WO2020048300A1 - 一种氮氧传感器陶瓷芯片 - Google Patents

一种氮氧传感器陶瓷芯片 Download PDF

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WO2020048300A1
WO2020048300A1 PCT/CN2019/100509 CN2019100509W WO2020048300A1 WO 2020048300 A1 WO2020048300 A1 WO 2020048300A1 CN 2019100509 W CN2019100509 W CN 2019100509W WO 2020048300 A1 WO2020048300 A1 WO 2020048300A1
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electrode
oxygen
layer
substrate
gas
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French (fr)
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WO2020048300A9 (zh
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王广平
吴国臣
王军
陈晨
张伟
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上海长园维安电子线路保护有限公司
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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
    • G01N27/416—Systems
    • G01N27/4162—Systems investigating the composition of gases, by the influence exerted on ionic conductivity in a liquid

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  • the invention belongs to the technical field of nitrogen and oxygen sensors, and particularly relates to a ceramic chip of a nitrogen and oxygen sensor.
  • the reported ceramic chips for nitrogen-oxygen sensors are made by laminating and sintering multilayer zirconia ceramic substrates. Under the condition that the heating electrode heats the nitrogen-oxygen sensor chip to a certain temperature, the catalytic decomposition reaction of the electrochemical unit is used to realize the measurement of the NOx gas concentration; and the measurement area of the nitrogen-oxygen sensor chip is designed with multiple gas cavity structures.
  • the nitrogen-oxygen sensor needs to be heated by the heater and maintained at about 950 ° C.
  • the multi-chamber structure will cause uneven heating and instability in the measurement area, affecting the oxygen ion conductivity of the zirconia material and the chemical properties of the electrode material. Accurate measurement of NOx gas concentration by nitrogen and oxygen sensors;
  • the multiple gas cavity design used by the nitrogen and oxygen sensor, the manufacturing process is relatively complicated, and the internal multi-cavity structure reduces the structural strength of the head of the nitrogen and oxygen sensor chip to a certain extent, and its own thermal shock resistance is reduced. , The edges of the cavity are prone to crack damage, reducing the service life.
  • the first electrode (main pump oxygen electrode) and the second electrode (auxiliary pump oxygen electrode) of the nitrogen and oxygen sensor are usually doped with a small amount of low catalytic activity metal material Au. Since the melting point of gold is 1064 ° C, no matter the chip's The sintering molding temperature (1400 to 1600 ° C), or the temperature at which the nitrogen-oxygen sensor chip works (about 950 ° C), can easily cause the volatilization of gold and the pollution of the activated electrode.
  • the present invention provides a Nitrogen and oxygen sensor ceramic chip, a more accurate measurement of NOx concentration, can improve the structural strength of the nitrogen and oxygen sensor chip, and can effectively avoid the contamination of the active electrode by the volatilization of Au during the high temperature sintering process.
  • Yet another object of the present invention is to provide a manufacturing process of the above-mentioned nitrogen-oxygen sensor ceramic chip, which has a simple manufacturing process and is easy to produce.
  • a nitrogen-oxygen sensor chip is characterized in that it comprises a first-layer substrate, a second-layer substrate, a third-layer substrate, a fourth-layer substrate, and a fifth-layer substrate, which are sequentially laminated from top to bottom.
  • the sixth-layer substrate the material of the six-layer substrate is zirconia;
  • An external electrode is provided on the first layer of the substrate, and the external electrode is covered with a porous protective layer;
  • a second layer substrate is disposed between the first layer substrate and the third layer substrate.
  • the second layer substrate is sequentially provided with a gas barrier of a porous structure, a first gas diffusion barrier, and a first pump.
  • a gas reference channel is provided in the third layer substrate, the gas reference channel is in communication with the atmosphere, and a reference electrode is provided between the third layer substrate and the fourth layer substrate. Covered with a porous diffusion barrier;
  • the fourth layer substrate is provided with small holes, and the small holes are in communication with the gas reference channel and the porous diffusion barrier layer;
  • a heating electrode is disposed between the fourth substrate and the fifth substrate, and an insulating layer is disposed above and below the heating electrode.
  • the NOx catalytic decomposition and the measurement area of the NOx sensor are both designed as a three-dimensional porous structure, which greatly increases the contact area between the gas and the electrode, and tightly combines the material interfaces of the functional layers, which is a good solution. The problems of heating uniformity and stability in the test area were discussed.
