JPH0443951A - Electrochemical system gas sensor - Google Patents
Electrochemical system gas sensorInfo
- Publication number
- JPH0443951A JPH0443951A JP2153564A JP15356490A JPH0443951A JP H0443951 A JPH0443951 A JP H0443951A JP 2153564 A JP2153564 A JP 2153564A JP 15356490 A JP15356490 A JP 15356490A JP H0443951 A JPH0443951 A JP H0443951A
- Authority
- JP
- Japan
- Prior art keywords
- gas detection
- sensor
- sensitivity
- detection section
- output signal
- 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.)
- Granted
Links
- 238000001514 detection method Methods 0.000 claims abstract description 128
- 230000035945 sensitivity Effects 0.000 claims abstract description 72
- 238000012937 correction Methods 0.000 claims description 18
- 239000003792 electrolyte Substances 0.000 claims description 17
- 230000009471 action Effects 0.000 claims description 4
- 230000007613 environmental effect Effects 0.000 abstract description 23
- 239000007784 solid electrolyte Substances 0.000 abstract description 17
- 238000003487 electrochemical reaction Methods 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 162
- 238000005259 measurement Methods 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 14
- 230000008859 change Effects 0.000 description 13
- 239000000758 substrate Substances 0.000 description 12
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910002090 carbon oxide Inorganic materials 0.000 description 3
- 230000000875 corresponding effect Effects 0.000 description 3
- 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
- 229910003480 inorganic solid Inorganic materials 0.000 description 3
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000011245 gel electrolyte Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 235000006693 Cassia laevigata Nutrition 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101100033673 Mus musculus Ren1 gene Proteins 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 241000735631 Senna pendula Species 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229940124513 senna glycoside Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Measuring Oxygen Concentration In Cells (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、電気化学式ガスセンサに関し、詳しくは、
電気化学反応を利用して、大気中のガス等を検出するガ
スセンサに関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an electrochemical gas sensor.
The present invention relates to a gas sensor that detects gases in the atmosphere using electrochemical reactions.
電気化学反応を利用したガスセンサの基本的な構造とし
ては、複数の電極をイオン伝導体すなわち電解質でつな
いで電気化学的な反応を起こさせるようになっている。The basic structure of a gas sensor that utilizes an electrochemical reaction is to connect multiple electrodes with an ion conductor, ie, an electrolyte, to cause an electrochemical reaction.
イオン伝導体の材料としては、従来、液体電解質やゲル
状電解質を用いていたが、液漏れや溶媒の蒸発が生じる
ために、センサの耐久性や信頼性に劣るという問題があ
った。Conventionally, liquid electrolytes or gel electrolytes have been used as materials for ion conductors, but this has resulted in problems such as poor sensor durability and reliability due to liquid leakage and solvent evaporation.
このような問題点を解決するために、無機あるいは有機
の固体電解質を用いたガスセンサの開発が進められた。In order to solve these problems, gas sensors using inorganic or organic solid electrolytes have been developed.
無機物の固体電解質としては、β−アルミナ、ナシコン
、リシコン、安定化ジルコニア等がある、しかし、これ
らの無機物からなる固定電解質では、常温におけるイン
ピーダンスが高いため、常温ではイオンが伝導し難い状
態になる。したがって、一般には、前記のような無機物
固体電解質は加熱してインピーダンスが低い状態にして
利用するが、このことはガスセンサの消費電力が大きく
なることを意味しており、実用上好ましくない。Examples of inorganic solid electrolytes include β-alumina, Nasicon, Risicon, and stabilized zirconia.However, fixed electrolytes made of these inorganic substances have high impedance at room temperature, making it difficult for ions to conduct at room temperature. . Therefore, in general, the inorganic solid electrolyte as described above is heated to have a low impedance before use, but this means that the power consumption of the gas sensor increases, which is not practical.
有機物の固体電解質としては、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等
のカチオン交換樹脂に属するポリマーがある。これらの
樹脂のうち、パーフルオロスルホネートポリマーが、実
用的に最も適したものとして広く使用されており、例え
ば、ナフィオン（商品名、デュポン社製）と呼ばれるも
のがある。Examples of organic solid electrolytes include polymers belonging to cation exchange resins such as polystyrene sulfonate, polyvinyl sulfonate, perfluorosulfonate polymer, and perfluorocarboxylate polymer. Among these resins, perfluorosulfonate polymers are widely used as the most suitable for practical use, and for example, there is one called Nafion (trade name, manufactured by DuPont).
上記パーフルオロスルホネートポリマーが好ましい理由
は、カチオンの解離度が大きいこと、すなわちインピー
ダンスが小さいこと、あるいは、熱的、電気化学的に比
較的安定であること等である。また、パーフルオロスル
ホネートポリマーは、溶媒に可溶であるため、溶液をキ
ャスティングすることによって、絶縁基板や電極の上に
容易にパーフルオロスルホネートポリマーからなる固体
電解質層を形成することができる。このことは、ガスセ
ンサの製造が容易であることを意味している。The reason why the perfluorosulfonate polymer is preferable is that it has a large degree of cationic dissociation, that is, has a small impedance, or is relatively stable thermally and electrochemically. Further, since the perfluorosulfonate polymer is soluble in a solvent, a solid electrolyte layer made of the perfluorosulfonate polymer can be easily formed on an insulating substrate or an electrode by casting a solution. This means that the gas sensor is easy to manufacture.
上記のようなパーフルオロスルホネートポリマーを電解
質に用いた電気化学式ガスセンサでは、パーフルオロス
ルホネートポリマーの物性値が、温度や湿度等の環境条
件に依存して大きく変動し、また、経時的にも変化する
。そのため、センサの感度にも、環境条件による変動や
経時変化を生し、正確な検出結果が得られないという問
題があった。In the electrochemical gas sensor using a perfluorosulfonate polymer as an electrolyte as described above, the physical properties of the perfluorosulfonate polymer vary greatly depending on environmental conditions such as temperature and humidity, and also change over time. . Therefore, the sensitivity of the sensor also fluctuates due to environmental conditions and changes over time, making it difficult to obtain accurate detection results.
