JPH06242061A - Concentration cell type carbon dioxide gas sensor - Google Patents
Concentration cell type carbon dioxide gas sensorInfo
- Publication number
- JPH06242061A JPH06242061A JP50A JP4614393A JPH06242061A JP H06242061 A JPH06242061 A JP H06242061A JP 50 A JP50 A JP 50A JP 4614393 A JP4614393 A JP 4614393A JP H06242061 A JPH06242061 A JP H06242061A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- sensor
- concentration
- carbonate
- carbon dioxide
- 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.)
- Withdrawn
Links
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 54
- 239000001569 carbon dioxide Substances 0.000 title claims description 27
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 22
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000011159 matrix material Substances 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 82
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000005587 carbonate group Chemical group 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 229910052593 corundum Inorganic materials 0.000 abstract 3
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 3
- 239000007787 solid Substances 0.000 abstract 1
- 238000005259 measurement Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002228 NASICON Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007102 metabolic function Effects 0.000 description 1
- 239000011533 mixed conductor Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
Landscapes
- Measuring Oxygen Concentration In Cells (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、炭酸ガスや酸素ガス等
のガスの濃度を測定するに好適なガスセンサーに関する
ものであり、さらに詳細には、特殊な固体電解質を用
い、被測定ガスの濃淡電池を構成し、このセルの起電力
からガス濃度を測定、検出できる濃淡電池式ガスセンサ
ーに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas sensor suitable for measuring the concentration of a gas such as carbon dioxide gas or oxygen gas. More specifically, the present invention relates to a gas sensor which uses a special solid electrolyte to measure a gas to be measured. The present invention relates to a concentration cell type gas sensor that constitutes a concentration cell and can measure and detect gas concentration from the electromotive force of this cell.
【０００２】[0002]
【従来の技術】最近、各種ガス濃度を測定する技術の開
発が進められているが、このうち特に大気中の二酸化炭
素ガス濃度測定、室内環境制御、農工業プロセス、生体
表面の代謝機能の測定ならびに医療関係など多岐にわた
る分野において、二酸化炭素ガスセンサーの利用が増大
してきている。従来の二酸化炭素ガスセンサーには、赤
外線吸収式（光学的測定法）、湿式（電解法）、半導
体、セラミックス（アルカリイオン導電体、ペロブスカ
イト型酸化物）を用いたものなどがあるが、これらは何
れも一長一短があり、特に水蒸気に対する影響が少ない
二酸化炭素ガスセンサーにはまだ満足すべきものがな
い。2. Description of the Related Art Recently, a technique for measuring various gas concentrations has been developed. Among them, particularly, measurement of carbon dioxide gas concentration in the atmosphere, indoor environment control, agricultural and industrial processes, and measurement of metabolic functions on living body surfaces. In addition, the use of carbon dioxide gas sensors is increasing in various fields such as medical fields. Conventional carbon dioxide gas sensors include those using infrared absorption type (optical measurement method), wet type (electrolysis method), semiconductor, ceramics (alkali ion conductor, perovskite type oxide). All of them have advantages and disadvantages, and there is still no satisfactory carbon dioxide gas sensor that has little influence on water vapor.
【０００３】[0003]
【発明が解決しようとする課題】例えば、光学的な測定
方法では赤外線吸収を利用するため、ガスを検知するセ
ンサー部分に塵や埃あるいは油分などが付着し汚染され
ていると正確なガス濃度が測定できない。このため、セ
ンサー部には測定ガス雰囲気中のダスト、水分などを除
去するための装置が必要であり、小型、軽量化が困難で
ある。かつ価格も高価である。ＮＡＳＩＣＯＮのような
炭酸塩以外のアルカリイオン導電体を用いた二酸化炭素
ガスセンサーは、ガス検知に使用している炭酸ナトリウ
ムが雰囲気中の水分を吸収しやすい性質を持っている。
このため、センサーを室温に放置したままにすると、検
知極が加水分解を起こし、正確な二酸化炭素の検知が行
えなくなる欠点がある。また、作動温度が５００℃以上
と高い。For example, since the optical measurement method uses infrared absorption, if the dust or dirt or oil adheres to the sensor portion for detecting gas, the accurate gas concentration will not be obtained. I can't measure. For this reason, the sensor unit needs a device for removing dust, water, and the like in the measurement gas atmosphere, and it is difficult to reduce the size and weight. And the price is expensive. A carbon dioxide gas sensor using an alkaline ion conductor other than carbonate such as NASICON has a property that sodium carbonate used for gas detection easily absorbs moisture in the atmosphere.
