JPH063323A - Electrochemical gas sensor - Google Patents
Electrochemical gas sensorInfo
- Publication number
- JPH063323A JPH063323A JP4159285A JP15928592A JPH063323A JP H063323 A JPH063323 A JP H063323A JP 4159285 A JP4159285 A JP 4159285A JP 15928592 A JP15928592 A JP 15928592A JP H063323 A JPH063323 A JP H063323A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- gas
- group
- sensing element
- solid electrolyte
- 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.)
- Pending
Links
- 238000001514 detection method Methods 0.000 claims abstract description 52
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 39
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 239000012528 membrane Substances 0.000 claims description 38
- 238000012360 testing method Methods 0.000 claims description 26
- 238000012545 processing Methods 0.000 claims description 19
- 239000003792 electrolyte Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 33
- 230000006866 deterioration Effects 0.000 abstract description 11
- 239000011248 coating agent Substances 0.000 abstract 2
- 238000000576 coating method Methods 0.000 abstract 2
- 239000007789 gas Substances 0.000 description 84
- 238000000034 method Methods 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 14
- 230000008859 change Effects 0.000 description 13
- 238000012937 correction Methods 0.000 description 12
- 230000007423 decrease Effects 0.000 description 12
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 238000003487 electrochemical reaction Methods 0.000 description 7
- 238000007689 inspection Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229920000557 Nafion® Polymers 0.000 description 4
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 4
- 229960002796 polystyrene sulfonate Drugs 0.000 description 4
- 239000011970 polystyrene sulfonate Substances 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Emergency Alarm Devices (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、詳しくは絶縁基板に形成された、作用極と対極
を含む電極群とこの電極群を一連に被覆する固体電解質
膜を備えた被検ガスを検知する検知素子を有する電気化
学式ガスセンサに関し、作用極と対極上で起こるガスの
電気化学反応を利用して、雰囲気中に含まれる、例えば
一酸化炭素ガス、アルコールガスなどの被検ガスを検知
する電気化学式ガスセンサに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrochemical gas sensor, and more particularly, to a test object having an electrode group including a working electrode and a counter electrode formed on an insulating substrate and a solid electrolyte membrane covering the electrode group in series. The present invention relates to an electrochemical gas sensor having a detection element for detecting a gas, utilizing an electrochemical reaction of a gas occurring on a working electrode and a counter electrode to detect a test gas such as carbon monoxide gas or alcohol gas contained in an atmosphere. The present invention relates to an electrochemical gas sensor for detecting.
【０００２】[0002]
【従来の技術】例えば特開昭５３−１１５２９３号、さ
らには特開昭６４−８８３５４号公報に開示されている
如く、絶縁基板上に複数の電極を形成し、これらの電極
を固体電解質膜でつないだ、電気化学反応を利用したガ
スセンサは、電極において起こる特定のガスが電気化学
反応にともなって流れる電流をもって、雰囲気中の特定
のガスを被検ガスとして検知する機能をはたすものであ
るが、この種の検知素子を有するガスセンサにあって
は、特に固体電解質膜の性能が雰囲気に含まれる種々の
ガス、あるいは熱気などの影響を受けて経時的に変化
し、被検ガスの検知能が低下あるいは失う。これは、固
体電解質膜として用いた電解質のポリスチレンスルホネ
ート、ポリビニルスルホネート、パーフルオロスルホネ
ートポリマー、パーフルオロカルボキシレートポリマー
の中でも最も実用的なパーフルオロスルホネートポリマ
ー（デュポン社製の商標ナフィオン）でも、経時ととも
にインピーダンスやガス透過性等の物性が変化すると、
初期の感度が低下し、特に火報に使用するガスセンサに
あっては、致命的欠陥を引き起こしかねない。そこで、
従来は定期的に被検ガスを人工的に打ち込み、センサ感
度を計測、点検する方法によっていたが、このような点
検は、時間と労力を要するのみならず、点検と点検との
一定期間内に感度が低下し寿命が来た場合には、それを
知ることができない。特に、常設型である火報に用いる
ガスセンサの劣化は、設置した環境に依存し、一律でな
い点で、保全、点検の重要性が増す。2. Description of the Related Art As disclosed in, for example, JP-A-53-115293 and JP-A-64-88354, a plurality of electrodes are formed on an insulating substrate and these electrodes are formed by a solid electrolyte membrane. The connected gas sensor using an electrochemical reaction has a function of detecting a specific gas in the atmosphere as a test gas by the electric current flowing through the electrode along with the electrochemical reaction. In a gas sensor having this type of detection element, the performance of the solid electrolyte membrane changes over time under the influence of various gases contained in the atmosphere, or hot air, and the ability to detect the test gas decreases. Or lose. This is because even with the most practical perfluorosulfonate polymer (trade name Nafion manufactured by DuPont) among polystyrene sulfonate, polyvinyl sulfonate, perfluorosulfonate polymer, and perfluorocarboxylate polymer of the electrolyte used as the solid electrolyte membrane, the impedance changes with time. Changes in physical properties such as gas permeability and
The initial sensitivity is lowered, which may cause a fatal defect especially in a gas sensor used for a fire alarm. Therefore,
Conventionally, the method has been to periodically inject the test gas artificially, measure and inspect the sensor sensitivity, but such inspection not only requires time and labor, but also within a certain period between inspection and inspection. When the sensitivity decreases and the life is reached, it cannot be known. In particular, the deterioration of the gas sensor used for the fire alarm, which is a permanent type, depends on the environment in which the gas sensor is installed and is not uniform, which makes maintenance and inspection more important.
【０００３】そこで、ガスセンサの感度低下を常に監視
する手段として、被検ガスに対する感度の経時的変化と
相関がある、基準ガスの感度の経時的変化を測定するた
め、基準ガスを検知する検知素子を別に備える解決手段
がある。この場合、被検ガス及び基準ガスの感度変化の
検知精度について一層の向上が求められている。Therefore, as a means for constantly monitoring the decrease in the sensitivity of the gas sensor, a sensing element for detecting the reference gas in order to measure the change over time in the sensitivity of the reference gas, which has a correlation with the change over time in the sensitivity to the test gas. There is a solution for separately providing. In this case, it is required to further improve the detection accuracy of the sensitivity change of the test gas and the reference gas.