すなわち、電極間をつなく電解質であるパーフルオロス
ルホネートポリマーのインピーダンスやガス透過性等の
物性値は、ガスセンサの感度に非常に大きな影響を与え
るため、環境条件や経時による物性の変動が、そのまま
センサ感度の変化となって表れるのである。In other words, the impedance, gas permeability, and other physical properties of the perfluorosulfonate polymer that connects the electrodes and serves as the electrolyte have a very large effect on the sensitivity of the gas sensor. This appears as a change in sensitivity.
しかし、ガスセンサとしては、前記のような温度や湿度
の変動あるいは時間の経過に関わらず、一定濃度のガス
に対して常に一定の感度を示さなければ、正確な検知情
報が得られず、センサとしての機能を充分に果たすこと
が出来ない。そのため、環境条件や経時によるセンｆ感
度の変化を補正して、正確な検出結果が得られるように
することが望まれていた。However, a gas sensor must always exhibit a constant sensitivity to a constant concentration of gas, regardless of changes in temperature and humidity or the passage of time, in order to obtain accurate detection information. unable to fully perform its functions. Therefore, it has been desired to correct changes in sensor f sensitivity due to environmental conditions and time so that accurate detection results can be obtained.
そこで、本願発明者らは、センサ内にガスセンサ素子と
は別に湿度センサを組み込んで、湿度変化に対する感度
補正ができるようにした電気化学式ガスセンサを発明し
、先に特願平２−７９８０４号にて特許出願している。Therefore, the inventors of the present invention have invented an electrochemical gas sensor in which a humidity sensor is incorporated in the sensor separately from the gas sensor element, and the sensitivity can be corrected for changes in humidity. A patent application has been filed.
しかし、このセンサの場合、ガスセンサ素子とは構造や
動作の異なる湿度センサを組み込んでいるために、制御
回路等の構造が複雑になって、センサ全体の外形寸法も
大きくなり、コストが高くつく問題がある。また、湿度
によるセンサ感度の変動は補正できるが、湿度以外の温
度その他の環境条件に対する感度補正はできない。However, since this sensor incorporates a humidity sensor that has a different structure and operation than the gas sensor element, the structure of the control circuit etc. becomes complicated, the external dimensions of the entire sensor become large, and the cost becomes high. There is. Further, although fluctuations in sensor sensitivity due to humidity can be corrected, sensitivity cannot be corrected for temperature and other environmental conditions other than humidity.
なお、異なる環境条件毎に、それぞれの環境条件の変動
を検知するセンサを組み込んでおけば、それぞれの環境
条件に対する感度補正ができるが、環境条件の数だけ異
なるセンサを組み込むのでは、センサの構造が極めて複
雑になり、コストも非常に高くつくことになる。Note that if you incorporate a sensor that detects changes in each environmental condition for each different environmental condition, you can correct the sensitivity for each environmental condition, but if you incorporate as many different sensors as the number of environmental conditions, the structure of the sensor would be extremely complex and costly.
さらに、従来のガスセンサでは、センサ素子の経時的な
感度変化を補正することはできながった環境条件の変動
または経時に伴う電解質の特性変化によるセンサの感度
補正が必要なのは、前記したパーフルオロスルホネート
ポリマーを用いた場合だけでなく、各種の固体電解質あ
るいは液体電解質を用いた場合でも同様である。Furthermore, with conventional gas sensors, it is not possible to compensate for changes in the sensitivity of the sensor element over time.It is necessary to correct the sensor sensitivity due to changes in environmental conditions or changes in electrolyte characteristics over time. The same applies not only when using a sulfonate polymer but also when using various solid electrolytes or liquid electrolytes.
そこで、この発明の課題は、環境条件の変動および経時
に対する感度補正を、簡単かつ確実に行うことができる
電気化学式ガスセンサを提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide an electrochemical gas sensor that can easily and reliably correct sensitivity to changes in environmental conditions and over time.
上記課題を解決する、この発明にかがる電気化学式ガス
センサは、複数の電極を電解質でつないで検知作用を行
わせる電気化学式ガスセンサにおいて、一つの素子内に
、使用環境に一定の濃度で存在する基準ガスを検知する
１組の電極および電解質からなる基準ガス検知部と、検
知対象となる対象ガスを検知する１組の電極および電解
質がらなる対象ガス検知部とを備え、さらに、基準ガス
検知部の出力信号をもとに対象ガス検知部の出力信号を
補正する感度補正手段を備えている。The electrochemical gas sensor according to the present invention, which solves the above problems, is an electrochemical gas sensor in which a plurality of electrodes are connected with an electrolyte to perform a detection action. A reference gas detection section comprising a set of electrodes and an electrolyte for detecting a reference gas; and a target gas detection section comprising a set of electrodes and an electrolyte for detecting a target gas to be detected; The sensor includes a sensitivity correction means for correcting the output signal of the target gas detection section based on the output signal of the target gas detection section.
電極は、金、白金その他の通常の電極材料からなり、作
用極、対極、参照極等と呼ばれ、それぞれの機能に対応
した形状や配置構造を有する複数の電極を１組にして、
絶縁基板等の支持部材に支持させておく。そして、これ
らの電極の上およびその間をパーフルオロスルホネート
ポリマー等の高分子固体電解質あるいは無機固体電解質
で覆ったり、液体やゲル状の電解質と電極を接触させた
りして、電極同士が電解質でつながれた状態にしてガス
センサ素子を構成する。これらの、ガスセンサ素子の基
本的な構造については、従来の通常の電気化学式ガスセ
ンサと同様の構造が採用できる。Electrodes are made of ordinary electrode materials such as gold, platinum, etc., and are called working electrodes, counter electrodes, reference electrodes, etc., and are made up of multiple electrodes with shapes and arrangement structures corresponding to their respective functions.
