EP1244905A2 - Element capteur d'un capteur de gaz destine a la determination de composantes gazeuses - Google Patents

Element capteur d'un capteur de gaz destine a la determination de composantes gazeuses

Info

Publication number
EP1244905A2
EP1244905A2 EP00991106A EP00991106A EP1244905A2 EP 1244905 A2 EP1244905 A2 EP 1244905A2 EP 00991106 A EP00991106 A EP 00991106A EP 00991106 A EP00991106 A EP 00991106A EP 1244905 A2 EP1244905 A2 EP 1244905A2
Authority
EP
European Patent Office
Prior art keywords
sensor element
element according
gas
sensor
solid electrolyte
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00991106A
Other languages
German (de)
English (en)
Inventor
Thomas Wahl
Thomas Brinz
Hermann Dietz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Robert Bosch GmbH
Original Assignee
Robert Bosch GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Robert Bosch GmbH filed Critical Robert Bosch GmbH
Publication of EP1244905A2 publication Critical patent/EP1244905A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4073—Composition or fabrication of the solid electrolyte
    • G01N27/4074—Composition or fabrication of the solid electrolyte for detection of gases other than oxygen

Definitions

  • the invention relates to a sensor element of a gas sensor for determining gas components, as is known, for example, from US Pat. No. 4,689,122.
  • the nitrogen oxides in the exhaust gas catalytic converter are largely converted to nitrogen, water and carbon dioxide by reducing components also present in the exhaust gas, such as hydrocarbons.
  • reducing components such as hydrocarbons.
  • a well-known method is the targeted dosing tion of ammonia or onia-generating substances in the exhaust gas flow. This takes place in the direction of the exhaust gas upstream of a further catalyst, on the surface of which the reaction of the nitrogen oxides with ammonia to nitrogen and water takes place.
  • a gas sensor which can be used to determine the concentration of hydrogen or hydrogen-containing compounds, is described in US Pat. No. 4,689,122.
  • This sensor has a measuring and a reference gas space, which are separated from each other by a proton-conducting solid electrolyte membrane.
  • a measuring electrode is arranged on the measuring gas side of the membrane and a reference electrode on the side of the reference gas. Both electrodes are made of platinum and are catalytically active.
  • the solid electrolyte membrane consists of a mixture of organic polymers with heteropolyacids or their salts.
  • Solid electrolyte membranes based on organic polymeric components have the disadvantage, however, that the corresponding gas sensor cannot be operated at higher temperatures for reasons of stability.
  • Gas sensors based on ceramic solid electrolytes are suitable for use at temperatures of 300 - 600 ° C. These are usually based on oxidic materials and therefore act as oxygen ion conductors within electrochemical measuring cells. ter. This is problematic since only solid gas components can be determined using this solid electrolyte. Compounds such as hydrogen or hydrocarbons, since they do not contain any bound oxygen, can only be determined indirectly.
  • the sensor element according to the invention with the features of claim 1 has the advantage that the sensor element can be operated at higher temperatures, as are common in exhaust gases from internal combustion engines. Furthermore, the concentrations of hydrogen-containing gas components and hydrogen can be determined without cross-sensitivity to water or oxygen-containing compounds.
  • the use of a catalytically inactive measuring electrode enables the gas sensor to be used as an imbalance sensor, ie a momentary determination of the gas components to be measured is possible in the gas mixture atmosphere. loaned without the result being falsified by catalytic processes taking place on the electrode surface.
  • Another advantage is that if a catalytically inactive measuring electrode is used, the reference electrode can also be exposed directly to the gas mixture. This increases the flexibility of the sensor structure.
  • a second reference electrode is particularly advantageous since it enables a completely currentless measurement of the voltage between measuring and reference electrodes and thus further increases the measuring accuracy of the sensor element.
  • FIG. 1 shows a cross section through a sensor element according to the invention
  • FIGS. 2 and 3 cross sections through sensor elements according to two further exemplary embodiments.
  • 10 designates a planar sensor element of an electrochemical gas sensor which has a proton-conducting solid electrolyte layer 11a.
  • further solid electrolyte layers 11b, 11c, 11d are provided, which for example consist of the same material as the solid electrolyte layer 11a.
  • All solid electrolyte layers 11a-11d are designed as ceramic foils and form a planar ceramic body.
  • the integrated shape of the planar ceramic body of the sensor element 10 is lamination of the ceramic films printed with functional layers and subsequent sintering of the laminated structure in a manner known per se.
  • the solid electrolyte layer 11a is made of a proton-conducting ceramic material such as Ce0 2 . Alkaline earth oxides such as CaO, SrO and BaO can be contained as dopants.
  • the sensor element 10 contains, for example, an air reference channel 19 which at one end leads out of the planar body of the sensor element 10 and is connected to the air atmosphere.
  • an air reference channel 19 which at one end leads out of the planar body of the sensor element 10 and is connected to the air atmosphere.
  • a measuring electrode 13 On the outer side of the solid electrolyte layer 11a directly facing the gas mixture there is a measuring electrode 13 which can be covered with a porous protective layer 21.
  • a porous protective layer 21 This consists of a gas-permeable, porous and catalytically inactive material such as A1 2 0 3 or Ce0 2 .
  • the electrode 13 consists of a catalytically inactive material.
  • Gold, palladium, silver and ruthenium, for example, are suitable. However, alloys or mixtures thereof can also be used, possibly with the addition of platinum.
  • a reference electrode 14 is located on the side of the solid electrolyte layer 11a facing the air reference channel 19. This is made of a catalytically active material, such as platinum.
  • the electrode material for both electrodes is in a manner known per se used as a cermet to sinter it with the ceramic foils.
  • a resistance heater 40 is also embedded in the ceramic base body of the sensor element 10 between two electrical insulation layers, not shown here.
  • the resistance heater serves to heat the sensor element 10 to the necessary operating temperature of approximately 500 ° C. Essentially the same temperature is present at the spatially closely spaced electrodes 13, 14.
  • the electrodes 13, 14 are operated as a so-called Nernst cell.
  • the EMF measured between the measuring and reference electrodes as voltage.
  • the EMF is characterized by different hydrogen or Proton concentration caused on the measuring and reference electrode (so-called Nernst principle).
  • the level of the measured voltage provides information about the hydrogen or proton concentration at the measuring electrode.
  • the voltage signal of the sensor element 10 naturally does not show any cross-sensitivity to oxygen-containing compounds due to the proton-conducting electrolyte used.
  • the reference electrode 14 consists of a catalytically active platinum layer and acts as an equilibrium electrode, since it catalyzes the establishment of a thermodynamic equilibrium of the gas components on its surface.
  • a catalytically inactive measuring electrode 13 with a catalytically active reference electrode 14 also enables the reference electrode to be arranged directly in the exhaust gas stream.
  • FIG. 2 Such a construction of the sensor element 10 is shown in FIG. 2.
  • the voltage measured here corresponds to the difference in the imbalance potential at the measuring electrode
  • the reference electrode 13 and the equilibrium potential at the reference electrode 14 and enables the concentration determination of hydrogen-containing compounds in the gas mixture.
  • a concentration cell consisting of a measuring and reference electrode is operated without current.
  • small current flows occur that can affect the voltage signal. Therefore, according to one another exemplary embodiment, a second reference electrode 15, as shown in FIG. 3, is incorporated into the sensor element 10. This enables a currentless voltage measurement between measuring and further reference electrodes 15, since in an arrangement according to FIG. 3 the current flow between measuring 13 and first reference electrode 14 takes place for geometrical reasons.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Measuring Oxygen Concentration In Cells (AREA)
  • Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)