【０００４】[0004]
【発明が解決しようとする課題】本発明は上記の事実に
鑑みてなされたもので、その目的とするところは、ガス
センサの感度低下を連続的に点検することができ、且つ
感度変化の検知精度の良い電気化学式ガスセンサを提供
することにある。SUMMARY OF THE INVENTION The present invention has been made in view of the above facts, and an object thereof is to be able to continuously inspect a decrease in sensitivity of a gas sensor and to detect a change in sensitivity. To provide a good electrochemical gas sensor.
【０００５】[0005]
【課題を解決するための手段】本発明に係る電気化学式
ガスセンサは、（１）絶縁基板１に形成された、作用極
２、対極３及び参照極４を含む電極群５、及びこれらの
電極群５を一連に被覆する固体電解質膜６とからなる被
検ガスを検知する検知素子７、（２）上記絶縁基板１に
形成された、上記電極群５と同一の構成を有する電極群
５１、及びこれらの電極群５１を一連に被覆し、上記固
体電解質膜６と相互に分離して形成された固体電解質膜
６１とからなる、雰囲気中に常に存在する基準ガスを検
知する検知素子７１、（３）検知素子７に接続された、
該検知素子７の出力信号を処理する信号処理回路１０
０、（４）検知素子７１に接続された、該検知素子７１
の出力信号が一定値以下になると検知素子７の寿命を告
知する信号処理回路１１０で構成され、さらに、（５）
上記電極群５１は作用極２１、対極３１および電極群５
の参照極４と共通の参照極４１を備えていることを特徴
とする。The electrochemical gas sensor according to the present invention comprises (1) an electrode group 5 including a working electrode 2, a counter electrode 3 and a reference electrode 4 formed on an insulating substrate 1; and these electrode groups. A detection element 7 for detecting a test gas, which comprises a solid electrolyte membrane 6 covering 5 in series, (2) an electrode group 51 formed on the insulating substrate 1 and having the same configuration as the electrode group 5, and A sensing element 71 ((3), which covers the electrode group 51 in series and is composed of the solid electrolyte membrane 6 and the solid electrolyte membrane 61 formed separately from each other, for sensing the reference gas that is always present in the atmosphere. ) Connected to the sensing element 7,
A signal processing circuit 10 for processing the output signal of the sensing element 7.
0, (4) the sensing element 71 connected to the sensing element 71
The signal processing circuit 110 notifies the life of the detecting element 7 when the output signal of the signal becomes less than a certain value, and further, (5)
The electrode group 51 includes a working electrode 21, a counter electrode 31, and an electrode group 5.
It is characterized in that it has a reference electrode 41 common to the reference electrode 4 of FIG.
【０００６】[0006]
【作用】本発明に係る電気化学式ガスセンサによると、
被検ガスを検知する検知素子７と同一の構成を有し、雰
囲気中に常に存在する基準ガスを検知する検知素子７１
と被検ガスを検知する検知素子７の両者の雰囲気から受
ける感度の経時的低下は、同一の傾向を示し、且つ検知
素子７１は雰囲気に常に存在するガスを基準ガスとする
ので、この検知素子７１の出力信号を受けて告知する信
号処理回路によって検知素子７の感度の低下と寿命を連
続的に点検する。感度の低下と寿命を連続的に点検する
に当たり、検知素子７の作用極２と検知素子７１の作用
極２１に対する基準電位として働く、検知素子７の参照
極４と検知素子７１の参照極４１を共通とするため、参
照極４と参照極４１の電位ズレがなく、検知素子７と検
知素子７１の感度変化の検知精度は検知素子７と検知素
子７１の参照極を別々に設けた場合よりも格段に向上す
る。According to the electrochemical gas sensor of the present invention,
A detection element 71 that has the same configuration as the detection element 7 that detects the test gas and that detects the reference gas that is always present in the atmosphere.
The decrease in sensitivity with time of both the sensing element 7 for detecting the test gas and the sensing element 7 shows the same tendency, and the sensing element 71 uses the gas always present in the atmosphere as the reference gas. The signal processing circuit which receives the output signal of 71 and notifies it continuously checks the deterioration of the sensitivity and the life of the detection element 7. In continuously checking the decrease in sensitivity and the life, the reference electrode 4 of the detection element 7 and the reference electrode 41 of the detection element 71, which serve as a reference potential for the working electrode 2 of the detection element 7 and the working electrode 21 of the detection element 71, are set. Since they are common to each other, there is no potential deviation between the reference electrode 4 and the reference electrode 41, and the detection accuracy of the sensitivity change of the detection element 7 and the detection element 71 is higher than that when the reference electrodes of the detection element 7 and the detection element 71 are provided separately. Greatly improved.
【０００７】[0007]
【実施例】以下、本発明を実施例として示した図面を参
照しながら説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to the drawings showing the embodiments.
【０００８】図１は本発明の一実施例に係り、電気化学
式ガスセンサを構成する検知素子の平面図を含む電気化
学式ガスセンサの回路図であり、図２は図１におけるＡ
−Ａ断面図、図３は図１におけるＢ−Ｂ断面図である。FIG. 1 is a circuit diagram of an electrochemical gas sensor according to an embodiment of the present invention, including a plan view of a detection element constituting the electrochemical gas sensor, and FIG.
-A sectional view, FIG. 3 is a BB sectional view in FIG.
