JP2002303602A - Method and instrument for solid electrolytic hydrogen/ steam measurement utilizing hydrogen pump - Google Patents
Method and instrument for solid electrolytic hydrogen/ steam measurement utilizing hydrogen pumpInfo
- Publication number
- JP2002303602A JP2002303602A JP2001104622A JP2001104622A JP2002303602A JP 2002303602 A JP2002303602 A JP 2002303602A JP 2001104622 A JP2001104622 A JP 2001104622A JP 2001104622 A JP2001104622 A JP 2001104622A JP 2002303602 A JP2002303602 A JP 2002303602A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- reference electrode
- measuring
- solid electrolyte
- electrode
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000001257 hydrogen Substances 0.000 title claims abstract description 87
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 87
- 238000005259 measurement Methods 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000007787 solid Substances 0.000 title claims 2
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 42
- 238000005086 pumping Methods 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims abstract 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 7
- 239000000446 fuel Substances 0.000 claims description 4
- 238000000691 measurement method Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 230000006870 function Effects 0.000 description 6
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 230000003915 cell function Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- -1 oxygen ions Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Fuel Cell (AREA)
- Measuring Oxygen Concentration In Cells (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はプロトン導電性をもつ固
体電解質を用いた水素及び水蒸気の測定方法と測定装置
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for measuring hydrogen and water vapor using a solid electrolyte having proton conductivity.
【０００２】[0002]
【従来の技術】プロトン導電性をもつ固体電解質を用い
た水素の測定方法としては、従来から水素濃淡電池を用
いる方法が知られている。たとえば、従来の水素濃淡電
池型水素ガス測定装置は、プロトン導電性をもつ固体電
解質の一方の面に基準電極を、背向する他方の面に測定
電極を設けて、基準電極側に水素ボンベなどの外部水素
源から水素を供給し基準電極側の水素分圧を一定に保つ
必要があった。すなわち、水素ガス測定装置の本体部は
固体電解質を用いて小型化できるが、外部水素源を必要
とするため、装置全体としては大型化し、可搬性に欠け
るとか、狭隈箇所への設置性に欠けるといった問題があ
った。2. Description of the Related Art As a method for measuring hydrogen using a solid electrolyte having proton conductivity, a method using a hydrogen concentration cell is conventionally known. For example, a conventional hydrogen concentration cell-type hydrogen gas measuring device is provided with a reference electrode on one surface of a solid electrolyte having proton conductivity, and a measurement electrode on the other surface opposite to the other, and a hydrogen cylinder or the like on the reference electrode side. It was necessary to supply hydrogen from an external hydrogen source and maintain a constant hydrogen partial pressure on the reference electrode side. In other words, the main body of the hydrogen gas measurement device can be miniaturized by using a solid electrolyte, but since it requires an external hydrogen source, the entire device becomes large and lacks portability or is difficult to install in narrow places. There was a problem of chipping.
【０００３】最近、図６に示すような水素ポンプ作用を
利用した外部水素源を必要としない水蒸気センサが Se
nsors and Actuators, B67, pp189-193(2000) に報告
された。これは二つのプロトン導電性固体電解質２０、
２４の背向する面に電極２２、２３及び２４、２５を設
けたセルをスペーサ２６を介してスタックし、スペーサ
２６と二つのセルで区画された領域３１が孔２７で外部
とつながった構造をしている。そして、電極２２、２３
には直流電源２８がリード線３０で接続され、電極２
４、２５には電位計２９がリード線３０で接続されてい
る。この水蒸気センサを水蒸気を含む空気中に配置する
と、上のセルの電極２２（アノード）では Ｈ2Ｏ（空気中の）→２Ｈ+＋ Ｏ2／2＋２ｅ- （１） なる反応が起きる。発生したプロトンは固体電解質２０
の中を通り電極２３に達する。電極２３(カソード)では ２Ｈ+＋２ｅ-→Ｈ2 (２) なる反応が起き、できた水素が区画領域３１に蓄えられ
る。すなわち、空気中から水素がポンプされて区画領域
３１の水素分圧が上昇し、区画領域３１が孔２７で外部
とつながっているので、水素１気圧で飽和する。この時
点で、下のセルは電極２４を基準電極とし、電極25を測
定電極とする水素―空気燃料電池として機能し、ネルン
ストの式（3）で表される起電力Ｅが電位計２９に発生
する。Recently, a steam sensor that does not require an external hydrogen source utilizing a hydrogen pump action as shown in FIG.
