WO2019154062A1 - 智能氮氧传感器及其检测方法 - Google Patents

智能氮氧传感器及其检测方法 Download PDF

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Publication number
WO2019154062A1
WO2019154062A1 PCT/CN2019/072623 CN2019072623W WO2019154062A1 WO 2019154062 A1 WO2019154062 A1 WO 2019154062A1 CN 2019072623 W CN2019072623 W CN 2019072623W WO 2019154062 A1 WO2019154062 A1 WO 2019154062A1
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Prior art keywords
electrode
measuring
pump
layer
unit
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PCT/CN2019/072623
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English (en)
French (fr)
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冯江涛
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常州联德电子有限公司
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Priority to US16/980,379 priority Critical patent/US11913927B2/en
Publication of WO2019154062A1 publication Critical patent/WO2019154062A1/zh

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • 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
    • G01N27/4071—Cells and probes with solid electrolytes for investigating or analysing gases using sensor elements of laminated structure
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • F01N3/2066—Selective catalytic reduction [SCR]
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • F01N3/2066—Selective catalytic reduction [SCR]
    • F01N3/208—Control of selective catalytic reduction [SCR], e.g. dosing of reducing agent
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/30—Arrangements for supply of additional air
    • F01N3/32—Arrangements for supply of additional air using air pump
    • 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
    • G01N27/27—Association of two or more measuring systems or cells, each measuring a different parameter, where the measurement results may be either used independently, the systems or cells being physically associated, or combined to produce a value for a further parameter
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/0037—NOx
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2560/00—Exhaust systems with means for detecting or measuring exhaust gas components or characteristics
    • F01N2560/02—Exhaust systems with means for detecting or measuring exhaust gas components or characteristics the means being an exhaust gas sensor
    • F01N2560/026—Exhaust systems with means for detecting or measuring exhaust gas components or characteristics the means being an exhaust gas sensor for measuring or detecting NOx
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2560/00—Exhaust systems with means for detecting or measuring exhaust gas components or characteristics
    • F01N2560/20—Sensor having heating means
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • 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
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the invention relates to a sensor, in particular to an intelligent nitrogen oxygen sensor and a detection method thereof.
  • NO2 in the original exhaust of the SCR front end accounts for about 10% of the total amount of NOX, and NO2 is fully involved in the rapid reaction of NH3 in the SCR, and there is basically no NO2 at the back end of the SCR.
  • Some NOx sensors do not measure inaccurately because of NO2 in NOX.
  • the DOC of the diesel engine after-treatment is almost a must.
  • the NO2 in the SCR front-end exhaust gas accounts for nearly 50% of the total NOX, which may cause the SCR back-end NOX to be all NO2, especially Under the condition that the national IV emission regulations have very low NOX limit requirements, the existing current-type nitrogen-oxygen sensors can not meet the requirements of measurement accuracy, and a nitrogen-oxygen sensor with high measurement accuracy for both NO and NO2 is urgently needed.
  • the present invention aims to solve the above drawbacks and provide an intelligent nitrogen-oxygen sensor sensing chip.
  • the smart NOx sensor sensing chip comprises a base layer, a printing functional layer and a closed structural cavity, and the base layer comprises an upper zirconia substrate, The middle layer zirconia substrate and the bottom zirconia substrate;
  • the printing functional layer comprises a common external electrode, a main pump internal electrode, a secondary pump internal electrode, a mixed potential sensitive electrode, a measuring pump internal electrode, a reference air electrode, an insulating coating layer, and an insulating package Layer 2, heating circuit and 8 electrode contacts;
  • the closed structure cavity comprises a first measuring cavity, a second measuring cavity and a reference air channel, and the common external electrode is connected by a lead and an electrode contact and printed and connected to the upper zirconia substrate The upper end surface; the main pump inner electrode and the sub-pump inner electrode and the lead printed on the lower end surface of the upper zirconia substrate, and through the through hole on the upper zirconia substrate and the electrode contact printed on the
  • the end face electrode contacts are connected; the insulating wrap layer 1 and the insulating wrap layer 2 are directly printed and connected to the lower end surface of the bottom zirconia substrate, and the printed connection heating circuit is wrapped, and the electrode contacts 5 and the electrode contacts are Sixth, the electrode contact seven is exposed outside the end; the middle zirconia substrate is provided with a first measuring cavity, a second measuring cavity and a reference air channel by punching, and also has a first diffusion barrier layer and a first Two diffusion barrier layers.
  • the hybrid potential sensitive electrode is further disposed within the first measurement chamber.
  • the method further includes the first diffusion barrier layer being disposed at a front end of the first measurement cavity, and the second diffusion barrier layer being disposed at a rear end of the first measurement cavity.
  • the mixed potential sensitive electrode is further composed of NiO and ZrO2 in a mass ratio of 2:1 to 1:1.