For this reason, if the sensor is left at room temperature, the detection electrode hydrolyzes, which makes it impossible to accurately detect carbon dioxide. Moreover, the operating temperature is as high as 500 ° C. or higher.
【０００４】ペロブスカイト型酸化物を用いた容量型Ｃ
Ｏ2 センサ〔第１３回化学センサシンポジウム要旨（１
９９１）１７３−１７６〕は、水蒸気の存在するガス下
よりも乾燥ガス下での使用が望まれている。また、プロ
トン−酸化物イオン混合導電体を用いたＣＯ2 センサ
も、被検ガス中の水蒸気の影響が問題として残されてい
る〔第１４回化学センサシンポジウム要旨（１９９２）
１０５−１０８〕。さらに半導体を用いたものは、二酸
化炭素ガス以外のイオンまで検知することがあり、測定
精度の点で問題が残されている（特開昭５６−２５４６
号公報参照）。そこで、本発明は上記問題を解決するた
めに、雰囲気中の共存ガス（例えば水蒸気）によって影
響を受けず、低温でも作動可能であり、小型、軽量化の
ほか装置の消費電力も少ない二酸化炭素ガス検出に好適
な濃淡電池式二酸化炭素ガスセンサーを提供するもので
ある。Capacitance type C using perovskite type oxide
O 2 sensor [Summary of the 13th Chemical Sensor Symposium (1
991) 173-176] is desired to be used under a dry gas rather than under a gas containing water vapor. In addition, a CO 2 sensor using a proton-oxide ion mixed conductor also has a problem that the influence of water vapor in the test gas remains a problem [14th Chemical Sensor Symposium Abstract (1992)]
105-108]. Further, in the case of using a semiconductor, even ions other than carbon dioxide gas may be detected, and a problem remains in terms of measurement accuracy (JP-A-56-2546).
(See Japanese Patent Publication). Therefore, in order to solve the above problems, the present invention is a carbon dioxide gas that is not affected by a coexisting gas (for example, water vapor) in the atmosphere, can operate at a low temperature, is small in size and lightweight, and consumes less power for the device. A concentration cell type carbon dioxide gas sensor suitable for detection is provided.
【０００５】[0005]
【課題を解決するための手段】このため本発明は、濃淡
電池式二酸化炭素ガスセンサーにおいて、センサーのセ
ルを構成する固体電解質材料としてアルミナ混合炭酸リ
チウムを用いたことを特徴とするものであり、さらに前
記固体電解質材料は炭酸リチウムをマトリックスとし、
リチウムの価数と異なる金属イオンの炭酸塩、また、炭
酸基と価数の異なる酸素酸基をもつリチウム塩を一種あ
るいは複数種添加した物質にアルミナを混合したもので
ある。Therefore, the present invention is characterized in that, in a concentration cell type carbon dioxide gas sensor, alumina-mixed lithium carbonate is used as a solid electrolyte material constituting a cell of the sensor, Furthermore, the solid electrolyte material has lithium carbonate as a matrix,
It is a mixture of alumina and a substance obtained by adding one or more kinds of carbonates of metal ions having different valences of lithium, and lithium salts having oxygen acid groups having different valences from carbonate groups.
