CN112946043B - Calibration-free wide-area oxygen sensor and detection method thereof - Google Patents
Calibration-free wide-area oxygen sensor and detection method thereof Download PDFInfo
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- CN112946043B CN112946043B CN202110139924.XA CN202110139924A CN112946043B CN 112946043 B CN112946043 B CN 112946043B CN 202110139924 A CN202110139924 A CN 202110139924A CN 112946043 B CN112946043 B CN 112946043B
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- oxygen pump
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000001301 oxygen Substances 0.000 title claims abstract description 74
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 74
- 238000001514 detection method Methods 0.000 title abstract description 5
- 238000009792 diffusion process Methods 0.000 claims abstract description 62
- 239000010410 layer Substances 0.000 claims abstract description 38
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000011159 matrix material Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000011241 protective layer Substances 0.000 claims abstract description 5
- 238000005498 polishing Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 6
- 238000004904 shortening Methods 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 abstract description 10
- 238000005259 measurement Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- G01N27/409—Oxygen concentration cells
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- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/40—Engine management systems
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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
The invention discloses a calibration-free wide-range oxygen sensor and a detection method thereof, wherein the calibration-free wide-range oxygen sensor comprises an outer protective layer, an oxygen pump outer electrode, an oxygen pump inner electrode, a zirconia matrix, a reference electrode, an upper insulating layer, a heating electrode and a lower insulating layer, wherein the oxygen pump inner electrode is arranged in the zirconia matrix, a first diffusion layer and a second diffusion layer are also arranged in the zirconia matrix, and the oxygen pump inner electrode is positioned between the first diffusion layer and the second diffusion layer; and applying a certain voltage to the heating electrode, enabling the internal resistance between the internal electrode of the oxygen pump of the sensor and the reference electrode to be 300 omega, applying a voltage between the external electrode of the oxygen pump and the internal electrode of the oxygen pump, and judging the oxygen concentration by the magnitude of limiting current. According to the technical scheme, the ceramic chip of the wide-area oxygen sensor can be directly calibrated to the target value, so that the cost of the plug-in components and the matched ceramic resistor is greatly reduced; the calibration method enables the limiting current to reach 1.4+/-0.02 mA.
Description
Technical Field
The invention relates to the technical field of wide-range oxygen sensors, in particular to a calibration-free wide-range oxygen sensor and a detection method thereof.
Background
In recent years, with the continuous development of the automobile industry, a wide-area oxygen sensor is used for controlling the ratio of fuel to air, and a five-wire six-plug-in type wide-area oxygen sensor is generally used, wherein a ceramic resistor printed by a thick film circuit is contained in a plug-in unit of the wide-area oxygen sensor, and is used for adjusting current signals to enable all the oxygen sensors to reach a standard range.
However, such existing wide-area oxygen sensors have the following drawbacks: the structure is unreasonable to set up, and plug-in components and ceramic resistor are more expensive, and the equipment is troublesome, and the practicality is poor.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide the calibration-free wide-area oxygen sensor which is reasonable in structural design, easy to assemble, convenient to use and good in practicability and the detection method thereof.
In order to achieve the above purpose, the present invention provides the following technical solutions: the utility model provides a wide-range oxygen sensor of exemption from to mark, includes outer protective layer, oxygen pump outer electrode, oxygen pump inner electrode, zirconia base member, reference electrode, upper insulating layer, heating electrode and lower insulating layer, the oxygen pump inner electrode sets up in the zirconia base member, and still is provided with first diffusion layer and second diffusion layer in the zirconia base member, the oxygen pump inner electrode is located between first diffusion layer and the second diffusion layer;
the method comprises the steps of applying a certain voltage to a heating electrode, enabling the internal resistance between an oxygen pump inner electrode and a reference electrode of a sensor to be 300 omega, then applying a voltage between an oxygen pump outer electrode and the oxygen pump inner electrode, and judging the oxygen concentration through the magnitude of limiting current;
the limiting current formula is i=4fd/rt×s/L (Po-Pe)
Wherein D is O 2 S is the cross-sectional area of the effective diffusion path, L is the length of the effective diffusion path, po is the partial pressure of oxygen in the measurement gas before diffusion, pe is the partial pressure of oxygen in the measurement chamber after diffusion, R is the gas constant, F is the Faraday constant, and T is the absolute temperature.