  • the method further includes a main pump unit VP0 that connects the external electrode and the internal pump internal electrode, and a sub-pump unit VP1 connected between the main pump inner electrode and the reference air electrode.
  • the measuring pump unit VP2 connected between the electrode and the measuring electrode inner electrode, the first measuring chamber inner electrode and the reference air electrode are connected between the first measuring chamber oxygen concentration battery unit V0, between the reference air electrode and the auxiliary pump inner electrode Connecting the second chamber oxygen concentration cell unit V1, the reference air electrode and the measuring pump internal electrode connected to the measuring pump catalytic decomposition electrode oxygen concentration cell unit V2, the main pump inner electrode and the mixed potential sensitive electrode connection and mixing
  • the potential measuring unit Vr further includes a heating unit.
  • the method further comprising:
  • the automobile exhaust gas is dispersed into the first measuring chamber through the first diffusion barrier layer, and the main pump VP0 maintains the oxygen concentration V0 of the first measuring chamber to a constant value through feedback adjustment, so that HC, CO, and H2 in the exhaust gas are oxidized.
  • the limit current IP0 generated by the main pump unit is proportional to the air-fuel ratio of the exhaust;
  • the atmosphere of the first measuring chamber is diffused to the second measuring chamber through the second diffusion barrier layer, and the oxygen concentration V1 of the second measuring chamber is maintained at a lower constant value by the sub-pump VP1 and the NO2 is converted into NO, and the limit current IP1 generated by the auxiliary pump unit determines the amount of oxygen entering the second measuring chamber;
  • the catalytic decomposition electrode in the second measuring chamber is further reduced to the surrounding oxygen concentration by measuring the action of the pump VP2, so that the NO can be completely decomposed into N2 and O2 under the action of the measuring pump internal electrode, and the decomposed oxygen is measured.
  • the fifth step by calculating the ratio of the measured pump current IP2 and the auxiliary pump unit limit current IP1, the total NOX concentration can be accurately measured; and according to the potential difference Vr of the mixed potential detecting unit, the NO and NO2 concentrations can be separately calculated. value.
  • the invention has the beneficial effects that the intelligent nitrogen-oxygen sensor can accurately measure not only the total amount of NOX in the exhaust gas through the current-type working principle, but also the ratio of NO/NO2 in the exhaust gas by the mixed potential characteristic, so that the accurate calculation can be accurately calculated.
  • the concentration of each of NO and NO2 in the exhaust gas is not only the total amount of NOX in the exhaust gas through the current-type working principle, but also the ratio of NO/NO2 in the exhaust gas by the mixed potential characteristic, so that the accurate calculation can be accurately calculated.
  • FIG. 1 is a schematic structural view of an oxygen sensor sensing chip of the present invention
  • FIG. 2 is a schematic structural view of an oxygen sensor
  • Figure 1 it is an intelligent nitrogen-oxygen sensor sensor chip.
  • Figure 2 provides an intelligent nitrogen-oxygen sensor that combines the characteristics of mixed potential and current signals. It can not only accurately measure the exhaust gas through the current-type working principle. The total amount of NOX can also be used to detect the ratio of NO/NO2 in the exhaust gas by the mixed potential characteristics, so that the respective concentrations of NO and NO2 in the exhaust gas can be accurately calculated.
  • the oxynitride sensor of the present invention integrates a first measurement chamber, a second measurement chamber, a reference air passage, and a heating unit from a three-layer substrate.
  • the measuring portion has a mixed potential detecting unit composed of 6 electrodes; and the heating portion is composed of 2 electrodes.
  • the mixed potential detecting unit is disposed in the first measuring chamber, and is composed of a sensitive electrode with NiO as a catalytic material and an internal electrode of the main pump unit as a reference electrode.
  • a diffusion barrier layer is disposed between the first measurement chamber and the outside and between the first and second measurement chambers.
  • the figure includes a base layer, a printing functional layer and a closed structure cavity.
  • the base layer comprises an upper zirconia substrate 1, a middle zirconia substrate 2 and a bottom zirconia substrate 3;
  • the printing functional layer comprises a common external electrode 11,
  • the main pump inner electrode 12, the sub pump inner electrode 13, the mixed potential sensitive electrode 31, the measuring pump inner electrode 32, the reference air electrode 33, the insulating wrap layer 41, the insulating wrap layer 42, the heating line 43, and the eight electrode contacts a closed structure cavity includes a first measurement chamber 21, a second measurement chamber 22, and a reference air passage 23, and the common external electrode 11 is connected by a lead and an electrode contact 111 and printedly connected to the upper end surface of the upper zirconia substrate 1;
  • the pump internal electrode 12 and the sub-pump internal electrode 13 and the lead printed on the lower end surface of the upper zirconia substrate 1 and pass through the through hole on the upper zirconia substrate 1 and the electrode contact 121 printed on the upper end surface, and the electrode contact
  • the common external electrode 11, the main pump inner electrode 12, the sub pump inner electrode 13, the measurement pump inner electrode 32, the reference air electrode 33, and the mixed potential sensitive electrode 31 are function signal measuring electrodes.