【０００６】[0006]
【作用】本発明では、アルカリ炭酸塩をマトリックスと
した物質にアルミナを混合した固体電解質を用いる。そ
の固体電解質の両面に多孔質Ａｕペースト電極２を形成
し、その表面にＡｕメッシュの集電体３とＡｕリード線
４を接続してセルを構成する。このセルをアルミナ管５
に装着し、高温接着剤によってガスシール６する。アル
ミナ管の内側には、基準ガスを流し、外側には被検ガス
を流すことで濃淡電池を構成する。ガス濃度は、両電極
上の二酸化炭素濃度の違いを起電力の差として取り出
し、測定する。In the present invention, a solid electrolyte prepared by mixing alumina with a substance having an alkali carbonate as a matrix is used. Porous Au paste electrodes 2 are formed on both surfaces of the solid electrolyte, and an Au mesh current collector 3 and an Au lead wire 4 are connected to the surfaces to form a cell. Alumina tube 5
And gas seal 6 with a high temperature adhesive. A concentration gas is formed by flowing a reference gas inside the alumina tube and a test gas outside. The gas concentration is measured by extracting the difference in carbon dioxide concentration on both electrodes as the difference in electromotive force.
【０００７】[0007]
【実施例】以下図面を参照して本発明に係わる濃淡電池
式二酸化炭素ガスセンサーを説明をする。 〔センサーの構成〕図１において１は固体電解質（詳細
は後述する）、２はＡｕぺースト、３はＡｕメッシュ、
４はＡｕリード線、５はアルミナ管、６はガスシール材
であり、これらによって濃淡電池式二酸化炭素ガスセン
サーが構成されている。固体電解質１の両面には多孔質
Ａｕペースト電極２が形成され、その表面にＡｕメッシ
ュの集電体３とＡｕリード線４が図のように接続されて
いる。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A concentration cell type carbon dioxide gas sensor according to the present invention will be described below with reference to the drawings. [Structure of Sensor] In FIG. 1, 1 is a solid electrolyte (details will be described later), 2 is Au paste, 3 is Au mesh,
4 is an Au lead wire, 5 is an alumina tube, and 6 is a gas sealing material, and these constitute a concentration battery type carbon dioxide gas sensor. Porous Au paste electrodes 2 are formed on both surfaces of the solid electrolyte 1, and an Au mesh current collector 3 and an Au lead wire 4 are connected to the surface thereof as shown in the figure.
【０００８】このセルをアルミナ管５に装着し、高温接
着剤によってガスシール６する。アルミナ管の内側に
は、酸素ガスと炭酸ガス分圧を制御したガスを流すか、
平衡酸素分圧と、炭酸ガス分圧が一義的に決定される酸
化物混合の炭酸塩を検知電極上に設ける。外側には被検
ガスを流すことで濃淡電池を構成する。ＣＯ2 濃度は、
濃淡電池の原理を利用して上記センサーの起電力から求
めることができる。This cell is attached to an alumina tube 5 and a gas seal 6 is made with a high temperature adhesive. Inside the alumina tube, a gas with a controlled partial pressure of oxygen gas and carbon dioxide gas, or
An equilibrium oxygen partial pressure and an oxide-mixed carbonate whose carbon dioxide partial pressure is uniquely determined are provided on the detection electrode. A concentration cell is constructed by flowing a test gas outside. CO 2 concentration is
It can be obtained from the electromotive force of the above-mentioned sensor by utilizing the principle of the concentration cell.
