WO2022134151A1 - Chip-type lambda sensor - Google Patents
Chip-type lambda sensor Download PDFInfo
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- WO2022134151A1 WO2022134151A1 PCT/CN2020/140752 CN2020140752W WO2022134151A1 WO 2022134151 A1 WO2022134151 A1 WO 2022134151A1 CN 2020140752 W CN2020140752 W CN 2020140752W WO 2022134151 A1 WO2022134151 A1 WO 2022134151A1
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- electrode
- zirconia layer
- layer
- cavity
- oxygen sensor
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 114
- 239000001301 oxygen Substances 0.000 claims abstract description 105
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 105
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 93
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- 239000010410 layer Substances 0.000 claims description 70
- 238000005259 measurement Methods 0.000 claims description 20
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 14
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 14
- 239000011241 protective layer Substances 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 7
- 239000011810 insulating material Substances 0.000 claims description 4
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 9
- -1 oxygen ions Chemical class 0.000 description 12
- 238000012360 testing method Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000013028 emission testing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002828 fuel tank Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
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Classifications
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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
- G01N27/41—Oxygen pumping cells
Definitions
- the invention relates to a chip oxygen sensor.
- oxygen sensors are required to measure the oxygen content in gases or gas mixtures in many fields.
- systems using natural gas, oil, biomass, etc. as feedstocks need to be measured when performing combustion control or automotive emissions testing or judging oxygen production in the medical and aerospace markets or inerting of aviation fuel tanks Oxygen content in a gas or gas mixture.
- the present invention provides a chip oxygen sensor in view of the problem of low measurement accuracy in harsh environments that an automotive oxygen sensor needs to rely on reference air to measure oxygen concentration in the prior art.
- the chip oxygen sensor of the present invention includes a first zirconium oxide layer and a second zirconium oxide layer that are stacked in sequence; wherein, the pump electrode and the measurement electrode are silk-printed on the upper surface of the first zirconium oxide layer, and the first zirconium oxide layer is A common electrode is screen-printed on the lower surface of the zirconia layer; the second zirconia layer is provided with a cavity structure with an open top, and a buffer block is placed in the cavity; the common electrode is located directly below the pump electrode and the measuring electrode, and the cavity The structure is located just below the common electrode; it also includes a heating device; the heating device is located directly below the cavity structure corresponding to the second zirconia layer, and the leads of the pump electrode, the measuring electrode and the common electrode are drawn from the upper surface of the first zirconia layer and are The external control device is connected; the first zirconia layer and the second zirconia layer are heated to the working temperature by the heating device, and the external control device pumps the external oxygen
- the buffer block is made of porous material.
- the thickness of the oxygen sensor is not more than 1 mm.
- the oxygen sensor further includes a third zirconia layer, a fourth zirconia layer and a temperature measuring electrode; the upper and lower surfaces of the heating device are provided with insulating layers, and the third zirconia layer is located between the heating device and the second zirconia layer In between, the fourth zirconia layer is located at the bottom of the entire oxygen sensor, and the lead wire of the temperature measuring electrode is connected to the external control device through the fourth zirconia layer.
- the oxygen sensor further includes a protective layer covering the pump electrode and the measuring electrode, and the protective layer is made of porous material.
- the pump electrodes are arranged in zigzag grooves, the measuring electrodes are arranged in zigzag protrusions, the zigzag protrusions of the measurement electrodes are embedded in the zigzag grooves of the pump electrodes, and the pump electrode and the measurement electrode are arranged in a zigzag groove. Separated by insulating material.
- the thickness of the oxygen sensor of the present invention is 1 mm, and it can be assembled into a product by placing it in the existing standard parts of the automobile oxygen sensor to replace the sensor chip in the existing automobile oxygen sensor, and the oxygen sensor of the present invention can be independent of The reference gas is used to measure the oxygen concentration, so that the oxygen sensor can complete the accurate measurement of the oxygen concentration even in a very harsh environment.
- Fig. 1 is the exploded view of the chip oxygen sensor of the present invention
- Fig. 2 is the arrangement pattern diagram of pump electrode and measuring electrode in the chip oxygen sensor of the present invention
- Fig. 3 is a different arrangement diagram of the pump electrode and the measurement electrode
- FIG. 4 is a graph showing the test error of the oxygen concentration in the concentration range of 0.5%-30% between the pump electrode and the measuring electrode in different arrangements.
- the chip oxygen sensor of the present invention includes a fourth zirconia layer 124 , a second insulating layer 162 , a heating device 140 , a first insulating layer 161 , and a third zirconia layer that are stacked in sequence along the longitudinal direction. 123.
- the second zirconia layer 122 and the first zirconia layer 121 (the chip oxygen sensor is formed by hot pressing the multilayer structure); wherein, the pump electrode 111 and the measuring electrode 112 are silk-printed on the upper surface of the first zirconia layer 121 (The pump electrode 111 and the measurement electrode 112 are both Pt electrodes), a common electrode 113 is silk-screened on the lower surface of the first zirconia layer 121 (the common electrode 113 is a Pt electrode); the second zirconia layer 122 is provided with a cavity with a top opening Structure 131, a buffer block 132 is placed in the cavity 131; the common electrode 113 is located directly under the pump electrode 111 and the measurement electrode 112, and the cavity structure 131 is located directly under the common electrode 113, that is, the second zirconia layer 122 is located in the first
- the zirconia layer 121 is screen-printed with a cavity structure 131 at the corresponding position of the common electrode 113; the heating device 140 is located directly below
- the fourth zirconium oxide layer 124 serves as the base of the entire oxygen sensor, so as to support various components.