Preferably, the first diffusion layer and the second diffusion layer are both arranged in a trapezoid structure.
Preferably, the diffusion resistance is adjusted by adjusting the size of the diffusion layer, and the longer the diffusion path is, the larger the diffusion resistance is, and the smaller the current value is, whereas shortening the diffusion path can effectively increase the pump current.
Preferably, the limiting current is increased by laser polishing or mechanical polishing of the diffusion surface, and finally the limiting current reaches 1.4+/-0.02 mA.
The invention has the advantages that: compared with the prior art, the invention has the advantages of more reasonable structure arrangement, capability of realizing the calibration of current in the ceramic chip, capability of realizing the consistency of samples after assembly, reasonable structure design, easy assembly, convenient use and good practicability.
The invention is further described below with reference to the drawings and specific examples.
Drawings
FIG. 1 is a schematic diagram of an embodiment of the present invention;
FIG. 2 is a schematic cross-sectional view of A-A of FIG. 1;
FIG. 3 is a schematic diagram of a wide-area oxygen sensor calibration target curve;
fig. 4 is a graph showing the relationship between IP and concentration of an actual sample and the relationship between standard IP and concentration.
Detailed Description
In the description of the present embodiment, it should be noted that, if terms such as "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", "front", "rear", and the like are presented, the indicated orientation or positional relationship is based on the orientation or positional relationship shown in the drawings, only for convenience of describing the present invention and simplifying the description, and does not indicate or imply that the indicated apparatus or element must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," "third," and the like, as used herein, are used for descriptive purposes only and are not to be construed as indicating or implying any relative importance.
Referring to fig. 1, 2, 3 and 4, a calibration-free wide-area oxygen sensor comprises an outer protective layer 1, an oxygen pump outer electrode 2, an oxygen pump inner electrode 3, a zirconia matrix 4, a reference electrode 5, an upper insulating layer 6, a heating electrode 7 and a lower insulating layer 8,
the oxygen pump internal electrode 3 is arranged in the zirconia matrix 4, a first diffusion layer 9 and a second diffusion layer 10 are also arranged in the zirconia matrix 4, and the oxygen pump internal electrode 3 is positioned between the first diffusion layer 9 and the second diffusion layer 10;
the wide-range oxygen sensor is a complex of a limiting current type oxygen sensor and a concentration difference type oxygen sensor, in the working process of the wide-range oxygen sensor, certain voltage is applied to a heating electrode, the internal resistance between an internal electrode of an oxygen pump of the sensor and a reference electrode is 300 omega (the temperature of the head of the sensor is about 780 ℃), then voltage is applied between an external electrode of the oxygen pump and the internal electrode of the oxygen pump, limiting current IP reaches a certain limiting current platform, and the oxygen concentration is judged according to the magnitude of the limiting current IP;
the limiting current formula is i=4fd/rt×s/L (Po-Pe)
Wherein D is O 2 S is the cross-sectional area of the effective diffusion path, L is the length of the effective diffusion path, po is the partial pressure of oxygen in the measurement gas before diffusion, pe is the partial pressure of oxygen in the measurement chamber after diffusion, R is the gas constant, F is the Faraday constant, and T is the absolute temperature.
F＝96490C/mol and D＝1.68cm 2 /sec,,R＝82.05atm*cm3/mol*K,T＝1073K
Preferably, the first diffusion layer and the second diffusion layer are both arranged in a trapezoid structure.
