JP3067532B2 - Electrochemical element and nitrogen oxide concentration measuring device - Google Patents
Electrochemical element and nitrogen oxide concentration measuring deviceInfo
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- JP3067532B2 JP3067532B2 JP6162025A JP16202594A JP3067532B2 JP 3067532 B2 JP3067532 B2 JP 3067532B2 JP 6162025 A JP6162025 A JP 6162025A JP 16202594 A JP16202594 A JP 16202594A JP 3067532 B2 JP3067532 B2 JP 3067532B2
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Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【産業上の利用分野】本発明は、窒素酸化物が存在する
ガス雰囲気において、電気化学的に窒素酸化物濃度を測
定するための電気化学素子に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrochemical device for electrochemically measuring the concentration of nitrogen oxides in a gas atmosphere containing nitrogen oxides.
【０００２】[0002]
【従来の技術】従来の電気化学的方法による窒素酸化物
（以下、ＮＯｘという）の濃度測定方法は、例えばＵＳ
Ｐ８４３８７７によれば、センサー本体が壁を隔てて、
２つのチャンバーを形成し、前記壁にはＮＯｘ（ＮＯ及
びＮＯ2とする）の触媒作用による分解状況が非対称と
なり、そこに測定可能な電位差が発生するように電極が
設けられており、この電位差が各チャンバーに導入され
るガス中のＮＯｘ濃度の判定に使用されるものである。2. Description of the Related Art A conventional method for measuring the concentration of nitrogen oxides (hereinafter referred to as NOx) by an electrochemical method is disclosed in US Pat.
According to P844877, the sensor body is separated from the wall,
Two chambers are formed, and an electrode is provided on the wall so that the decomposition state by the catalytic action of NOx (NO and NO2) becomes asymmetric and a measurable potential difference is generated there. It is used to determine the concentration of NOx in the gas introduced into each chamber.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら上記従来
の構成では、ＮＯｘガス中の酸素濃度が５０ｐｐｍレベ
ルの低濃度であり、しかも測定温度が６２０℃〜９３０
℃と比較的高温であった。However, in the above conventional configuration, the oxygen concentration in the NOx gas is as low as 50 ppm, and the measurement temperature is 620 ° C. to 930 °.
It was relatively high at ℃.
【０００４】本発明は上記課題を解決するもので、酸素
濃度が２０％程度でも比較的低温で窒素酸化物濃度を測
定できる素子あるいは装置を提供することを目的とした
ものである。An object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to provide an element or an apparatus capable of measuring a nitrogen oxide concentration at a relatively low temperature even when the oxygen concentration is about 20%.
【０００５】[0005]
【課題を解決するための手段】本発明は上記目的を達成
するため、酸素イオン伝導性の第１固体電解質を介して
対向して配置した第１負電極及び第１正電極とから構成
された第１の電気化学素子と、酸素イオン伝導性の第２
固体電解質を介して対向して配置した第２負電極及び第
２正電極とから構成された第２の電気化学素子と、前記
第１の電気化学素子の前記第１負電極を雰囲気ガスと接
触させる第１のガス拡散抵抗と、前記第２の電気化学素
子の第２負電極を前記第１の電気化学素子の第１負電極
と接触させた雰囲気ガスに接触させるための第２のガス
拡散抵抗とから成り，前記第２負電極が酸素存在下にお
いて窒素酸化物吸着性の化合物を含有する電気化学素子
である。In order to achieve the above object, the present invention provides an oxygen ion-conductive first solid electrolyte.
Consisting of a first negative electrode and a first positive electrode arranged to face each other
The first electrochemical device and the oxygen ion conductive second
A second negative electrode and a second negative electrode which are opposed to each other via a solid electrolyte;
A second electrochemical element comprising: a second positive electrode;
The first negative electrode of the first electrochemical device is brought into contact with an atmospheric gas.
A first gas diffusion resistance to be touched, and the second electrochemical element
The second negative electrode of the first electrochemical device to the first negative electrode of the first electrochemical device
Gas for contacting the atmospheric gas contacted with the second gas
A diffusion resistance, wherein the second negative electrode is provided in the presence of oxygen.
And an electrochemical device containing a compound capable of adsorbing nitrogen oxides .