nsors and Actuators, B67, pp189-193 (2000). This consists of two proton conducting solid electrolytes 20,
A cell in which electrodes 22, 23 and 24, 25 are provided on the surface opposite to 24 is stacked via a spacer 26, and a region 31 defined by the spacer 26 and the two cells is connected to the outside by a hole 27. are doing. And the electrodes 22, 23
A DC power supply 28 is connected to the
An electrometer 29 is connected to 4 and 25 via a lead wire 30. When this water vapor sensor is placed in air containing water vapor, the electrode 22 (anode) of the upper cell has H 2 O (in air) → 2H ++ . O 2/2 + 2e - ( 1) comprising reaction occurs. The generated protons are solid electrolyte 20
To the electrode 23. At the electrode 23 (cathode), a reaction of 2H + + 2e − → H 2 (2) occurs, and the produced hydrogen is stored in the partitioned area 31. That is, hydrogen is pumped from the air to increase the partial pressure of hydrogen in the partitioned area 31, and the partitioned area 31 is connected to the outside through the hole 27, and is saturated at 1 atm of hydrogen. At this time, the lower cell functions as a hydrogen-air fuel cell using the electrode 24 as a reference electrode and the electrode 25 as a measurement electrode, and an electromotive force E represented by Nernst equation (3) is generated in the electrometer 29. I do.
【０００４】 E=(RT/2F)lnK+(RT/2F)ln[[PH2(1)PO2(2)1/2]/PH2O(2)] （３） ここで、Ｒは気体定数、Ｔは温度、Ｋは平衡定数、Ｆは
ファラデー定数、ＰＨ2（１）は基準電極２４側の水素
分圧、ＰＯ2（２）は測定電極２５側の酸素分圧、ＰＨ2
Ｏ（２）は測定電極25側の水蒸気分圧、である。（３）
式でＰＨ2（１）は１気圧一定であり、固体電解質２４
は酸素イオンを通さないので、起電力Eは測定電極２５
側の水蒸気分圧ＰＨ2Ｏ（２）でのみ変化することにな
り、水蒸気を測定することができる。しかし、この従来
の水蒸気センサは二つの固体電解質からなるセルと二つ
の回路（直流印加回路及び起電力測定回路）を必要と
し、複雑であり、小型化ができず高価であるといった問
題を有している。E = (RT / 2F) lnK + (RT / 2F) ln [[PH 2 (1) PO 2 (2) 1/2] / PH 2 O (2)] (3) where R is a gas Constant, T is temperature, K is equilibrium constant, F is Faraday constant, PH 2 (1) is hydrogen partial pressure on the reference electrode 24 side, PO 2 (2) is oxygen partial pressure on the measurement electrode 25 side, PH 2
O (2) is the partial pressure of water vapor on the measurement electrode 25 side. (3)
In the formula, PH 2 (1) is constant at 1 atm.
Does not pass oxygen ions, the electromotive force E is
It changes only with the partial pressure of water vapor PH 2 O (2) on the side, and water vapor can be measured. However, this conventional water vapor sensor requires a cell composed of two solid electrolytes and two circuits (a DC application circuit and an electromotive force measurement circuit), and has a problem that it is complicated, cannot be miniaturized, and is expensive. ing.
【０００５】[0005]
【本発明が解決しようとする課題】本発明は、外部水素
源及び二つの固体電解質からなるセルと二つの回路を必
要としないすなわち、一つのセルと一つの回路でよい小
型化・低コスト化に適した水素・水蒸気の測定方法及び
測定装置を提供することを目的とする。SUMMARY OF THE INVENTION The present invention does not require a cell comprising an external hydrogen source and two solid electrolytes and two circuits, that is, one cell and one circuit can be used for miniaturization and cost reduction. It is an object of the present invention to provide a method and a device for measuring hydrogen and water vapor which are suitable for water.
【０００６】[0006]
【課題を解決するための手段】上記課題を解決した本発
明に係る水素・水蒸気測定方法は、プロトン導電性をも
つ固体電解質とその一方の面に設けられた基準電極と他
方の面に設けられた測定電極との間で電池を形成して水
素又は水蒸気を測定する方法であって、前記基準電極と
前記測定電極の間に直流を印加して水素をポンプする第
１工程と、前記基準電極と前記測定電極の間の起電力を
測定する第２工程と、からなることを特徴とする。A method for measuring hydrogen and water vapor according to the present invention, which has solved the above-described problems, comprises a solid electrolyte having proton conductivity, a reference electrode provided on one surface thereof, and a reference electrode provided on the other surface. Forming a battery between the reference electrode and the measurement electrode to measure hydrogen or water vapor, wherein a first step of applying a direct current between the reference electrode and the measurement electrode to pump hydrogen, and the reference electrode And a second step of measuring an electromotive force between the measurement electrodes.