  • the mixed potential sensitive electrode 31 is disposed within the first measurement chamber 21.
  • the first diffusion barrier layer 211 is placed at the front end of the first measurement chamber 21, and the second diffusion barrier layer 221 is placed at the rear end of the first measurement chamber 21.
  • the figure includes the induction chip of FIG. 1, and the main pump unit VP0, the main pump inner electrode 12 and the reference air electrode 33 connected between the common outer electrode 11 of the induction chip and the main pump inner electrode 12.
  • the auxiliary pump unit VP1 connected between the common electrode 11 and the measuring pump unit VP2 connected between the measuring pump inner electrode 32, and the first measuring chamber oxygen concentration difference between the main pump inner electrode 12 and the reference air electrode 33
  • the battery unit V0, the reference air electrode 33 and the auxiliary pump inner electrode 13 are connected to the second chamber oxygen concentration cell unit V1, and the reference air electrode 33 and the measuring pump inner electrode 32 are connected to the measuring pump to catalyze the electrode oxygen.
  • the concentration battery unit V2, the main pump inner electrode 12 and the mixed potential sensitive electrode 31 are connected to the mixed potential measuring unit Vr, and further includes a heating unit.
  • the six measuring electrodes of the nitrogen-oxygen sensor are the main electrode of the main pump (also the external electrode of the auxiliary pump and the measuring pump), the internal electrode of the main pump (also the reference electrode of the mixed potential unit), the sensitive electrode of the mixed potential unit, and the internal electrode of the auxiliary pump. , measuring the pump internal electrode and the reference air electrode.
  • the heating unit is composed of only two electrodes, and the temperature in the working state is adjusted by the PID controller based on the internal resistance of the first measuring chamber concentration battery unit between the inner pump unit and the reference air electrode of the main pump unit. The control is then maintained at around 800 degrees and remains stable.
  • Another feature in actual operation and control is that the constant concentration of the first measurement chamber and the second measurement chamber keeps the closed-loop control logic of the signal controller simpler, and the accuracy of each sensor individual signal and measurement value passes through the main The pump limit current, the secondary pump limit current, and the measured pump current are calibrated and calculated.
  • the automobile exhaust gas passes through the first diffusion barrier layer 211 to the first measuring chamber 21, and the main pump VP0 maintains the oxygen concentration V0 of the first measuring chamber 21 to a constant value through feedback adjustment, so that HC, CO in the exhaust gas, H2 is oxidized and ensures that NO and NO2 remain stable, and the limit current IP0 generated by the main pump unit is proportional to the air-fuel ratio of the exhaust gas;
  • the atmosphere of the first measuring chamber 21 is diffused to the second measuring chamber 22 through the second diffusion barrier layer 221, and the oxygen concentration V1 of the second measuring chamber 22 is maintained at a lower constant value by the action of the sub-pump VP1.
  • Converting NO2 to NO, and the limiting current IP1 generated by the auxiliary pump unit determines the amount of oxygen entering the second measuring chamber;
  • the catalytic decomposition electrode in the second measuring chamber 22 is further reduced to the surrounding oxygen concentration by the action of the measuring pump VP2, so that the NO can be completely decomposed into N2 and O2 under the action of the measuring pump internal electrode 32, and the decomposed oxygen is decomposed.
  • the fifth step by calculating the ratio of the measured pump current IP2 and the auxiliary pump unit limit current IP1, the total NOX concentration can be accurately measured; and according to the potential difference Vr of the mixed potential detecting unit, the NO and NO2 concentrations can be separately calculated. value.
  • the closed-loop control logic of the signal controller is simpler, and the accuracy of each sensor individual signal and measured value is measured by the auxiliary pump limit current IP1.
  • the pump current IP2 and the magnitude of the mixed potential signal Vr are calibrated and calculated.
  • the main pump limit current IP0 can accurately detect the air-fuel ratio of the exhaust gas by calibration.
  • the technical route of detecting NOx concentration by mixed potential is to use metal oxide MOS as sensitive electrode, ZrO2 as oxygen ion conductor and noble electrode Pt as reference electrode. Nitrogen oxide will react at the sensitive electrode to affect the transport of oxygen ions and form a response. Potential. Specifically, NOx diffuses through the sensitive electrode layer to the three-phase interface, and NOx and O2 undergo different electrochemical redox reactions at the three-phase interface of the sensitive electrode (SE) and the reference electrode (RE) side:
  • the intelligent nitrogen-oxygen sensor of the invention realizes accurate detection of the respective concentrations of NO and NO2, and has a mixed potential signal and a current signal, but the number of electrodes of the sensing element and the position of the pin are not changed compared with the conventional pure current type sensor.