【０００６】[0006]
【作用】本発明は上記構成により、第１の電気化学素子
が酸素ポンピング作用によりＮＯｘを含むガス中の酸素
濃度を低下させ、この低酸素濃度ガス中のＮＯｘが、酸
素存在下において窒素酸化物吸着性の化合物を含有する
第２負電極を有する第２の電気化学素子により窒素と酸
素に分解され、ガス中のＮＯｘ濃度と分解により生成さ
れる酸素量つまり第２の電気化学素子に流れる酸素イオ
ン電流の比例関係からガス中のＮＯｘ濃度が測定でき
る。また、第１の電気化学素子を流れる酸素イオン電流
からガス中の酸素濃度測定が可能となる。According to the present invention, the first electrochemical device reduces the oxygen concentration in the gas containing NOx by the oxygen pumping action, and the NOx in the low-oxygen gas becomes nitrogen oxide in the presence of oxygen. Contains adsorptive compounds
The gas is decomposed into nitrogen and oxygen by the second electrochemical element having the second negative electrode, and the gas is determined from the proportional relationship between the NOx concentration in the gas and the amount of oxygen generated by the decomposition, that is, the oxygen ion current flowing through the second electrochemical element. The NOx concentration in can be measured. Further, the oxygen concentration in the gas can be measured from the oxygen ion current flowing through the first electrochemical element.
【０００７】第２の電気化学素子によるＮＯｘの分解反
応は、窒素酸化物吸着性化合物が第２負電極上に窒素酸
化物を固定することから開始する。第２の電気化学素子
の第２負電極側で、窒素酸化物吸着性化合物と貴金属
（例えば白金）と第２酸素イオン伝導性電解質との接触
界面近傍で、窒素酸化物の窒素−酸素結合が弱められ、
酸素は酸素イオンとして前記第２酸素イオン伝導性電解
質を透過して、第２負電極側から第２正電極側へ移動し
酸素分子として雰囲気ガス中に排出される。一方、第２
負電極側では窒素分子が生成されガス中に脱離してい
く。[0007] The decomposition reaction of NOx by the second electrochemical element starts when the nitrogen oxide-adsorbing compound fixes nitrogen oxide on the second negative electrode. On the second negative electrode side of the second electrochemical element, near the contact interface between the nitrogen oxide-adsorbing compound, the noble metal (for example, platinum), and the second oxygen ion-conductive electrolyte, the nitrogen-oxygen bond of the nitrogen oxide is formed. Weakened,
Oxygen passes through the second oxygen-ion conductive electrolyte as oxygen ions, it is discharged into the atmospheric gas as the oxygen molecules move from the second negative electrode side to the second positive electrode side. On the other hand, the second
On the negative electrode side, nitrogen molecules are generated and desorbed into the gas.
【０００８】[0008]
【実施例】以下、本発明の実施例を図１を参照して説明
する。An embodiment of the present invention will be described below with reference to FIG.
【０００９】図１は、電気化学素子の概略断面図であ
る。１及び２、３は第１の電気化学素子のそれぞれ正電
第１極及び第１負電極、第１固体電解質（８ｍｏｌ％Ｙ
2Ｏ3−ＺｒＯ2，以下ＹＳＺと記す）であり、４、及び
５、６は第２の電気化学素子のそれぞれ第２正電極及び
第２負電極、第２固体電解質（ＹＳＺ）７及び８はそれ
ぞれ第１及び第２のガス拡散抵抗、９は支持壁、１０、
及び１１はそれぞれ第１及び第２のガス室である。第１
正電極１、第２正電極４及び第１負電極２は、白金から
なり、第２負電極５はＢａ2ＹＣｕ3Ｏ7-xと白金からな
る。FIG. 1 is a schematic sectional view of an electrochemical device. 1, 2 and 3 are positive electrodes of the first electrochemical device, respectively.
A first electrode, a first negative electrode, a first solid electrolyte (8 mol% Y
2 O 3 -ZrO 2 , hereinafter referred to as YSZ), and 4, 5 and 6 represent the second positive electrode and the second positive electrode of the second electrochemical element, respectively .
A second negative electrode, second solid electrolytes ( YSZ ) 7 and 8 are first and second gas diffusion resistances, respectively, 9 is a support wall,
And 11 are first and second gas chambers, respectively. First
The positive electrode 1, the second positive electrode 4, and the first negative electrode 2 are made of platinum, and the second negative electrode 5 is made of Ba 2 YCu 3 O 7-x and platinum.