【０００７】上記課題を解決した本発明に係る水素・水
蒸気測定装置は、プロトン導電性をもつ固体電解質と、
該固体電解質の一方の面に設けられ且つ被測定雰囲気と
隔絶するシールドをもつ基準電極と、該基準電極と背向
する該固体電解質の他方の面に設けられ且つ被測定雰囲
気と接触する測定電極と、該基準電極と該測定電極に接
続された電圧印加手段及び起電力測定手段と、からなる
ことを特徴とする。[0007] The hydrogen / water vapor measuring device according to the present invention, which has solved the above-mentioned problems, comprises: a solid electrolyte having proton conductivity;
A reference electrode provided on one surface of the solid electrolyte and having a shield to isolate the atmosphere to be measured; and a measurement electrode provided on the other surface of the solid electrolyte opposite to the reference electrode and in contact with the atmosphere to be measured. And a voltage application unit and an electromotive force measurement unit connected to the reference electrode and the measurement electrode.
【０００８】[0008]
【発明の実施の形態】プロトン導電性をもつ固体電解質
は、ＳｒＣｅＯ3やＣａＺｒＯ3を母体とするペロブスカ
イト型で、ＣｅとＺｒの一部を希土類元素（Ｓｃ、Ｙ、
Ｌａ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｄｙ、Ｈｏ、Ｙｂ）か
らなる群から選択された一種以上の元素で１〜３０モル
％置換固溶されたものである。BEST MODE FOR CARRYING OUT THE INVENTION The solid electrolyte having proton conductivity is a perovskite type having SrCeO 3 or CaZrO 3 as a matrix, and a part of Ce and Zr is a rare earth element (Sc, Y,
La, Nd, Sm, Eu, Gd, Dy, Ho, and Yb) are substituted and solid-solved by 1 to 30 mol% with one or more elements selected from the group consisting of La, Nd, Sm, Eu, Gd, Dy, Ho and Yb).
【０００９】基準電極と測定電極は、通常のＰＶＤ法や
ＣＶＤ法でも形成できるが、Ｎｉ、Ｐｔ、Ａｕ等のペー
ストを固体電解質の表面に塗布し、還元性雰囲気中で８
００℃以上で焼き付ける方法（ペースト塗布法）で形成
する方が多孔質膜になって水素ガスの侵入が容易になる
ので望ましい。なお、ＰｔやＡｕのように酸化しにくい
金属の場合は空気中で焼き付けてもよい。The reference electrode and the measurement electrode can be formed by a usual PVD method or CVD method. However, a paste of Ni, Pt, Au or the like is applied to the surface of the solid electrolyte, and the paste is formed in a reducing atmosphere.
Baking at a temperature of 00 ° C. or more (paste coating method) is preferable because a porous film is formed and the penetration of hydrogen gas becomes easy. In the case of a metal that is hardly oxidized such as Pt or Au, the metal may be baked in the air.
【００１０】基準電極はシールドをもち、被測定雰囲気
から隔絶されている。固体電解質に形成された基準電極
の外面全体をガラス等で被覆するシールドでも良いが、
基準電極を誘電体基板でサンドイッチし、且つ外周端を
ガラス等で融着するシールドでも良い。後者の方が基板
に固体電解質と同じ熱膨張係数の材料を使うことでサー
マルショックによるクラックなどを避けることができ有
利である。The reference electrode has a shield and is isolated from the atmosphere to be measured. Although a shield covering the entire outer surface of the reference electrode formed on the solid electrolyte with glass or the like may be used,
A shield in which the reference electrode is sandwiched by a dielectric substrate and the outer peripheral end is fused with glass or the like may be used. The latter is more advantageous by using a material having the same coefficient of thermal expansion as the solid electrolyte for the substrate so that cracks due to thermal shock can be avoided.
【００１１】水素をポンプする第１工程が被測定雰囲気
と接触する測定電極から水素をポンプして被測定雰囲気
と隔絶された基準電極の水素分圧を一定にする工程であ
る水素・水蒸気測定方法の場合は、被測定雰囲気と接触
する測定電極をアノード、被測定雰囲気と隔絶された基
準電極をカソードとなるように直流電圧を印加して電流
を流す。印加電圧は１Ｖ以上、好ましくは２Ｖ以上がよ
い。２Ｖ以上では基準電極側にポンプされた水素分圧が
一定になるからである。The first step of pumping hydrogen is a step of pumping hydrogen from a measurement electrode in contact with the atmosphere to be measured and keeping the hydrogen partial pressure of a reference electrode isolated from the atmosphere to be measured constant. In the case of (1), a DC voltage is applied so that a measurement electrode in contact with the atmosphere to be measured is an anode, and a reference electrode separated from the atmosphere to be measured is a cathode, and a current flows. The applied voltage is 1 V or more, preferably 2 V or more. This is because the partial pressure of hydrogen pumped to the reference electrode side becomes constant at 2 V or more.