It is supported by a support member such as an insulating substrate. Then, the electrodes are connected to each other by an electrolyte, by covering the tops and spaces between these electrodes with a solid polymer electrolyte such as perfluorosulfonate polymer or an inorganic solid electrolyte, or by bringing the electrodes into contact with a liquid or gel electrolyte. state to configure a gas sensor element. Regarding the basic structure of these gas sensor elements, the same structure as that of a conventional normal electrochemical gas sensor can be adopted.
この発明では、一つの素子内に、前記のような電極組か
らなる検知部を２組備えている。まず、基準ガス検知部
として、使用環境に一定の濃度で存在する基準ガスを検
知するための１組の電極を備えている。基準ガスとして
は、例えば、大気中で使用する場合には、酸素ガスが前
記のような条件を満たし、好ましいものとなるが、酸素
ガス以外の大気成分を用いることもでき、使用環境が違
えば、その環境に対応した基準ガスを選択すればよい。In this invention, one element is provided with two sets of detection sections each consisting of the above-mentioned electrode sets. First, the reference gas detection section includes a set of electrodes for detecting a reference gas present at a constant concentration in the usage environment. As a reference gas, for example, when used in the atmosphere, oxygen gas satisfies the above conditions and is preferable, but atmospheric components other than oxygen gas can also be used, and if the usage environment is different, , it is sufficient to select a reference gas that corresponds to the environment.
基準ガス検知部では、上記のような基準ガスを検知でき
るように、作用極と参照極の間にかける印加電圧等を設
定しておく。つぎに、対象ガス検知部として、検知対象
となる対象ガスを検知するための１組の電極を備えてい
る。検知対象となるガスは、−酸化炭素、アルコール、
硫化水素その他、各種のガスがあり、検知対象となるガ
スの種類に合わせて、作用極と参照極の間にかける印加
電圧等を設定しておく、基準ガス検知部と対象ガス検知
部は、感度特性が同一もしくはほぼ同等になるように、
電極や電解質の材料や構造を設定しておくことが好まし
い。そのためには、基準ガス検知部と対象ガス検知部と
が、全く同一の寸法形状および材料からなるものを用い
ればよいが、両方の感度特性に一定の相関関係があって
実質的に同等の感度特性が発揮できれば、それぞれの検
知部の機能や検知するガスの種類等に合わせて、電極の
材料等が一部異なるものを採用することもできる。In the reference gas detection section, the voltage applied between the working electrode and the reference electrode is set so that the reference gas as described above can be detected. Next, the target gas detection section includes a set of electrodes for detecting a target gas to be detected. Gases to be detected include - carbon oxide, alcohol,
There are various gases such as hydrogen sulfide, and the applied voltage between the working electrode and the reference electrode is set according to the type of gas to be detected.The reference gas detection part and the target gas detection part are So that the sensitivity characteristics are the same or almost the same,
It is preferable to set the materials and structures of the electrodes and electrolyte in advance. To this end, the reference gas detection section and the target gas detection section should be made of exactly the same size, shape, and material, but there is a certain correlation between the sensitivity characteristics of both, so that they have substantially the same sensitivity. As long as the characteristics can be exhibited, it is also possible to use electrodes with partially different materials depending on the function of each detection section, the type of gas to be detected, etc.
対象ガス検知部および基準ガス検知部には、通常の電気
化学式ガスセンサと同様に、電圧を印加する電源回路や
作用極と対極の間を流れる電流を検出する検出回路等か
らなる電子回路が接続される。これらの電子回路は、前
記したセンサ部分を形成する絶縁基板とは別の基板上に
形成しておき、リード線等でつないでもよいし、同一基
板上にセンサ部分と電子回路部分の両方を形成しておい
てもよい。The target gas detection section and the reference gas detection section are connected to an electronic circuit, which consists of a power supply circuit that applies voltage, a detection circuit that detects the current flowing between the working electrode and the counter electrode, etc., as in a normal electrochemical gas sensor. Ru. These electronic circuits may be formed on a separate substrate from the insulating substrate that forms the sensor portion described above and connected with lead wires, or both the sensor portion and the electronic circuit portion may be formed on the same substrate. You can leave it as is.
上記電子回路の一部に、基準ガス検知部の出力信号をも
とに対象ガス検知部の出力信号を補正する感度補正回路
を組み込んでおく等して感度補正手段を設けておく、感
度補正手段としては、対象ガス検知部の出力信号から環
境条件や経時の影響を除いて、対象ガスの正確な検知情
報を出力できるように信号を処理できれば、任意０電子
回路等で構成することができ、具体的には、予め基準ガ
ス検知部と対象ガス検知部の感度特性を測定して、基準
ガス検知部と対象ガス検知部の感度特性の相関関係を求
め、この相関関係をもとにして適切な感度補正が行われ
るように感度補正回路を設計しておけばよい。Sensitivity correction means is provided, such as by incorporating a sensitivity correction circuit that corrects the output signal of the target gas detection section based on the output signal of the reference gas detection section into a part of the electronic circuit. As long as the signal can be processed to output accurate detection information of the target gas by removing the effects of environmental conditions and aging from the output signal of the target gas detection unit, it can be configured with any electronic circuit, etc. Specifically, the sensitivity characteristics of the reference gas detection section and the target gas detection section are measured in advance, the correlation between the sensitivity characteristics of the reference gas detection section and the target gas detection section is determined, and the appropriate The sensitivity correction circuit may be designed in such a way that appropriate sensitivity correction can be performed.