- the first zirconia layer 121 and the second zirconia layer 122 are heated to the working temperature (600-700° C.) by the heating device 140 , and the control device pumps the external oxygen by changing the direction of the current between the pump electrode 111 and the common electrode 113 .
- the first zirconia layer 121 generates a Nernst voltage based on the oxygen concentration difference on both sides of the first zirconia layer 121, and the measuring electrode 112 and the common electrode 113 are used to detect the Nernstian voltage. Extra voltage.
- the size of the area enclosed by the pump electrode 111 and the measurement electrode 112 is consistent with the size of the common electrode 113 , the cavity structure 131 , the buffer block 132 and the heating device 140 .
- the cavity structure 131 should not be too large, which will lead to high energy consumption (ie, large heating area) and poor temperature uniformity.
- the oxygen sensor also includes a protective layer 170 covering the pump electrode 111 and the measuring electrode 112.
- the protective layer 170 is made of porous material, so that the gas can pass through the protective layer 170.
- the protective layer 170 is located between the pump electrode 111 and the measuring electrode 112. On the outside, the pump electrode 111 and the measurement electrode 112 can be protected.
- the pump electrode 111 is arranged in a zigzag groove, and the measuring electrode 112 is arranged in a zigzag protrusion.
- the zigzag protrusion of the measurement electrode 112 is embedded in the zigzag groove of the pump electrode 111.
- Insulating material 116 is used to separate them, the protrusion width a of the pump electrode 111 is about 2/3 to 3/4 of the protrusion width b of the measuring electrode 112, and insulating material is applied between the protrusion of the pump electrode 111 and the protrusion of the measuring electrode 112
- the width c of the pump electrode 111 is 1/2 to 9/10 of the convex width a of the pump electrode 111 .
- the lead wires 115 of the pump electrode 111 and the measurement electrode 112 are connected to an external control device through the second electrode pin 152 .
- the oxygen sensor also includes a temperature measuring electrode 114, which is used to measure the real-time temperature after heating by the heating device 140, and the lead wire of the temperature measuring electrode 114 protrudes from the lower surface of the fourth zirconia layer 124 and passes through the first electrode pin 151. Connect to the control unit. When the current temperature of the heating device 140 reaches the target temperature, the control device controls the heating and heat dissipation of the heating device 140 to reach a balance, so that the oxygen sensor is stabilized at the target temperature.
- the external control device converts oxygen on the pump electrode 111 side into oxygen ions by applying a corresponding current direction between the pump electrode 111 and the common electrode 113, and the oxygen ions pass through the first zirconia layer 121 and then change from oxygen ions on the common electrode 113 side.
- Oxygen enters the cavity 131 , and the oxygen enters the cavity 131 to change the partial pressure of oxygen in the cavity 131 .
- the cavity 131 is provided with a buffer block 132 made of porous material (gas can pass through the buffer block 132 ).
- the oxygen entering the cavity 131 is relatively gentle, so the final measured data is smoother; the buffer block 132 can be made of porous materials, or the buffer block 132 can be made of organic matter.
- the buffer block 132 It plays a supporting role to prevent the corresponding area of the multi-layer structure from collapsing during hot pressing.
- the structure is heat-treated.
- the organic matter in the cavity 131 is decomposed into gas and escapes, so that the second zirconia layer 122 cavity is obtained.
- the first zirconia layer 121 generates a corresponding Nernst voltage according to the partial pressure of oxygen in the cavity 131, that is, the first zirconia layer 121 generates a Nernst voltage based on the difference in oxygen concentration on both sides of the first zirconia layer 121, and the measuring electrode 112 and the common Electrode 113 measures the Nernst voltage.
- the control device changes the direction of the current between the pump electrode 111 and the common electrode 113 , thereby converting the oxygen gas on the side of the common electrode 113 into oxygen ions and pumping out the cavity 131 .
- the working process of the oxygen sensor of the present invention is as follows: the heating device 140 starts heating, and the temperature measuring electrode 114 measures its temperature in real time during the heating process, and feeds back the measured current temperature to the control device.
- the control device controls the heating and heat dissipation of the heating device 140 to reach a balance, so that the oxygen sensor is stabilized at the target temperature; after reaching the target temperature, the oxygen sensor starts to measure oxygen.
- the control device applies the current flowing from the common electrode 113 to the pump electrode 111 between the pump electrode 111 and the common electrode 113, so that the oxygen on the side of the pump electrode 111 is converted into oxygen ions, and the converted oxygen ions pass through the first zirconia layer 121.
- the side of the common electrode 113 changes from oxygen ions to oxygen into the cavity 131 of the second zirconia layer 122.
- the buffer block 132 is arranged in the cavity 131, so that the oxygen enters relatively slowly In the cavity 131, oxygen enters the cavity 131 to change the partial pressure of oxygen in the cavity 131; the first zirconia layer 121 generates a corresponding Nernst voltage according to the partial pressure of oxygen, and the measuring electrode 112 and the common electrode 113 measure in real time The magnitude of the Nernst voltage, and after the Nernst voltage reaches the target voltage, the current direction between the pump electrode 111 and the common electrode 113 is changed, that is, the flow between the pump electrode 111 and the common electrode 113 is applied from the pump electrode 111 to the common electrode 113.