【００１２】水素をポンプする第１工程が被測定雰囲気
と隔絶された基準電極から水素をポンプして該基準電極
の水素分圧を一定にする工程である水素・水蒸気測定方
法の場合は、被測定雰囲気と接触する測定電極をカソー
ド、被測定雰囲気と隔絶された基準電極をアノードとな
るように直流電圧を印加して電流を流す。In the case of the hydrogen / steam measurement method in which the first step of pumping hydrogen is a step of pumping hydrogen from a reference electrode separated from the atmosphere to be measured and keeping the hydrogen partial pressure at the reference electrode constant. A current is applied by applying a DC voltage so that the measurement electrode in contact with the measurement atmosphere is the cathode, and the reference electrode isolated from the measurement atmosphere is the anode.
【００１３】起電力を測定する第２工程は、基準電極と
測定電極の間で電池を構成して両電極に接続された電位
計で起電力を測定する。In the second step of measuring the electromotive force, a battery is formed between the reference electrode and the measurement electrode, and the electromotive force is measured by an electrometer connected to both electrodes.
【００１４】前記電池は、測定電極側の水素ガス分圧と
基準電極側の水素ガス分圧が異なる場合は水素濃淡電池
として機能し、測定電極が接触する被測定雰囲気の水素
ガス分圧に比例する起電力を発生する。また、前記電池
は、測定電極が接触する被測定雰囲気がウエット空気す
なわち水蒸気を含む空気の場合は水素−空気燃料電池と
して機能し、水蒸気分圧に比例する起電力を発生する。The battery functions as a hydrogen concentration cell when the hydrogen gas partial pressure on the measurement electrode side is different from the hydrogen gas partial pressure on the reference electrode side, and is proportional to the hydrogen gas partial pressure of the atmosphere to be measured in contact with the measurement electrode. Generates an electromotive force. When the atmosphere to be measured with which the measurement electrode contacts is wet air, that is, air containing water vapor, the cell functions as a hydrogen-air fuel cell and generates an electromotive force proportional to the partial pressure of water vapor.
【００１５】水素をポンプする第１工程と起電力を測定
する第２工程は交互に行われても良いし、同時に行われ
ても良い。交互に行われる場合は、第１工程の直流電圧
印加時間が第２工程の起電力測定時間とリンクし、印加
時間が長ければ、測定時間を長くできる。たとえば、印
加時間が２secのとき測定時間が１０secである。電圧印
加と起電力測定を一定時間繰り返すことによって連続的
に水素・水蒸気を測定することができる。The first step of pumping hydrogen and the second step of measuring electromotive force may be performed alternately or simultaneously. When alternately performed, the DC voltage application time in the first step is linked to the electromotive force measurement time in the second step, and the longer the application time, the longer the measurement time. For example, when the application time is 2 seconds, the measurement time is 10 seconds. By repeating voltage application and electromotive force measurement for a certain period of time, hydrogen and water vapor can be continuously measured.
【００１６】プロトン導電性をもつ固体電解質と、該固
体電解質の一方の面に設けられ且つ被測定雰囲気と隔絶
するシールドをもつ基準電極と、該基準電極と背向する
該固体電解質の他方の面に設けられ且つ被測定雰囲気と
接触する測定電極と、該基準電極と該測定電極に接続さ
れた電圧印加手段及び起電力測定手段と、からなること
を特徴とする水素ポンプを利用した固体電解質式水素測
定装置において、電圧印加手段は直流電圧を印加して電
流を供給できれば良く,通常の直流電源やバッテリーを
使うことができる。起電力測定手段は市販の電位計で良
い。シールドをもつ基準電極は、孔で被測定雰囲気につ
ながっていてもよい。A solid electrolyte having proton conductivity, a reference electrode provided on one surface of the solid electrolyte and having a shield for isolating from the atmosphere to be measured, and the other surface of the solid electrolyte opposed to the reference electrode A solid electrolyte type using a hydrogen pump, comprising: a measuring electrode provided in the chamber and in contact with the atmosphere to be measured; and a voltage applying means and an electromotive force measuring means connected to the reference electrode and the measuring electrode. In the hydrogen measuring device, the voltage applying means only needs to be able to apply a DC voltage and supply a current, and a normal DC power supply or battery can be used. The electromotive force measuring means may be a commercially available electrometer. The reference electrode having the shield may be connected to the atmosphere to be measured by a hole.