【００１０】雰囲気ガスはガス拡散抵抗７として設けら
れた小孔より、第１のガス室１０内に拡散し、ガス中に
含まれる酸素は第１負電極２でイオン化され酸素イオン
としてＹＳＺ中を拡散移動し第１正電極１から酸素分子
として雰囲気ガス中に放出される。第１のガス室１０で
酸素濃度が低下したガスは、第２のガス拡散抵抗８とし
て設けられた小孔より第２のガス室１１へと拡散する。
ここで、ガス中のＮＯｘは、第２の電気化学素子により
第２負電極５で窒素と酸素に分解され、生成した酸素は
酸素イオンとしてＹＳＺを拡散移動し、第２正電極４か
ら酸素分子として雰囲気ガス中へ放出される。動作温度
としては４５０℃程度が好ましい。The atmosphere gas diffuses into the first gas chamber 10 through the small holes provided as the gas diffusion resistance 7, and oxygen contained in the gas is ionized by the first negative electrode 2 and travels through the YSZ as oxygen ions. It diffuses and moves and is released from the first positive electrode 1 as oxygen molecules into the atmospheric gas. The gas having a reduced oxygen concentration in the first gas chamber 10 diffuses into the second gas chamber 11 from a small hole provided as the second gas diffusion resistor 8.
Here, NOx in the gas is separated by the second electrochemical element.
The second negative electrode 5 decomposes into nitrogen and oxygen, and the generated oxygen diffuses and moves through YSZ as oxygen ions, and is released from the second positive electrode 4 as oxygen molecules into the atmosphere gas. The operating temperature is preferably about 450 ° C.
【００１１】（表１）に、４５０℃における第２の電気
化学素子によるＮＯｘ分解性能の一例を示した。反応は
ガス流通系で、ガス分析は化学発光式ＮＯｘ計及びガス
クロにより行なった。酸素濃度が大気レベル（２０％）
であっても、高い分解性能を示す。このことが、第２の
電気化学素子の大きな特長である。[0011] Table 1 shows an example of the NOx decomposition performance of the second electrochemical element at 450 ° C. The reaction was performed in a gas flow system, and gas analysis was performed by a chemiluminescence NOx meter and gas chromatography. Oxygen concentration at atmospheric level (20%)
However, it exhibits high decomposition performance. This is a great feature of the second electrochemical device.
【００１２】[0012]
【表１】 [Table 1]
【００１３】図２に、第２の電気化学素子にＮＯｘ分解
によって生じる電流（Ｉ）とガス中のＮＯｘ濃度（Ｃ）
との関係を示した。図２から電流Ｉの対数とＮＯｘ濃度
Ｃの対数がほぼ直線的な比例関係にあることが分かる。
この関係から、雰囲気ガス中のＮＯｘ濃度が測定でき
る。（図２の場合、ガス拡散抵抗は設けていない。）上
記第１及び第２の電気化学素子は、以下のようにして作
成した。ＹＳＺの表面に正負の電極用導電ペーストをそ
れぞれ交互に印刷と乾燥を繰り返した後、大気中約８２
０℃で焼成して、ＹＳＺ表面に正負の多孔質電極膜を形
成した。さらに、電気的特性の測定に必要な白金線を各
電極端部に結合剤を用い焼結した。第２の電気化学素子
に使用した負電極用導電ペーストの組成は白金対Ｂａ2
ＹＣｕ3Ｏ7-xの比がモル比でおよそ１：１であるが、組
成は必ずしもこの限りではない。また、上記焼成温度も
８２０℃に限るものではない。焼成後の第２負電極５は
ＳＥＭ観察によれば、多孔質な膜であり、ガス反応に適
当である。FIG. 2 shows the current (I) generated by NOx decomposition in the second electrochemical element and the NOx concentration (C) in the gas.
The relationship was shown. FIG. 2 shows that the logarithm of the current I and the logarithm of the NOx concentration C are in a substantially linear proportional relationship.