  • the gas barrier, the first gas diffusion barrier, the first electrode, the second gas barrier, the second electrode, the third gas barrier, and the test electrode are all arranged to be in contact with the first layer substrate and the second layer substrate.
  • the contact interface with the third substrate is integrated into one body. To further increase strength.
  • the gas barrier is made of porous zirconia or alumina.
  • the first gas diffusion barrier layer, the second gas diffusion barrier layer and the third gas diffusion barrier layer are all made of porous zirconia.
  • the third gas diffusion barrier layer is also called the third row of diffusion barrier layers, which can not only pass the test gas effectively, but also can effectively avoid the pollution of the test electrode caused by the volatilization of Au during the high temperature sintering process.
  • the first pump oxygen electrode and the second pump oxygen electrode are porous cermets that have no catalytic activity against nitrogen oxides. They are composed of platinum, non-catalytically active materials (such as Au), zirconia, and carbon powder. Sintered.
  • the test electrode is a porous cermet with high catalytic activity to nitrogen oxide compounds, and is made of metal platinum, a highly catalytically active material (for example, Rh), zirconia, and carbon powder and then sintered at high temperature.
  • the porous protective layer and porous diffusion barrier layer are made of porous alumina.
  • the insulating layer is made of dense alumina.
  • the material of the reference electrode consists of precious metals platinum and zirconia.
  • the heating electrode material is composed of precious metal platinum and zirconia.
  • the invention also provides a method for preparing a nitrogen-oxygen sensor chip.
  • Each porous functional layer is manufactured by a screen printing process.
  • the nitrogen-oxygen sensor structure of the present invention is designed with a three-dimensional porous structure for the catalytic decomposition of nitrogen and oxygen sensors and the measurement area of NOX, which greatly increases the contact area between the gas and the electrode, and the material interfaces of the functional layers are tight. In combination, it solves the problems of heating uniformity and stability in the test area, and measures the NOx gas concentration more accurately;
  • the functional layers of the nitrogen-oxygen sensor measurement area of the invention are designed as a porous structure, and the interfaces between the functional layers are integrated into one body, which greatly improves the structural strength of the nitrogen-oxygen sensor chip;
  • Each of the porous functional layers in the measurement area of the nitrogen-oxygen sensor chip of the present invention is completed by a screen printing process.
  • the manufacturing process is simple and easy to produce, and the third column of the diffusion barrier layer can effectively pass the test gas and effectively Avoiding the pollution of the test electrode caused by the volatilization of Au during the high temperature sintering process.
  • FIG. 1 is a sectional view of a structure of a nitrogen-oxygen sensor provided by the present invention
  • FIG. 2 is a plan view of a structure of a test area of a nitrogen-oxygen sensor provided by the present invention
  • the nitrogen-oxygen sensor provided by the present invention can be used to accurately measure the NO X content in automobile exhaust.
  • a ceramic chip of a nitrogen-oxygen sensor provided by the present invention specifically includes first to six layers of zirconia substrates (hereinafter referred to as substrates) laminated in sequence, and the first substrate 1
  • An external electrode 14 is provided on the external electrode, and the external electrode is covered with a porous protective layer 15; a second substrate 2 is provided between the first substrate 1 and the third substrate 3 as a test area for the nitrogen and oxygen sensors, as shown in FIG.
  • the second layer substrate 2 is provided with a porous gas barrier 10, a first gas diffusion barrier 7, a first pump oxygen electrode 11, a second gas diffusion barrier 8, a second pump oxygen electrode 12, a first Three gas diffusion barriers 9 and test electrodes 13; porous gas barriers 10, first gas diffusion barrier 7, first pump oxygen electrode 11, second gas barrier 8, second pump oxygen electrode 12, third gas protection
  • the barrier 9 and the test electrode 13 are both integrated with the contact interface of the first layer substrate 1, the second layer substrate 2 and the third layer substrate 3;
  • the third layer substrate 3 is provided with a gas communicating with the atmosphere
  • the reference channel 19 is provided with a reference electrode 16 between the third layer substrate 3 and the fourth layer substrate 4, and the reference electrode 16 is covered with The porous gas diffusion layer 17; the fourth substrate 4 is provided with small holes 18, the small holes 18, the gas reference channel 19 and the porous diffusion layer 17 communicate with each other;
  • a heating electrode 21 is provided between the heating electrodes 21, and an aluminum oxide insulating layer 20 is provided above and below the heating electrode 21, that is, the heating electrode is covered with the aluminum oxide
  • the test principle of automobile exhaust is: the exhaust gas passes through the porous gas barrier 10 and enters the first gas diffusion barrier 7, the gas gets a certain buffering effect in the first gas diffusion barrier 7, and then enters the first pump oxygen electrode of the porous structure.