【００１７】[0017]
【作用】本発明に係る水素ポンプを利用した固体電解質
式水素・水蒸気測定方法及び測定装置は、第１工程の水
素ポンプ作用と第２工程の起電力発生作用からなる。The method and apparatus for measuring solid electrolyte hydrogen and water vapor using a hydrogen pump according to the present invention include a hydrogen pump function in a first step and an electromotive force generating function in a second step.
【００１８】第１工程の水素ポンプ作用は、被測定雰囲
気と接触する測定電極と被測定雰囲気と隔絶された基準
電極の間に直流を印加することにより機能する。被測定
雰囲気と接触する測定電極をアノード、被測定雰囲気と
隔絶された基準電極をカソードとなるように直流電圧を
印加する場合は、被測定雰囲気がウエット空気のとき測
定電極で（１）式で表される反応が、被測定雰囲気が水
素を含む気体のとき測定電極で Ｈ2→２Ｈ+＋２ｅ- （４） なる反応が起き、プロトンが発生する。発生したプロト
ンは固体電解質を通り抜け基準電極に達し、（２）式の
反応が起き、水素を生成する。すなわち、測定電極側か
ら基準電極側に水素がポンプされ、基準電極側の水素分
圧が増加し飽和する。被測定雰囲気と接触する測定電極
をカソード、被測定雰囲気と隔絶された基準電極をアノ
ードとなるように直流電圧を印加する場合は,基準電極
で（４）式で表される反応が起き、プロトンを発生す
る。発生したプロトンは固体電解質を通り抜け測定電極
に達し、（２）式の反応が起き、水素を生成する。すな
わち,基準電極側から測定電極側に水素がポンプされ、
基準電極側の水素分圧が減少し一定値になる。The hydrogen pumping function of the first step works by applying a direct current between the measuring electrode in contact with the atmosphere to be measured and the reference electrode isolated from the atmosphere to be measured. When a DC voltage is applied so that the measurement electrode in contact with the atmosphere to be measured is the anode and the reference electrode separated from the atmosphere to be measured is the cathode, when the atmosphere to be measured is wet air, the measurement electrode is expressed by formula (1). When the atmosphere to be measured is a gas containing hydrogen, a reaction represented by H 2 → 2H + + 2e − (4) occurs at the measurement electrode, and protons are generated. The generated protons pass through the solid electrolyte and reach the reference electrode, and the reaction represented by the formula (2) occurs to generate hydrogen. That is, hydrogen is pumped from the measurement electrode side to the reference electrode side, and the hydrogen partial pressure on the reference electrode side increases and saturates. When a DC voltage is applied such that the measurement electrode in contact with the atmosphere to be measured is a cathode and the reference electrode separated from the atmosphere to be measured is an anode, a reaction expressed by the formula (4) occurs at the reference electrode, and protons are generated. Occurs. The generated protons pass through the solid electrolyte and reach the measurement electrode, where the reaction of the formula (2) occurs to generate hydrogen. That is, hydrogen is pumped from the reference electrode side to the measurement electrode side,
The hydrogen partial pressure on the reference electrode side decreases and becomes constant.
【００１９】第２工程の起電力発生作用は、基準電極側
の水素分圧が増加あるいは減少した時点で、基準電極と
測定電極の間に電位計を接続することにより電池として
機能し、起電力を発生する。すなわち、被測定雰囲気が
ウエット空気の場合は水素―空気燃料電池として機能
し、（３）式で表される起電力が発生する。被測定雰囲
気が水素を含む気体の場合は水素濃淡電池として機能
し、測定電極が接触する被測定雰囲気の水素ガス分圧Ｐ
Ｈ2（２）に比例する起電力 E=(RT/2F)ln[PH2(1)/PH2(2)] （5） を発生する。In the second step, the electromotive force is generated by connecting a potentiometer between the reference electrode and the measurement electrode when the hydrogen partial pressure on the reference electrode side increases or decreases. Occurs. That is, when the atmosphere to be measured is wet air, it functions as a hydrogen-air fuel cell, and generates an electromotive force represented by Expression (3). When the measured atmosphere is a gas containing hydrogen, it functions as a hydrogen concentration cell, and the hydrogen gas partial pressure P
An electromotive force E = (RT / 2F) ln [PH 2 (1) / PH 2 (2)] (5) proportional to H 2 (2) is generated.