【０００９】本発明の電気化学式ガスセンサは、例えば
一酸化炭素、アルコール、硫化水素等のガスを被検ガス
とする検知素子７を有する。この検知素子７は、図に示
す如く、表面に絶縁処理を施したシリコン基板、又は有
機の高分子基板などの絶縁基板１に作用極２、対極３、
及び参照極４を含む電極群５と固体電解質膜６を備え
る。作用極２、対極３、および作用極２と対極３の間に
位置する参照極４は平行に形成されている。The electrochemical gas sensor of the present invention has a detection element 7 which uses a gas such as carbon monoxide, alcohol or hydrogen sulfide as a test gas. As shown in the figure, this sensing element 7 has a working electrode 2, a counter electrode 3, and an insulating substrate 1 such as a silicon substrate whose surface is subjected to an insulation treatment, or an organic polymer substrate.
And an electrode group 5 including the reference electrode 4 and a solid electrolyte membrane 6. The working electrode 2, the counter electrode 3, and the reference electrode 4 located between the working electrode 2 and the counter electrode 3 are formed in parallel.
【００１０】電極群５は、白金や金その他の電極材料が
用いられ、例えばスパッタリングや蒸着等種々の方法に
よって形成することができる。固体電解質膜６は、上記
の電極群５を構成する作用極２、対極３、および参照極
４の上に一連に被覆し、この固体電解質膜６を透過した
一定量以上の被検ガスが作用極２に到達すると、作用極
２と対極３において電気化学反応が起きる。その結果、
作用極２と参照極４間の印加電圧に従い、作用極２と対
極３に電流が流れ、この電流が検知素子７の出力信号と
して生ずる。なお、固体電解質膜６としては、ポリスチ
レンスルホネート、ポリビニルスルホネート、パーフル
オロスルホネートポリマー、パーフルオロカルボキシレ
ートポリマーが用いられ、中でも電解質として安定なパ
ーフルオロスルホネートポリマー（デュポン社製の商標
ナフィオン）が適当である。The electrode group 5 is made of an electrode material such as platinum or gold, and can be formed by various methods such as sputtering and vapor deposition. The solid electrolyte membrane 6 is coated on the working electrode 2, the counter electrode 3, and the reference electrode 4 which form the electrode group 5 in series, and a certain amount or more of the test gas that has passed through the solid electrolyte membrane 6 acts on the working electrode 2. When reaching the pole 2, an electrochemical reaction occurs in the working electrode 2 and the counter electrode 3. as a result,
According to the applied voltage between the working electrode 2 and the reference electrode 4, a current flows through the working electrode 2 and the counter electrode 3, and this current is generated as an output signal of the sensing element 7. As the solid electrolyte membrane 6, polystyrene sulfonate, polyvinyl sulfonate, perfluorosulfonate polymer, and perfluorocarboxylate polymer are used. Among them, perfluorosulfonate polymer (Nafion trademark manufactured by DuPont) which is stable as an electrolyte is suitable. .
【００１１】感度の低下を引き起こす固体電解質膜６の
経時的劣化を防止するために、この固体電解質膜６の表
面にフッ素系樹脂等の保護膜、例えばテトラフルオロエ
チレンのプラズマ重合体を形成してもよい。In order to prevent deterioration of the solid electrolyte membrane 6 with time, which causes a decrease in sensitivity, a protective film of fluorine resin or the like, for example, a plasma polymer of tetrafluoroethylene is formed on the surface of the solid electrolyte membrane 6. Good.
【００１２】作用極２、対極３、および参照極４は端部
に端子２ａ、端子３ｂ、および端子４ｃを備えている。
これらの各端子２ａ，３ｂ，４ｃは検知素子７の出力信
号を処理する信号処理回路１００に接続している。例え
ば火報に利用するときには、この信号処理回路１００
は、警報器等を有する。The working electrode 2, the counter electrode 3 and the reference electrode 4 have terminals 2a, 3b and 4c at their ends.
Each of these terminals 2a, 3b, 4c is connected to a signal processing circuit 100 which processes the output signal of the sensing element 7. For example, when used for fire alarm, this signal processing circuit 100
Has an alarm device and the like.
【００１３】次に雰囲気中に常に存在する酸素等のガス
を基準ガスとして検知する検知素子７１について説明す
ると、検知素子７１は上記の検知素子７と大きさが小さ
いだけで同一の構成を有し、作用極２１、対極３１、及
び参照極４と共通の参照極４１を含む電極群５１と固体
電解質膜６１を備える。この検知素子７１の大きさは、
被検ガスと基準ガスの種類や濃度等により設計できる。
検知素子７１は検知素子７の作用極２と対極３の間に位
置し、この検知素子７１を構成する作用極２１、対極３
１、および作用極２１と対極３１の間にある参照極４１
は平行に形成されている。参照極４と参照極４１はそれ
ぞれ作用極２と作用極２１に印加する電位の基準となる
電極である。Next, the detection element 71 for detecting a gas such as oxygen, which is always present in the atmosphere, as a reference gas will be described. The detection element 71 has the same structure as the above-mentioned detection element 7 except that the size is small. , A working electrode 21, a counter electrode 31, and an electrode group 51 including a reference electrode 41 common to the reference electrode 4 and a solid electrolyte membrane 61. The size of the detection element 71 is
It can be designed according to the types and concentrations of the test gas and the reference gas.
The sensing element 71 is located between the working electrode 2 and the counter electrode 3 of the sensing element 7, and the working electrode 21 and the counter electrode 3 constituting this sensing element 71.
1 and the reference electrode 41 between the working electrode 21 and the counter electrode 31.
Are formed in parallel. The reference electrode 4 and the reference electrode 41 are electrodes serving as a reference of the potential applied to the working electrode 2 and the working electrode 21, respectively.
【００１４】上記固体電解質膜６１と上述の固体電解質
膜６は相互に分離されており、したがって、検知素子７
の電極群５は固体電解質膜６で被覆され、検知素子７１
の電極群５１は固体電解質膜６１で被覆され、電極群５
と電極群５１の境界となる区域には固体電解質膜は存在
しない。The solid electrolyte membrane 61 and the solid electrolyte membrane 6 are separated from each other, and therefore the sensing element 7
The electrode group 5 of is covered with the solid electrolyte membrane 6, and the sensing element 71
Of the electrode group 51 is covered with a solid electrolyte membrane 61,
The solid electrolyte membrane does not exist in the area serving as the boundary between the electrode group 51 and the electrode group 51.
