Ａを介してガス用セル１１に被検知
ガスが導入されると、この被検知ガスが定電位電解式ガ
スセンサ２０の第１のガス透過膜３１を透過することに
よって作用極４０において電気分解され、この作用極４
０と、対極３５とにおいて、各々、電気化学反応が起こ
ることに起因して当該作用極４０および対極３５との間
に流れる電解電流値を制御部において測定し、この電解
電流値の大きさと、被検知ガス濃度とが比例関係にある
ことを利用して被検知ガス濃度を検知することができ
る。The gas detector having the above structure is
Gas detection operation becomes possible by containing an appropriate amount of electrolyte solution in which at least the working electrode 40, the counter electrode 35, and the reference electrode 36 are immersed in the electrolyte solution storage space 21A of the electrolyte solution cell 21. During the gas detection operation, the potential between the working electrode 40 and the reference electrode 36 is kept constant by the potentiostat circuit 39, and the gas cell 11 is connected to the gas cell 11 via the gas inlet 11A. When the gas to be detected is introduced, the gas to be detected passes through the first gas permeable membrane 31 of the potentiostatic electrolysis gas sensor 20 and is electrolyzed at the working electrode 40.
0 and the counter electrode 35 respectively measure the electrolytic current value flowing between the working electrode 40 and the counter electrode 35 due to the occurrence of an electrochemical reaction in the control unit, and the magnitude of this electrolytic current value, The concentration of the detected gas can be detected by utilizing the fact that the concentration of the detected gas is in a proportional relationship.
【００２４】以上のガス検知装置においては、定電位電
解式ガスセンサ２０が作用極４０として特定の比表面積
を有する金粒子よりなる金焼結体層が形成されてなるガ
ス拡散電極が設けられているため、後述する実験例の結
果から明らかなように、電解液である硫酸水溶液の湿度
依存性に基づく濃度変化によってガス濃度検知性能が変
化することが抑制されることから、高い信頼性のあるガ
ス検知を行うことができる。In the above gas detector, the potentiostatic electrolysis gas sensor 20 is provided with the gas diffusion electrode as the working electrode 40 in which the gold sintered body layer made of gold particles having a specific surface area is formed. Therefore, as is clear from the results of the experimental example described later, since the change in gas concentration detection performance due to the concentration change based on the humidity dependency of the sulfuric acid aqueous solution that is the electrolytic solution is suppressed, a highly reliable gas Detection can be performed.
【００２５】この定電位電解式ガスセンサ２０は、二酸
化硫黄ガス、ホスフィンガスを被検知ガスとして好適に
用いることができる。The potentiostatic electrolysis gas sensor 20 can preferably use sulfur dioxide gas or phosphine gas as the gas to be detected.
【００２６】以上において、定電位電解式ガスセンサを
備えたガス検知装置について説明したが、本発明はこれ
に限定されるものではなく、ガス透過膜の一面に、特定
の範囲の比表面積を有し、金粒子を焼結して得られる金
焼結体層が形成されてなるガス拡散電極を備えるもので
あれば、その他の構成部材としては種々のものを用いる
ことができる。Although the gas detection device equipped with the potentiostatic electrolytic gas sensor has been described above, the present invention is not limited to this, and one surface of the gas permeable membrane has a specific surface area within a specific range. As long as it has a gas diffusion electrode having a gold sintered body layer obtained by sintering gold particles, various other components can be used.
【００２７】以下、本発明の作用効果を確認するために
行った実験について説明する。Experiments carried out to confirm the effects of the present invention will be described below.