Preferably, the diffusion resistance k=l/S is adjusted by adjusting the size of the diffusion layer, and the longer the diffusion path is, the larger the diffusion resistance is, and the smaller the current value is, whereas shortening the diffusion path can effectively increase the pump current.
Preferably, the limit current IP is increased by laser polishing or mechanical polishing of the diffusion surface, and finally reaches 1.4±0.02mA.
The novel process is designed, the current of the chip can be controlled to be less than 1.4mA when the limiting current IP is in an air state, then the diffusion surface is polished by laser or machinery, the diffusion area is increased while the diffusion path is shortened, and the purpose of calibration is achieved. The oxygen concentration of each oxygen sensor was controlled to be 20.5.+ -. 0.5% when tested in the air condition.
The correspondence between oxygen concentration and current is shown in table 1:
| O 2 ％ | 0.00 | 3 | 6 | 8.29 | 20.95 |
| IP(mA) | -0.02 | 0.17 | 0.36 | 0.52 | 1.4 |
TABLE 1
The smart design of the wide-area oxygen sensor is that a diffusion layer is designed into a trapezoid, the diffusion of the sensor is most difficult in the initial calibration stage, the limit current IP value is minimum at the moment, the limit current IP is set to be smaller than 1.4mA, then the limit current IP is increased by a laser polishing or mechanical polishing diffusion surface method, the limit current IP finally reaches 1.4+/-0.02 mA, and the laser polishing can adopt a controller to test the chip current when a sensor chip works, set a target value and determine the laser polishing amount; the mechanical polishing requires multiple intermittent tests to judge the polishing amount, is relatively complicated and is easy to damage the chip, so the laser polishing method is preferably recommended.
The zirconia layer is prepared by adopting a tape casting method, various electrodes, protective layers, diffusion layers, insulating layers and the like are printed on a zirconia tape casting sheet, each layer is fixed at a corresponding position by adopting a warm water isostatic pressing method, and finally the wide-area oxygen sensor ceramic chip is obtained by high-temperature sintering.
The invention can directly calibrate the ceramic chip of the wide-area oxygen sensor to a target value, and directly simplifies the commonly used five-wire six-plug-in wide-area oxygen sensor (the ceramic resistor printed by a thick film circuit is contained in the plug-in unit of the wide-area oxygen sensor for adjusting current signals to enable all the oxygen sensors to reach the standard range) into the five-wire five-plug-in wide-area oxygen sensor, thereby greatly reducing the cost of the plug-in unit and the matched ceramic resistor.
The current of the ceramic chip of the wide-area oxygen sensor designed by the calibration method is controlled to be smaller than 1.4mA when the limiting current IP is in an air state, then the diffusion surface is polished by laser or mechanically, the diffusion area is increased, the diffusion path is shortened, and finally the limiting current IP reaches 1.4+/-0.02 mA. That is, when the oxygen concentration in the air is 21%, the oxygen sensor shows that the deviation of the oxygen concentration is controlled to 21.+ -. 0.3% at the time of air condition test.
The foregoing embodiments are provided for further explanation of the present invention and are not to be construed as limiting the scope of the present invention, and some insubstantial modifications and variations of the present invention, which are within the scope of the invention, will be suggested to those skilled in the art in light of the foregoing teachings.