【００２０】[0020]
【実施例】以下、実施例により本発明を具体的に説明す
る。The present invention will be described below in detail with reference to examples.
【００２１】実施例１ 実施例１は水素ガス測定装置で、装置構成を図１に、端
子電圧の変化を図３に、水素ガス分圧と起電力の関係を
図４に示す。Example 1 Example 1 is a hydrogen gas measuring device, and FIG. 1 shows the configuration of the device, FIG. 3 shows changes in terminal voltage, and FIG. 4 shows the relationship between the partial pressure of hydrogen gas and the electromotive force.
【００２２】本水素ガス測定装置は、プロトン導電性を
もつ固体電解質１の上面に測定電極２が、下面に基準電
極３が形成され、基準電極３が基板４ａでサンドイッチ
され外周端をシールド材としてのガラス４ｂで溶着され
ている。すなわち、基板４ａとシールド材４ｂでシール
ド４を構成して基準電極３を外部から隔絶している。測
定電極２には電圧印加手段としての直流電源５のマイナ
スがスイッチ７を介して、基準電極３にはプラスがリー
ド線８で接続されている。さらに、測定電極２と基準電
極３には、起電力測定手段としての電位計６が直流電源
５と並列に接続されている。In this hydrogen gas measuring apparatus, a measuring electrode 2 is formed on an upper surface of a solid electrolyte 1 having proton conductivity, and a reference electrode 3 is formed on a lower surface. The reference electrode 3 is sandwiched by a substrate 4a and an outer peripheral end is used as a shielding material. Of glass 4b. That is, the shield 4 is constituted by the substrate 4a and the shield material 4b to isolate the reference electrode 3 from the outside. The negative electrode of a DC power supply 5 as a voltage applying means is connected to the measuring electrode 2 via a switch 7, and the positive electrode of the reference electrode 3 is connected to a lead wire 8. Further, an electrometer 6 as an electromotive force measuring means is connected to the measurement electrode 2 and the reference electrode 3 in parallel with the DC power supply 5.
【００２３】固体電解質１は、組成がＳｒＣｅ0.95Ｙｂ
0.05Ｏ3-αの緻密セラミックスディスクで、直径が１
４．５ｍｍ、厚さが０．５ｍｍである。測定電極２と基
準電極３は多孔質電極とするため、固体電解質１の上面
と下面にポーラスＰｔが接着された。両電極とも面積は
０．６ｃｍ2である。基板４ａは、固体電解質１と同じ
材料で作られており、熱膨張係数が同じにされている。
これは、サーマルショックでの破損を防止するためであ
る。リード線8はPt線で、測定電極２と基準電極３には
半田ペーストで接続されている。The solid electrolyte 1 has a composition of SrCe 0.95 Yb
0.05 O 3- α dense ceramic disc with diameter 1
4.5 mm, thickness 0.5 mm. Since the measurement electrode 2 and the reference electrode 3 were porous electrodes, porous Pt was bonded to the upper and lower surfaces of the solid electrolyte 1. Both electrodes have an area of 0.6 cm 2 . The substrate 4a is made of the same material as the solid electrolyte 1 and has the same coefficient of thermal expansion.
This is to prevent damage due to thermal shock. The lead wire 8 is a Pt wire, and is connected to the measurement electrode 2 and the reference electrode 3 with solder paste.
【００２４】直流電源５から２ｍＡの電圧を測定電極２
と基準電極３の間に通電して水素をポンプしながら、７
００℃の被測定雰囲気の水素濃度を変化させて電位計６
で起電力応答と端子電圧の変化を測定した。本水素ガス
測定装置が水素濃度の変化に高速応答（応答速度〜５０
sec）することがわかる。図４は、起電力を縦軸に、水
素濃度を横軸にして図３を書き直したもので、起電力が
水素分圧の対数に比例しており、水素ガスを測定できる
ことがわかる。A voltage of 2 mA is applied from the DC power supply 5 to the measuring electrode 2.
While pumping hydrogen by supplying a current between the
Electrometer 6 by changing the hydrogen concentration of the atmosphere to be measured at 00 ° C.
And the change in terminal voltage was measured. This hydrogen gas measurement device responds quickly to changes in hydrogen concentration (response speed ~ 50
sec). FIG. 4 is a rewrite of FIG. 3 with the electromotive force on the vertical axis and the hydrogen concentration on the horizontal axis. It can be seen that the electromotive force is proportional to the logarithm of the hydrogen partial pressure, and that hydrogen gas can be measured.