  • the package of the overall assembly device is more compatible, and it is easy to mass produce and promote use.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
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  • Exhaust Gas After Treatment (AREA)

Abstract

一种智能氮氧传感器及其检测方法。该传感器包括感应芯片，感应芯片包括基体层、印刷功能层和闭合结构腔，基体层包括上层氧化锆基板（1）、中层氧化锆基板（2）和底层氧化锆基板（3）；印刷功能层包括共用外电极（11）、主泵内电极（12）、副泵内电极（13）、混合电势敏感电极（31）、测量泵内电极（32）、参比空气电极（33）、绝缘包裹层一（41）、绝缘包裹层二（42）、加热线路（43）和8个电极触点，闭合结构腔包括第一测量腔（21）、第二测量腔（22）和参比空气通道（23），这种智能氮氧传感器感应芯片不仅能通过电流型工作原理精确测量尾气中NO X的总量，还能通过混合电势特征检测尾气中NO/NO 2的比例，这样就能准确计算出尾气中NO和NO 2各自的浓度。

Description

智能氮氧传感器及其检测方法 技术领域
本发明涉及一种传感器，尤其涉及一种智能氮氧传感器及其检测方法。
 背景技术
柴油发动机在富氧条件下高温燃烧会产生大量的氮氧化物，在柴油机尾气处理中，选择催化反应（SCR）方法由于其能高效处理NOx而被广泛地使用，在此方法中会添加尿素作为反应物质，因此需要在SCR处理的前端和后端强制加入氮氧传感器来精确测量NOx的浓度以满足尾气后处理系统精确控制和车载诊断的功能。目前唯一大批量应用的氮氧传感器是基于电流型工作原理的，是以NOX分解后氧含量的增量作为依据判断和检测NOX总含量的，在对以NO为主要成分的尾气气氛测量时，其精度可以确保稳定，但当对以NO2为主要成分或者占有相当比例的尾气进行测量时，因为NO2中的氧量比NO多一倍，其测量值是不准确的。
由于国Ⅳ排放后处理一半不安装DOC，SCR前端的原排气中NO2占NOX总量的10%左右，且NO2在SCR中充分参与和NH3的快反应，到SCR后端基本没有NO2，现有的氮氧传感器不会因为NOX中的NO2而测量不准确。但排放升级到国Ⅵ后，柴油发动机后处理安装DOC几乎成为必选，SCR前端尾气中NO2占NOX总量接近甚至超过50%，这就造成SCR后端NOX可能全部是NO2的情况，尤其是在国Ⅳ排放法规对NOX限值要求很低的情况下，现有的电流型氮氧传感器已无法满足测量精度的要求，急需一种对NO和NO2均有较高测量精度的氮氧传感器。
 技术问题
本发明旨在解决上述缺陷，提供一种智能氮氧传感器感应芯片。
 技术解决方案
为了克服背景技术中存在的缺陷，本发明解决其技术问题所采用的技术方案是：这种智能氮氧传感器感应芯片包括基体层、印刷功能层和闭合结构腔，基体层包括上层氧化锆基板、中层氧化锆基板和底层氧化锆基板；印刷功能层包括共用外电极、主泵内电极、副泵内电极、混合电势敏感电极、测量泵内电极、参比空气电极、绝缘包裹层一、绝缘包裹层二、加热线路和8个电极触点；闭合结构腔包括第一测量腔、第二测量腔和参比空气通道，共用外电极通过引线和电极触点相连并印刷连接在上层氧化锆基板的上端面；主泵内电极和副泵内电极以及引线印刷连接在上层氧化锆基板的下端面、并通过上层氧化锆基板上的通孔与印刷在上端面的电极触点一、电极触点二连接；所述混合电势敏感电极和测量泵内电极印刷连接在底层氧化锆基板的上端面、并通过引线延伸至端头与两侧的电极触点三、电极触点四连接；参比空气电极及引线也印刷连接在底层氧化锆基板的上端面、并通过底层氧化锆基板上的过孔与下端面电极触点五连接；所述的绝缘包裹层一、绝缘包裹层二直接印刷连接在底层氧化锆基板的下端面、并把印刷连接的加热线路包裹起来，而电极触点五、电极触点六、电极触点七则裸露在端头外面；中层氧化锆基板上通过冲切加工设有第一测量腔、第二测量腔和参比空气通道，并且还设有第一扩散障碍层和第二扩散障碍层。
根据本发明的另一个实施例，进一步包括所述混合电势敏感电极设置在第一测量腔内。
根据本发明的另一个实施例，进一步包括所述第一扩散障碍层置于第一测量腔的前端，第二扩散障碍层置于第一测量腔的后端。
根据本发明的另一个实施例，进一步包括所述混合电势敏感电极由NiO和ZrO2构成，质量比例为2：1到1：1。
