EP2401604A1 - Capteur de gaz à électrolyte solide pour la mesure de différentes espèces gazeuses - Google Patents

Capteur de gaz à électrolyte solide pour la mesure de différentes espèces gazeuses

Info

Publication number
EP2401604A1
EP2401604A1 EP10704800A EP10704800A EP2401604A1 EP 2401604 A1 EP2401604 A1 EP 2401604A1 EP 10704800 A EP10704800 A EP 10704800A EP 10704800 A EP10704800 A EP 10704800A EP 2401604 A1 EP2401604 A1 EP 2401604A1
Authority
EP
European Patent Office
Prior art keywords
pumping
sensor element
autonomous
electrode
element according
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Withdrawn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
EP10704800A
Other languages
German (de)
English (en)
Inventor
Dirk Liemersdorf
Berndt Cramer
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 EP2401604A1 publication Critical patent/EP2401604A1/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Withdrawn legal-status Critical Current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
    • G01N27/416—Systems
    • G01N27/417—Systems using cells, i.e. more than one cell and probes with solid electrolytes
    • 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
    • G01N27/416—Systems
    • G01N27/417—Systems using cells, i.e. more than one cell and probes with solid electrolytes
    • G01N27/419—Measuring voltages or currents with a combination of oxygen pumping cells and oxygen concentration cells