【０００９】〔固体電解質の作製〕本発明では、上記の
構成のセンサーに使用する固体電解質として、アルカリ
炭酸塩をマトリックスとした物質にアルミナを混合した
固体電解質を用いた点に特徴がある。炭酸リチウムは他
の金属炭酸塩（例えばＮａ2 ＣＯ3 ，Ｋ2 ＣＯ3 等）に
比べて水との親和性が小さいため、水蒸気存在下におい
ても炭酸塩として融点近くまで安定に存在することがで
きる。また炭酸塩を電解質とするため酸素以外の共存ガ
スの影響を受けにくく、二酸化炭素ガス濃度の変化を的
確に捕らえることができる。さらに、請求項２の金属塩
とアルミナを炭酸リチウムに添加することによって、固
体電解質自身の抵抗を小さくすることができるので、二
酸化炭素ガスセンサーの低温作動化が可能となる。ま
た、アルミナを均一に分散させることによって、固体電
解質の機械的強度を高めることができるので、センサー
素子の小型化が可能になる等々の優れた特性を有してい
る。[Production of Solid Electrolyte] The present invention is characterized in that a solid electrolyte obtained by mixing alumina with a substance having an alkali carbonate as a matrix is used as the solid electrolyte used in the sensor having the above-mentioned configuration. Lithium carbonate has a smaller affinity for water than other metal carbonates (for example, Na 2 CO 3 , K 2 CO 3 etc.), so that it may exist stably as a carbonate up to its melting point even in the presence of water vapor. it can. Further, since the carbonate is used as the electrolyte, it is hardly affected by the coexisting gas other than oxygen, and the change in the carbon dioxide gas concentration can be accurately captured. Furthermore, by adding the metal salt and alumina of claim 2 to lithium carbonate, the resistance of the solid electrolyte itself can be reduced, so that the carbon dioxide gas sensor can be operated at a low temperature. Further, since the mechanical strength of the solid electrolyte can be increased by uniformly dispersing the alumina, the sensor element has excellent properties such as downsizing of the sensor element.
【００１０】上記センサーで使用する固体電解質の作製
方法を説明すると、乾燥したＬｉ2ＣＯ3 ，Ｌｉ3 ＰＯ
4 ，Ａｌ2 Ｏ3 各粉末を準備し、それぞれ秤量後、アル
ミナ乳鉢で混合する。これをアルミナるつぼに入れ、溶
融させたのち、内径１１mm、高さ１０mmのセラミックス
容器に流し込み、急冷固化させる。大気中で放冷後、容
器から電解質を取出し、厚さ３mm以下に切出す。その
後、所望の形状に加工する。これを１０００番のエメリ
ー紙で研磨、エタノールで洗浄し、固体電解質とする。The method for preparing the solid electrolyte used in the above sensor will be described. Dry Li 2 CO 3 , Li 3 PO
4 , Al 2 O 3 powders are prepared, weighed, and then mixed in an alumina mortar. This is put into an alumina crucible, melted, poured into a ceramics container having an inner diameter of 11 mm and a height of 10 mm, and rapidly cooled and solidified. After left to cool in the air, take out the electrolyte from the container and cut it to a thickness of 3 mm or less. After that, it is processed into a desired shape. This is polished with No. 1000 emery paper and washed with ethanol to obtain a solid electrolyte.
【００１１】〔二酸化炭素ガスの測定例）図２に上記セ
ンサーの起電力のＣＯ2 ガス濃度依存性及び温度依存性
を示す。固体電解質はＬｉ2 ＣＯ3 −５ｍｏｌ％Ｌｉ3
ＰＯ4 ＋２５ｗｔ％Ａｌ2 Ｏ3 を用いた。センサーの作
動温度は摂氏４００度および５００度、アルミナ管の内
側に基準ガスとしてＮ2 −２１％Ｏ2 −９７４ｐｐｍＣ
Ｏ2 の乾燥ガスを導入した。被検ガスはＮ2 −２１％Ｏ
2 −９７４ｐｐｍＣＯ2 ガスをＮ2 −２１％Ｏ2 で希釈
して用いた。起電力は、被検ガス中のＣＯ2 ガス濃度が
低くなるに従って増加する。作動温度が高ければ起電力
はさらに増加する。なお、基準のＣＯ2 ガス濃度を変え
ることによって、センサーのＣＯ2 ガス濃度測定精度、
ＣＯ2 ガス濃度検出領域を設定することが可能である。[Measurement Example of Carbon Dioxide Gas] FIG. 2 shows the dependence of the electromotive force of the sensor on the CO 2 gas concentration and the temperature. The solid electrolyte is Li 2 CO 3 -5 mol% Li 3
PO 4 +25 wt% Al 2 O 3 was used. Operating temperature of the sensor is 400 ° and 500 ° C, N 2 -21% as the reference gas inside the alumina tube O 2 -974ppmC
A dry gas of O 2 was introduced. The gas to be detected is N 2 -21% O
2 -974ppmCO 2 gas was used diluted with N 2 -21% O 2. The electromotive force increases as the CO 2 gas concentration in the test gas decreases. If the operating temperature is high, the electromotive force will increase further. By changing the standard CO 2 gas concentration, the sensor's CO 2 gas concentration measurement accuracy,
It is possible to set the CO 2 gas concentration detection region.