From this relationship, the NOx concentration in the atmospheric gas can be measured. (In the case of FIG. 2, no gas diffusion resistance is provided.) The first and second electrochemical elements were prepared as follows. After alternately printing and drying the positive and negative electrode conductive pastes alternately on the surface of YSZ, about 82
By baking at 0 ° C., positive and negative porous electrode films were formed on the YSZ surface. Further, a platinum wire required for measurement of electrical characteristics was sintered at each electrode end using a binder. The composition of the negative electrode conductive paste used in the second electrochemical element was platinum to Ba 2
The ratio of YCu 3 O 7-x is about 1: 1 by mole, but the composition is not necessarily limited to this. Further, the firing temperature is not limited to 820 ° C. The second negative electrode 5 after firing is a porous film according to SEM observation, and is suitable for gas reaction.
【００１４】図３に、それぞれ酸素存在下でのＢａ2Ｙ
Ｃｕ3Ｏ7-xのＮＯｘの吸着特性を示した。また、Ｂａ2
ＹＣｕ3Ｏ7-x中のＢａサイトがアルカリ土類元素のＳｒ
で置換されたり、Ｙサイトが他のランタノイド元素で置
換されても、ＮＯｘ吸着特性は発現するということが、
確かめられた。従って、Ｂａ2ＹＣｕ3Ｏ7-xの代わりに
他のＢａ2ＹＣｕ3Ｏ7型酸化物を使用しても良い。さら
にＢａ2ＹＣｕ3Ｏ7型酸化物でなくとも、ＮＯｘを酸素
中で安定的に吸収あるいは吸着する化合物であれば、第
２負電極５の材料として適用できる。FIG. 3 shows Ba 2 Y in the presence of oxygen.
Shows adsorption characteristics of NOx Cu 3 O 7-x. In addition, Ba 2
Ba site in YCu 3 O 7-x is Sr of alkaline earth element
, Or the Y site is replaced with another lanthanoid element, the NOx adsorption property is expressed.
I was assured. Thus, instead of Ba 2 YCu 3 O 7-x may use other Ba 2 YCu 3 O 7 type oxides. Furthermore, even if it is not Ba 2 YCu 3 O 7 type oxide, if it is a compound that stably absorbs or adsorbs NOx in oxygen, it can be a second compound .
2 It can be applied as a material for the negative electrode 5 .
【００１５】また、第２負電極５としては、高温でもＮ
Ｏｘを吸着する点で白金と混合することが望ましいの
で、Ｂａ2ＹＣｕ3Ｏ7-xと白金を混合した組成としてい
る。第１正電極１、第２正電極３は実使用環境を考慮す
れば、酸素イオンの酸化反応（正極反応）を進めるため
にも、耐環境性にすぐれた白金等の貴金属が好ましい。 The second negative electrode 5 is made of N
Since it is desirable to mix with platinum in terms of adsorbing Ox, the composition is such that Ba 2 YCu 3 O 7-x and platinum are mixed. In consideration of the actual use environment, the first positive electrode 1 and the second positive electrode 3 are preferably precious metals such as platinum having excellent environmental resistance in order to promote the oxidation reaction of oxygen ions (positive electrode reaction).
【００１６】図４には、第１の電気化学素子による酸素
濃度に対するイオン電流特性を示した。図４のイオン電
流はガス拡散抵抗を設けない場合であるが、ガス拡散抵
抗を設けることでより明確に濃度依存性を示し、この特
性から、雰囲気ガス中の酸素濃度が測定できることは従
来からも明かなことである。FIG. 4 shows an ion current characteristic with respect to an oxygen concentration by the first electrochemical device. The ion current shown in FIG. 4 is a case where no gas diffusion resistance is provided. However, the provision of the gas diffusion resistance shows the concentration dependence more clearly. From this characteristic, it has been conventionally possible to measure the oxygen concentration in the atmosphere gas. It is clear.
【００１７】次に、ＮＯｘ濃度測定装置の一実施例の概
略構成について、図５を用いて説明する。Next, a schematic configuration of an embodiment of the NOx concentration measuring device will be described with reference to FIG.
【００１８】図５において、１２−ａ及び１２−ｂがそ
れぞれ第１及び第２の電気化学素子、１３及び１４がそ
れぞれ第１の抵抗及び第２の抵抗、１５及び１６がそれ
ぞれ第１及び第２の電気化学素子に電圧印可する第１及
び第２の電圧印可手段、１７及び１８が第１及び第２の
電圧検出手段、１９が加熱手段、２０が回路手段であ
る。In FIG. 5, 12-a and 12-b are first and second electrochemical devices, respectively, 13 and 14 are first and second resistors, respectively, and 15 and 16 are first and second resistors, respectively. First and second voltage applying means for applying a voltage to the second electrochemical element, 17 and 18 are first and second voltage detecting means, 19 is a heating means, and 20 is a circuit means.