【００１５】作用極２１、対極３１、および参照極４１
も同様に端部に端子２１ａ、端子３１ｂ、および端子４
１ｃを備えている。これらの各端子２１ａ，３１ｂ，４
１ｃは検知素子７１の出力信号が一定値以下になると検
知素子７の寿命を告知する信号処理回路１１０に接続さ
れている。出力信号の電流が一定値以下に落ちる原因
は、検知素子７１の常時雰囲気中に含まれる基準ガスの
電極における電気化学反応の感度特性の低下に起因する
もので、固体電解質膜の劣化は被検ガスの検知素子７に
おいても潜在しているものである。この様な信号は、検
知素子７の寿命を告知する信号処理回路１１０によって
表示又は報知される。表示又は報知は、例えばランプで
もよいし又は警報でもよく、制限はない。Working electrode 21, counter electrode 31, and reference electrode 41
Similarly, the terminals 21a, 31b, and 4 are attached to the ends.
It is equipped with 1c. Each of these terminals 21a, 31b, 4
1c is connected to a signal processing circuit 110 that notifies the life of the detection element 7 when the output signal of the detection element 71 becomes a certain value or less. The reason why the current of the output signal drops below a certain value is that the sensitivity characteristic of the electrochemical reaction in the electrode of the reference gas contained in the constant atmosphere of the sensing element 71 is lowered, and the deterioration of the solid electrolyte membrane is not detected. It is also latent in the gas detection element 7. Such a signal is displayed or notified by the signal processing circuit 110 which notifies the life of the detection element 7. The display or notification may be, for example, a lamp or an alarm, without limitation.
【００１６】以下に、検知素子７と検知素子７１の感度
低下の相関を、次の実験で証明する。Below, the correlation between the reductions in the sensitivity of the sensing element 7 and the sensing element 71 will be proved by the following experiment.
【００１７】絶縁基板１として１０ｍｍ角のガラス板を
用い、絶縁基板１と電極群５及び電極群５１の密着性を
高めるために、ガラス板の表面にスパッタリングで厚み
２０００Ａ程度のポリシリコン層を形成した。この絶縁
基板１の上にスパッタリングで白金からなる作用極２と
作用極２１、対極３と対極３１、及び金からなる参照極
４と４１を形成し、電極群５及び電極群５１とし、それ
ぞれの端部を作用極２の端子２ａ、対極３の端子３ｂ、
参照極４の端子４ｃ、作用極２１の端子２１ａ、対極３
１の端子３１ｂとし、さらに電極群５の参照極４と共通
の端子４ｃをもって参照極４１の端子４１ｃとした。こ
の電極群５及び電極群５１の上に、上記各端子２ａ，３
ｂ，４ｃ，２１ａ，３１ｂ，４１ｃと、電極群５と電極
群５１の境界区域とを残して、パーフルオロスルホネー
トポリマを５重量％含む溶液をキャステングすることに
より、相互に分離した固体電解質膜６と６１を電極群
５，電極群５１上に一連に形成して検知素子７と７１と
した。As the insulating substrate 1, a glass plate of 10 mm square is used, and in order to improve the adhesion between the insulating substrate 1 and the electrode group 5 and the electrode group 51, a polysilicon layer having a thickness of about 2000 A is formed on the surface of the glass plate by sputtering. did. On this insulating substrate 1, a working electrode 2 and a working electrode 21 made of platinum, a counter electrode 3 and a counter electrode 31 made of platinum, and reference electrodes 4 and 41 made of gold were formed by sputtering to form an electrode group 5 and an electrode group 51, respectively. The end portion is the terminal 2a of the working electrode 2, the terminal 3b of the counter electrode 3,
Terminal 4c of reference electrode 4, terminal 21a of working electrode 21, counter electrode 3
The terminal 31b of No. 1 and the terminal 4c common to the reference electrode 4 of the electrode group 5 were used as the terminal 41c of the reference electrode 41. On the electrode group 5 and the electrode group 51, the terminals 2a, 3
b, 4c, 21a, 31b, 41c, and the boundary area between the electrode group 5 and the electrode group 51, the solid electrolyte membrane 6 separated from each other by casting a solution containing 5% by weight of a perfluorosulfonate polymer. And 61 are formed in series on the electrode group 5 and the electrode group 51 to form sensing elements 7 and 71.
【００１８】このようにして作製した電気化学式ガスセ
ンサの被検ガスを検知する検知素子７の感度の経時的変
化と雰囲気中に常に含まれる基準ガスを検知する検知素
子７１の感度の経時的変化の関係を測定した。図４に示
す如く、被検ガスとして一酸化炭素ガスを封入したチャ
ンバー２００内にガスセンサを収容し、基準ガスとして
大気中に存在する酸素を選定して測定した。検知素子７
と７１の出力信号の測定には、各端子２ａ，３ｂ，４
ｃ、並びに２１ａ，３１ｂ，４１ｃを介して各検知素子
７と７１用のそれぞれのポテンショスタット３０１、３
１１に接続し、さらにこれらのポテンショスタット３０
１、３１１は、それぞれレコーダ４０１、４１１に接続
した測定装置を用いた。In the electrochemical gas sensor thus manufactured, the sensitivity of the detecting element 7 for detecting the test gas and the sensitivity of the detecting element 71 for detecting the reference gas constantly contained in the atmosphere are changed. The relationship was measured. As shown in FIG. 4, a gas sensor was housed in a chamber 200 filled with carbon monoxide gas as a test gas, and oxygen existing in the atmosphere was selected and measured as a reference gas. Sensing element 7
And 71 for measuring the output signal of each terminal 2a, 3b, 4
c, and 21a, 31b, 41c via the respective potentiostats 301, 3 for the respective sensing elements 7 and 71.