  • area 11 the main pump oxygen discharge function is realized in this area, reducing the oxygen concentration in the exhaust gas to a very low concentration value; the remaining gas in the first pump oxygen electrode 11 area passes through the second gas diffusion barrier 8 to enter In the region of the second pump oxygen electrode 12 of the porous structure, the second pump oxygen electrode 12 in this region further realizes the auxiliary pump oxygen drainage function, further reducing the oxygen concentration in the exhaust gas to a very low concentration value; this gas is further 9 through the third gas diffusion barrier 13 into the porous structure of the electrode area of the test, the test electrode 13 to achieve accurate measurement of the gas concentration of NO X.
  • an external electrode 14 is provided on the upper surface of the first substrate 1, and the external electrode 14 is covered with a layer of porous protective layer 15 made of alumina.
  • the function is to protect the external electrode from impurities and oily substances in the exhaust gas. Pollution;
  • a gas barrier 10 with a certain porosity is set at the exhaust gas inlet.
  • the material of the gas barrier 10 can be alumina or zirconia, and carbon powder doped with a certain ratio is sintered at high temperature. Because the carbon powder is completely volatilized during the high-temperature sintering of the nitrogen-oxygen sensor chip, the protective barrier layer has a certain gap and the gas can pass through.
  • the first gas diffusion barrier layer 7, the second gas diffusion barrier layer 8 and the third gas diffusion barrier 9 are all diffusion barrier layers with a certain porosity, and the materials are all zirconia and are doped. A certain percentage of carbon powder is sintered at high temperature.
  • the third gas diffusion barrier layer 9 can not only pass the gas, but also effectively prevent the volatilization of gold during the high-temperature sintering process from contaminating the test electrode 13, so it plays a role in gas circulation and protects the test electrode 13 from pollution. effect.
  • the first pump oxygen electrode 11 and the second pump oxygen electrode 12 are both porous cermets that have no catalytic activity against nitrogen oxides, and are made of platinum, non-catalytically active materials such as gold (Au), Zirconia and carbon powder are mixed and sintered at high temperature.
  • the test electrode 13 is a cermet having a high catalytic activity to an oxynitride.
  • the test electrode 13 is made of platinum, a highly catalytically active material, such as Rh, zirconia, and carbon powder, and sintered at a high temperature.
  • a reference electrode 16 is provided between the third substrate 3 and the fourth substrate 4, and the upper surface of the reference electrode is covered with a layer of porous diffusion barrier layer 17 made of alumina.
  • the small holes 18 and the reference gas channel 19 on the fourth substrate are in communication with the atmosphere, thereby ensuring that the reference electrode 16 is always in contact with the reference air.
  • a heating electrode 21 for a nitrogen-oxygen sensor is disposed between the fourth substrate 5 and a fifth substrate 5, and the upper and lower surfaces of the heating electrode 21 are provided with a dense alumina insulating layer 20 and the heating electrode 21 It is used to heat the reaction test area of the nitrogen and oxygen sensor chip, so that it can reach the working temperature required by the nitrogen and oxygen sensor in a short time.
  • the external electrode 14, the first substrate 1 and the first pump oxygen electrode 11 constitute the main pump oxygen unit.
  • an adjustable voltage is applied to the two poles of the main pump oxygen unit, and the first is controlled by adjusting the voltage change.
  • the amount of oxygen pumped out in the region of the pump oxygen electrode 11 keeps the concentration of oxygen in the gas passing through this region constant within a range of several PPM.
  • the external electrode 14, the first substrate 1 and the second pump oxygen electrode 12 constitute an auxiliary pump oxygen unit.