- the current of the electrode 113 promotes the conversion of oxygen on the side of the common electrode 113 to oxygen ions, and the oxygen ions pass through the first zirconia layer 121 and are released from the cavity 131 to the outside world (the oxygen ions on the pump electrode 111 side become oxygen).
- the timer in the control device counts the time from when the pump electrode 111 and the common electrode 113 start converting oxygen into oxygen ions to the time when the direction of the current between the pump electrode 111 and the common electrode 113 changes, that is, the time for one pump oxygen cycle of the oxygen sensor (one pump
- the oxygen cycle time is the time between when the pump electrode 111 and the common electrode 113 start to convert oxygen into oxygen ions and the current direction changes between the pump electrode 111 and the common electrode 113), which can be calculated according to the time of one pump oxygen cycle of the oxygen sensor.
- partial pressure of oxygen The longer the time of a pump oxygen cycle, the greater the oxygen partial pressure, the control device automatically calculates the oxygen partial pressure according to the pump oxygen cycle time (by establishing a standard curve, different pump oxygen cycle times correspond to different oxygen concentrations) .
- the pump electrode 111 and the measurement electrode 112 have different arrangements.
- the oxygen concentration in the range of 0.5%-30% (known The measurement accuracy of concentration) is shown in Table 1:
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Abstract
A chip-type lambda sensor, comprising a first zirconia layer (121) and a second zirconia layer (122) that are stacked in sequence, wherein pump electrodes (111) and measuring electrodes (112) are screen-printed on the upper surface of the first zirconia layer (121), and a common electrode (113) is screen-printed on the lower surface of the first zirconia layer (121); a cavity (131) that has an open top part is provided in the second zirconia layer (122), and a buffer block (132) is placed inside the cavity (131); and the common electrode (113) is located directly below the pump electrodes (111) and the measuring electrodes (112), and the cavity (131) is located directly below the common electrode (113). The chip-type lambda sensor further comprises a heating device (140). The heating device (140) is located directly below the cavity (131) correspondingly provided in the second zirconia layer (122), and leads of the pump electrodes (111), the measuring electrodes (112) and the common electrode (113) are led out from the upper surface of the first zirconia layer (121) and connected to an external control device. The lambda sensor is able to be assembled into a product by being placed in existing automotive lambda sensor standard parts, replaces the sensor chip in existing automotive lambda sensors, and does not rely on the reference gas to measure the oxygen concentration, so that the lambda sensor is able to accurately measure oxygen concentration even in very harsh environments.
Description
本发明涉及一种片式氧传感器。The invention relates to a chip oxygen sensor.
目前，在很多领域需要运用氧传感器测量气体或气体混合物中的氧气含量。例如，使用天然气、石油、生物质等为原料的系统，当其进行燃烧控制或汽车排放测试或判断医疗和航空航天市场中氧气的产生量或航空燃油箱的惰化情况时，均需要去测量气体或气体混合物中的氧气含量。At present, oxygen sensors are required to measure the oxygen content in gases or gas mixtures in many fields. For example, systems using natural gas, oil, biomass, etc. as feedstocks need to be measured when performing combustion control or automotive emissions testing or judging oxygen production in the medical and aerospace markets or inerting of aviation fuel tanks Oxygen content in a gas or gas mixture.
传统的汽车氧传感器大多需要依赖参考空气去测量氧的浓度，在环境恶劣时，容易使得测量得到的氧的浓度不准确。Most of the traditional automotive oxygen sensors need to rely on the reference air to measure the oxygen concentration. In harsh environments, it is easy to make the measured oxygen concentration inaccurate.
发明内容SUMMARY OF THE INVENTION
发明目的：本发明针对现有技术中汽车氧传感器需要依赖参考空气去测量氧气浓度存在的处于恶劣环境下测量精度低的问题，提供一种片式氧传感器。Purpose of the invention: The present invention provides a chip oxygen sensor in view of the problem of low measurement accuracy in harsh environments that an automotive oxygen sensor needs to rely on reference air to measure oxygen concentration in the prior art.
技术方案：本发明所述的片式氧传感器，包括依次层叠设置的第一氧化锆层和第二氧化锆层；其中，所述第一氧化锆层上表面丝印有泵电极和测量电极，第一氧化锆层下表面丝印有公共电极；所述第二氧化锆层上设有顶部开口的空腔结构，空腔内放置有缓冲块；公共电极位于泵电极和测量电极的正下方，空腔结构位于公共电极的正下方；还包括加热装置；加热装置位于第二氧化锆层对应设置空腔结构的正下方，泵电极、测量电极和公共电极的引线从第一氧化锆层上表面引出与外部控制装置连接；第一氧化锆层和第二氧化锆层通过加热装置将其加热至工作温度，外部控制装置通过改变泵电极与公共电极之间电流的方向将外界氧气泵入空腔中或将空腔中氧气泵出至外界，第一氧化锆层基于其两侧的氧气浓度差产生能斯特电压，测量电极和公共电极用于检测该能斯特电压。Technical solution: The chip oxygen sensor of the present invention includes a first zirconium oxide layer and a second zirconium oxide layer that are stacked in sequence; wherein, the pump electrode and the measurement electrode are silk-printed on the upper surface of the first zirconium oxide layer, and the first zirconium oxide layer is A common electrode is screen-printed on the lower surface of the zirconia layer; the second zirconia layer is provided with a cavity structure with an open top, and a buffer block is placed in the cavity; the common electrode is located directly below the pump electrode and the measuring electrode, and the cavity The structure is located just below the common electrode; it also includes a heating device; the heating device is located directly below the cavity structure corresponding to the second zirconia layer, and the leads of the pump electrode, the measuring electrode and the common electrode are drawn from the upper surface of the first zirconia layer and are The external control device is connected; the first zirconia layer and the second zirconia layer are heated to the working temperature by the heating device, and the external control device pumps the external oxygen into the cavity by changing the direction of the current between the pump electrode and the common electrode. The oxygen in the cavity is pumped out to the outside, the first zirconia layer generates a Nernst voltage based on the oxygen concentration difference between its two sides, and the measuring electrode and the common electrode are used to detect the Nernst voltage.