Abstract

L'invention concerne un élément capteur d'un capteur de gaz, pouvant être utilisé pour la détermination de la concentration d'hydrogène ou de composantes gazeuses contenant de l'hydrogène telles que l'ammoniac ou les hydrocarbures, présents dans un mélange gazeux. Ledit élément capteur comporte une électrode de mesure (13) exposée au mélange gazeux, et au moins une électrode de référence (14) disposée sur un électrolyte solide (11a) conduisant les protons, cet électrolyte solide (11a) étant composé d'un matériau purement céramique.
EP00991106A 1999-12-24 2000-12-20 Element capteur d'un capteur de gaz destine a la determination de composantes gazeuses Withdrawn EP1244905A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19963008 1999-12-24
DE19963008A DE19963008B4 (de) 1999-12-24 1999-12-24 Sensorelement eines Gassensors zur Bestimmung von Gaskomponenten
PCT/DE2000/004555 WO2001048466A2 (fr) 1999-12-24 2000-12-20 Element capteur d'un capteur de gaz destine a la determination de composantes gazeuses

Publications (1)

Publication Number Publication Date
EP1244905A2 true EP1244905A2 (fr) 2002-10-02

Family

ID=7934503

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00991106A Withdrawn EP1244905A2 (fr) 1999-12-24 2000-12-20 Element capteur d'un capteur de gaz destine a la determination de composantes gazeuses