【００１２】図３に被検ガスが乾燥ガスと水分を含むガ
スとにおけるセンサーの応答速度を示す。乾燥ガスでは
定常起電力の９０％まで達するのにかかる時間は、ガス
を導入してから１分以内である。被検ガス中に水分が含
まれると応答時間は乾燥ガスに比べて遅くなる。しかし
ながら、起電力は殆ど変化しない。このため、応答時間
の遅れを見込んで被検ガスを測定すれば、被検ガス中の
水分には影響を受けずにＣＯ2 ガス濃度を測定できる。FIG. 3 shows the response speed of the sensor when the test gas is a dry gas and a gas containing water. With dry gas, the time required to reach 90% of the steady electromotive force is within 1 minute after introducing the gas. If the test gas contains water, the response time becomes slower than that of the dry gas. However, the electromotive force hardly changes. Therefore, if the test gas is measured in anticipation of a delay in response time, the CO 2 gas concentration can be measured without being affected by the water content in the test gas.
【００１３】図４に水蒸気分圧依存性を示す。この図か
ら明らかなように、本実施例では被検ガス中の水蒸気分
圧が変化しても起電力には変化がなかった。これより、
被検ガス中の水蒸気の影響を受けないセンサーとなって
いる。なお、本発明では、基準ガスおよび被検ガス中の
Ｏ2 ガス濃度を一致させることによって、ＣＯ2 ガス濃
度を測定しているが、同じ構成のセンサーで酸素ガス濃
淡電池を構成すれば酸素ガスセンサーとしても機能を果
たす。FIG. 4 shows the water vapor partial pressure dependency. As is clear from this figure, in this example, the electromotive force did not change even if the partial pressure of water vapor in the test gas changed. Than this,
The sensor is not affected by water vapor in the test gas. In the present invention, the CO 2 gas concentration is measured by matching the O 2 gas concentrations in the reference gas and the test gas. However, if the oxygen gas concentration cell is configured with the same sensor, the oxygen gas concentration gas is It also functions as a sensor.
【００１４】[0014]
【発明の効果】以上詳細に説明したように本発明によれ
ば、アルカリ炭酸塩をマトリックスとした物質にアルミ
ナを混合した固体電解質を用い、被検出ガスの濃淡電池
を構成し、このセルの起電力からガス濃度を測定、検出
するものである。このため耐水蒸気性の小型、低温作動
型濃淡電池式ガスセンサーを作製することが可能であ
る。特に本発明において使用する炭酸リチウムは、他の
金属炭酸塩（例えばＮａ2ＣＯ3 ，Ｋ2 ＣＯ3 等）に比
べて水との親和性が小さいため、水蒸気存在下におても
炭酸塩として融点近くまで安定に存在することができ、
さらに炭酸塩を電解質とするため酸素以外の共存ガスの
影響を受けにくく、二酸化炭素ガス濃度の変化を的確に
捕らえることができる。固体電解質自身の抵抗を小さく
することもできるので、濃淡電池式二酸化炭素ガスセン
サーの低温作動化が可能となる。また、アルミナを均一
に分散させることによって、固体電解質の機械的強度を
高めることができるので、センサー素子の小型化が可能
になる。等々のすぐれた効果を上げることができる。As described above in detail, according to the present invention, a solid electrolyte in which alumina is mixed with a substance having an alkali carbonate as a matrix is used to form a concentration battery for a gas to be detected, and the concentration of this cell is increased. It measures and detects gas concentration from electric power. Therefore, it is possible to manufacture a small-sized, low-temperature operation type concentration cell type gas sensor having steam resistance. Particularly, the lithium carbonate used in the present invention has a smaller affinity for water than other metal carbonates (for example, Na 2 CO 3 , K 2 CO 3 etc.), so that it can be used as a carbonate even in the presence of steam. Can exist stably up to near the melting point,
Furthermore, since carbonate is used as an electrolyte, it is less affected by coexisting gases other than oxygen, and it is possible to accurately capture changes in carbon dioxide gas concentration. Since the resistance of the solid electrolyte itself can be reduced, the concentration cell type carbon dioxide gas sensor can be operated at a low temperature. Moreover, since the mechanical strength of the solid electrolyte can be increased by uniformly dispersing the alumina, the sensor element can be downsized. You can increase the excellent effect of etc.