Claims (1)
1. A calibration-free wide-area oxygen sensor is characterized in that: the oxygen pump comprises an outer protective layer, an oxygen pump outer electrode, an oxygen pump inner electrode, a zirconia matrix, a reference electrode, an upper insulating layer, a heating electrode and a lower insulating layer, wherein the oxygen pump inner electrode is arranged in the zirconia matrix, a first diffusion layer and a second diffusion layer are also arranged in the zirconia matrix, and the oxygen pump inner electrode is positioned between the first diffusion layer and the second diffusion layer;
the method comprises the steps of applying a certain voltage to a heating electrode, enabling the internal resistance between an oxygen pump inner electrode and a reference electrode of a sensor to be 300 omega, then applying a voltage between an oxygen pump outer electrode and the oxygen pump inner electrode, and judging the oxygen concentration through the magnitude of limiting current;
the limiting current formula is i=4fd/rt×s/L (Po-Pe)
Wherein D is O 2 S is the cross-sectional area of the effective diffusion path, L is the length of the effective diffusion path, po is the partial pressure of oxygen in the measured gas before diffusion, pe is the partial pressure of oxygen in the measured chamber after diffusion, R is the gas constant, F is the Faraday constant, and T is the absolute temperature;
the first diffusion layer and the second diffusion layer are both arranged in a trapezoid structure;
the diffusion resistance is adjusted by adjusting the size of the diffusion layer, the longer the diffusion path is, the larger the diffusion resistance is, the smaller the current value is, otherwise, the pump current can be effectively increased by shortening the diffusion path;
the limiting current is increased by a laser polishing or mechanical polishing method of the diffusion surface, and finally the limiting current reaches 1.4+/-0.02 mA.
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| CN202110139924.XA CN112946043B (en) | 2021-02-02 | 2021-02-02 | Calibration-free wide-area oxygen sensor and detection method thereof |
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| CN112946043B true CN112946043B (en) | 2023-08-29 |
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Citations (8)
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|---|---|---|---|---|
| JP2003107049A (en) * | 2001-09-28 | 2003-04-09 | Toyota Motor Corp | Laminated oxygen sensor |
| WO2005124330A1 (en) * | 2004-06-17 | 2005-12-29 | Robert Bosch Gmbh | Method for calibrating a sensor element for a limiting current probe |
| CN101943675A (en) * | 2010-07-28 | 2011-01-12 | 金坛鸿鑫电子科技有限公司 | Automobile chip wide domain oxygen sensor using standard signal output |
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| CN205643237U (en) * | 2016-03-29 | 2016-10-12 | 武汉科技大学 | Wide territory of piece formula car oxygen sensor chip structure |
| CN111141803A (en) * | 2020-01-14 | 2020-05-12 | 浙江百岸科技有限公司 | Nitrogen-oxygen sensor |
| CN210690468U (en) * | 2019-08-23 | 2020-06-05 | 厦门宏发电力电器有限公司 | Wide-area oxygen sensor |
| CN111936847A (en) * | 2018-04-12 | 2020-11-13 | 株式会社电装 | Method for manufacturing gas sensor element |
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2021
- 2021-02-02 CN CN202110139924.XA patent/CN112946043B/en active Active
Patent Citations (8)
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|---|---|---|---|---|
| JP2003107049A (en) * | 2001-09-28 | 2003-04-09 | Toyota Motor Corp | Laminated oxygen sensor |
| WO2005124330A1 (en) * | 2004-06-17 | 2005-12-29 | Robert Bosch Gmbh | Method for calibrating a sensor element for a limiting current probe |
| CN101943675A (en) * | 2010-07-28 | 2011-01-12 | 金坛鸿鑫电子科技有限公司 | Automobile chip wide domain oxygen sensor using standard signal output |
| CN102954993A (en) * | 2011-08-29 | 2013-03-06 | 比亚迪股份有限公司 | Oxygen sensor and preparation method thereof |
| CN205643237U (en) * | 2016-03-29 | 2016-10-12 | 武汉科技大学 | Wide territory of piece formula car oxygen sensor chip structure |
| CN111936847A (en) * | 2018-04-12 | 2020-11-13 | 株式会社电装 | Method for manufacturing gas sensor element |
| CN210690468U (en) * | 2019-08-23 | 2020-06-05 | 厦门宏发电力电器有限公司 | Wide-area oxygen sensor |
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Denomination of invention: A calibration free wide range oxygen sensor and its detection method Granted publication date: 20230829 Pledgee: Bank of China Limited Rui'an Sub branch Pledgor: Zhejiang Baian Technology Co.,Ltd. Registration number: Y2024980001884 |