根据本发明的另一个实施例，进一步包括还包括共用外电极与主泵内电极之间连接的主泵单元VP0，主泵内电极与参比空气电极之间连接的副泵单元VP1，共用外电极与测量泵内电极之间连接的测量泵单元VP2，主泵内电极与参比空气电极之间连接第一测量腔室氧浓差电池单元V0，参比空气电极与副泵内电极之间连接第二腔室氧浓差电池单元V1，参比空气电极与测量泵内电极之间连接的测量泵催化分解电极氧浓差电池单元V2，主泵内电极与混合电势敏感电极之间连接混合电势测量单元Vr，还包括加热单元。
根据本发明的另一个实施例，进一步包括该方法包括：
第一步，汽车尾气经过第一扩散障碍层散到第一测量腔，主泵VP0通过反馈调节使第一测量腔的氧浓度V0维持到一恒定值，使尾气中HC、CO、H2被氧化并确保NO和NO2保持稳定，主泵单元产生的极限电流IP0就跟尾气空燃比值成正比；
第二步，在第一测量腔固定氧浓度条件下，检测混合电势敏感电极和主泵内电极之间的电势差Vr，就能得到NO/NO2相对含量比，Vr= NO/NO2；
第三步，第一测量腔的气氛经过第二扩散障碍层扩散到第二测量腔，通过副泵VP1作用将第二测量腔的氧浓度V1维持在一个较低的恒定值并使NO2转化为NO，而副泵单元产生的极限电流IP1决定了进入第二测量腔的氧量；
第四步，通过测量泵VP2作用将第二测量腔内催化分解电极至周围氧浓度进一步降低至V2，使得NO在测量泵内电极作用下刚好能完全分解成N2和O2，分解的氧气被测量泵泵出并形成泵电流IP2，那么该测量泵电流IP2的大小与NOx总量浓度成正比，IP2=NOx；
第五步，通过计算测量泵电流IP2和副泵单元极限电流IP1的比例，就能精确测出NOX总量浓度；再根据混合电势检测单元的电势差Vr，就能分别计算出NO和NO2的浓度值。
 有益效果
本发明的有益效果是：这种智能氮氧传感器不仅能通过电流型工作原理精确测量尾气中NOX的总量，还能通过混合电势特征检测尾气中NO/NO2的比例，这样就能准确计算出尾气中NO和NO2各自的浓度。
 附图说明
下面结合附图和实施例对本发明进一步说明。
图1是本发明氧传感器感应芯片的结构示意图；
图2是氧传感器的结构示意图；
其中：1、上层氧化锆基板，11、共用外电极，12、主泵内电极，13、副泵内电极，111、电极触点，121、电极触点一，131、电极触点二，2、中层氧化锆基板，21、第一测量腔，22、第二测量腔，23、参比空气通道，211、第一扩散障碍层，221、第二扩散障碍层，3、底层氧化锆基板，31、混合电势敏感电极，32、测量泵内电极，33、参比空气电极，311、电极触点三，321、电极触点四，331、电极触点五，41、绝缘包裹层一，42、绝缘包裹层二，43、加热线路，431、电极触点六，432、电极触点七。
 本发明的实施方式
如图1所示，是一种用于智能氮氧传感器感应芯片，图2提供了一种兼具混合电势和电流信号特征的智能氮氧传感器，其不仅能通过电流型工作原理精确测量尾气中NOX的总量，还能通过混合电势特征检测尾气中NO/NO2的比例，这样就能准确计算出尾气中NO和NO2各自的浓度。
本发明氮氧传感器由三层基板集成第一测量腔、第二测量腔、参比空气通道和加热单元。特别之处在于其测量部分除了主泵单元、副泵单元和测量泵单元之外，还有一个混合电势检测单元，共有6个电极组成；而其加热部分由2个电极组成。混合电势检测单元设置在第一测量腔，由以NiO为催化材料的敏感电极和主泵单元内电极作为参比电极组成。第一测量腔和外界之间以及第一和第二测量腔之间设置有扩散障碍层。
如图1所示，图中包括基体层、印刷功能层和闭合结构腔，基体层包括上层氧化锆基板1、中层氧化锆基板2和底层氧化锆基板3；印刷功能层包括共用外电极11、主泵内电极12、副泵内电极13、混合电势敏感电极31、测量泵内电极32、参比空气电极33、绝缘包裹层一41、绝缘包裹层二42、加热线路43和8个电极触点；闭合结构腔包括第一测量腔21、第二测量腔22和参比空气通道23，共用外电极11通过引线和电极触点111相连并印刷连接在上层氧化锆基板1的上端面；主泵内电极12和副泵内电极13以及引线印刷连接在上层氧化锆基板1的下端面、并通过上层氧化锆基板1上的通孔与印刷在上端面的电极触点一121、电极触点二131连接；所述混合电势敏感电极31和测量泵内电极32印刷连接在底层氧化锆基板3的上端面、并通过引线延伸至端头与两侧的电极触点三311、电极触点四321连接；参比空气电极33及引线也印刷连接在底层氧化锆基板3的上端面、并通过底层氧化锆基板3上的过孔与下端面电极触点五331连接；绝缘包裹层一41、绝缘包裹层二42直接印刷连接在底层氧化锆基板3的下端面、并把印刷连接的加热线路43包裹起来，而电极触点五331、电极触点六431、电极触点七432则裸露在端头外面；所述中层氧化锆基板2上通过冲切加工设有第一测量腔21、第二测量腔22和参比空气通道23，并且还设有第一扩散障碍层211和第二扩散障碍层221。