11 and also these potentiostats 30
The measuring devices 1 and 311 were connected to the recorders 401 and 411, respectively.
【００１９】試験条件は、一酸化炭素を検知する検知素
子７の作用極２と参照極４の間の印加電圧を０．４Ｖに
設定し、酸素を基準ガスとして検知する検知素子７１の
作用極２１と参照極４の間の印加電圧を−０．６Ｖに設
定した。そして、検知素子７１の作用極２１と対極３１
の間を流れる酸素検知電流は、常時レコーダ４１１で記
録した。また、２００時間ごとにチャンバー２００内の
雰囲気を空気のみの状態から一酸化炭素を１０００ｐｐ
ｍ含む空気に置き換え、その際に検知素子７の作用極２
と対極３に流れる一酸化炭素検知電流をレコーダ４０１
で測定した。この測定結果を示す図５から明らかなよう
に、一酸化炭素に対する検知素子７の感度の経時的変化
と、酸素に対する検知素子７１の感度の経時的変化は、
殆ど同等の速度で進行する。したがって基準ガスの検知
素子７１の感度が低下して出力信号が一定値以下に達す
ると、被検ガスの検知素子７の感度も相関関係をもって
低下する事実から、検知素子７１の出力信号を基準とし
て検知素子７の寿命を信号処理回路により判別すること
ができた。The test condition is that the applied voltage between the working electrode 2 of the sensing element 7 for detecting carbon monoxide and the reference electrode 4 is set to 0.4 V, and the working electrode of the sensing element 71 for detecting oxygen as a reference gas. The applied voltage between 21 and the reference electrode 4 was set to -0.6V. Then, the working electrode 21 and the counter electrode 31 of the detection element 71
The oxygen detection current flowing between the two was constantly recorded by the recorder 411. In addition, the atmosphere in the chamber 200 is changed from the state of air only to 1000 pp of carbon monoxide every 200 hours.
It is replaced with air containing m, and at that time, the working electrode 2 of the sensing element 7
The recorder 401 detects the carbon monoxide detection current flowing through the counter electrode 3 and the counter electrode 3.
It was measured at. As is clear from FIG. 5 showing the measurement result, the change in sensitivity of the sensing element 7 with respect to carbon monoxide with time and the change in sensitivity of the sensing element 71 with respect to oxygen with time are as follows.
It proceeds at almost the same speed. Therefore, when the sensitivity of the detection element 71 for the reference gas decreases and the output signal reaches a certain value or less, the sensitivity of the detection element 7 for the test gas also decreases in a correlated manner. The life of the sensing element 7 could be determined by the signal processing circuit.
【００２０】検知精度を高めるために、電極面はいろい
ろな工夫がなされる。その一例を示す図６は電気化学式
ガスセンサを構成する検知素子の平面図を含む電気化学
式ガスセンサの回路図である。In order to improve the detection accuracy, various modifications are made to the electrode surface. FIG. 6 showing an example thereof is a circuit diagram of an electrochemical gas sensor including a plan view of a detection element constituting the electrochemical gas sensor.
【００２１】本実施例は固体電解質膜６に被覆された電
極の表面積を大きくて、検知素子７の被検ガスに対する
感度をさらに向上させたもので、絶縁基板１上に形成さ
れた、対極３は矩形の一辺に沿ってほぼ全長に延びる長
直線ａ、この長直線ａの一端から隣接する辺に沿ってほ
ぼ全長に延びる長直線ｂ、さらに隣接する辺の中間点ま
で沿った短直線ｃとで連なる線上に形成されている。作
用極２は、上記長直線ａと短直線ｃの間で短直線ｃに近
接し、短直線ｃと平行に走る短直線ｄと、この短直線ｄ
に接続し且つ上記短直線ｃとほぼ同一線上にある屈折線
ｅとで連なる線上に形成されている。参照極４は、上記
短直線ｄと上記長直線ａの間で短直線ｄと平行に走る短
直線ｆ、この短直線ｆに接続し且つ上記屈折線ｅと長直
線ａの間で屈折線ｅと平行な屈折線ｇとで連なる線上に
形成されている。作用極２１は上記屈折線ｅと上記屈折
線ｇの間にあり、且つ短直線ｄとほぼ同一の線上に形成
され、対極３１は上記屈折線ｇと上記長直線ａの間にあ
り、且つ短直線ｆとほぼ同一の線上に形成されている。In this embodiment, the surface area of the electrode coated with the solid electrolyte membrane 6 is increased to further improve the sensitivity of the detection element 7 to the test gas. The counter electrode 3 formed on the insulating substrate 1 is used. Is a long straight line a extending substantially along the entire length of one side of the rectangle, a long straight line b extending substantially from the one end of the long straight line a to the adjacent side, and a short straight line c extending to the midpoint of the adjacent side. It is formed on the line connecting with. The working electrode 2 is a short straight line d that runs close to the short straight line c between the long straight line a and the short straight line c and runs parallel to the short straight line c, and the short straight line d.
Is formed on a line which is connected to the short straight line c and is continuous with the refraction line e substantially on the same line. The reference pole 4 is connected to the short straight line f running parallel to the short straight line d between the short straight line d and the long straight line a, and is connected to the short straight line f, and the refraction line e is formed between the refraction line e and the long straight line a. And a refraction line g parallel to the line. The working electrode 21 is formed between the refraction line e and the refraction line g, and is formed on substantially the same line as the short straight line d, and the counter electrode 31 is between the refraction line g and the long straight line a and is short. It is formed on almost the same line as the straight line f.