其中，所述缓冲块采用多孔材料制备而成。Wherein, the buffer block is made of porous material.
其中，所述氧传感器的厚度不大于1mm。Wherein, the thickness of the oxygen sensor is not more than 1 mm.
其中，所述氧传感器还包括第三氧化锆层、第四氧化锆层和测温电极；所述加热装置上下表面均设有绝缘层，第三氧化锆层位于加热装置与第二氧化锆层之间，第四氧化锆层位于整个氧传感器的底部，测温电极的引线穿过第四氧化锆层与外部控制装置连接。Wherein, the oxygen sensor further includes a third zirconia layer, a fourth zirconia layer and a temperature measuring electrode; the upper and lower surfaces of the heating device are provided with insulating layers, and the third zirconia layer is located between the heating device and the second zirconia layer In between, the fourth zirconia layer is located at the bottom of the entire oxygen sensor, and the lead wire of the temperature measuring electrode is connected to the external control device through the fourth zirconia layer.
其中，所述氧传感器还包括覆盖在泵电极和测量电极上方的保护层，保护层采用多孔材料制备而成。Wherein, the oxygen sensor further includes a protective layer covering the pump electrode and the measuring electrode, and the protective layer is made of porous material.
其中，所述泵电极呈锯齿状凹槽排布，测量电极呈锯齿状凸起排布，测量电 极的锯齿状凸起嵌入到泵电极的锯齿状凹槽中，所述泵电极和测量电极之间采用绝缘材料隔开。The pump electrodes are arranged in zigzag grooves, the measuring electrodes are arranged in zigzag protrusions, the zigzag protrusions of the measurement electrodes are embedded in the zigzag grooves of the pump electrodes, and the pump electrode and the measurement electrode are arranged in a zigzag groove. Separated by insulating material.
有益效果：本发明氧传感器的厚度为1mm，能够将其放在现有的汽车氧传感器标准件中来组装成产品，替代现有汽车氧传感器中的传感器芯片，本发明氧传感器能够不依赖于参考气体进行测量氧气的浓度，使得该氧传感器即使在非常恶劣的环境中也能完成对氧浓度的准确测量。Beneficial effects: the thickness of the oxygen sensor of the present invention is 1 mm, and it can be assembled into a product by placing it in the existing standard parts of the automobile oxygen sensor to replace the sensor chip in the existing automobile oxygen sensor, and the oxygen sensor of the present invention can be independent of The reference gas is used to measure the oxygen concentration, so that the oxygen sensor can complete the accurate measurement of the oxygen concentration even in a very harsh environment.
图1为本发明片式氧传感器的爆炸图；Fig. 1 is the exploded view of the chip oxygen sensor of the present invention;
图2为本发明片式氧传感器中泵电极与测量电极的排布方式图；Fig. 2 is the arrangement pattern diagram of pump electrode and measuring electrode in the chip oxygen sensor of the present invention;
图3为泵电极与测量电极不同的排布方式图；Fig. 3 is a different arrangement diagram of the pump electrode and the measurement electrode;
图4为不同排布方式的泵电极与测量电极对浓度范围为0.5％-30％的氧气浓度的测试误差图。FIG. 4 is a graph showing the test error of the oxygen concentration in the concentration range of 0.5%-30% between the pump electrode and the measuring electrode in different arrangements.