電気化学式ガスセンサにおいては、ガス成分が作用極と
電解質との界面で電気化学反応を起こすことによって、
ガス成分を検出する。したがって、センナ感度が変化す
る原因としては、ガス成分が作用極と電解質の界面まで
到達する速度が変化すること、電気化学反応の反応速度
が変化すること、反応でできた生成物が対極まで移動す
る速度が変化すること等があり、これらの現象の発生や
その進行は、電極や電解質の構成によって決まってくる
。したがって、電極や電解質の構成をほぼ同じにしてお
く等により、基準ガス検知部の感度特性を対象ガズ検知
部の感度特性とほぼ同等にすることが可能である。この
ようにすれば、対象ガス検知部と基準ガス検知部は、種
々の環境条件の変動や経時に伴う−センサ感度の変化が
同じように生じる。言い換えれば、対象ガス検知部と基
準ガス検知部は、センサ感度の変化に一定の相関関係を
有することになる。In an electrochemical gas sensor, gas components cause an electrochemical reaction at the interface between the working electrode and the electrolyte, resulting in
Detect gas components. Therefore, the causes of changes in senna sensitivity are changes in the speed at which gas components reach the interface between the working electrode and electrolyte, changes in the reaction rate of the electrochemical reaction, and movement of reaction products to the counter electrode. The occurrence and progress of these phenomena are determined by the composition of the electrodes and electrolyte. Therefore, it is possible to make the sensitivity characteristics of the reference gas detection section substantially equivalent to the sensitivity characteristics of the target gas detection section by keeping the configurations of the electrodes and electrolyte substantially the same. In this way, the target gas detection section and the reference gas detection section undergo the same changes in sensor sensitivity due to changes in various environmental conditions and over time. In other words, the target gas detection section and the reference gas detection section have a certain correlation with respect to changes in sensor sensitivity.
基準ガス検知部では、使用環境に一定濃度で存在する基
準ガスを検知するので、この一定濃度の基準ガスに対す
る基準ガス検知部の出力信号を継続的に監視しておけば
、基準ガス検知部の出力信号は、センサ感度の変化を表
すことになり、環境条件や経時によってセンサ感度がど
のように変化するのかを知ることができる。基準ガス検
知部におけるセンサ感度の変化は、前記したように、対
象ガス検知部におけるセンサ感度の変化と相関関係があ
るので、基準ガス検知部における出力信号をもとにして
対象ガス検知部の出力信号を補正すれば、対象ガス検知
部の出力信号から、環境条件や経時によるセンサ感度の
変化の影響を取り除いて、対象ガスに対する正確な検知
情報を得ることができる。The reference gas detection unit detects a reference gas that exists at a constant concentration in the usage environment, so if you continuously monitor the output signal of the reference gas detection unit for this constant concentration of reference gas, the reference gas detection unit will detect the reference gas. The output signal represents the change in sensor sensitivity, and it is possible to know how the sensor sensitivity changes depending on environmental conditions and over time. As mentioned above, the change in sensor sensitivity in the reference gas detection section is correlated with the change in sensor sensitivity in the target gas detection section, so the output of the target gas detection section is determined based on the output signal in the reference gas detection section. By correcting the signal, it is possible to remove the effects of changes in sensor sensitivity due to environmental conditions and time from the output signal of the target gas detection unit, and to obtain accurate detection information for the target gas.
ついで、この発明の実施例について、図面を参照しなが
ら以下に詳しく説明する。Next, embodiments of the present invention will be described in detail below with reference to the drawings.
第１図および第２図は電気化学式ガスセンサの模式的構
造を示しており、絶縁基板１０の表面に、白金や金その
他の電極材料からなる複数組の電極が形成されている。1 and 2 schematically show the structure of an electrochemical gas sensor, in which multiple sets of electrodes made of platinum, gold, or other electrode material are formed on the surface of an insulating substrate 10.
すなわち、検知対象ガスを検知するための作用極２０、
対極３０および参照極４０の３本の矩形状電極からなる
対象ガス用の電極組と、この電極組と対称的に向かい合
うように配置され、基準ガスである＠素を検知するため
の作用極５０、対極６０および参照極７０の３本の矩形
状電極からなる基準ガス用の電極組を備えている。電極
の形成はスパッタや蒸着等の通常の電極形成手段が利用
され、各電極の構造は通常のガスセンサと同様でよい。That is, a working electrode 20 for detecting the gas to be detected;
An electrode set for target gas consisting of three rectangular electrodes, a counter electrode 30 and a reference electrode 40, and a working electrode 50, which is arranged symmetrically to face this electrode set and is used to detect @element, which is a reference gas. , a counter electrode 60 , and a reference electrode 70 . The electrodes may be formed using a normal electrode forming method such as sputtering or vapor deposition, and the structure of each electrode may be the same as that of a normal gas sensor.
２組の電極２０〜４０と電極５０〜７０には、それぞれ
の上および間を覆って、パーフルオロスルホネートポリ
マー等からなる固体電解質Ｆｉｉ８０．８２が形成され
ている。固体電解質層８０と８２とは、互いに分離して
形成されている。固体電解質層８０．８２の材料や形成
手段は、通常のガスセンサと同様でよい、各電極２０〜
７０の一端は、固体電解質層８０．８２の外部まで延長
されて露出しており、外部回路への接続用端子部２２．
３２．４２．５２．６２．７２となっている。A solid electrolyte Fii80.82 made of perfluorosulfonate polymer or the like is formed over and between the two sets of electrodes 20-40 and electrodes 50-70. Solid electrolyte layers 80 and 82 are formed separately from each other. The materials and forming means for the solid electrolyte layers 80 and 82 may be the same as those for ordinary gas sensors.