【００２２】以下、前実施例と同様に、検知素子７は作
用極２、対極３、及び参照極４を含む電極群５、および
これら電極群５を一連に被覆する固体電解質膜６とで構
成し、検知素子７１は作用極２１、対極３１、及び参照
極４１を含む電極群５１、およびこれら電極群５１を一
連に被覆する固体電解質膜６１とで構成されている。こ
れら作用極２，２１、対極３，３１、参照極４，４１は
端部に端子２ａ，２１ａ，３ｂ，３１ｂ，４ｃ，及び４
ｃと共通の４１ｃを設られ、上記の端子２ａ，３ｂ，４
ｃは検知素子７の出力信号を処理する信号処理回路１０
０に接続し、端子２１ａ，３１ｂ，４１ｃは検知素子７
１の出力信号を処理する信号処理回路１１０に接続され
ている。Hereinafter, as in the previous embodiment, the sensing element 7 is composed of an electrode group 5 including a working electrode 2, a counter electrode 3, and a reference electrode 4, and a solid electrolyte membrane 6 that covers these electrode groups 5 in series. The sensing element 71 is composed of the electrode group 51 including the working electrode 21, the counter electrode 31, and the reference electrode 41, and the solid electrolyte membrane 61 that covers the electrode group 51 in series. These working electrodes 2, 21, counter electrodes 3, 31, and reference electrodes 4, 41 have terminals 2a, 21a, 3b, 31b, 4c, and 4 at their ends.
41c, which is common with C, is provided, and the terminals 2a, 3b, 4 described above are provided.
c is a signal processing circuit 10 for processing the output signal of the detection element 7.
0, and the terminals 21a, 31b, 41c are connected to the sensing element 7
1 is connected to the signal processing circuit 110 which processes the output signal.
【００２３】[0023]
【発明の効果】検知素子７と検知素子７１の経時的劣化
に起因する感度低下は相関を有するので、検知素子７１
によって検知素子７の感度特性の低下ないし寿命を連続
的に点検することができる。且つ検知素子７と検知素子
７１のそれぞれの参照極４と参照極４１は共通であるの
で、参照極４と参照極４１の電位ズレがなく、したがっ
て、感度変化の検知精度が向上する。EFFECTS OF THE INVENTION Since the sensitivity deterioration due to the deterioration of the sensing element 7 and the sensing element 71 with time has a correlation, the sensing element 71
Thus, it is possible to continuously check the deterioration of the sensitivity characteristic or the life of the detection element 7. Moreover, since the reference electrode 4 and the reference electrode 41 of the detection element 7 and the detection element 71 are common, there is no potential deviation between the reference electrode 4 and the reference electrode 41, and therefore, the detection accuracy of the sensitivity change is improved.
【図１】本発明の一実施例に係り、電気化学式ガスセン
サを構成する検知素子の平面図を含む電気化学式ガスセ
ンサの回路図である。FIG. 1 is a circuit diagram of an electrochemical gas sensor including a plan view of a detection element constituting an electrochemical gas sensor according to an embodiment of the present invention.
【図２】図１におけるＡ−Ａ断面図である。FIG. 2 is a sectional view taken along line AA in FIG.
【図３】図１におけるＢ−Ｂ断面図である。FIG. 3 is a sectional view taken along line BB in FIG.
【図４】本発明のガスセンサを構成する被検ガスの検知
素子と基準ガスの検知素子の感度の低下について相関を
調べた測定装置の回路図である。FIG. 4 is a circuit diagram of a measuring device in which a correlation is examined with respect to a decrease in sensitivity of a detection element of a test gas and a detection element of a reference gas which form the gas sensor of the present invention.
【図５】図４で得た被検ガスの検知素子と基準ガスの検
知素子の出力信号の変化を経時で測定した結果を示すグ
ラフである。5 is a graph showing the results of measuring changes in output signals of the test gas detection element and the reference gas detection element obtained in FIG. 4 over time.
【図６】本発明の他の実施例に係り、電気化学式ガスセ
ンサを構成する検知素子の平面図を含む電気化学式ガス
センサの回路図である。FIG. 6 is a circuit diagram of an electrochemical gas sensor including a plan view of a detection element constituting the electrochemical gas sensor according to another embodiment of the present invention.
１ 絶縁基板 ２ 作用極 ３ 対極 ４ 参照極 ５ 電極群 ６ 固体電解質膜 ７ 検知素子 ２１ 作用極 ３１ 対極 ４１ 参照極 ５１ 電極群 ６１ 固体電解質膜 ７１ 検知素子 １００ 信号処理回路 １１０ 信号処理回路 1 Insulating Substrate 2 Working Electrode 3 Counter Electrode 4 Reference Electrode 5 Electrode Group 6 Solid Electrolyte Membrane 7 Sensing Element 21 Working Electrode 31 Counter Electrode 41 Reference Electrode 51 Electrode Group 61 Solid Electrolyte Membrane 71 Sensing Element 100 Signal Processing Circuit 110 Signal Processing Circuit
【手続補正書】[Procedure amendment]
【提出日】平成４年９月４日[Submission date] September 4, 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】０００２[Name of item to be corrected] 0002
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００２】[0002]
【従来の技術】例えば特開昭５３−１１５２９３号、さ
らには特開昭６４−８８３５４号公報に開示されている
如く、絶縁基板上に複数の電極を形成し、これらの電極
を固体電解質膜でつないだ、電気化学反応を利用したガ
スセンサは、電極において起こる特定のガスの電気化学
反応にともなって流れる電流をもって、雰囲気中の特定
のガスを被検ガスとして検知する機能をはたすものであ
るが、この種の検知素子を有するガスセンサにあって
は、特に固体電解質膜の性能が雰囲気に含まれる種々の
ガス、あるいは熱気などの影響を受けて経時的に変化
し、被検ガスの検知能が低下あるいは失う。これは、固
体電解質膜として用いた電解質のポリスチレンスルホネ
ート、ポリビニルスルホネート、パーフルオロスルホネ
ートポリマー、パーフルオロカルボキシレートポリマー
の中でも最も実用的なパーフルオロスルホネートポリマ
ー（デュポン社製の商標ナフィオン）でも、経時ととも
にインピーダンスやガス透過性等の物性が変化すると、
初期の感度が低下し、特に火報に使用するガスセンサに
あっては、致命的欠陥を引き起こしかねない。そこで、
従来は定期的に被検ガスを人工的に打ち込み、センサ感
度を計測、点検する方法によっていたが、このような点
検は、時間と労力を要するのみならず、点検と点検との
一定期間内に感度が低下し寿命が来た場合には、それを
知ることができない。特に、常設型である火報に用いる
ガスセンサの劣化は、設置した環境に依存し、一律でな