如图1～2所示，本发明片式氧传感器，沿纵向包括依次层叠设置的第四氧化锆层124、第二绝缘层162、加热装置140、第一绝缘层161、第三氧化锆层123、第二氧化锆层122和第一氧化锆层121(片式氧传感器通过将多层结构热压而成)；其中，第一氧化锆层121上表面丝印有泵电极111和测量电极112(泵电极111和测量电极112均为Pt电极)，第一氧化锆层121下表面丝印有公共电极113(公共电极113为Pt电极)；第二氧化锆层122上设有顶部开口的空腔结构131，空腔131内放置有缓冲块132；公共电极113位于泵电极111和测量电极112的正下方，空腔结构131位于公共电极113的正下方，即第二氧化锆层122在第一氧化锆层121丝印有公共电极113的对应位置处开有空腔结构131；加热装置140位于第二氧化锆层122对应设置空腔结构131的正下方，泵电极111、测量电极112和公共电极113的引线从第一氧化锆层121上表面引出，通过第二电极引脚152与外部控制装置连接；第一绝缘层161和第二绝缘层162分别位于加热装置140的两侧，从而起到绝缘保护的作用，在氧传感器的温度达到预设温度后，氧传感器开始测氧工作；第三氧化锆层123起到导热的作用，加热装置140开始加热后产生的热量通过第三氧化锆层123传递给第二氧化锆层122和第一氧化锆层121，避免直接将温度较高的加热装置140与第二氧化锆层122直接接触。第四氧化锆层124作为整个氧传感器的底座，从而起到支撑各个部件的作用。第一氧化锆层121和第二氧化锆层122通过加热装置140将其加热至工作温度(600～700℃)，控制装置通过改变泵电极111与公共电极113之间电流的方向将外界氧气泵入空腔131中或将空腔131中氧气泵出至外界，第一氧化锆层121 基于其两侧的氧气浓度差产生能斯特电压，测量电极112和公共电极113用于检测该能斯特电压。泵电极111和测量电极112围合的区域大小与公共电极113、空腔结构131、缓冲块132以及加热装置140的大小一致。空腔结构131不能过大，太大导致能耗大(即加热面积大)，且均温性也不好。As shown in FIGS. 1 to 2 , the chip oxygen sensor of the present invention includes a fourth zirconia layer 124 , a second insulating layer 162 , a heating device 140 , a first insulating layer 161 , and a third zirconia layer that are stacked in sequence along the longitudinal direction. 123. The second zirconia layer 122 and the first zirconia layer 121 (the chip oxygen sensor is formed by hot pressing the multilayer structure); wherein, the pump electrode 111 and the measuring electrode 112 are silk-printed on the upper surface of the first zirconia layer 121 (The pump electrode 111 and the measurement electrode 112 are both Pt electrodes), a common electrode 113 is silk-screened on the lower surface of the first zirconia layer 121 (the common electrode 113 is a Pt electrode); the second zirconia layer 122 is provided with a cavity with a top opening Structure 131, a buffer block 132 is placed in the cavity 131; the common electrode 113 is located directly under the pump electrode 111 and the measurement electrode 112, and the cavity structure 131 is located directly under the common electrode 113, that is, the second zirconia layer 122 is located in the first The zirconia layer 121 is screen-printed with a cavity structure 131 at the corresponding position of the common electrode 113; the heating device 140 is located directly below the cavity structure 131 corresponding to the second zirconia layer 122, the pump electrode 111, the measurement electrode 112 and the common electrode The leads of 113 are drawn out from the upper surface of the first zirconia layer 121, and are connected to the external control device through the second electrode pins 152; The function of insulation protection, after the temperature of the oxygen sensor reaches the preset temperature, the oxygen sensor starts to measure oxygen; the third zirconia layer 123 plays the role of heat conduction, and the heat generated after the heating device 140 starts to heat passes through the third zirconia layer 123 is transmitted to the second zirconium oxide layer 122 and the first zirconium oxide layer 121 , so as to avoid directly contacting the heating device 140 with a higher temperature with the second zirconium oxide layer 122 . The fourth zirconium oxide layer 124 serves as the base of the entire oxygen sensor, so as to support various components. The first zirconia layer 121 and the second zirconia layer 122 are heated to the working temperature (600-700° C.) by the heating device 140 , and the control device pumps the external oxygen by changing the direction of the current between the pump electrode 111 and the common electrode 113 . The first zirconia layer 121 generates a Nernst voltage based on the oxygen concentration difference on both sides of the first zirconia layer 121, and the measuring electrode 112 and the common electrode 113 are used to detect the Nernstian voltage. Extra voltage. The size of the area enclosed by the pump electrode 111 and the measurement electrode 112 is consistent with the size of the common electrode 113 , the cavity structure 131 , the buffer block 132 and the heating device 140 . The cavity structure 131 should not be too large, which will lead to high energy consumption (ie, large heating area) and poor temperature uniformity.
氧传感器还包括覆盖在泵电极111和测量电极112上方的保护层170，保护层170采用多孔材料制备而成，从而气体能够穿过保护层170，保护层170位于泵电极111和测量电极112的外侧，可以对泵电极111和测量电极112起到保护作用。The oxygen sensor also includes a protective layer 170 covering the pump electrode 111 and the measuring electrode 112. The protective layer 170 is made of porous material, so that the gas can pass through the protective layer 170. The protective layer 170 is located between the pump electrode 111 and the measuring electrode 112. On the outside, the pump electrode 111 and the measurement electrode 112 can be protected.
泵电极111呈锯齿状凹槽排布，测量电极112呈锯齿状凸起排布，测量电极112的锯齿状凸起嵌入到泵电极111的锯齿状凹槽中，泵电极111和测量电极112之间采用绝缘材料116隔开，泵电极111的凸起宽度a约为测量电极112凸起宽度b的2/3～3/4，泵电极111凸起与测量电极112凸起之间涂绝缘材料的宽度c为泵电极111凸起宽度a的1/2～9/10。泵电极111和测量电极112的引线115通过第二电极引脚152与外部控制装置连接。The pump electrode 111 is arranged in a zigzag groove, and the measuring electrode 112 is arranged in a zigzag protrusion. The zigzag protrusion of the measurement electrode 112 is embedded in the zigzag groove of the pump electrode 111. Insulating material 116 is used to separate them, the protrusion width a of the pump electrode 111 is about 2/3 to 3/4 of the protrusion width b of the measuring electrode 112, and insulating material is applied between the protrusion of the pump electrode 111 and the protrusion of the measuring electrode 112 The width c of the pump electrode 111 is 1/2 to 9/10 of the convex width a of the pump electrode 111 . The lead wires 115 of the pump electrode 111 and the measurement electrode 112 are connected to an external control device through the second electrode pin 152 .