One end of the solid electrolyte layer 80.82 is extended and exposed to the outside of the solid electrolyte layer 80.82, and is a terminal portion 22.70 for connection to an external circuit.
32.42.52.62.72.
このようにして、ひとつの絶縁基板１０上に、全く構造
の同じ基準ガス検知部Ｂと対象ガス検知部Ａとが並んで
設けられていることになる。In this way, the reference gas detection section B and the target gas detection section A, which have completely the same structure, are provided side by side on one insulating substrate 10.
対象ガス検知部Ａは、各端子部２２〜４２にリード線１
０２を介して検出回路部１００が接続されており、検出
回路部１００は感度補正回路部１２０に接続されている
。基準ガス検知部Ｂは、各端子部２２〜４２にリード線
１０４を介して検出回路部１１０が接続されており、検
出回路部１１０は前記感度補正回路部１２０に接続され
ている、検出回路部１００，１１０は、通常のガスセン
サと同様に、対象ガス検知部Ａおよび基準ガス検知部Ｂ
に電源を供給したり、作用極２０と対極３０または作用
極５０と対極６０の間を流れる電流を検知したりして、
得られた検出信号を感度補正回路部１２０へと出力する
。感度補正回路部１２０では、基準ガス検知部Ｂからの
出力信号をもとにして、対象ガス検知部Ａの出力信号を
補正し、環境条件や経時によるセンサ感度の変動の影響
を除いた対象ガスの正確な検知情報を出力する。感度補
正回路１２０は、各種計測装置やセン号装置に利用され
ているのと同様の適当な電子回路により構成されている
。The target gas detection section A has lead wires 1 to each terminal section 22 to 42.
The detection circuit section 100 is connected to the sensitivity correction circuit section 120 via the 02. The reference gas detection section B has a detection circuit section 110 connected to each terminal section 22 to 42 via a lead wire 104, and the detection circuit section 110 is connected to the sensitivity correction circuit section 120. 100 and 110 are a target gas detection section A and a reference gas detection section B, similar to a normal gas sensor.
or detecting the current flowing between the working electrode 20 and the counter electrode 30 or between the working electrode 50 and the counter electrode 60,
The obtained detection signal is output to the sensitivity correction circuit section 120. The sensitivity correction circuit section 120 corrects the output signal of the target gas detection section A based on the output signal from the reference gas detection section B, and corrects the output signal of the target gas detection section A to obtain a target gas excluding the influence of fluctuations in sensor sensitivity due to environmental conditions and time. Outputs accurate detection information. The sensitivity correction circuit 120 is constituted by an appropriate electronic circuit similar to that used in various measuring devices and sensor devices.
以上のような構造を有するガスセンサのセンサ作用を説
明する。検知対象ガスのガス成分は、対象ガス検知部Ａ
で、固体電解質層８０の表面から内部を透過して作用極
２０に到達し、ここで電気化学反応を起こす、対極３０
では、上記作用極２０と対になる反応が起きる。その結
果、作用極２０と対極３０の間に検知電流が流れて、ガ
ス成分の検知および定量が行える。参照極４０は、作用
極２０の電位を一定に維持するための基準としての機能
を果たす、すなわち、作用極２０の、電位を、検知対象
となるガス成分に対応して、一定の電位に維持しておく
ことによって、目的とする対象ガスのみを検知できるよ
うにする。このようなセンサ作用は、通常のガスセンサ
の場合と全く同様である。但し、対象ガス検知部Ａの出
力信号は、温度や湿度等の環境条件の変動あるいは経時
に伴うセンサ感度の変化の影響を含んでおり、このまま
では、対象ガスの正確な検知情報とは言えないついで、
センサの感度補正作用について説明する。基準ガス検知
部Ｂでは、固体電解質層８２の表面から内部を透過して
作用極５０に基準ガスである酸素が到達し、ここで電気
化学反応を起こす、対極６０は、上記作用極５０と対に
なる反応が起こり、作用極５０と対極６０の間に酸素検
知電流が流れるのである。なお、この基準ガス検知部Ｂ
では、作用極５０の電位を、参照極７０を基準にして、
酸素に対応する一定の電位に維持しておき、酸素のみを
検知できるようにしておく。すなわち、対象ガス検知部
Ａと基準ガス検知部Ｂでは、作用極２０と５０の電位設
定が異なるだけで、電気化学反応や検知電流が流れる原
理作用は全く同じである。このようにして得られた基準
ガス検知部Ａの出力信号にも、温度や湿度等の環境条件
の変動あるいは経時に伴うセンサ感度の変化の影響を含
んでいる。The sensor action of the gas sensor having the above structure will be explained. The gas component of the detection target gas is detected by the target gas detection part A.
The counter electrode 30 passes through the surface of the solid electrolyte layer 80 and reaches the working electrode 20, where an electrochemical reaction occurs.
Then, a reaction that is paired with the working electrode 20 occurs. As a result, a detection current flows between the working electrode 20 and the counter electrode 30, and gas components can be detected and quantified. The reference electrode 40 serves as a reference for maintaining the potential of the working electrode 20 constant, that is, it maintains the potential of the working electrode 20 at a constant potential corresponding to the gas component to be detected. By doing so, only the desired target gas can be detected. Such a sensor action is exactly the same as that of a normal gas sensor. However, the output signal of the target gas detection unit A includes the effects of changes in environmental conditions such as temperature and humidity, or changes in sensor sensitivity over time, so it cannot be said to be accurate detection information for the target gas as it is. Then,
The sensitivity correction effect of the sensor will be explained. In the reference gas detection section B, oxygen, which is a reference gas, passes through the interior from the surface of the solid electrolyte layer 82 and reaches the working electrode 50, where an electrochemical reaction occurs. The following reaction occurs, and an oxygen detection current flows between the working electrode 50 and the counter electrode 60. In addition, this reference gas detection part B
Now, the potential of the working electrode 50 is based on the reference electrode 70,
It is maintained at a constant potential corresponding to oxygen so that only oxygen can be detected. That is, the target gas detection section A and the reference gas detection section B differ only in the potential setting of the working electrodes 20 and 50, but the electrochemical reaction and the principle of flow of detection current are completely the same. The output signal of the reference gas detection unit A obtained in this manner also includes the influence of changes in environmental conditions such as temperature and humidity, or changes in sensor sensitivity over time.