【００２５】実施例２ 実施例２はウエット空気中で動作する水蒸気測定装置
で、装置構成を図２に、起電力と水蒸気分圧の関係を図
５に示す。Embodiment 2 Embodiment 2 is a water vapor measuring device that operates in wet air. FIG. 2 shows the configuration of the device, and FIG. 5 shows the relationship between electromotive force and water vapor partial pressure.
【００２６】本実施例の水蒸気測定装置は、シールド４
が直径２０μｍの孔９で被測定雰囲気とつながっている
点と、測定電極２に電圧印加手段としての直流電源５の
プラスが、基準電極３にはマイナスがリード線7で接続
されている点以外は実施例１と同じである（実施例１と
同じ構成要素には同じ番号を付して説明を省略する）。The water vapor measuring apparatus of the present embodiment has a shield 4
Is connected to the atmosphere to be measured by a hole 9 having a diameter of 20 μm, the plus of a DC power supply 5 as a voltage applying means is connected to the measuring electrode 2, and the minus is connected to the reference electrode 3 by a lead wire 7. Are the same as those in the first embodiment (the same components as those in the first embodiment are denoted by the same reference numerals and description thereof is omitted).
【００２７】スイッチ７をオンにして直流電源5から２
Ｖの電圧を測定電極２と基準電極３の間に印加して水素
のポンプを開始し、３ｍｉｎ後に電位計６で起電力を測
定することを、７００℃の被測定雰囲気の水蒸気濃度を
変化させて繰り返した。その結果が図５で、起電力が水
蒸気分圧の対数に比例しており、水蒸気を測定できるこ
とがわかる。When the switch 7 is turned on, the DC power
Applying a voltage of V between the measuring electrode 2 and the reference electrode 3 to start pumping hydrogen, and measuring the electromotive force with the electrometer 6 after 3 minutes is performed by changing the water vapor concentration of the atmosphere at 700 ° C. I repeated. The result is shown in FIG. 5, where the electromotive force is proportional to the logarithm of the water vapor partial pressure, and it can be seen that the water vapor can be measured.
【００２８】[0028]
【効果】本発明の水素ポンプを利用した固体電解質式気
体測定方法及び測定装置は、水素ポンプを利用して基準
電極側の水素分圧を一定にするので、外部水素源を必要
とせず、測定装置の小型化・可搬性向上が図られる。さ
らに、背向する面に電極が形成された固体電解質一つ
（１セル）で、水素のポンプと被測定気体の濃度に比例
する起電力の測定をするので、小型化・低コスト化が図
れる。The solid electrolyte gas measuring method and measuring apparatus using the hydrogen pump of the present invention use a hydrogen pump to make the hydrogen partial pressure on the reference electrode side constant, so that an external hydrogen source is not required and the measurement can be performed. The size and portability of the device can be reduced. Furthermore, since the hydrogen pump and the electromotive force in proportion to the concentration of the gas to be measured are measured with one solid electrolyte (one cell) having an electrode formed on the opposite surface, miniaturization and cost reduction can be achieved. .
【図１】実施例１の水素ガス測定装置の断面図。FIG. 1 is a cross-sectional view of a hydrogen gas measuring device according to a first embodiment.
【図２】実施例２の水蒸気測定装置の断面図。FIG. 2 is a cross-sectional view of a water vapor measurement device according to a second embodiment.
【図３】水素ガス測定装置の起電力応答と端子電圧の変
化を示すグラフ。FIG. 3 is a graph showing an electromotive force response and a change in terminal voltage of the hydrogen gas measurement device.
【図４】実施例１の水素ガス測定装置の起電力と水素分
圧の関係を示すグラフ。FIG. 4 is a graph showing the relationship between the electromotive force and the hydrogen partial pressure of the hydrogen gas measurement device of Example 1.
【図５】実施例２の水蒸気測定装置の起電力と水蒸気分
圧の関係を示すグラフ。FIG. 5 is a graph showing the relationship between the electromotive force and the partial pressure of water vapor of the water vapor measurement device of the second embodiment.
【図６】従来の水蒸気センサの断面図。FIG. 6 is a sectional view of a conventional water vapor sensor.