Definitions

  • the invention relates to a sensor element for a solid electrolyte gas sensor, a corresponding solid electrolyte gas sensor and a method for operating such a sensor according to the preambles of the respective independent claims.
  • broadband lambda probes designed as solid electrolyte oxygen sensors are known, by means of which the oxygen partial pressure or the residual oxygen partial pressure of an exhaust gas can be measured.
  • These consist of a solid electrolyte, in which a serving as a pumping chamber cavity is arranged, which communicates via a diffusion barrier with the exhaust, for example, a respective internal combustion engine in combination.
  • these probes include an air reference channel connected to the ambient air.
  • oxygen-rich exhaust gas oxygen is continuously removed from said pumping chamber electrochemically, the oxygen diffusion stream on which it is based serves as a measure of the oxygen partial pressure in the exhaust gas.
  • the pumping direction is reversed.
  • Proportionalsonden exist, which can be operated either in the exhaust gas with excess oxygen or in the exhaust gas with oxygen deficiency, but not for the entire broadband range.
  • a diffusion-limited pumping chamber is also freed of oxygen in these probes.
  • the oxygen diffusion stream then continues as an electrically measurable pumping current and serves as a measure of the oxygen partial pressure in the exhaust gas. Since there is no information about the rich or lean state of the exhaust gas due to the missing control variable from the unloaded Nernst cell, there is no possibility there, depending on the exhaust gas composition in the pumping chamber Sauer- electrochemically pumped into or out, in order to realize a broadband probe.
  • mixed potential sensors which are constructed similar to a lambda jump probe and consist of an electrochemical cell, in which a first platinum electrode is located in the exhaust gas.
  • a second platinum electrode is separated by the solid electrolyte from the exhaust gas space and is located by means of a said air reference channel in compensation with the ambient air.
  • the present invention is based on the idea that, in the case of a solid electrolyte gas sensor in question in the respective sensor element, instead of the diffusion barrier mentioned, an autonomous pump cell should be arranged as the gas flow restriction.
  • the autonomous pump cell comprises in a preferred embodiment, two loaded or short-circuited pumping electrodes, namely an outer and an inner autonomous pumping electrode, which need not be contacted from the outside.
  • the short circuit or ohmic load i.e., use of an ohmic load resistor
  • the pump properties can be set by means of the respectively set ohmic load.
  • the autonomous pumping cell is formed by an outer and an inner autonomous pumping electrode which are contacted or connected from outside with a control, for example a control circuit, evaluation circuit or the like, whereby the at least two pumping electrodes are externally connected. are changeable in situ.
  • a diffusion behavior similar to that of a diffusion barrier is preferably simulated, preferably by changing the electrical resistance of the two pumping electrodes.
  • the function of a diffusion barrier can be realized by means of such a pumping cell, the diffusion barrier, in contrast to the prior art, still being adjustable or trimmable during operation of the pumping cell (ie in-situ).
  • the main advantage of the solid electrolyte gas sensor according to the invention is the reduction in the number of contacts.
  • the expense compared to the calibration step required in the prior art is reduced and aging processes on such diffusion barriers are completely avoided or can be compensated in situ, as a result of which the invention
  • the oxygen partial pressure or residual oxygen partial pressure can be determined quantitatively in the entire lambda range.
  • an adaptation of the sensor for detecting further (different) gas species can also be carried out.
  • the present invention further relates to a method for operating a sensor element according to the invention or a corresponding solid electrolyte gas sensor for the quantitative detection of oxygen, wherein between two measuring electrodes, a constant voltage is applied and wherein the resulting at the applied constant voltage electric pumping current as a measure of the oxygen partial pressure in Exhaust gas is used.
  • different states of the autonomous pump cell can be adjusted by means of the applied constant voltage.
  • a negative pressure can also be set in the closed pumping chamber, whereby even with relatively rich exhaust gas, i. an exhaust gas with a relatively low air value lambda, still a positive pumping current is generated.
  • solid electrolyte gas sensor of the present invention is not limited to
  • FIG. 1 shows a longitudinal section through a sensor element of a broadband lambda probe according to the prior art
  • FIG. 3 shows a cross section through a sensor element of a mixed potential sensor according to the prior art
  • FIG. 4 shows a longitudinal section through a sensor element according to a first exemplary embodiment of the solid electrolyte gas sensor according to the invention
  • FIG. 5 shows a longitudinal section through a sensor element according to a second embodiment of the solid electrolyte gas sensor according to the invention
  • FIG. 6 is a plan view of a trimmable resistance meander for calibration of the oxygen transport in a solid electrolyte gas sensor according to the invention
  • FIG. 7 shows a longitudinal section through a sensor element according to a third exemplary embodiment of the solid electrolyte gas sensor according to the invention.
  • Fig. 8 typical measurement results when using a solid electrolyte gas sensor according to the invention on a propane gas burner.
  • Description of exemplary embodiments 1 shows schematically a sensor element 105 of a broadband lambda probe according to the prior art in a lateral sectional view.
  • the probe shown there consists of a yttrium-doped zirconium dioxide body 110 forming an ion-conducting solid electrolyte, within which a cavity (pumping chamber or pump cell) 15 is arranged, which communicates with the exhaust gas to be sensed via a diffusion barrier 120.
  • the sensor element includes an air reference passage 125 connected to the ambient air.
  • a cermet electrode 130, 135 is arranged, which via separate leads with (not shown here) electrical connection contacts (pads ) are connected.
  • a heater 140 with associated heater insulation 145 is arranged in the lower region of the sensor element 105, by means of which the operating temperature of the sensor element 105 can be adjusted.
  • oxygen-rich exhaust gas oxygen is continuously removed electrochemically from the pumping chamber 15 via the pair of electrodes IPE 130 and APE 150, until the pair of electrodes IPE 130 and RE 135 has a voltage of e.g. 400 mV.
  • the potential present at the electrode APE 150 is then positive, based on the potential of the electrode IPE 130.
  • the oxygen diffusion current continues in this case as an electrically measurable pumping current at the electrodes IPE 130 and APE 150 and serves as a measured variable for the oxygen Partial pressure in the exhaust gas.
  • the pumping direction is reversed.
  • the potential of the APE 140 is then more negative than that of the IPE 130.