い点で、保全、点検の重要性が増す。2. Description of the Related Art As disclosed in, for example, JP-A-53-115293 and JP-A-64-88354, a plurality of electrodes are formed on an insulating substrate and these electrodes are formed by a solid electrolyte membrane. The connected gas sensor using an electrochemical reaction has a function of detecting a specific gas in the atmosphere as a test gas by using an electric current flowing with the electrochemical reaction of the specific gas that occurs at the electrode. In a gas sensor having this type of detection element, the performance of the solid electrolyte membrane changes over time under the influence of various gases contained in the atmosphere, or hot air, and the ability to detect the test gas decreases. Or lose. This is because even with the most practical perfluorosulfonate polymer (trade name Nafion manufactured by DuPont) among polystyrene sulfonate, polyvinyl sulfonate, perfluorosulfonate polymer, and perfluorocarboxylate polymer of the electrolyte used as the solid electrolyte membrane, the impedance changes with time. Changes in physical properties such as gas permeability and
The initial sensitivity is lowered, which may cause a fatal defect especially in a gas sensor used for a fire alarm. Therefore,
Conventionally, the method has been to periodically artificially inject the test gas, measure the sensor sensitivity, and inspect, but such inspection not only requires time and labor, but also within a certain period between inspections. When the sensitivity decreases and the life is reached, it cannot be known. In particular, the deterioration of the gas sensor used for the fire alarm, which is a permanent type, depends on the environment in which the gas sensor is installed and is not uniform, which makes maintenance and inspection more important.
【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】００１０[Correction target item name] 0010
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１０】電極群５は、白金や金その他の電極材料が
用いられ、例えばスパッタリングや蒸着等種々の方法に
よって形成することができる。固体電解質膜６は、上記
の電極群５を構成する作用極２、対極３、および参照極
４の上に一連に被覆し、この固体電解質膜６を透過した
被検ガスが作用極２に到達すると、作用極２と対極３に
おいて、作用極２と参照極４間の印加電圧に従い電気化
学反応が起きる。その結果、作用極２と対極３に電流が
流れ、この電流が検知素子７の出力信号として生ずる。
なお、固体電解質膜６としては、ポリスチレンスルホネ
ート、ポリビニルスルホネート、パーフルオロスルホネ
ートポリマー、パーフルオロカルボキシレートポリマー
が用いられ、中でも電解質として安定なパーフルオロス
ルホネートポリマー（デュポン社製の商標ナフィオン）
が適当である。The electrode group 5 is made of an electrode material such as platinum or gold, and can be formed by various methods such as sputtering and vapor deposition. The solid electrolyte membrane 6 was coated on the working electrode 2, the counter electrode 3, and the reference electrode 4 constituting the electrode group 5 in series, and passed through this solid electrolyte membrane 6 .
When the test gas reaches the working electrode 2, the working electrode 2 and the counter electrode 3
And electrification according to the applied voltage between the working electrode 2 and the reference electrode 4.
Academic reaction occurs. As a result, a current is applied to the working electrode 2 and the counter electrode 3.
Flow and this current is produced as the output signal of the sensing element 7.
As the solid electrolyte membrane 6, polystyrene sulfonate, polyvinyl sulfonate, perfluorosulfonate polymer, or perfluorocarboxylate polymer is used. Among them, perfluorosulfonate polymer stable as an electrolyte (trademark Nafion manufactured by DuPont)
Is appropriate.
【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】００１５[Name of item to be corrected] 0015
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１５】作用極２１、対極３１、および参照極４１
も同様に端部に端子２１ａ、端子３１ｂ、および端子４
１ｃを備えている。これらの各端子２１ａ，３１ｂ，４
１ｃは検知素子７１の出力信号が一定値以下になると検
知素子７の寿命を告知する信号処理回路１１０に接続さ
れている。出力信号の電流が一定値以下に落ちる原因
は、検知素子７１の固体電解質膜６１の劣化に起因する
もので、検知素子７の固体電解質膜６の劣化も同様に潜
在しているものである。この様な信号は、検知素子７の
寿命を告知する信号処理回路１１０によって表示又は報
知される。表示又は報知は、例えばランプでもよいし又
は警報でもよく、制限はない。Working electrode 21, counter electrode 31, and reference electrode 41
Similarly, the terminals 21a, 31b, and 4 are attached to the ends.
It is equipped with 1c. Each of these terminals 21a, 31b, 4
1c is connected to a signal processing circuit 110 that notifies the life of the detection element 7 when the output signal of the detection element 71 becomes a certain value or less. The reason why the current of the output signal drops below a certain value is due to the deterioration of the solid electrolyte membrane 61 of the sensing element 71, and the deterioration of the solid electrolyte membrane 6 of the sensing element 7 is also latent. There is something. Such a signal is displayed or notified by the signal processing circuit 110 which notifies the life of the detection element 7. The display or notification may be, for example, a lamp or an alarm, without limitation.