【図１】本発明に係わる実施例としての濃淡電池式二酸
化炭素ガスセンサーの概略図である。FIG. 1 is a schematic view of a concentration cell type carbon dioxide gas sensor as an example according to the present invention.
【図２】本発明に係わる実施例としての濃淡電池式二酸
化炭素ガスセンサーのＣＯ2 ガス濃度依存性及び温度依
存性を示す作動特性図である。FIG. 2 is an operating characteristic diagram showing CO 2 gas concentration dependency and temperature dependency of a concentration cell type carbon dioxide gas sensor as an example according to the present invention.
【図３】本発明に係わる実施例としての濃淡電池式二酸
化炭素ガスセンサーの応答速度を示す作動特性図であ
る。FIG. 3 is an operating characteristic diagram showing a response speed of a concentration cell type carbon dioxide gas sensor as an example according to the present invention.
【図４】本発明に係わる実施例としての濃淡電池式二酸
化炭素ガスセンサーの水蒸気分圧依存性を示す作動特性
図である。FIG. 4 is an operating characteristic diagram showing the dependence of the concentration cell type carbon dioxide gas sensor as an example according to the present invention on the water vapor partial pressure.
１ 固体電解質 ２，２’ Ａｕぺースト ３，３’ Ａｕメッシュ ４，４’ Ａｕリード線 ５ アルミナ管 ６，６’ ガスシール材 1 Solid Electrolyte 2,2 'Au Paste 3,3' Au Mesh 4,4 'Au Lead Wire 5 Alumina Tube 6,6' Gas Sealing Material
Claims (2)
いて、センサーのセルを構成する固体電解質材料１とし
てアルミナ混合炭酸リチウムを用いたことを特徴とする
ガスセンサー。1. A concentration sensor type carbon dioxide gas sensor, characterized in that alumina mixed lithium carbonate is used as a solid electrolyte material 1 constituting a cell of the sensor.
マトリックスとし、リチウムの価数と異なる金属イオン
の炭酸塩、また、炭酸基と価数の異なる酸素酸基をもつ
リチウム塩を一種あるいは複数種添加した物質にアルミ
ナを混合したものであることを特徴とする請求項１に記
載のガスセンサー。2. The solid electrolyte material 1 uses lithium carbonate as a matrix, and a carbonate of a metal ion having a valence different from that of lithium, or one or more species of a lithium salt having an oxygen acid group having a valence different from that of a carbonate group. The gas sensor according to claim 1, wherein the added substance is a mixture of alumina and the added substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50A JPH06242061A (en) | 1993-02-12 | 1993-02-12 | Concentration cell type carbon dioxide gas sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50A JPH06242061A (en) | 1993-02-12 | 1993-02-12 | Concentration cell type carbon dioxide gas sensor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06242061A true JPH06242061A (en) | 1994-09-02 |
Family
ID=12738752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP50A Withdrawn JPH06242061A (en) | 1993-02-12 | 1993-02-12 | Concentration cell type carbon dioxide gas sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06242061A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5766433A (en) * | 1996-02-22 | 1998-06-16 | Akebono Brake Industry Co., Ltd. | Solid electrolyte type gas sensor |
-
1993
- 1993-02-12 JP JP50A patent/JPH06242061A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5766433A (en) * | 1996-02-22 | 1998-06-16 | Akebono Brake Industry Co., Ltd. | Solid electrolyte type gas sensor |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20000509 |