酸素は、大気中に常に一定濃度で存在しているので、セ
ンサ感度の変化がなければ、基準ガス検知部Ｂでは常に
一定の検知電流すなわち出力信号が得られるはずである
。しかし、前記したように、基準ガス検知部Ｂのセンサ
感度は環境条件や経時によって変化するので、出力信号
も変化する。Since oxygen always exists in the atmosphere at a constant concentration, if there is no change in sensor sensitivity, the reference gas detection section B should always be able to obtain a constant detection current, that is, an output signal. However, as described above, the sensor sensitivity of the reference gas detection section B changes depending on environmental conditions and over time, so the output signal also changes.
すなわち、この基準ガス検知部Ｂにおける出力信号の変
化は、センサ感度の変化をそのまま表していることにな
る。したがって、基準ガス検知部Ｂにおける出力信号を
常時モニターしておき、この基準ガス検知部Ｂの出力信
号すなわちセンサ感度の変化量をもとにして、対象ガス
検知部Ａの出力信号を補正すれば、対象ガス検知部Ａの
出力信号からセンサ感度の変化の影響のみを取り除くこ
とができる。具体的には、例えば、対象ガス検知部Ａの
出力値から基準ガス検知部Ｂの出力値を差し引いたり、
基準ガス検知部Ｂの出力値に適当な係数をかけてから対
象ガス検知部Ａの出力値を割ったり差し引いたりする等
、適当な演算処理を行えばよく、このような演算処理を
前記感度補正回路１２０で実行させればよいのである。In other words, the change in the output signal from this reference gas detection section B directly represents the change in sensor sensitivity. Therefore, if the output signal of the reference gas detection section B is constantly monitored and the output signal of the target gas detection section A is corrected based on the output signal of the reference gas detection section B, that is, the amount of change in sensor sensitivity. , only the influence of changes in sensor sensitivity can be removed from the output signal of the target gas detection section A. Specifically, for example, subtracting the output value of the reference gas detection section B from the output value of the target gas detection section A,
Appropriate arithmetic processing such as multiplying the output value of the reference gas detection section B by an appropriate coefficient and then dividing or subtracting the output value of the target gas detection section A may be performed, and such arithmetic processing can be used for the sensitivity correction described above. It is sufficient if the circuit 120 executes it.
つぎに、上記した構造の電気化学式ガスセンサを製造し
て、環境条件の変動や経時に伴う感度変化を測定した結
果について説明する。Next, the results of manufacturing an electrochemical gas sensor having the above structure and measuring changes in sensitivity due to changes in environmental conditions and over time will be described.
一実施例１−
絶縁基板１０の材料として１０ｗ角のガラス板を用いた
。但し、基板と電極との密着性を上げるために、ガラス
板の上にスパッタリングで厚さ２０００人程度０ポリシ
リコン層を形成した。この絶縁基板ｌＯＯ上にスパッタ
リングで白金からなる作用極２０．５０、対極３０．６
０および参照極４０．７０を作製した。その後、パーフ
ルオロスルホネートポリマーを５重量％含む溶液を、各
電極２０〜７０および絶縁基板１０の上にキャスティン
グすることにより、厚さ３鶴の固体電解質層８０．８２
を形成した。Example 1 - A 10w square glass plate was used as the material for the insulating substrate 10. However, in order to improve the adhesion between the substrate and the electrodes, a polysilicon layer with a thickness of about 2,000 layers was formed on the glass plate by sputtering. A working electrode 20.50 and a counter electrode 30.6 made of platinum were sputtered onto this insulating substrate lOO.
0 and reference electrode 40.70 were prepared. Thereafter, a solution containing 5% by weight of perfluorosulfonate polymer is cast onto each of the electrodes 20 to 70 and the insulating substrate 10 to form a solid electrolyte layer 80.82 with a thickness of 3.
was formed.
このようにして製造されたセンサが、対象ガスに対する
センサ機能および感度補正機能を有していることを確認
するために、−酸化炭素と［に対するセンサ感度の変化
を測定した。In order to confirm that the sensor manufactured in this manner had a sensor function and a sensitivity correction function for the target gas, changes in sensor sensitivity for -carbon oxide and [ were measured.
測定には、第３図に示す試験装置を用いた。測定用チェ
ンバー９０内にガスセンサを収容し、各電極２０・・・
の端子部２２・・・をリード線９１を介して、対象ガス
検知部用と基準ガス検知部用のそれぞれのポテンショス
タンド９２．９３に接続した、各ポテンショスタンド９
２．９３には、それぞれレコーダ９４．９５が接続され
ている。The test device shown in FIG. 3 was used for the measurement. A gas sensor is housed in a measurement chamber 90, and each electrode 20...
The terminal portions 22... of the potentiometer stands 9 are connected to respective potentiometer stands 92 and 93 for the target gas detection section and the reference gas detection section via lead wires 91.
Recorders 94 and 95 are connected to 2 and 93, respectively.