【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】００２１[Correction target item name] 0021
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２１】本実施例は固体電解質膜６に被覆された作
用極２の表面積を大きくして、検知素子７の被検ガスに
対する感度をさらに向上させたもので、絶縁基板１上に
形成された、作用極２は矩形の一辺に沿ってほぼ全長に
延びる長直線ａ、この長直線ａの一端から隣接する辺に
沿ってほぼ全長に延びる長直線ｂ、さらに隣接する辺の
中間点まで沿った短直線ｃとで連なる線上に形成されて
いる。対極３は、上記長直線ａと短直線ｃの間で短直線
ｃに近接し、短直線ｃと平行に走る短直線ｄと、この短
直線ｄに接続し且つ上記短直線ｃとほぼ同一線上にある
屈折線ｅとで連なる線上に形成されている。参照極４
は、上記短直線ｄと上記長直線ａの間で短直線ｄと平行
に走る短直線ｆ、この短直線ｆに接続し且つ上記屈折線
ｅと長直線ａの間で屈折線ｅと平行な屈折線ｇとで連な
る線上に形成されている。作用極２１は上記屈折線ｅと
上記屈折線ｇの間にあり、且つ短直線ｄとほぼ同一の線
上に形成され、対極３１は上記屈折線ｇと上記長直線ａ
の間にあり、且つ短直線ｆとほぼ同一の線上に形成され
ている。[0021] The present embodiment is coated on the solid electrolyte membrane 6 create
By increasing the surface area of the working electrode 2 to further improve the sensitivity of the detection element 7 to the test gas, the working electrode 2 formed on the insulating substrate 1 extends substantially along the entire length along one side of the rectangle. It is formed on a line connecting a long straight line a, a long straight line b extending from one end of the long straight line a to almost the entire length along the adjacent side, and a short straight line c extending to the midpoint of the adjacent side. The counter electrode 3 is adjacent to the short straight line c between the long straight line a and the short straight line c, runs along the short straight line c, and is connected to the short straight line d, and is substantially on the same line as the short straight line c. It is formed on a line continuous with the refraction line e at. Reference pole 4
Is a short straight line f running parallel to the short straight line d between the short straight line d and the long straight line a, connected to the short straight line f and parallel to the refraction line e between the refraction line e and the long straight line a. It is formed on a line continuous with the refraction line g. The working electrode 21 is formed between the refraction line e and the refraction line g, and is formed substantially on the same line as the short straight line d, and the counter electrode 31 is the counter electrode 31.
Is formed on the same line as the short straight line f.
【手続補正５】[Procedure Amendment 5]
【補正対象書類名】図面[Document name to be corrected] Drawing
【補正対象項目名】図６[Name of item to be corrected] Figure 6
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図６】 [Figure 6]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山鹿 範行 大阪府門真市大字門真1048番地松下電工株 式会社内 (72)発明者 渡部 祥文 大阪府門真市大字門真1048番地松下電工株 式会社内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Noriyuki Yamaga 1048 Kadoma, Kadoma, Osaka Prefecture Matsushita Electric Works Co., Ltd. (72) Yoshifumi Watanabe 1048, Kadoma, Kadoma City, Osaka Matsushita Electric Co., Ltd.
Claims (1)
２、対極３及び参照極４を含む電極群５、及びこれらの
電極群５を一連に被覆する固体電解質膜６とからなる被
検ガスを検知する検知素子７、（２）上記絶縁基板１に
形成された、上記電極群５と同一の構成を有する電極群
５１、及びこれらの電極群５１を一連に被覆し、上記固
体電解質膜６と相互に分離して形成された固体電解質膜
６１とからなる、雰囲気中に常に存在する基準ガスを検
知する検知素子７１、（３）検知素子７に接続された、
該検知素子７の出力信号を処理する信号処理回路１０
０、（４）検知素子７１に接続された、該検知素子７１
の出力信号が一定値以下になると検知素子７の寿命を告
知する信号処理回路１１０で構成され、さらに、（５）
上記電極群５１は作用極２１、対極３１および電極群５
の参照極４と共通の参照極４１を備えていることを特徴
とする電気化学式ガスセンサ。(1) An electrode group 5 including a working electrode 2, a counter electrode 3 and a reference electrode 4 formed on an insulating substrate 1, and a solid electrolyte membrane 6 covering the electrode group 5 in series. A detection element 7 for detecting a test gas, (2) an electrode group 51 formed on the insulating substrate 1 and having the same configuration as the electrode group 5, and a series of these electrode groups 51, and the solid Connected to a sensing element 71 composed of an electrolyte membrane 6 and a solid electrolyte membrane 61 formed separately from each other, which senses a reference gas always present in the atmosphere, and (3) a sensing element 7.
A signal processing circuit 10 for processing the output signal of the sensing element 7.
0, (4) the sensing element 71 connected to the sensing element 71
The signal processing circuit 110 notifies the life of the detecting element 7 when the output signal of the signal becomes less than a certain value, and further, (5)
The electrode group 51 includes a working electrode 21, a counter electrode 31, and an electrode group 5.
An electrochemical gas sensor having a reference electrode 41 common to the reference electrode 4 of 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4159285A JPH063323A (en) | 1992-06-18 | 1992-06-18 | Electrochemical gas sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4159285A JPH063323A (en) | 1992-06-18 | 1992-06-18 | Electrochemical gas sensor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH063323A true JPH063323A (en) | 1994-01-11 |
Family
ID=15690459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4159285A Pending JPH063323A (en) | 1992-06-18 | 1992-06-18 | Electrochemical gas sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH063323A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6773563B2 (en) | 2000-08-09 | 2004-08-10 | Nec Corporation | Electrochemical sensor having a reference electrode |
| US7975497B2 (en) | 2007-06-27 | 2011-07-12 | Hoshizaki Denki Kabushiki Kaisha | Refrigeration unit having variable performance compressor operated based on high-pressure side pressure |
| JP2022080743A (en) * | 2020-11-18 | 2022-05-30 | 理研計器株式会社 | Constant potential electrolytic gas sensor |
-
1992
- 1992-06-18 JP JP4159285A patent/JPH063323A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6773563B2 (en) | 2000-08-09 | 2004-08-10 | Nec Corporation | Electrochemical sensor having a reference electrode |
| US7975497B2 (en) | 2007-06-27 | 2011-07-12 | Hoshizaki Denki Kabushiki Kaisha | Refrigeration unit having variable performance compressor operated based on high-pressure side pressure |
| JP2022080743A (en) * | 2020-11-18 | 2022-05-30 | 理研計器株式会社 | Constant potential electrolytic gas sensor |
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