  • the exhaust gas having a low oxygen concentration in the area of the first pump oxygen electrode 11 passes through the second gas diffusion barrier. 8 into the auxiliary pump oxygen electrode, that is, the second pump oxygen electrode 12, the auxiliary pump oxygen electrode 12 further pumps out the remaining oxygen passing through this area, reducing the oxygen concentration to a few 10-3 ppm.
  • the exhaust gas with a low oxygen concentration in the second pump oxygen electrode 12 region that is, the auxiliary pump oxygen electrode region, continues to pass through the third gas diffusion layer 9 and enters the test electrode 13 region.
  • the catalytic action of the test electrode 13 Next, NO gas is decomposed into N 2 and O 2 .
  • the decomposed O 2 is pumped out by the test electrode.
  • a corresponding pump current I is generated in the circuit composed of the measurement unit. According to the magnitude of the pump current I, the concentration of NO X gas can be accurately calculated.
  • the reference electrode 16, the third layer substrate 3, the fourth layer substrate 4 and the first pump oxygen electrode 11 constitute a loop unit.
  • the real-time monitoring and feedback within the area of the first pump oxygen electrode 11 is performed.
  • the oxygen concentration in the first pump oxygen electrode 11 is controlled by the main pump oxygen unit.
  • the reference electrode 16, the third layer substrate 3, the fourth layer substrate 4 and the second pump oxygen electrode 12 constitute a loop unit.
  • real-time monitoring and feedback of The oxygen concentration content is controlled by the auxiliary pump oxygen unit in the area of the second pump oxygen electrode 12.
  • a heating electrode 21 is provided between the fourth substrate 5 and the fifth substrate 5.
  • the heating electrode 21 is used to heat the test area of the nitrogen and oxygen sensor chip, so that it can reach the working temperature required by the sensor in a short time.