上記のような試験装置を用い、−酸化炭素を検知する対
象ガス検知部Ａの作用極２０と参照極４０の間の印加電
圧を０．４５ Ｖに設定し、酸素を検知する基準ガス検
知部Ｂの作用極５０と参照極７０の間の印加電圧を一〇
、４Ｖに設定した。そして、基準ガス検知部Ｂの作用極
５０と対極６０の間を流れる＠素検知電流は、レコーダ
９５で常時監視した。また、チェンバー９０内の雰囲気
を、空気のみの状態から一酸化炭素を１１０００ｐｐ含
む空気に置き換え、その際に対象ガス検知部Ａの作用極
２０と対極３０の間を流れる一酸化炭素検知電流−をレ
コーダ９４で測定した。チェンバー９０内に一定時間毎
に一酸化炭素を供給したり、湿度や温度を様々に変えた
りしながら測定を繰り返した第４図は湿度を変化させた
場合の測定結果、第５図は温度を変化させた場合の測定
結果、第８図は経時変化を示す測定結果であり、何れの
場合も、対象ガス検知部Ａにおける一酸化炭素に対する
感度特性と、基準ガス検知部Ｂにおける酸素に対する感
度特性とは、同じような傾向を示しており一定の相関関
係があることが判る。上記試験における対象ガス検知部
Ａと基準ガス検知部Ｂの感度の比率等から感度補正係数
その他の条件を決めて感度補正回路部１２０を設計した
ところ１、環境条件や経時に関わらず、一定量の一酸化
炭素に対しては常に一定の出力信号が得られた。このこ
とから、基準ガス検知部Ｂの出力信号をもとにして、対
象ガス検知部Ａの出力信号を補正すれば、温度や湿度お
よび経時による感度変化の影響を除いた、対象ガスの正
確な検知情報を得られることが実証された。Using the test apparatus as described above, - set the applied voltage between the working electrode 20 and the reference electrode 40 of the target gas detection section A that detects carbon oxide to 0.45 V, and set the reference gas detection section that detects oxygen; The voltage applied between the working electrode 50 and the reference electrode 70 of B was set to 10.4V. The @element detection current flowing between the working electrode 50 and the counter electrode 60 of the reference gas detection section B was constantly monitored by the recorder 95. In addition, the atmosphere in the chamber 90 is changed from air only to air containing 11,000 pp of carbon monoxide, and at this time, the carbon monoxide detection current flowing between the working electrode 20 and the counter electrode 30 of the target gas detection section A is It was measured with a recorder 94. Measurements were repeated while supplying carbon monoxide into the chamber 90 at regular intervals and varying the humidity and temperature. Figure 4 shows the measurement results when the humidity was changed, and Figure 5 shows the measurement results when the temperature was changed. Figure 8 shows the measurement results when the change is made, and the measurement results show the change over time. In both cases, the sensitivity characteristics for carbon monoxide in the target gas detection section A and the sensitivity characteristics for oxygen in the reference gas detection section B are shown. It can be seen that they show similar trends and there is a certain correlation. The sensitivity correction coefficient and other conditions were determined from the sensitivity ratio of the target gas detection section A and the reference gas detection section B in the above test, and the sensitivity correction circuit section 120 was designed.1. A constant output signal was always obtained for carbon monoxide. Therefore, if the output signal of the target gas detection unit A is corrected based on the output signal of the reference gas detection unit B, it is possible to accurately detect the target gas, excluding the effects of sensitivity changes due to temperature, humidity, and time. It has been demonstrated that detection information can be obtained.
一実施例２−
前記実施例１において、基準ガス検知部Ｂにおける作用
極５０の材料として金を用いた以外は、実施例１と同様
の工程を経てガスセンサを製造した。Example 2 - A gas sensor was manufactured through the same steps as in Example 1 except that gold was used as the material for the working electrode 50 in the reference gas detection section B in Example 1.
このよ−うにして製造されたガスセンサについても、前
記実施例１と同様の測定を行った。第６図、第７図およ
び第９図にその測定結果を示している。実施例２の場合
は、実施例１に比べて基準ガス検知部Ｂの酸素に対する
センサ感度が低いが、感度変化の挙動は、対象ガス検知
部における一酸化炭素に対するセンサ感度の感度変化の
挙動と同様であり、このガスセンサの場合も、基準ガス
検知部Ｂの検知出力をもとにして感度補正できることが
判る。The gas sensor manufactured in this way was also subjected to the same measurements as in Example 1 above. The measurement results are shown in FIGS. 6, 7, and 9. In the case of Example 2, the sensor sensitivity of the reference gas detection section B to oxygen is lower than that of Example 1, but the behavior of the sensitivity change is similar to the behavior of the sensitivity change of the sensor sensitivity to carbon monoxide in the target gas detection section. Similarly, it can be seen that in the case of this gas sensor as well, the sensitivity can be corrected based on the detection output of the reference gas detection section B.
以上に述べた、この発明にかかる電気化学式ガスセンサ
によれば、通常のガスセンサと同様の対象ガス検知部に
加えて、使用環境に一定の濃度で存在する基準ガスを検
知する基準ガス検知部を備えていることにより、対象ガ
ス検知部の出力信号を感度補正し、環境条件や経時に伴
うセンサ感度の変化の影響を取り除いて、対象ガスの正
確な検知情報を得ることができる。しかも、基準ガス検
知部と対象ガス検知部の感度特性の間に相関関係のある
全ての環境条件に対して同時にかつ自動的に感度補正を
行うことが可能になる。その結果、使用環境や時間経過
に関わらず常に一定の感度を有し、環境依存性や経時変
化のない信頼性の高いガスセンサを提供できることにな
る。According to the electrochemical gas sensor of the present invention as described above, in addition to the target gas detection section similar to a normal gas sensor, it includes a reference gas detection section that detects a reference gas that is present at a constant concentration in the usage environment. By doing so, it is possible to correct the sensitivity of the output signal of the target gas detection unit, remove the influence of changes in sensor sensitivity due to environmental conditions and time, and obtain accurate detection information of the target gas. Furthermore, it becomes possible to simultaneously and automatically perform sensitivity correction for all environmental conditions in which there is a correlation between the sensitivity characteristics of the reference gas detection section and the target gas detection section. As a result, it is possible to provide a highly reliable gas sensor that always has a constant sensitivity regardless of the usage environment or the passage of time, and is free from environmental dependence and changes over time.