【００１９】上記ＮＯｘ濃度測定装置において、電気化
学素子１２−ａ及び１２−ｂを、ＮＯｘを含むガスに接
触させながら、加熱手段１９にて約４５０℃に加熱保持
する。電圧印可手段１５、１６により電気化学素子１２
−ａ及び１２−ｂに電圧を印可すると各々の電気化学素
子には、酸素イオン電流が発生する。このイオン電流を
電圧検出手段１７及び１８にて、抵抗１３及び１４の両
端電圧として測定する。既に、各々の素子に発生する酸
素イオン電流と酸素濃度、ＮＯｘ濃度の相対的な関係
は、分かっているので、電圧検出手段１８で得られる電
圧値からＮＯｘ濃度が、電圧検出手段１７で得られる電
圧値からＯ2濃度が求められる。In the above-mentioned NOx concentration measuring apparatus, the heating means 19 heats and holds the electrochemical elements 12-a and 12-b at about 450 ° C. while making contact with the gas containing NOx. The voltage applying means 15 and 16 allow the electrochemical element 12
When a voltage is applied to -a and 12-b, an oxygen ion current is generated in each electrochemical element. This ion current is measured by the voltage detecting means 17 and 18 as a voltage across the resistors 13 and 14. Since the relative relationship between the oxygen ion current generated in each element and the oxygen concentration and NOx concentration is already known, the NOx concentration can be obtained by the voltage detection unit 17 from the voltage value obtained by the voltage detection unit 18. The O 2 concentration is determined from the voltage value.
【００２０】電気化学素子１２−ｂに接するガスは、電
気化学素子１２−ａの酸素ポンピング作用により低酸素
濃度になってはいるが、いくらかの酸素を含有する。電
気化学素子１２−ｂに流れる酸素イオン電流は、ガス中
の酸素濃度依存性を示すのでＮＯｘ濃度測定には、ガス
中の酸素濃度の測定が必要になる。これに対しては、電
気化学素子１２−ａを用いた酸素濃度測定によって対応
できる。The gas in contact with the electrochemical element 12-b has a low oxygen concentration due to the oxygen pumping action of the electrochemical element 12-a, but contains some oxygen. Since the oxygen ion current flowing through the electrochemical element 12-b shows oxygen concentration dependency in the gas, measurement of the NOx concentration requires measurement of the oxygen concentration in the gas. This can be dealt with by measuring the oxygen concentration using the electrochemical element 12-a.
【００２１】また、ＮＯｘを含むガスは、例えば燃焼排
気のように、水や未燃分（炭化水素）、ＣＯ、ＣＯ2、
粉塵等を含むことがある。これらは、ＮＯｘ分解等の電
極反応の阻害物質として電気化学素子に副反応を誘発し
たり、あるいは電極表面を被毒や汚染することが考えら
れる。従って、ガスが電気化学素子に至る前に、このよ
うな阻害物質を、予め除去することが好ましい。この問
題を解決するために、フィルターや除湿器等の前処理部
を設けてもよい。The gas containing NOx includes water, unburned components (hydrocarbons), CO, CO 2 ,
May contain dust and the like. These are considered to induce a side reaction in the electrochemical element as an inhibitor of the electrode reaction such as NOx decomposition or to poison or contaminate the electrode surface. Therefore, it is preferable to remove such inhibitors before the gas reaches the electrochemical device. In order to solve this problem, a pre-processing unit such as a filter or a dehumidifier may be provided.
【００２２】[0022]
【発明の効果】以上説明したように本発明によれば、酸
素が存在する雰囲気において、低温動作するＮＯｘ濃度
測定のための電気化学素子と、それを用いたＮＯｘ濃度
測定装置が得られる。As described above, according to the present invention, it is possible to obtain an electrochemical element for NOx concentration measurement which operates at a low temperature in an atmosphere where oxygen is present, and a NOx concentration measuring apparatus using the same.