  • a control is used whose input variable is the voltage between
  • RE 135 and IPE 130 forms.
  • FIG. 2 shows a longitudinal section through a sensor element of a proportional probe according to the prior art. Similar to the broadband probe, a diffusion-limited pumping chamber 200 is freed from oxygen in the proportional probes.
  • Oxygen diffusion current then continues as an electrically measurable pumping current between an inner sensor electrode 205 and an (inner) reference electrode 210 and serves as a measure of the oxygen partial pressure in the exhaust gas.
  • an inner sensor electrode 205 and an (inner) reference electrode 210 and serves as a measure of the oxygen partial pressure in the exhaust gas.
  • control variable the lack of information (control variable) from the unloaded Nernst cell no statement about the rich or lean condition of the exhaust gas is present, there is also no possibility, depending on the exhaust gas composition in the pumping chamber, to reverse the pumping direction, ie to pump oxygen electrochemically into or out, thereby realizing a wideband probe.
  • FIG. 3 now shows a mixing potential sensor known from the prior art in a view similar to the previous figures.
  • Mixed potential sensors are constructed from an electrochemical cell with a first electrode 300 disposed in the exhaust path.
  • a second platinum electrode 305 is separated by a solid electrolyte 110 from the here above the first electrode 300 arranged exhaust space 310 and is located by means of an air reference channel not shown herein (corresponding to the reference numeral, 125 'in Fig. 2) in compensation with the ambient air.
  • the reference electrode (RE) is at reference potential of the measuring circuit (GND).
  • the reference potential is thus set independent of the gas atmosphere.
  • the sensor element 400 has a similar construction to the probe types described above and has a pumping chamber 115, a heater 140, an inner pumping electrode PE2 130 arranged in the pumping chamber and a further pumping electrode PE1 405.
  • the pumping electrode PE1 405 is arranged either in the exhaust gas (FIG. 5) or in the air reference channel 125 (FIG. 4).
  • the sensor element 400 is set by the heater 140 to the required operating temperature.
  • the pumping chamber 1 15 is gas-tightly sealed relative to the exhaust gas 410.
  • a further electrode AUPE1 415 and AUPE2 420 both in the exhaust gas and in the pumping chamber 15, which, depending on the embodiment, does not follow outside, ie from the sensor element to an evaluation circuit, are contacted and are therefore referred to below in all cases as “autonomous" pumping electrodes.
  • the gas inlet or the gas inlet limit is realized in this sensor element 400, instead of the diffusion barrier known in the prior art, by the said autonomous pump cell 415, 10, 420, 15, 410. According to the oxygen concentration gradient between the exhaust gas and the gas-tight pumping chamber 1 15,
  • Nernst voltage two Nernst or oxygen electrodes, eg Pt-Pt
  • Pt-Pt two Nernst or oxygen electrodes
  • a mixed potential electrode (FIG. 3) can also be used as the outer autonomous pumping electrode (AUPE1), whereby the sensor can detect oxygen depending on the electrode material (mixed potential formation among others for HC and CO with oxygen) as well as for detection of further gas species (selective mixed potential formation eg NH 3 , NO x , CO, etc.) is suitable.
  • electrode materials for the sensor element according to the invention are preferably considered:
  • Nernst electrodes for example Pt, Pd, Ir, Ta
  • ceramic components such as the so-called “cermets”.
  • the oxygen transport can be adjusted by the load of the autonomous pump cell 415, 1 10, 420 via a resistor (open circuit to short circuit). This can be done, for example, by means of a trimmable resistance meander (eg laser adjustment). In the case of an unexpected specimen scattering, this could at the same time be used in the production process as a simple and favorable possibility of sensor calibration (FIG. 6). Under normal production conditions, however, no adjustment will usually be necessary.
  • the resulting voltage is determined in the case of two oxygen electrodes by the self-adjusting oxygen partial pressure (concentration and / or change in the absolute pressure).
  • a gas-tight pumping chamber 15, 410 defined gas flow via the autonomous pumping chamber and through the active pumping process
  • a porous diffusion barrier according to the prior art
  • changes in pressure and / or overpressure and / or due to a very low oxygen partial pressure in the pumping chamber also occur electrode voltages greater than 0.9 V.
  • a Nernst voltage of greater than 900 mV can be achieved against an air reference.
  • Oxygen transport is possible without applying an external voltage or current (otherwise 2 additional electrical contacts would be required).
  • Characteristic of the gas inflow depends on the difference of the oxygen partial pressures (concentration and / or change of the absolute pressure) between AUPE1 and AUPE2.
  • Oxygen sensor can be used as well as for the detection of other gas species.
  • the load factor can be determined by the Level of electrical conductivity (material properties of the electrolyte) can be adjusted.
  • the autonomous pump cell 415, 110, 420 described can also be used as a replacement for the diffusion barrier of a standard
  • LSU Broadband probe
  • FIG. 4 for the quantitative detection of oxygen.
  • an analogue measuring principle can be used taking into account the modified mixed potential electrodes.
  • the gas inlet limitation is based on the properties of the autonomous pump cell
  • the associated electric pumping current of the pumping chamber 1 15, 410 tapped via PE1 130 and PE2 405, which is directly proportional to the oxygen-ion flow, can thus be used as a measured variable for the oxygen partial pressure in the exhaust gas.
  • FIG. 7 shows a sensor element according to the invention according to a third exemplary embodiment (variant 3) of the invention, wherein the measuring principles already described above according to FIGS. 2 and 5 are combined with one another.
  • the variant 3 is therefore used in the above-described broadband probes
  • the associated sensor characteristics change according to the set characteristics of the autonomous pumping chamber (i.e., electrode material and load) of the present invention as described above.
  • FIG. 8 shows a step change of the oxygen excess
  • the closed pumping chamber was arranged in the exhaust gas jet of a propane gas burner.
  • the electrode inside the pumping chamber is less than 1V below the potential of the air reference electrode due to the chamber negative pressure intentionally set in this mode and / or due to a very low oxygen partial pressure (L / A UPE2-PE2 ⁇ - 1V), there is still a positive pump current, which can be assigned to a unique characteristic curve.
  • L / A UPE2-PE2 ⁇ - 1V very low oxygen partial pressure
  • the sensor variants described here can be used for the detection of the oxygen partial pressure (broadband) and the like. a. be used in the exhaust system of motor vehicles. In principle, however, depending on the sensor variant used, in particular the electrode material used and the temperature, and the quantitative determination of various other gas constituents conceivable, such as:
  • Oxygen-containing gases nitrogen oxides, carbon monoxide, etc.