さらに、基準ガス検知部は、対象ガス検知部と同じ素子
内に設けられているので、基準ガス検知部を対象ガス検
知部と同し製造工程で同時に作製することが可能であり
、ガスセンサとは別に湿度セン号等を組み込むのに比べ
て、はるかに構造が簡単になり、製造が容易になって製
造コストも削減され、センサ装置全体を小型化すること
が可能になる。Furthermore, since the reference gas detection section is provided in the same element as the target gas detection section, it is possible to manufacture the reference gas detection section and the target gas detection section at the same time in the manufacturing process, and the gas sensor is Compared to incorporating a separate humidity sensor or the like, the structure is much simpler, manufacturing is easier, manufacturing costs are reduced, and the entire sensor device can be made smaller.
第１図はこの発明の実施例を示すガスセンサの全体構成
図、第２図は検知部の断面図、第３図はセンサ感度の試
験装置の概略構成図、第４図は湿度変化に対する測定結
果を示すグラフ図、第５図は温度変化に対する測定結果
を示すグラフ図、第６図は別の実施例の湿度変化に対す
る測定結果を示すグラフ図、第７図は温度変化に対する
測定結果を示すグラフ図、第８図および第９図はそれぞ
れ経時変化に対する測定結果を示すグラフ図である。
Ａ・・・対象ガス検知部 Ｂ・・・基準ガス検知部 １
０・・・絶縁基板 ２０，３０．４０．５０．６０゜７
０・・・電極 ８０．８２・・固体電解質 １００゜１
１０・・・検出回路部 １２０・・・感度補正回路部代
理人 弁理士 松 本 武 彦
第
図
第５図
温度（０Ｃ）
第７図
手続補正書（帥
１゜
事件の表示
４゜
１呵牛との謙系 特許辻傭１入
住 所 大阪府門真市大字門真１０４８番地名
称（５＆３）松下電工株式会社
代表者 ｆ懐□三好俊夫Fig. 1 is an overall configuration diagram of a gas sensor showing an embodiment of the present invention, Fig. 2 is a cross-sectional view of the detection section, Fig. 3 is a schematic configuration diagram of a sensor sensitivity testing device, and Fig. 4 is the measurement results for humidity changes. FIG. 5 is a graph showing measurement results for temperature changes. FIG. 6 is a graph showing measurement results for humidity changes of another example. FIG. 7 is a graph showing measurement results for temperature changes. 8 and 9 are graphs showing measurement results over time, respectively. A...Target gas detection section B...Reference gas detection section 1
0...Insulating substrate 20, 30.40.50.60°7
0...Electrode 80.82...Solid electrolyte 100°1
10... Detection circuit section 120... Sensitivity correction circuit section agent Patent attorney Takehiko Matsumoto Tono Kenkei Patent Tsuji Ren 1 Address 1048 Oaza Kadoma, Kadoma City, Osaka Name (5 & 3) Representative of Matsushita Electric Works Co., Ltd. f Kai □ Toshio Miyoshi
Claims (1)
電気化学式ガスセンサにおいて、一つの素子内に、使用
環境に一定の濃度で存在する基準ガスを検知する１組の
電極および電解質からなる基準ガス検知部と、検知対象
となる対象ガスを検知する１組の電極および電解質から
なる対象ガス検知部とを備え、さらに、基準ガス検知部
の出力信号をもとに対象ガス検知部の出力信号を補正す
る感度補正手段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. In an electrochemical gas sensor that performs a detection action by connecting multiple electrodes with an electrolyte, a reference gas detection device consists of a set of electrodes and an electrolyte that detects a reference gas that is present at a constant concentration in the usage environment within one element. and a target gas detection unit consisting of a set of electrodes and an electrolyte for detecting the target gas to be detected, and further corrects the output signal of the target gas detection unit based on the output signal of the reference gas detection unit. An electrochemical gas sensor characterized by being equipped with a sensitivity correction means.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2153564A JP2813423B2 (en) | 1990-06-11 | 1990-06-11 | Electrochemical gas sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2153564A JP2813423B2 (en) | 1990-06-11 | 1990-06-11 | Electrochemical gas sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0443951A true JPH0443951A (en) | 1992-02-13 |
| JP2813423B2 JP2813423B2 (en) | 1998-10-22 |
Family
ID=15565257
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2153564A Expired - Fee Related JP2813423B2 (en) | 1990-06-11 | 1990-06-11 | Electrochemical gas sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2813423B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5338430A (en) * | 1992-12-23 | 1994-08-16 | Minnesota Mining And Manufacturing Company | Nanostructured electrode membranes |
| JP2005069820A (en) * | 2003-08-22 | 2005-03-17 | Riken Keiki Co Ltd | Electrochemical gas detector |
| KR100497991B1 (en) * | 2002-07-29 | 2005-07-01 | 세주엔지니어링주식회사 | Portable gas detector and re-calibration method thereof |
-
1990
- 1990-06-11 JP JP2153564A patent/JP2813423B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5338430A (en) * | 1992-12-23 | 1994-08-16 | Minnesota Mining And Manufacturing Company | Nanostructured electrode membranes |
| KR100497991B1 (en) * | 2002-07-29 | 2005-07-01 | 세주엔지니어링주식회사 | Portable gas detector and re-calibration method thereof |
| JP2005069820A (en) * | 2003-08-22 | 2005-03-17 | Riken Keiki Co Ltd | Electrochemical gas detector |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2813423B2 (en) | 1998-10-22 |
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