共用外电极11、主泵内电极12、副泵内电极13、测量泵内电极32、参比空气电极33、混合电势敏感电极31为功能信号测量电极。
混合电势敏感电极31设置在第一测量腔21内。
第一扩散障碍层211置于第一测量腔21的前端，第二扩散障碍层221置于第一测量腔21的后端。
如图2所示，图中包括图1中感应芯片，并且在感应芯片的共用外电极11与主泵内电极12之间连接的主泵单元VP0，主泵内电极12与参比空气电极33之间连接的副泵单元VP1，共用外电极11与测量泵内电极32之间连接的测量泵单元VP2，主泵内电极12与参比空气电极33之间连接第一测量腔室氧浓差电池单元V0，参比空气电极33与副泵内电极13之间连接第二腔室氧浓差电池单元V1，参比空气电极33与测量泵内电极32之间连接的测量泵催化分解电极氧浓差电池单元V2，主泵内电极12与混合电势敏感电极31之间连接混合电势测量单元Vr，还包括加热单元。
氮氧传感器的6个测量电极分别为主泵外电极（同时也是副泵和测量泵外电极）、主泵内电极（同时也是混合电势单元参考电极）、混合电势单元敏感电极、副泵内电极、测量泵内电极和参比空气电极。加热单元仅由2个电极组成，其工作状态时的温度是由PID控制器以主泵单元内电极与参比空气电极之间的第一测量腔浓差电池单元的内阻为基准进行调节和控制，进而维持在800度左右并保持稳定。在实际工作和控制中另外一个特点是，保持第一测量腔和第二测量腔浓度的恒定，使得信号控制器的闭环控制逻辑更加简单，而每个传感器个体信号和测量值的准确度通过主泵极限电流、副泵极限电流和测量泵电流的大小进行标定和计算。
如图2所示，在工作时，汽车尾气的检测方法为：
第一步，汽车尾气经过第一扩散障碍层散211到第一测量腔21，主泵VP0通过反馈调节使第一测量腔21的氧浓度V0维持到一恒定值，使尾气中HC、CO、H2被氧化并确保NO和NO2保持稳定，主泵单元产生的极限电流IP0就跟尾气空燃比值成正比；
第二步，在第一测量腔21固定氧浓度条件下，检测混合电势敏感电极31和主泵内电极12之间的电势差Vr，就能得到NO/NO2相对含量比，Vr= NO/NO2；
第三步，第一测量腔21的气氛经过第二扩散障碍层221扩散到第二测量腔22，通过副泵VP1作用将第二测量腔22的氧浓度V1维持在一个较低的恒定值并使NO2转化为NO，而副泵单元产生的极限电流IP1决定了进入第二测量腔的氧量；
第四步，通过测量泵VP2作用将第二测量腔22内催化分解电极至周围氧浓度进一步降低至V2，使得NO在测量泵内电极32作用下刚好能完全分解成N2和O2，分解的氧气被测量泵泵出并形成泵电流IP2，那么该测量泵电流IP2的大小与NOx总量浓度成正比，IP2=NOx。
第五步，通过计算测量泵电流IP2和副泵单元极限电流IP1的比例，就能精确测出NOX总量浓度；再根据混合电势检测单元的电势差Vr，就能分别计算出NO和NO2的浓度值。
保持第一测量腔氧浓度V0、第二测量腔氧浓度V1的恒定，使得信号控制器的闭环控制逻辑更加简单，而每个传感器个体信号和测量值的准确度通过副泵极限电流IP1、测量泵电流IP2和混合电势信号Vr的大小进行标定和计算。主泵极限电流IP0通过标定可准确检测尾气空燃比值。
混合电势检测NOx浓度的技术路线是采用金属氧化物MOS作为敏感电极、ZrO2作为氧离子导体、贵电极Pt作为参比电极，氮氧化物会在敏感电极发生催化反应影响氧离子的传输，形成响应电势。具体为NOx通过敏感电极层扩散至三相界面，NOx和O2在敏感电极（SE）和参比电极（RE）侧的三相界面处会发生不同的电化学氧化还原反应:
RE（Pt）侧：
（对NO） 
Figure 237478dest_path_image001
   (1)
（对NO2）
Figure 367108dest_path_image002
(2)
SE（MOS）侧：
（对NO） 
Figure 853584dest_path_image003
  (3)
（对NO2）
Figure 941625dest_path_image004
  (4)
在SE端有NOx的吸附和反应，而Pt-RE则无此作用。因此即使在同一样气下，SE和RE之间也会产生电势。但由于NO反应会消耗氧离子提供电子，而NO2恰好相反。因此在NO和NO2混合气氛响应时，两者会出现抵消的情况。据此响应原理，在混合气氛下敏感电极和参比电极之间产生的电势差在一定程度上可以反应出NO和NO2的比例。
本发明智能氮氧传感器实现了NO和NO2各自浓度的精确检测，兼具混合电势信号和电流信号，但在感应元件电极数量和引脚位置排布跟传统纯电流型传感器相比没有发生变化，使得整体总成器件的封装更具兼容性，容易大批量生产和推广使用。