  • the upper and lower surfaces are covered with a dense alumina junction layer 20.

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Abstract

一种氮氧传感器陶瓷芯片，包括从上到下依次叠压而成的六层基片(1,2,3,4,5,6)，第二层基片(2)中依次设置有多孔结构的气体保护障(10)、第一气体扩散障碍层(7)、第一泵氧电极(11)、第二气体扩散障碍层(8)、第二泵氧电极(12)、第三气体扩散障碍层(9)和测试电极(13)，第三层基片(3)与第四层基片(4)之间设置有参比电极(16)，参比电极(16)上设置覆盖有一层多孔扩散障层(17)，气体保护障(10)、第一气体扩散障碍层(7)、第一泵氧电极(11)、第二气体扩散障碍层(8)、第二泵氧电极(12)、第三气体扩散障碍层(9)和测试电极(13)均设置为与第一层基片(1)、第二层基片(2)和第三层基片(3)接触界面结合为一体。氮氧传感器芯片的制备方法及使用方法。

Description

一种氮氧传感器陶瓷芯片 技术领域
本发明属于氮氧传感器的技术领域，特别涉及一种氮氧传感器陶瓷芯片。
背景技术
随着经济的飞速发展，汽车已是人类不可缺少的现代交通工具，但汽车尾气却成为大气中NOX气体污染物的主要来源。为了保护环境，世界各国制定的汽车尾气排放标准越来越严格，这就需要对汽车尾气排放中的NOX气体进行实时监测和处理，而氮氧传感器是该监测系统中的核心部件之一。
目前，报道的氮氧传感器陶瓷芯片，均采用多层氧化锆陶瓷基片叠压烧结而成。在加热电极给氮氧传感器芯片加热到一定温度条件下，通过电化学单元的催化分解反应，以实现对NOX气体浓度的测量；而氮氧传感器芯片测量区域设计有多个气体空腔室结构，氮氧传感器工作时需要加热器加热并维持在950℃左右，多腔室结构将导致测量区域受热不均匀和不稳定性，影响氧化锆材料的氧离子电导率和电极材料的化学性能，因此影响氮氧传感器对NOX气体浓度的精确测量；
氮氧传感器采用的多个气体空腔室设计，制作工艺比较复杂，且为内部多空腔室结构，在一定程度上也降低了氮氧传感器芯片头部的结构强度，自身抗热震性能下降，空腔室边缘容易出现裂纹损坏，降低使用寿命。
氮氧传感器中的第一电极(主泵氧电极)和第二电极(辅助泵氧电极)通常采用掺杂有少量低催化活性的金属材料Au，由于金的熔点为1064℃，无论是芯片的烧结成型温度(1400～1600℃)，还是氮氧传感器芯片工作时的温度(约950℃)，都极易造成金的挥发而对活化电极的污染。
发明内容
针对现有技术中由于设计多个气体空腔室结构，致使氮氧传感器测量区域受热不均匀和不稳定，而导致氮氧传感器对NOX气体浓度测量精度不高的缺点，本发明提供了一种氮氧传感器陶瓷芯片，对NOX浓度的测量更加精确的氮氧传感器，可以提高氮氧传感器芯片的结构强度，且可以有效避免高温烧结过程中Au的挥发对活性电极的污染。
本发明的再一目的在于：提供一种上述氮氧传感器陶瓷芯片的制作工艺，制作工艺简单、易于生产。
本发明采用的技术方案是：
一种氮氧传感器芯片，其特征在于，包括从上到下依次叠压而成的第一层基片、第二层基片、第三层基片、第四层基片、第五层基片和第六层基片，六层基片的材质均为氧化锆；
所述第一层基片上设置有外电极，外电极上覆盖有多孔保护层；
所述的第一层基片与第三层基片之间设置第二层基片，所述第二层基片中依次设置有多孔结构的气体保护障、第一气体扩散障、第一泵氧电极、第二气体扩散障、第二泵氧电 极、第三气体扩散障和测试电极；和，
所述的第三层基片中设置有气体参比通道，所述气体参比通道与大气相连通，第三层基片与第四层基片之间设置有参比电极，参比电极上覆盖有一层多孔扩散障碍层；
所述的第四层基片中设置有小孔，小孔与气体参比通道以及多孔扩散障碍层相互连通；
所述第四层基片与第五层基片之间设置有加热电极，加热电极上下设置有一层绝缘层。本发明将氮氧传感器催化NOX催化分解和测量区域均设计为三维多孔结构，在很大程度上增加了气体与电极之间的接触面积，各功能层材料界面之间紧密结合，很好的解决了测试区域受热均匀性和稳定性问题。
所述的气体保护障、第一气体扩散障、第一电极、第二气体保护障、第二电极、第三气体保护障和测试电极均设置为与第一层基片、第二层基片和第三层基片接触界面结合为一体。以进一步提高强度。