【００２８】〔実験例１〕図１の構成に従い、定電位電
解式ガスセンサを備えたガス検知装置を作製した。この
ガス検知装置の定電位電解式ガスセンサにおいては、作
用極として、最大粒子径が４５μｍである金粒子と、樹
脂バインダーとしてフッ素樹脂とを、その質量比が１
０：１となる割合で混合した混合材料によってガス透過
膜用材料の表面に、厚さ１００μｍの混合材料層を形成
し、この混合材料層を、例えば温度３２０℃で焼結処理
することによって得られた、比表面積が９．０ｍ2 ／ｇ
である金焼結体層よりなるガス拡散電極を用いた。ま
た、参照極としては、最大粒子径が４５μｍである白金
粒子と、樹脂バインダーとしてフッ素樹脂とを、その質
量比が５：１となる割合で混合した混合材料によってガ
ス透過膜用材料の表面に、厚さ１００μｍの混合材料層
を形成し、この混合材料層を、例えば温度３２０℃で焼
結処理することによって得られた白金黒電極、対極とし
ては、参照極と同様の方法によって得られた白金黒電極
を用い、ガス透過膜としては、気孔率４０％、気孔径
０．３μｍ、厚さ２００μｍのＰＴＦＥ樹脂製の多孔質
シートを用いた。[Experimental Example 1] A gas detection apparatus having a potentiostatic electrolysis gas sensor was manufactured in accordance with the configuration shown in FIG. In the potentiostatic electrolysis gas sensor of this gas detection device, gold particles having a maximum particle diameter of 45 μm are used as working electrodes, and fluororesin is used as a resin binder, and the mass ratio thereof is 1.
A mixed material layer having a thickness of 100 μm is formed on the surface of the material for gas permeable membrane by the mixed material mixed at a ratio of 0: 1, and the mixed material layer is obtained by sintering treatment at a temperature of 320 ° C., for example. With a specific surface area of 9.0 m 2 / g
The gas diffusion electrode composed of the gold sintered body layer was used. Further, as the reference electrode, platinum particles having a maximum particle diameter of 45 μm and fluororesin as a resin binder were mixed on the surface of the gas permeable membrane material by a mixed material in a mass ratio of 5: 1. A platinum black electrode obtained by forming a mixed material layer having a thickness of 100 μm and sintering the mixed material layer at, for example, a temperature of 320 ° C. The counter electrode was obtained by the same method as the reference electrode. A platinum black electrode was used, and a porous sheet made of PTFE resin having a porosity of 40%, a pore diameter of 0.3 μm, and a thickness of 200 μm was used as the gas permeable film.
【００２９】このガス検知装置により、二酸化硫黄ガス
を被検知ガスとし、濃度が２０質量％、３０質量％、５
０質量％、６０質量％、７０質量％である３．０ｃｍ3
の硫酸水溶液を電解液としてこの順に用い、各々、被検
知ガスに対する１ｐｐｍ当たりの電界電流値を測定し
た。なお、用いる電解液を入れ替える際にはとも洗いを
１回行った。With this gas detection device, sulfur dioxide gas was used as the gas to be detected, and the concentration was 20% by mass, 30% by mass, and 5% by mass.
3.0 cm 3 which is 0% by mass, 60% by mass and 70% by mass
The sulfuric acid aqueous solution was used as the electrolytic solution in this order, and the electric field current value per 1 ppm with respect to the gas to be detected was measured. In addition, when replacing the electrolyte solution used, washing was performed once.
【００３０】得られた測定値により、硫酸水溶液の濃度
が２０質量％である場合の電界電流値を基準値とし、こ
の基準値に対する各測定値の相対比で表される感度と、
平衡相対湿度との関係を調べた。結果を図２において曲
線ａにより示す。なお、各濃度の硫酸水溶液の２０℃に
おける平衡相対湿度を表１に示す。From the obtained measured values, the electric field current value when the concentration of the sulfuric acid aqueous solution was 20% by mass was used as a reference value, and the sensitivity represented by the relative ratio of each measured value to this reference value,
The relationship with equilibrium relative humidity was investigated. The result is shown by the curve a in FIG. Table 1 shows the equilibrium relative humidity at 20 ° C. of the sulfuric acid aqueous solution of each concentration.
【００３１】[0031]
【表１】 [Table 1]
【００３２】〔比較実験例１〕作用極として真空蒸着法
によって形成した厚さ０．１μｍの金薄膜を用いたこと
以外は実験例１と同様の方法によって感度と平衡相対湿
度との関係とを調べた。結果を図２において曲線ｂによ
り示す。[Comparative Experimental Example 1] The relationship between the sensitivity and the equilibrium relative humidity was measured by the same method as in Experimental Example 1 except that a gold thin film having a thickness of 0.1 μm formed by the vacuum deposition method was used as the working electrode. Examined. The result is shown by the curve b in FIG.