氧传感器还包括测温电极114，测温电极114用于测量加热装置140加热后的实时温度，测温电极114的引线从第四氧化锆层124下表面穿出，通过第一电极引脚151与控制装置连接。当加热装置140当前温度达到目标温度后，控制装置控制加热装置140的加热与散热达到平衡，使氧传感器稳定在目标温度。The oxygen sensor also includes a temperature measuring electrode 114, which is used to measure the real-time temperature after heating by the heating device 140, and the lead wire of the temperature measuring electrode 114 protrudes from the lower surface of the fourth zirconia layer 124 and passes through the first electrode pin 151. Connect to the control unit. When the current temperature of the heating device 140 reaches the target temperature, the control device controls the heating and heat dissipation of the heating device 140 to reach a balance, so that the oxygen sensor is stabilized at the target temperature.
外部控制装置通过在泵电极111和公共电极113之间施加对应的电流方向，将泵电极111侧氧气转换为氧离子，氧离子通过第一氧化锆层121后在公共电极113侧由氧离子变成氧气进入空腔131中，氧气进入空腔131后改变空腔131内氧的分压。空腔131内设有由多孔材料制备而成的缓冲块132(气体能够穿过缓冲块132)，缓冲块132一方面能够防止多层结构在热压时对应区域发生塌陷，一方面还能使氧气进入空腔131中时较为平缓，从而最终测得的数据更为平滑；缓冲块132可以采用多孔材料制备而成，也可以缓冲块132采用有机物制备而成，在层压时，缓冲块132起到支撑作用，防止多层结构在热压时对应区域发生塌陷，在层压后，对结构进行热处理，此时空腔131中的有机物被分解成气体跑出，从而在第二氧化锆层122中得到空腔。第一氧化锆层121根据空腔131内氧的分压大小产生对应的能斯特电压，即第一氧化锆层121基于其两侧的氧气浓度差产生能斯特电压，测量电极112和公共电极113测量该能斯特电压。当能斯特电压达到目标电压后，控制装置改变泵电极111和公共电极113之间电流的方向，从而将公共电极113侧氧气转换为氧离子，泵出空腔131。The external control device converts oxygen on the pump electrode 111 side into oxygen ions by applying a corresponding current direction between the pump electrode 111 and the common electrode 113, and the oxygen ions pass through the first zirconia layer 121 and then change from oxygen ions on the common electrode 113 side. Oxygen enters the cavity 131 , and the oxygen enters the cavity 131 to change the partial pressure of oxygen in the cavity 131 . The cavity 131 is provided with a buffer block 132 made of porous material (gas can pass through the buffer block 132 ). The oxygen entering the cavity 131 is relatively gentle, so the final measured data is smoother; the buffer block 132 can be made of porous materials, or the buffer block 132 can be made of organic matter. During lamination, the buffer block 132 It plays a supporting role to prevent the corresponding area of the multi-layer structure from collapsing during hot pressing. After lamination, the structure is heat-treated. At this time, the organic matter in the cavity 131 is decomposed into gas and escapes, so that the second zirconia layer 122 cavity is obtained. The first zirconia layer 121 generates a corresponding Nernst voltage according to the partial pressure of oxygen in the cavity 131, that is, the first zirconia layer 121 generates a Nernst voltage based on the difference in oxygen concentration on both sides of the first zirconia layer 121, and the measuring electrode 112 and the common Electrode 113 measures the Nernst voltage. When the Nernst voltage reaches the target voltage, the control device changes the direction of the current between the pump electrode 111 and the common electrode 113 , thereby converting the oxygen gas on the side of the common electrode 113 into oxygen ions and pumping out the cavity 131 .
本发明氧传感器的工作过程为：加热装置140开始加热，在加热过程中测温 电极114对其进行实时测温，并将测得的当前温度反馈给控制装置，当加热装置140当前温度达到目标温度后，控制装置控制加热装置140的加热与散热达到平衡，使氧传感器稳定在目标温度；达到目标温度后，氧传感器开始测氧工作。控制装置对泵电极111和公共电极113之间施加由公共电极113流向泵电极111的电流，促使泵电极111侧氧气转换为氧离子，转换而成的氧离子通过第一氧化锆层121后在公共电极113侧由氧离子变成氧气进入第二氧化锆层122的空腔131中，在氧气进入空腔131的过程中，由于空腔131内设置有缓冲块132，使得氧气较为缓慢的进入空腔131内，氧气进入空腔131后改变空腔131内氧的分压；第一氧化锆层121根据氧的分压大小产生对应的能斯特电压，测量电极112和公共电极113实时测量该能斯特电压的大小，并在能斯特电压达到目标电压后改变泵电极111和公共电极113之间的电流方向，即对泵电极111和公共电极113之间施加由泵电极111流向公共电极113的电流，促使公共电极113侧氧气转换为氧离子，氧离子通过第一氧化锆层121后从空腔131中释放到外界(其在泵电极111侧由氧离子变成氧气)。控制装置中的计时器计时从泵电极111和公共电极113开始将氧气转换为氧离子到泵电极111和公共电极113之间电流方向改变的时间，即氧传感器一个泵氧循环的时间(一个泵氧循环的时间为泵电极111和公共电极113开始将氧气转换为氧离子到泵电极111和公共电极113之间电流方向改变之间的时间)，根据氧传感器一个泵氧循环的时间可以计算得到氧的分压。一个泵氧循环的时间越长，则氧的分压越大，控制装置根据泵氧循环的时间自动计算出氧的分压(通过建立标准曲线，不同的泵氧循环时间对应不同的氧气浓度)。