【図１】本発明の一実施例における電気化学素子の概略
断面図FIG. 1 is a schematic cross-sectional view of an electrochemical device according to one embodiment of the present invention.
【図２】本発明の一実施例における第２の電気化学素子
による電流−ＮＯｘ濃度特性図FIG. 2 is a diagram showing a current-NOx concentration characteristic by a second electrochemical element in one embodiment of the present invention.
【図３】本発明の一実施例におけるＢａ2ＹＣｕ3Ｏ7-X
のＮＯｘ吸着特性図FIG. 3 shows Ba2YCu3O7-X in one embodiment of the present invention.
NOx adsorption characteristics
【図４】本発明の一実施例における第１の電気化学素子
による電流−酸素濃度特性図FIG. 4 is a current-oxygen concentration characteristic diagram by a first electrochemical device in one embodiment of the present invention.
【図５】本発明の一実施例におけるＮＯｘ濃度測定装置
の概略構成図FIG. 5 is a schematic configuration diagram of a NOx concentration measuring device according to an embodiment of the present invention.
１ 第１正電極 ２ 第１負電極 ３ 第１固体電解質 ４ 第２正電極 ５ 第２負電極 ６ 第２固定電解質 ７ 第１のガス拡散抵抗 ８ 第２のガス拡散抵抗 ９ 支持壁 １０ 第１のガス室 １１ 第２のガス室 １２−ａ 第１の電気化学素子 １２−ｂ 第２の電気化学素子 １３ 第１の抵抗 １４ 第２の抵抗 １５ 第１の電圧印可手段 １６ 第２の電圧印可手段 １７ 第１の電圧検出手段 １８ 第２の電圧検出手段 １９ 加熱手段 ２０ 回路手段1 1st positive electrode 2 1st negative electrode 3 1st solid electrolyte 4 2nd positive electrode 5 2nd negative electrode 6 2nd fixed electrolyte 7 1st gas diffusion resistance 8 2nd gas diffusion resistance 9 support wall 10 1st Gas chamber 11 second gas chamber 12-a first electrochemical element 12-b second electrochemical element 13 first resistor 14 second resistor 15 first voltage application means 16 second voltage application Means 17 First voltage detecting means 18 Second voltage detecting means 19 Heating means 20 Circuit means
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｇ０１Ｎ 27/419 Ｇ０１Ｎ 27/46 ３３１ Ｈ０１Ｍ 14/00 ３２５Ｅ ３２５Ｎ (58)調査した分野(Int.Cl.7，ＤＢ名) G01N 27/409 B01D 53/32 ZAB B01D 53/56 G01N 27/41 G01N 27/416 G01N 27/419 H01M 14/00 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 identification code FI G01N 27/419 G01N 27/46 331 H01M 14/00 325E 325N (58) Field surveyed (Int.Cl. 7 , DB name) G01N 27/409 B01D 53/32 ZAB B01D 53/56 G01N 27/41 G01N 27/416 G01N 27/419 H01M 14/00
Claims (4)
て対向して配置した第１負電極及び第１正電極とから構
成された第１の電気化学素子と、酸素イオン伝導性の第
２固体電解質を介して対向して配置した第２負電極及び
第２正電極とから構成された第２の電気化学素子と、前
記第１の電気化学素子の前記第１負電極を雰囲気ガスと
接触させる第１のガス拡散抵抗と、前記第２の電気化学
素子の第２負電極を前記第１の電気化学素子の第１負電
極と接触させた雰囲気ガスに接触させるための第２のガ
ス拡散抵抗とから成り，前記第２負電極が酸素存在下に
おいて窒素酸化物吸着性の化合物を含有する電気化学素
子。 1. A first electrochemical device comprising a first negative electrode and a first positive electrode disposed to face each other via an oxygen ion conductive first solid electrolyte, and a first electrochemical device comprising an oxygen ion conductive first solid electrolyte .
(2) a second negative electrode disposed to face through a solid electrolyte;
A second electrochemical device including a second positive electrode, a first gas diffusion resistor for bringing the first negative electrode of the first electrochemical device into contact with an atmospheric gas, and a second electrochemical device. A second gas diffusion resistance for bringing the second negative electrode of the device into contact with the atmospheric gas brought into contact with the first negative electrode of the first electrochemical device , wherein the second negative electrode is exposed to oxygen.