【００３３】〔実験例２〕被検知ガスをホスフィンガス
としたこと以外は実験例１と同様の方法によって感度と
平衡相対湿度との関係とを調べた。結果を図３において
曲線ａにより示す。[Experimental Example 2] The relationship between the sensitivity and the equilibrium relative humidity was examined by the same method as in Experimental Example 1 except that the gas to be detected was phosphine gas. The result is shown by the curve a in FIG.
【００３４】〔比較実験例２〕作用極として真空蒸着法
によって形成した厚さ０．１μｍの金薄膜を用いたこと
以外は実験例２と同様の方法によって感度と平衡相対湿
度との関係とを調べた。結果を図３において曲線ｂによ
り示す。Comparative Experimental Example 2 The relationship between sensitivity and equilibrium relative humidity was measured in the same manner as in Experimental Example 2 except that a 0.1 μm thick gold thin film formed by vacuum deposition was used as the working electrode. Examined. The result is shown by the curve b in FIG.
【００３５】以上の結果から、作用極としてガス拡散電
極を用いた実験例１および実験例２に係るガス検知装置
においては、平衡相対湿度が変化しても感度が大きく変
化せず、特に、ホスフィンガスを被検知ガスとした実験
例２に係るガス検知装置においては、感度が平衡相対湿
度に影響されず殆ど一定となっていることがわかる。一
方、比較用実験例１および比較用実験例２に係るガス検
知装置においては、平衡相対湿度が変化することによっ
て感度が大きく変化していることがわかる。From the above results, in the gas detectors according to Experimental Example 1 and Experimental Example 2 in which the gas diffusion electrode was used as the working electrode, the sensitivity did not significantly change even when the equilibrium relative humidity changed, and in particular, phosphine was used. It can be seen that in the gas detection apparatus according to Experimental Example 2 in which the gas is the gas to be detected, the sensitivity is almost constant regardless of the equilibrium relative humidity. On the other hand, in the gas detectors according to Comparative Experimental Example 1 and Comparative Experimental Example 2, it is found that the sensitivity greatly changes due to the change in the equilibrium relative humidity.
【００３６】以上の実験により、電解液である硫酸水溶
液の湿度依存性に基づく濃度変化によってガス濃度検知
性能が変化することが抑制されることが確認された。From the above experiment, it was confirmed that the change of the gas concentration detection performance due to the change of the concentration of the sulfuric acid aqueous solution which is the electrolytic solution based on the humidity dependency is suppressed.
【００３７】[0037]
【発明の効果】本発明の定電位電解式ガスセンサによれ
ば、特定の比表面積を有する金粒子よりなる金焼結体層
が形成されてなるガス拡散電極が設けられており、この
ガス拡散電極が作用極として作用するため、電解液であ
る硫酸水溶液の湿度依存性に基づく濃度変化によってガ
ス濃度検知性能が変化することが抑制されることから、
信頼性の高いガス検知を行うことができる。According to the potentiostatic electrolysis type gas sensor of the present invention, the gas diffusion electrode having the gold sintered body layer formed of the gold particles having the specific surface area is provided. Since it acts as a working electrode, it is possible to suppress the change in gas concentration detection performance due to the concentration change based on the humidity dependency of the sulfuric acid aqueous solution that is the electrolytic solution.
It is possible to perform highly reliable gas detection.
【００３８】本発明のガス検知装置によれば、上記の定
電位電解式ガスセンサを備えてなるものであるため、信
頼性の高いガス検知を行うことができる。According to the gas detecting device of the present invention, since the above-mentioned constant potential electrolysis type gas sensor is provided, it is possible to perform highly reliable gas detection.
【図１】本発明のガス検知装置の構成の一例を示す説明
図である。FIG. 1 is an explanatory diagram showing an example of the configuration of a gas detection device of the present invention.
【図２】被検知ガスが二酸化硫黄ガスである場合の感度
と平衡相対湿度との関係を示す説明図である。FIG. 2 is an explanatory diagram showing the relationship between sensitivity and equilibrium relative humidity when the gas to be detected is sulfur dioxide gas.