The working process of the oxygen sensor of the present invention is as follows: the heating device 140 starts heating, and the temperature measuring electrode 114 measures its temperature in real time during the heating process, and feeds back the measured current temperature to the control device. When the current temperature of the heating device 140 reaches the target After the temperature is reached, the control device controls the heating and heat dissipation of the heating device 140 to reach a balance, so that the oxygen sensor is stabilized at the target temperature; after reaching the target temperature, the oxygen sensor starts to measure oxygen. The control device applies the current flowing from the common electrode 113 to the pump electrode 111 between the pump electrode 111 and the common electrode 113, so that the oxygen on the side of the pump electrode 111 is converted into oxygen ions, and the converted oxygen ions pass through the first zirconia layer 121. The side of the common electrode 113 changes from oxygen ions to oxygen into the cavity 131 of the second zirconia layer 122. During the process of oxygen entering the cavity 131, the buffer block 132 is arranged in the cavity 131, so that the oxygen enters relatively slowly In the cavity 131, oxygen enters the cavity 131 to change the partial pressure of oxygen in the cavity 131; the first zirconia layer 121 generates a corresponding Nernst voltage according to the partial pressure of oxygen, and the measuring electrode 112 and the common electrode 113 measure in real time The magnitude of the Nernst voltage, and after the Nernst voltage reaches the target voltage, the current direction between the pump electrode 111 and the common electrode 113 is changed, that is, the flow between the pump electrode 111 and the common electrode 113 is applied from the pump electrode 111 to the common electrode 113. The current of the electrode 113 promotes the conversion of oxygen on the side of the common electrode 113 to oxygen ions, and the oxygen ions pass through the first zirconia layer 121 and are released from the cavity 131 to the outside world (the oxygen ions on the pump electrode 111 side become oxygen). The timer in the control device counts the time from when the pump electrode 111 and the common electrode 113 start converting oxygen into oxygen ions to the time when the direction of the current between the pump electrode 111 and the common electrode 113 changes, that is, the time for one pump oxygen cycle of the oxygen sensor (one pump The oxygen cycle time is the time between when the pump electrode 111 and the common electrode 113 start to convert oxygen into oxygen ions and the current direction changes between the pump electrode 111 and the common electrode 113), which can be calculated according to the time of one pump oxygen cycle of the oxygen sensor. partial pressure of oxygen. The longer the time of a pump oxygen cycle, the greater the oxygen partial pressure, the control device automatically calculates the oxygen partial pressure according to the pump oxygen cycle time (by establishing a standard curve, different pump oxygen cycle times correspond to different oxygen concentrations) .
如图3～4所示，泵电极111与测量电极112有不同的排布方式，对于不同的排布方式，在相同测试条件下，对浓度范围为0.5％-30％的氧气浓度(已知浓度)的测量精度如表1所示：As shown in Figures 3-4, the pump electrode 111 and the measurement electrode 112 have different arrangements. For different arrangements, under the same test conditions, the oxygen concentration in the range of 0.5%-30% (known The measurement accuracy of concentration) is shown in Table 1:
| O2O2 | AA | BB | CC | DD | EE |
| 0.5％0.5% | 0.53％0.53% | 0.62％0.62% | 1.27％1.27% | 1.43％1.43% | 0.60％0.60% |
| 1.0％1.0% | 1.09％1.09% | 1.11％1.11% | 1.46％1.46% | 1.56％1.56% | 1.06％1.06% |
| 5.0％5.0% | 4.93％4.93% | 5.05％5.05% | 5.23％5.23% | 5.52％5.52% | 4.88％4.88% |
| 10.0％10.0% | 9.95％9.95% | 9.89％9.89% | 10.23％10.23% | 10.20％10.20% | 9.79％9.79% |
| 15.0％15.0% | 14.77％14.77% | 14.85％14.85% | 15.04％15.04% | 15.05％15.05% | 14.79％14.79% |
| 20.0％20.0% | 20.05％20.05% | 20.00％20.00% | 20.00％20.00% | 20.00％20.00% | 20.00％20.00% |
| 25.0％25.0% | 25.14％25.14% | 25.31％25.31% | 25.10％25.10% | 25.06％25.06% | 25.43％25.43% |
| 30.0％30.0% | 30.36％30.36% | 30.91％30.91% | 30.29％30.29% | 30.34％30.34% | 30.91％30.91% |
对于不同的排布方式，在相同测试条件下，对浓度范围为0.5％-30％的氧气浓度的测试误差如表2所示：For different arrangements, under the same test conditions, the test error of oxygen concentration in the concentration range of 0.5%-30% is shown in Table 2:
通过表1和表2可知，本发明氧传感器中泵电极与测量电极的排布方式对一定浓度范围内的氧气浓度的测量精度要远远高于其他的排布方式，测量误差要远远小于其他的排布方式。From Table 1 and Table 2, it can be seen that the arrangement of the pump electrode and the measuring electrode in the oxygen sensor of the present invention has a much higher measurement accuracy for the oxygen concentration within a certain concentration range than other arrangements, and the measurement error is much smaller than other arrangements.