Claims (6)

  1. 一种智能氮氧传感器，包括感应芯片，感应芯片包括基体层、印刷功能层和闭合结构腔，基体层包括上层氧化锆基板（1）、中层氧化锆基板（2）和底层氧化锆基板（3）；印刷功能层包括共用外电极（11）、主泵内电极（12）、副泵内电极（13）、混合电势敏感电极（31）、测量泵内电极（32）、参比空气电极（33）、绝缘包裹层一（41）、绝缘包裹层二（42）、加热线路（43）和8个电极触点；闭合结构腔包括第一测量腔（21）、第二测量腔（22）和参比空气通道（23），其特征在于：所述共用外电极（11）通过引线和电极触点（111）相连并印刷连接在上层氧化锆基板（1）的上端面；所述主泵内电极（12）和副泵内电极（13）以及引线印刷连接在上层氧化锆基板（1）的下端面、并通过上层氧化锆基板（1）上的通孔与印刷在上端面的电极触点一（121）、电极触点二（131）连接；所述混合电势敏感电极（31）和测量泵内电极（32）印刷连接在底层氧化锆基板（3）的上端面、并通过引线延伸至端头与两侧的电极触点三（311）、电极触点四（321）连接；所述参比空气电极（33）及引线也印刷连接在底层氧化锆基板（3）的上端面、并通过底层氧化锆基板（3）上的过孔与下端面电极触点五（331）连接；所述的绝缘包裹层一（41）、绝缘包裹层二（42）直接印刷连接在底层氧化锆基板（3）的下端面、并把印刷连接的加热线路（43）包裹起来，而电极触点五（331）、电极触点六（431）、电极触点七（432）则裸露在端头外面；所述中层氧化锆基板（2）上通过冲切加工设有第一测量腔（21）、第二测量腔（22）和参比空气通道（23），并且还设有第一扩散障碍层（211）和第二扩散障碍层（221）。
  2. 如权利要求1所述的智能氮氧传感器，其特征在于：所述混合电势敏感电极（31）设置在第一测量腔（21）内。
  3. 如权利要求1所述的智能氮氧传感器，其特征在于：所述第一扩散障碍层（211）置于第一测量腔（21）的前端，第二扩散障碍层（221）置于第一测量腔（21）的后端。
  4. 如权利要求1所述的智能氮氧传感器，其特征在于：所述混合电势敏感电极（31）由NiO和ZrO2构成，质量比例为2：1到1：1。
  5. 如权利要求1所述的智能氮氧传感器，其特征在于：还包括共用外电极（11）与主泵内电极（12）之间连接的主泵单元VP0，主泵内电极（12）与参比空气电极（33）之间连接的副泵单元VP1，共用外电极（11）与测量泵内电极（32）之间连接的测量泵单元VP2，主泵内电极（12）与参比空气电极（33）之间连接第一测量腔室氧浓差电池单元V0，参比空气电极（33）与副泵内电极（13）之间连接第二腔室氧浓差电池单元V1，参比空气电极（33）与测量泵内电极（32）之间连接的测量泵催化分解电极氧浓差电池单元V2，主泵内电极（12）与混合电势敏感电极（31）之间连接混合电势测量单元Vr，还包括加热单元。
  6. 如权利要求1所述的智能氮氧传感器的检测方法，其特征在于：该方法包括：
    第一步，汽车尾气经过第一扩散障碍层散（211）到第一测量腔（21），主泵VP0通过反馈调节使第一测量腔（21）的氧浓度V0维持到一恒定值，使尾气中HC、CO、H2被氧化并确保NO和NO2保持稳定，主泵单元产生的极限电流IP0就跟尾气空燃比值成正比；
    第二步，在第一测量腔（21）固定氧浓度条件下，检测混合电势敏感电极（31）和主泵内电极（12）之间的电势差Vr，就能得到NO/NO2相对含量比，Vr= NO/NO2；
    第三步，第一测量腔（21）的气氛经过第二扩散障碍层（221）扩散到第二测量腔（22），通过副泵VP1作用将第二测量腔（22）的氧浓度V1维持在一个较低的恒定值并使NO2转化为NO，而副泵单元产生的极限电流IP1决定了进入第二测量腔的氧量；
    第四步，通过测量泵VP2作用将第二测量腔（22）内催化分解电极至周围氧浓度进一步降低至V2，使得NO在测量泵内电极（32）作用下刚好能完全分解成N2和O2，分解的氧气被测量泵泵出并形成泵电流IP2，那么该测量泵电流IP2的大小与NOx总量浓度成正比，IP2=NOx；
    第五步，通过计算测量泵电流IP2和副泵单元极限电流IP1的比例，就能精确测出NOX总量浓度；再根据混合电势检测单元的电势差Vr，就能分别计算出NO和NO2的浓度值。
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Publication number Priority date Publication date Assignee Title