【符号の説明】 １…プロトン導電性をもつ固体電解質、２…測定電極、
３…基準電極、４…シールド、４ａ…基板、４ｂ…シー
ルド材、５…電圧印加手段、６…起電力測定手段、７…
スイッチ、８…リード線、９…孔[Description of References] 1 ... Solid electrolyte having proton conductivity, 2 ... Measurement electrode,
3 Reference electrode 4 Shield 4 a Substrate 4 b Shield material 5 Voltage applying means 6 Electromotive force measuring means 7
Switch, 8 ... Lead wire, 9 ... Hole
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 2G004 ZA01 ZA05 5H026 AA06 ──────────────────────────────────────────────────続 き Continued on front page F-term (reference) 2G004 ZA01 ZA05 5H026 AA06
Claims (8)
体電解質の一方の面に設けられ且つ被測定雰囲気と隔絶
された基準電極と他方の面に設けられ且つ被測定雰囲気
と接触する測定電極との間で電池を形成して気体を測定
する方法であって、 前記基準電極と前記測定電極の間に直流を印加して水素
をポンプする第１工程と、 前記基準電極と前記測定電極の間の起電力を測定する第
２工程と、からなることを特徴とする水素ポンプを利用
した固体電解質式水素・水蒸気測定方法。1. A solid electrolyte having proton conductivity, a reference electrode provided on one surface of the solid electrolyte and isolated from an atmosphere to be measured, and a measurement electrode provided on the other surface and in contact with the atmosphere to be measured. A method of measuring a gas by forming a battery between: a first step of applying a direct current between the reference electrode and the measurement electrode to pump hydrogen; and a method of applying a direct current between the reference electrode and the measurement electrode. And a second step of measuring the electromotive force of the solid electrolyte.
記載の水素ポンプを利用した固体電解質式水素・水蒸気
測定方法。2. The method according to claim 1, wherein the battery is a hydrogen concentration battery.
項１に記載の水素ポンプを利用した固体電解質式水素・
水蒸気測定方法。3. The solid electrolyte type hydrogen source using a hydrogen pump according to claim 1, wherein the battery is a hydrogen-air fuel cell.
Water vapor measurement method.
準電極の水素分圧を一定にする工程である請求項１に記
載の水素ポンプを利用した固体電解質式水素・水蒸気測
定方法。4. The method according to claim 1, wherein the first step is a step of making the hydrogen partial pressure of the reference electrode constant by a hydrogen pump.
ンプして前記基準電極の水素分圧を一定にする工程であ
る請求項１に記載の水素ポンプを利用した固体電解質式
水素・水蒸気測定方法。5. The solid electrolyte type hydrogen / water vapor using a hydrogen pump according to claim 1, wherein the first step is a step of pumping hydrogen from the measurement electrode to make the hydrogen partial pressure of the reference electrode constant. Measuring method.
ンプして該基準電極の水素分圧を一定にする工程である
請求項１に記載の水素ポンプを利用した固体電解質式水
素・水蒸気測定方法。6. The solid electrolyte type hydrogen / water vapor using a hydrogen pump according to claim 1, wherein said first step is a step of pumping hydrogen from said reference electrode to keep the hydrogen partial pressure of said reference electrode constant. Measuring method.
体電解質の一方の面に設けられ且つ被測定雰囲気と隔絶
するシールドをもつ基準電極と、該基準電極と背向する
該固体電解質の他方の面に設けられ且つ被測定雰囲気と
接触する測定電極と、該基準電極と該測定電極に接続さ
れた直流印加手段及び起電力測定手段と、からなること
を特徴とする水素ポンプを利用した固体電解質式水素・
水蒸気測定装置。7. A solid electrolyte having proton conductivity, a reference electrode provided on one surface of the solid electrolyte and having a shield for isolating the atmosphere to be measured, and the other of the solid electrolyte opposed to the reference electrode A solid electrode utilizing a hydrogen pump, comprising: a measurement electrode provided on the surface of the substrate and in contact with the atmosphere to be measured; and a DC application unit and an electromotive force measurement unit connected to the reference electrode and the measurement electrode. Electrolyte hydrogen
Water vapor measurement device.
がっている請求項７に記載の水素ポンプを利用した固体
電解質式水素・水蒸気測定装置。8. The solid electrolyte type hydrogen / steam measuring apparatus using a hydrogen pump according to claim 7, wherein said reference electrode is connected to said measuring atmosphere by a hole.
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| JP2001104622A JP4819239B2 (en) | 2001-04-03 | 2001-04-03 | Solid electrolyte type hydrogen / water vapor measuring method and measuring apparatus using hydrogen pump |
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|---|---|---|---|
| JP2001104622A JP4819239B2 (en) | 2001-04-03 | 2001-04-03 | Solid electrolyte type hydrogen / water vapor measuring method and measuring apparatus using hydrogen pump |
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| JP4819239B2 (en) | 2011-11-24 |
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