Claims (6)
- 一种片式氧传感器，其特征在于：包括依次层叠设置的第一氧化锆层和第二氧化锆层；其中，所述第一氧化锆层上表面丝印有泵电极和测量电极，第一氧化锆层下表面丝印有公共电极；所述第二氧化锆层上设有顶部开口的空腔结构，空腔内放置有缓冲块；公共电极位于泵电极和测量电极的正下方，空腔结构位于公共电极的正下方；还包括加热装置；加热装置位于第二氧化锆层对应设置空腔结构的正下方，泵电极、测量电极和公共电极的引线从第一氧化锆层上表面引出与外部控制装置连接；第一氧化锆层和第二氧化锆层通过加热装置将其加热至工作温度，外部控制装置通过改变泵电极与公共电极之间电流的方向将外界氧气泵入空腔或将空腔内氧气泵出，第一氧化锆层基于空腔与外界的氧气浓度差产生能斯特电压，测量电极和公共电极用于检测该能斯特电压。A chip oxygen sensor is characterized in that: it comprises a first zirconia layer and a second zirconia layer which are stacked in sequence; wherein, pump electrodes and measuring electrodes are silk-printed on the upper surface of the first zirconia layer, and the first zirconia layer is A common electrode is silk-printed on the lower surface of the zirconium layer; the second zirconia layer is provided with a cavity structure with an open top, and a buffer block is placed in the cavity; the common electrode is located directly below the pump electrode and the measurement electrode, and the cavity structure is located in Directly below the common electrode; also includes a heating device; the heating device is located directly below the cavity structure corresponding to the second zirconia layer, and the leads of the pump electrode, the measuring electrode and the common electrode are led out from the upper surface of the first zirconia layer for external control The device is connected; the first zirconium oxide layer and the second zirconium oxide layer are heated to the working temperature by the heating device, and the external control device pumps the external oxygen into the cavity or the cavity by changing the direction of the current between the pump electrode and the common electrode. The inner oxygen is pumped out, the first zirconia layer generates a Nernst voltage based on the oxygen concentration difference between the cavity and the outside, and the measuring electrode and the common electrode are used to detect the Nernst voltage.
- 根据权利要求1所述的片式氧传感器，其特征在于：所述缓冲块采用多孔材料制备而成。The chip oxygen sensor according to claim 1, wherein the buffer block is made of porous material.
- 根据权利要求1所述的片式氧传感器，其特征在于：所述氧传感器的厚度不大于1mm。The chip oxygen sensor according to claim 1, wherein the thickness of the oxygen sensor is not more than 1 mm.
- 根据权利要求1所述的片式氧传感器，其特征在于：所述氧传感器还包括第三氧化锆层、第四氧化锆层和测温电极；所述加热装置上下表面均设有绝缘层，第三氧化锆层位于加热装置与第二氧化锆层之间，第四氧化锆层位于整个氧传感器的底部，测温电极的引线从第四氧化锆层穿出与控制装置连接。The chip oxygen sensor according to claim 1, wherein the oxygen sensor further comprises a third zirconia layer, a fourth zirconia layer and a temperature measuring electrode; the upper and lower surfaces of the heating device are provided with insulating layers, The third zirconium oxide layer is located between the heating device and the second zirconium oxide layer, the fourth zirconium oxide layer is located at the bottom of the entire oxygen sensor, and the lead wire of the temperature measuring electrode passes through the fourth zirconium oxide layer and is connected to the control device.
- 根据权利要求1所述的片式氧传感器，其特征在于：所述氧传感器还包括覆盖在泵电极和测量电极上方的保护层，保护层采用多孔材料制备而成。The chip oxygen sensor according to claim 1, wherein the oxygen sensor further comprises a protective layer covering the pump electrode and the measuring electrode, and the protective layer is made of porous material.
- 根据权利要求1所述的片式氧传感器，其特征在于：所述泵电极呈锯齿状凹槽排布，测量电极呈锯齿状凸起排布，测量电极的锯齿状凸起嵌入到泵电极的锯齿状凹槽中，所述泵电极和测量电极之间采用绝缘材料隔开。The chip oxygen sensor according to claim 1, wherein the pump electrode is arranged in a zigzag groove, the measurement electrode is arranged in a zigzag protrusion, and the zigzag protrusion of the measurement electrode is embedded in the pump electrode. In the serrated groove, the pump electrode and the measuring electrode are separated by insulating material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011555341.7 | 2020-12-24 | ||
| CN202011555341.7A CN112763564B (en) | 2020-12-24 | 2020-12-24 | Sheet type oxygen sensor |
Publications (1)
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| PCT/CN2020/140752 WO2022134151A1 (en) | 2020-12-24 | 2020-12-29 | Chip-type lambda sensor |
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Cited By (3)
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| CN115791930A (en) * | 2022-08-12 | 2023-03-14 | 江苏惟哲新材料有限公司 | Preparation method of limiting current type oxygen sensor |
| CN117418925A (en) * | 2023-12-19 | 2024-01-19 | 四川智感蔚蓝科技有限公司 | Pump oxygen control method, device, medium and equipment of nitrogen-oxygen sensor |
| CN117907406A (en) * | 2024-03-19 | 2024-04-19 | 四川智感蔚蓝科技有限公司 | Performance test method and device for ceramic chip, medium and terminal |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113203784B (en) * | 2021-05-20 | 2022-10-18 | 安徽中科国瓷新型元器件有限公司 | Variable frequency oxygen sensor |
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| CN117907406A (en) * | 2024-03-19 | 2024-04-19 | 四川智感蔚蓝科技有限公司 | Performance test method and device for ceramic chip, medium and terminal |
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| Publication number | Publication date |
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| CN112763564B (en) | 2022-01-14 |
| CN112763564A (en) | 2021-05-07 |
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