所述的气体保护障为多孔氧化锆或氧化铝材质。
所述的第一气体扩散障碍层、第二气体扩散障碍层和第三气体扩散障碍层均为多孔氧化锆材质。第三气体扩散障碍层又称为第三列扩散障碍层，既可有效通过测试气体，又能够有效的避免因高温烧结过程中Au的挥发对测试电极造成的污染问题。
所述的第一泵氧电极和第二泵氧电极为对氮氧化合物无催化活性的多孔性金属陶瓷，由金属铂、无催化活性材料(例如：Au)、氧化锆和碳粉混合经高温烧结而成。
所述的测试电极为对氮氧化合物具有高催化活性的多孔性金属陶瓷，由金属铂、高催化活性材料(例如：Rh)、氧化锆和碳粉混合经高温烧结而成。
所述的多孔保护层和多孔扩散障碍层为多孔氧化铝材质。
所述的绝缘层为致密氧化铝材质。
参比电极的材料，由贵金属铂和氧化锆组成。
所述的加热电极材料，由贵金属铂和氧化锆组成。
本发明还提供一种氮氧传感器芯片的制备方法，各多孔功能层，均通过丝网印刷的工艺制作完成。
本发明有益效果为：
本发明的氮氧传感器结构上将氮氧传感器催化NOX催化分解和测量区域均设计为三维多孔结构，在很大程度上增加了气体与电极之间的接触面积，各功能层材料界面之间紧密结合，很好的解决了测试区域受热均匀性和稳定性问题，对NOX气体浓度的测量更加精确；
本发明的氮氧传感器测量区域各功能层设计为多孔结构，功能层之间界面结合为一体，在很大程度上提高了氮氧传感器芯片的结构强度；
本发明的氮氧传感器芯片测量区域各多孔功能层，均通过丝网印刷的工艺制作完成，制作工艺简单，易于生产化，且第三列扩散障碍层既可有效通过测试气体，又能够有效的避免了因高温烧结过程中，Au的挥发对测试电极的造成的污染问题。
附图说明
图1是本发明提供的氮氧传感器结构剖面视图；
图2是本发明提供的氮氧传感器测试区域结构俯视图；
图中标号说明：
1——第一层基片；2——第二层基片；3——第三层基片；
4——第四层基片；5——第五层基片；6——第六层基片；
7、8、9——第一、二、三气体扩散障碍层；、
10——多孔结构的气体保护障；
11——第一泵氧电极；12——第二泵氧电极；
13——测试电极；
14——外电极；
15——多孔保护层；
16——参比电极；
17——多孔扩散障碍层；
18——小孔；
19——参比气体通道；
20——绝缘层；
21——加热电极；
具体实施方式
为了清楚说明本发明的目的、技术方案以及优点，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施方式仅用于解释本发明，并不用于限定本发明。
本发明提供的氮氧传感器可用于对汽车尾气中的NO X含量进行精确测量。
如图1和2所示，本发明提供的一种氮氧传感器陶瓷芯片，具体包括依次叠合而成的第一至六层氧化锆基片(以下简称基片)，第一层基片1上设置有外电极14，外电极上覆盖有多孔保护层15；第一层基片1与第三层基片3之间设置第二层基片2，作为氮氧传感器测试区域，如图2所示，第二层基片2中依次设置有多孔结构的气体保护障10、第一气体扩散障7、第一泵氧电极11、第二气体扩散障8、第二泵氧电极12、第三气体扩散障9和测试电极13；多孔结构的气体保护障10、第一气体扩散障7、第一泵氧电极11、第二气体保护障8、第二泵氧电极12、第三气体保护障9和测试电极13均设置为与第一层基片1、第二层基片2和第三层基片3接触界面结合为一体；第三层基片3设置有与大气相连通的气体参比通道19，第三层基片3与第四层基片4之间设置有参比电极16，该参比电极16上覆盖有多孔气体扩散层17；第四层基片4上设置有小孔18，小孔18、气体参比通道19和多孔扩散层17相互连通；第四层基片4与第五层基片5之间设置有加热电极21，加热电极21上、下各设置有一层氧化铝绝缘层20，即加热电极被氧化铝绝缘层20包覆。
汽车尾气的测试原理为：尾气经过多孔结构的气体保护障10进入到第一气体扩散障7， 气体在第一气体扩散障7得到一定的缓冲作用，再进入到多孔结构的第一泵氧电极11区域中，在此区域实现主泵氧引排功能，将尾气中的氧气浓度降低到很低的浓度值；第一泵氧电极11区域中剩余的气体再经过第二气体扩散障8进入到多孔结构的第二泵氧电极12区域中，在此区域中第二泵氧电极12进一步实现辅助泵氧引排功能，进一步将尾气中的氧气浓度降低到一个极低的浓度值；此气体再经过第三气体扩散障9进入到多孔结构的测试电极13区域中，测试电极13实现对NO X气体浓度的精确测量。