An electrochemical device containing a compound capable of adsorbing nitrogen oxides .
る窒素酸化物吸着性の化合物がＢａ2ＹＣｕ3Ｏ7型構造
を持つ酸化物である請求項１記載の電気化学素子。2. The electrochemical device according to claim 1, wherein the nitrogen oxide-adsorbing compound contained in the second negative electrode of the second electrochemical device is an oxide having a Ba 2 YCu 3 O 7 type structure.
くとも貴金属と前記窒素酸化物吸着性の化合物とからな
る請求項１記載の電気化学素子。3. The electrochemical device according to claim 1, wherein the second negative electrode of the second electrochemical device comprises at least a noble metal and the nitrogen oxide-adsorbing compound.
圧として検出するための第１の抵抗と、前記第２の電気
化学素子を流れる第２電流を電圧として検出するための
第２の抵抗と、前記第１の電気化学素子に電圧を印加す
るための第１の電圧印可手段と、前記第２の電気化学素
子に電圧を印加するための第２の電圧印可手段とを電気
的接続した回路手段と、前記第１及び第２の抵抗の両端
電圧の検出手段と、前記第１及び第２の電気化学素子を
動作温度に加熱する加熱手段とからなる請求項１記載の
窒素酸化物濃度測定装置。4. A first resistor for detecting a first current flowing through a first electrochemical device as a voltage, and a second resistor for detecting a second current flowing through the second electrochemical device as a voltage. , A first voltage applying means for applying a voltage to the first electrochemical element, and a second voltage applying means for applying a voltage to the second electrochemical element. 2. The nitrogen oxidation according to claim 1, comprising: connected circuit means; means for detecting voltages across the first and second resistors; and heating means for heating the first and second electrochemical devices to an operating temperature. Object concentration measuring device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6162025A JP3067532B2 (en) | 1994-07-14 | 1994-07-14 | Electrochemical element and nitrogen oxide concentration measuring device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6162025A JP3067532B2 (en) | 1994-07-14 | 1994-07-14 | Electrochemical element and nitrogen oxide concentration measuring device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0829387A JPH0829387A (en) | 1996-02-02 |
| JP3067532B2 true JP3067532B2 (en) | 2000-07-17 |
Family
ID=15746647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6162025A Expired - Fee Related JP3067532B2 (en) | 1994-07-14 | 1994-07-14 | Electrochemical element and nitrogen oxide concentration measuring device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3067532B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101894346B1 (en) * | 2011-12-09 | 2018-09-04 | 코와 가부시키가이샤 | Support |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3050781B2 (en) * | 1995-10-20 | 2000-06-12 | 日本碍子株式会社 | Method and apparatus for measuring predetermined gas component in gas to be measured |
| US5948964A (en) * | 1995-10-20 | 1999-09-07 | Ngk Insulators, Ltd. | NOx sensor and method of measuring NOx |
| EP0862056B1 (en) * | 1996-09-17 | 2006-02-22 | Kabushiki Kaisha Riken | Gas sensor |
| US6695964B1 (en) | 1996-12-02 | 2004-02-24 | Ngk Spark Plug Co., Ltd. | Method and apparatus for measuring NOx gas concentration |
| US6228252B1 (en) | 1997-02-13 | 2001-05-08 | Ngk Spark Plug Co. Ltd. | Apparatus for detecting concentration of nitrogen oxide |
| US6068747A (en) * | 1997-03-10 | 2000-05-30 | Denso Corporation | Solid electrolyte gas sensor |
| US6375828B2 (en) | 1997-03-21 | 2002-04-23 | Ngk Spark Plug Co., Ltd. | Methods and apparatus for measuring NOx gas concentration, for detecting exhaust gas concentration and for calibrating and controlling gas sensor |
| JP3648063B2 (en) * | 1997-09-22 | 2005-05-18 | 日本特殊陶業株式会社 | Gas sensor, gas sensor system using the same, and method of manufacturing gas sensor |
| JP4516168B2 (en) * | 1998-11-16 | 2010-08-04 | 株式会社デンソー | Gas concentration measurement method |
-
1994
- 1994-07-14 JP JP6162025A patent/JP3067532B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101894346B1 (en) * | 2011-12-09 | 2018-09-04 | 코와 가부시키가이샤 | Support |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0829387A (en) | 1996-02-02 |
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