【図３】被検知ガスがホスフィンガスである場合の感度
と平衡相対湿度との関係を示す説明図である。FIG. 3 is an explanatory diagram showing the relationship between sensitivity and equilibrium relative humidity when the gas to be detected is phosphine gas.
１１ ガス用セル １１Ａ ガス導入口 １１Ｂ ガス排出口 ２０ 定電位電解式ガスセンサ ２１ 電解液用セル ２１Ａ 電解液収容用空間 ２１Ｂ 開口 ２２ 連結用部材 ２３ 第１の開口 ２４ 第２の開口 ３１ 第１のガス透過膜 ３２ 第２のガス透過膜 ３５ 対極 ３６ 参照極 ３９ ポテンショスタット回路 ４０ 作用極 11 Gas cell 11A gas inlet 11B gas outlet 20 Constant potential electrolytic gas sensor 21 Electrolyte cell 21A Electrolyte storage space 21B opening 22 Connection member 23 First opening 24 Second opening 31 First gas permeable membrane 32 Second gas permeable membrane 35 opposite pole 36 reference pole 39 potentiostat circuit 40 Working pole
Claims (3)
位電解式ガスセンサにおいて、 ガス透過膜の一面に、比表面積が４〜１６ｍ2 ／ｇの金
粒子を焼結して得られる金焼結体層が形成されてなるガ
ス拡散電極を備えることを特徴とする定電位電解式ガス
センサ。1. A potentiostatic electrolysis gas sensor using an electrolytic solution comprising a sulfuric acid aqueous solution, a gold sintered body obtained by sintering gold particles having a specific surface area of 4 to 16 m 2 / g on one surface of a gas permeable membrane. A potentiostatic electrolytic gas sensor comprising a gas diffusion electrode having a layer formed thereon.
フィンガスであることを特徴とする請求項１に記載の定
電位電解式ガスセンサ。2. The potentiostatic electrolysis gas sensor according to claim 1, wherein the gas to be detected is sulfur dioxide gas or phosphine gas.
電解式ガスセンサを備えていることを特徴とするガス検
知装置。3. A gas detection device, comprising the potentiostatic electrolysis gas sensor according to claim 1 or 2.
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| JP2001343034A JP3881540B2 (en) | 2001-11-08 | 2001-11-08 | Constant potential electrolysis gas sensor and gas detector |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2005043147A1 (en) * | 2003-10-30 | 2005-05-12 | Riken Keiki Co., Ltd. | Electrochemical gas sensor |
| JP2009115680A (en) * | 2007-11-08 | 2009-05-28 | Keio Gijuku | Electrochemical gas sensor, operation electrode suitable for the same, and detection method of arsine using electrochemical gas sensor |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005043147A1 (en) * | 2003-10-30 | 2005-05-12 | Riken Keiki Co., Ltd. | Electrochemical gas sensor |
| JP2005134248A (en) * | 2003-10-30 | 2005-05-26 | Riken Keiki Co Ltd | Electrochemical gas sensor |
| JP4507235B2 (en) * | 2003-10-30 | 2010-07-21 | 理研計器株式会社 | Electrochemical gas sensor |
| KR101127043B1 (en) * | 2003-10-30 | 2012-03-26 | 나가카즈 후루야 | Electrochemical gas sensor |
| JP2009115680A (en) * | 2007-11-08 | 2009-05-28 | Keio Gijuku | Electrochemical gas sensor, operation electrode suitable for the same, and detection method of arsine using electrochemical gas sensor |
| JP2016176946A (en) * | 2013-06-18 | 2016-10-06 | 新コスモス電機株式会社 | Constant potential electrolysis-type gas sensor |
| JP2015083926A (en) * | 2013-10-25 | 2015-04-30 | 理研計器株式会社 | Constant potential electrolysis type oxygen gas sensor |
| JP2015083924A (en) * | 2013-10-25 | 2015-04-30 | 理研計器株式会社 | Constant potential electrolysis type gas sensor |
| WO2015060328A1 (en) * | 2013-10-25 | 2015-04-30 | 理研計器株式会社 | Potentiostatic electrolytic gas sensor |
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