在本发明实施例中，第一基片1上表面设置有外电极14，外电极14上覆盖有一层氧化铝材质的多孔保护层15，作用是防止外电极免受尾气中的杂质和油性物质污染；
在本发明实施例中，尾气进气口处设置有一定孔隙率的气体保护障10，气体保护障10材质可以是氧化铝或氧化锆，掺杂一定比率的碳粉经高温烧结而成。由于碳粉在氮氧传感器芯片高温烧结过程中完全挥发，因此保护障碍层具有一定的空隙，气体可以通过。
在本发明实施例中，第一气体扩散障碍层7、第二气体扩散障碍层8和第三气体扩散障9均为具有一定孔隙率的扩散障碍层，其材质均为氧化锆，为掺杂一定比率的碳粉经高温烧结而成。
本发明实施例中，第三气体扩散障碍层9既可以通过气体，也可以有效防止高温烧结过程中金的挥发对测试电极13的污染，因此起到了气体流通和保护测试电极13免受污染的作用。
在本发明实施例中，第一泵氧电极11和第二泵氧电极12均为对氮氧化合物无催化活性的多孔性金属陶瓷，由金属铂、无催化活性材料例如：金(Au)、氧化锆和碳粉混合经高温烧结而成。
在本发明实施例中，测试电极13为对氮氧化合物具有高催化活性的金属陶瓷，由金属铂、高催化活性材料，例如:Rh、氧化锆和碳粉混合经高温烧结而成。
本发明实施例中，第三基片3与第四基片4之间设置有参比电极16，参比电极上表面覆盖有一层氧化铝材质的多孔扩散障碍层17，多孔扩散障碍层17、第四基片上的小孔18、参比气体通道19均与大气相连通，从而保证参比电极16始终与参比空气接触。
本发明实施例中，第四基片4与第五基片5之间设置有氮氧传感器的加热电极21，加热电极21上下表面均设置覆盖有一层致密的氧化铝绝缘层20，加热电极21用于为氮氧传感器芯片反应测试区域加热，使其在很短时间内达到氮氧传感器所需要的工作温度。
外电极14、第一层基片1以及第一泵氧电极11构成主泵氧单元，氮氧传感器工作过程中，在主泵氧单元的两极施加可调节电压，通过调节电压变化来控制第一泵氧电极11区域内氧的泵出量，将通过此区域气体中的氧气浓度恒定保持在几个PPM的范围。
外电极14、第一层基片1以及第二泵氧电极12构成辅助泵氧单元，在氮氧传感器工作过程中，第一泵氧电极11区域中低氧浓度的尾气经过第二气体扩散障8进入到辅助泵氧电极即第二泵氧电极12区域，辅助泵氧电极12进一步把通过此区域内的剩余氧气泵出，将氧气浓度降低至几个10-3ppm。
外电极14、第一层基片1以及测试电极13构成氮氧传感器NO X浓度测量单元。在氮氧传感器工作过程中，第二泵氧电极12区域即辅助泵氧电极区域中低氧浓度的尾气继续经过第三气体扩散层9进入到测试电极13区域中，在测试电极13的催化作用下，NO气体发生分解成N 2和O 2。分解的O 2被测试电极泵出，此时测量单元组成的回路中产生相应的泵电流I，根据泵电流I的大小进而可以精确计算出NO X气体的浓度含量。
参比电极16、第三层基片3、第四层基片4及第一泵氧电极11构成一个回路单元，在氮氧传感器工作过程中，实时监测和反馈第一泵氧电极11区域内的氧气浓度含量，通过主泵氧单元实现对第一泵氧电极11区域内氧气浓度含量的控制。
参比电极16、第三层基片3、第四层基片4及第二泵氧电极12构成一个回路单元，在氮氧传感器工作过程中，实时监测和反馈第二泵氧电极区域内的氧气浓度含量，通过辅助泵氧单元实现对第二泵氧电极12区域内氧气浓度含量的控制。
第四基片4和第五基片5之间设置有加热电极21，加热电极21用于为氮氧传感器芯片测试区域加热，使其在短时间内达到传感器所需要的工作温度，加热电极21的上下表面均覆盖有一层致密的氧化铝结缘层20。
以上所述仅为本发明型的较佳实施例方式，本领域的技术人员容易理解，并不用以限制本发明，故凡依本所附权利要求限定的原则之内所作的任何修改和等效变化，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种氮氧传感器芯片，其特征在于，包括从上到下依次叠压而成的第一层基片(1)、第二层基片(2)、第三层基片(3)、第四层基片(4)、第五层基片(5)和第六层基片(6)，六层基片的材质均为氧化锆；
    所述第一层基片上设置有外电极(14)，外电极(14)上覆盖有多孔保护层(15)；
    所述第一层基片(1)与第三层基片(3)之间设置第二层基片(2)，所述第二层基片(2)中依次设置有多孔结构的气体保护障(10)、第一气体扩散障碍层(7)、第一泵氧电极(11)、第二气体扩散障碍层(8)、第二泵氧电极(12)、第三气体扩散障碍层(9)和测试电极(13)；