CN108375618B (zh) * 2018-02-11 2020-07-14 常州联德电子有限公司 智能氮氧传感器及其检测方法
CN109342533A (zh) * 2018-09-28 2019-02-15 宁波安创电子科技有限公司 一种氮氧传感器加热控制方法
CN114689651A (zh) * 2020-12-31 2022-07-01 长城汽车股份有限公司 一种氮氧传感器、氮氧化物的测量方法和车辆
CN114660154B (zh) * 2022-03-11 2024-04-16 四方光电股份有限公司 一种氮氧传感器芯片及其制备方法
CN115266856B (zh) * 2022-06-15 2024-02-27 常州联德电子有限公司 高温多组分烟气传感器及其制备方法
CN115166000A (zh) * 2022-06-21 2022-10-11 湖北天瑞电子股份有限公司 一种用于燃油惰化测氧传感器芯片及其制备方法
CN115308373A (zh) * 2022-08-08 2022-11-08 徐州芯源诚达传感科技有限公司 一种自动测试氮氧传感器总成的装置及方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN201594086U (zh) * 2009-11-13 2010-09-29 宁波工程学院 一种全固化混合电势型NOx传感器
CN102608183A (zh) * 2012-03-13 2012-07-25 华中科技大学 一种氮氧传感器
CN104267089A (zh) * 2014-09-22 2015-01-07 金坛鸿鑫电子科技有限公司 氮氧化物传感器
CN204924863U (zh) * 2015-06-30 2015-12-30 中国第一汽车股份有限公司 一种组合式传感器
US20160356199A1 (en) * 2012-08-30 2016-12-08 Ngk Spark Plug Co., Ltd. Deterioration diagnosis device for oxidation catalyst
CN107643330A (zh) * 2017-06-28 2018-01-30 陈强 一种氮氧化物气体传感器
CN108375618A (zh) * 2018-02-11 2018-08-07 常州联德电子有限公司 智能氮氧传感器及其检测方法
CN207866752U (zh) * 2018-02-11 2018-09-14 常州联德电子有限公司 智能氮氧传感器

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6346524B2 (ja) * 2014-08-29 2018-06-20 日本碍子株式会社 ガスセンサおよびガスセンサにおけるガス導入口の形成方法
US10775341B2 (en) * 2016-03-25 2020-09-15 Ngk Insulators, Ltd. Sensor element, manufacturing method therefor, and gas sensor

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN201594086U (zh) * 2009-11-13 2010-09-29 宁波工程学院 一种全固化混合电势型NOx传感器
CN102608183A (zh) * 2012-03-13 2012-07-25 华中科技大学 一种氮氧传感器
US20160356199A1 (en) * 2012-08-30 2016-12-08 Ngk Spark Plug Co., Ltd. Deterioration diagnosis device for oxidation catalyst
CN104267089A (zh) * 2014-09-22 2015-01-07 金坛鸿鑫电子科技有限公司 氮氧化物传感器
CN204924863U (zh) * 2015-06-30 2015-12-30 中国第一汽车股份有限公司 一种组合式传感器
CN107643330A (zh) * 2017-06-28 2018-01-30 陈强 一种氮氧化物气体传感器
CN108375618A (zh) * 2018-02-11 2018-08-07 常州联德电子有限公司 智能氮氧传感器及其检测方法
CN207866752U (zh) * 2018-02-11 2018-09-14 常州联德电子有限公司 智能氮氧传感器

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