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  • 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)

Abstract

L'invention concerne un élément capteur pour un capteur de gaz à électrolyte solide comprenant une chambre de pompage étanche aux gaz, un chauffage et une première électrode de pompage placée dans la chambre de pompage, ainsi qu'au moins une deuxième électrode de pompage. À la place d'une barrière de diffusion, est disposée une cellule de pompage autonome comme limitation d'entrée de gaz. La cellule de pompage autonome possède des électrodes de pompage extérieure et intérieure qui sont contactées ou court-circuitées de l'extérieur à l'aide d'une résistance ajustable.
EP10704800A 2009-02-27 2010-02-11 Capteur de gaz à électrolyte solide pour la mesure de différentes espèces gazeuses Withdrawn EP2401604A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009001249A DE102009001249A1 (de) 2009-02-27 2009-02-27 Festelektrolytgassensor für die Messung diverser Gasspezies (I)
PCT/EP2010/051713 WO2010097296A1 (fr) 2009-02-27 2010-02-11 Capteur de gaz à électrolyte solide pour la mesure de différentes espèces gazeuses

Publications (1)

Publication Number Publication Date
EP2401604A1 true EP2401604A1 (fr) 2012-01-04

Family

ID=42124499

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10704800A Withdrawn EP2401604A1 (fr) 2009-02-27 2010-02-11 Capteur de gaz à électrolyte solide pour la mesure de différentes espèces gazeuses

Country Status (5)

Country Link
US (1) US20120006692A1 (fr)
EP (1) EP2401604A1 (fr)
CN (1) CN102334027A (fr)
DE (1) DE102009001249A1 (fr)
WO (1) WO2010097296A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2614154T3 (es) * 2008-07-10 2017-05-29 Robert Bosch Gmbh Elemento sensor y procedimiento para determinar componentes gaseosos en mezclas gaseosas y su utilización
DE102014200063A1 (de) * 2014-01-07 2015-07-09 Robert Bosch Gmbh Verfahren und Vorrichtung zur Überwachung der Fettgas-Messfähigkeit einer Abgas-Sonde
JP6523144B2 (ja) * 2015-11-17 2019-05-29 日本碍子株式会社 ガスセンサ
US10859526B2 (en) 2017-11-22 2020-12-08 Delphi Technologies Ip Limited Gas sensor with a pump cell
WO2019144134A2 (fr) * 2018-01-22 2019-07-25 InSyte Systems, Inc. Capteur à faible impédance pour matériaux à faible densité
JP7057741B2 (ja) * 2018-09-18 2022-04-20 株式会社Soken ガスセンサの診断装置
CN111257390B (zh) * 2019-12-27 2023-04-07 苏州溢亮材料科技有限公司 对称双泵结构的高温湿度传感器

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Publication number Priority date Publication date Assignee Title
JPH03130657A (ja) * 1989-10-17 1991-06-04 Tokuyama Soda Co Ltd 酸素センサ
DE4007856A1 (de) * 1990-03-13 1991-09-19 Bosch Gmbh Robert Sensorelement fuer eine sauerstoffgrenzstromsonde zur bestimmung des (lambda)-wertes von gasgemischen
DE4231966A1 (de) * 1992-09-24 1994-03-31 Bosch Gmbh Robert Planare polarograhische Sonde zur Bestimmung des Lambda-Wertes von Gasgemischen
DE4341278B4 (de) * 1993-12-03 2004-05-06 Robert Bosch Gmbh Grenzstromsensor zur Bestimmung des Lambdawertes in Gasgemischen
JP2003512044A (ja) * 1999-10-15 2003-04-02 ヒューマン ジノーム サイエンシーズ， インコーポレイテッド プロテインチロシンキナーゼレセプターポリヌクレオチド、ポリペプチド、および抗体
DE10332519A1 (de) * 2003-07-17 2005-02-03 Robert Bosch Gmbh Elektrochemische Pumpzelle für Gassensoren
DE102007049716A1 (de) * 2006-12-29 2008-07-03 Robert Bosch Gmbh Gassensor mit gasdicht abgeschirmtem Hohlraum
ES2614154T3 (es) * 2008-07-10 2017-05-29 Robert Bosch Gmbh Elemento sensor y procedimiento para determinar componentes gaseosos en mezclas gaseosas y su utilización
DE102008040314A1 (de) * 2008-07-10 2010-01-14 Robert Bosch Gmbh Verfahren zur Messung von einer Gasspezies geringer Konzentration in einem Gasstrom

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010097296A1 *

Also Published As

Publication number Publication date
DE102009001249A1 (de) 2010-09-02
CN102334027A (zh) 2012-01-25
WO2010097296A1 (fr) 2010-09-02
US20120006692A1 (en) 2012-01-12

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