    所述第三层基片(3)中设置有气体参比通道(19)，所述气体参比通道(19)与大气相连通，第三层基片(3)与第四层基片(4)之间设置有参比电极(16)，参比电极(16)上设置覆盖有一层多孔扩散障层(17)；
    所述第四层基片(4)中设置有小孔(18)，小孔(18)与气体参比通道(19)以及多孔扩散障层(17)相互连通；
    所述第四层基片(4)与第五层基片(5)之间设置有加热电极(21)，加热电极(21)上下设置有一层绝缘层(20)。
  2. 根据权利要求1所述的氮氧传感器芯片，其特征在于：所述的气体保护障(10)、第一气体扩散障(7)、第一泵氧电极(11)、第二气体保护障(8)、第二泵氧电极(12)、第三气体保护障(9)和测试电极(13)均设置为与第一层基片、第二层基片和第三层基片接触界面结合为一体。
  3. 根据权利要求1和2所述的氮氧传感器芯片，其特征在于：所述气体保护障(10)为多孔氧化锆或氧化铝材质。
  4. 根据权利要求1和2所述的氮氧传感器芯片，其特征在于：所述第一气体扩散障层(7)、第二气体扩散障层(8)和第三气体扩散障层(9)均为氧化锆材质。
  5. 根据权利要求1和2所述的氮氧传感器芯片，其特征在于：所述第一泵氧电极(11)和第二泵氧电极(12)为对氮氧化合物无催化活性的多孔性金属陶瓷。
  6. 根据权利要求1和2所述的氮氧传感器芯片，其特征在于：所述测试电极(13)为对氮氧化合物具有高催化活性的多孔性金属陶瓷。
  7. 根据权利要求1所述的氮氧传感器芯片，其特征在于：所述多孔保护层(15)和多孔扩散障层(17)为多孔氧化铝材质。
  8. 根据权利要求1所述的氮氧传感器芯片，其特征在于：所述绝缘层(20)为致密氧化铝材质。
  9. 一种根据权利要求1至8任项所述的氮氧传感器芯片的制备方法，各多孔功能层，包括多孔保护层(15)、多孔结构的气体保护障(10)、第一气体扩散障碍层(7)、第二气体 扩散障碍层(8)、第三气体扩散障碍层(9)和多孔扩散障层(17)均通过丝网印刷的工艺制作完成。
  10. 一种根据权利要求1至8任项所述的氮氧传感器芯片的使用方法，多孔结构的气体保护障(10)作为尾气进气口，其中，
    外电极(14)、第一层基片(1)以及第一泵氧电极(11)构成主泵氧单元，氮氧传感器工作过程中，在主泵氧单元的两极施加可调节电压，通过调节电压变化来控制第一泵氧电极(11)区域内氧的泵出量，将通过此区域气体中的氧气浓度恒定保持在几个PPM的范围；
    外电极(14)、第一层基片(1)以及第二泵氧电极(12)构成辅助泵氧单元，在氮氧传感器工作过程中，第一泵氧电极(11)区域中低氧浓度的尾气经过第二气体扩散障碍(8)进入到辅助泵氧电极即第二泵氧电极(12)区域，该辅助泵氧电极进一步把通过此区域内的剩余氧气泵出，将氧气浓度降低至几个10 -3ppm；
    外电极(14)、第一层基片(1)以及测试电极(13)构成氮氧传感器NO X浓度测量单元，在氮氧传感器工作过程中，第二泵氧电极(12)区域中低氧浓度的尾气继续经过第三气体扩散障碍层(9)进入到测试电极13区域中，在测试电极(13)的催化作用下，NO X气体发生分解成N 2和O 2，分解的O 2被测试电极(13)泵出，此时测量单元组成的回路中产生相应的泵电流I，根据泵电流I的大小进而可以精确计算出NO X气体的浓度含量；
    参比电极(16)、第三层基片(3)、第四层基片(4)及第一泵氧电极(11)构成一个回路单元，在氮氧传感器工作过程中，实时监测和反馈第一泵氧电极(11)区域内的氧气浓度含量，通过主泵氧单元实现对第一泵氧电极(11)区域内氧气浓度含量的控制；
    参比电极(16)、第三层基片(3)、第四层基片(4)及第二泵氧电极(12)构成一个回路单元，在氮氧传感器工作过程中，实时监测和反馈第二泵氧电极区域内的氧气浓度含量，通过辅助泵氧单元实现对第二泵氧电极(12)区域内氧气浓度含量的控制。
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CN207488226U (zh) * 2017-07-26 2018-06-12 深圳安培龙科技股份有限公司 一种进气保护的氮氧传感器
CN109298057A (zh) * 2018-09-03 2019-02-01 上海长园维安电子线路保护有限公司 一种氮氧传感器陶瓷芯片

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