Country Status (5)

Country Link
US (1) US20030121800A1 (fr)
EP (1) EP1244905A2 (fr)
JP (1) JP2003518619A (fr)
DE (1) DE19963008B4 (fr)
WO (1) WO2001048466A2 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10221392B4 (de) * 2002-05-14 2004-07-22 Siemens Ag Verfahren und Vorrichtung zur Messung einer Gas-Konzentration
JP3993122B2 (ja) 2002-05-29 2007-10-17 株式会社デンソー ガスセンサ素子及び含水素ガスの測定方法
DE102006062058A1 (de) 2006-12-29 2008-07-03 Robert Bosch Gmbh Sensorelement zur Bestimmung der Konzentration einer oxidierbaren Gaskomponente in einem Messgas
TW200902968A (en) * 2007-07-06 2009-01-16 Univ Nat Taiwan Science Tech Gas sensor
JP4901825B2 (ja) * 2008-08-20 2012-03-21 株式会社日本自動車部品総合研究所 アンモニア検出素子及びこれを備えたアンモニアセンサ
DE102011084653A1 (de) * 2011-10-17 2013-04-18 Robert Bosch Gmbh Sprungsonde für den gepumpten und ungepumten Betrieb
DE102013208939A1 (de) * 2013-05-15 2014-11-20 Robert Bosch Gmbh Mikromechanische Sensorvorrichtung
DE102013010561A1 (de) * 2013-06-25 2015-01-08 Volkswagen Aktiengesellschaft Sensor zur Detektion von Kohlenwasserstoffen in einem Gasgemisch, seine Verwendung zur Bestimmung eines HC-Partialdrucks im Abgas eines Verbrennungsmotors sowie Kraftfahrzeug mit einem solchen
RU2583162C1 (ru) * 2015-03-05 2016-05-10 Федеральное государственное бюджетное учреждение науки Институт высокотемпературной электрохимии Уральского отделения Российской Академии наук Амперометрический способ измерения концентрации аммиака в азоте
DE102015217305A1 (de) * 2015-09-10 2017-03-16 Robert Bosch Gmbh Mikromechanisches Festkörperelektrolyt-Sensorelement und Verfahren zu seiner Herstellung
JP6517727B2 (ja) * 2016-05-02 2019-05-22 トヨタ自動車株式会社 電気加熱式触媒コンバーターとその製造方法
PL3357558T3 (pl) * 2017-02-03 2020-03-31 Umicore Ag & Co. Kg Katalizator do oczyszczania gazów spalinowych silników wysokoprężnych
JP6758215B2 (ja) * 2017-02-14 2020-09-23 株式会社Ｓｏｋｅｎ アンモニアセンサ素子

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5777954A (en) * 1980-10-31 1982-05-15 Fuji Electric Co Ltd Hydrogen sensor
US4689122A (en) * 1983-12-29 1987-08-25 Uop Inc. Gas detection apparatus and method with novel electrolyte membrane
US4664757A (en) * 1985-12-27 1987-05-12 Uop Inc. Method and apparatus for gas detection using proton-conducting polymers
US4976991A (en) * 1987-11-23 1990-12-11 Battelle-Institut E.V. Method for making a sensor for monitoring hydrogen concentrations in gases
US5672258A (en) * 1993-06-17 1997-09-30 Rutgers, The State University Of New Jersey Impedance type humidity sensor with proton-conducting electrolyte
US5393404A (en) * 1993-06-17 1995-02-28 Rutgers, The State University Of New Jersey Humidity sensor with nasicon-based proton-conducting electrolyte
JP3680232B2 (ja) * 1997-03-31 2005-08-10 トヨタ自動車株式会社 固体電解質と、これを用いた燃料電池、水素ポンプ、酸素濃度センサおよび水蒸気濃度センサ
DE19734861C2 (de) * 1997-08-12 1999-10-28 Bosch Gmbh Robert Sensorelement zur Bestimmung der Konzentration oxidierbarer Bestandteile in einem Gasgemisch

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0148466A2 *

Also Published As

Publication number Publication date
DE19963008A1 (de) 2001-07-12
US20030121800A1 (en) 2003-07-03
JP2003518619A (ja) 2003-06-10
WO2001048466A2 (fr) 2001-07-05
WO2001048466A3 (fr) 2002-02-21
DE19963008B4 (de) 2009-07-02

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