CN111474230A - Nitrogen oxygen sensor ceramic chip - Google Patents

Nitrogen oxygen sensor ceramic chip Download PDF

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Publication number
CN111474230A
CN111474230A CN202010433518.XA CN202010433518A CN111474230A CN 111474230 A CN111474230 A CN 111474230A CN 202010433518 A CN202010433518 A CN 202010433518A CN 111474230 A CN111474230 A CN 111474230A
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substrate
cavity
tail gas
oxygen
gas treatment
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CN111474230B (en
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王纯强
陈志�
赵锋
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Jiangsu Weizhe New Material Co ltd
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Jiangsu Weizhe New Material Co ltd
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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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Abstract

The invention provides a nitrogen-oxygen sensor ceramic tablet core, which reduces a cavity structure, simplifies a processing technology, reduces the possibility of product defects caused by excessive cavities needing to be processed, simultaneously omits a reference air passage and avoids the problem of sensor failure caused by pollution of the reference air passage. The device comprises first to sixth substrates which are arranged up and down, wherein an outer electrode is arranged on the outer side of the first substrate, a reference electrode is arranged between the third substrate and the fourth substrate, a tail gas treatment cavity, a first detection cavity and a second detection cavity are sequentially arranged in the middle of the second substrate, diffusion barriers are arranged among the tail gas treatment cavity, the first detection cavity and the second detection cavity, and the front parts of the two sides of the tail gas treatment cavity are provided with the diffusion barriers; and only an installation cavity used for installing a reference electrode is arranged between the third substrate and the fourth substrate, and the oxygen in the tail gas is pumped into the installation cavity by applying current between the external electrode and the reference electrode, so that the oxygen partial pressure in the installation cavity is consistent with the oxygen partial pressure in the atmosphere.

Description

Nitrogen oxygen sensor ceramic chip
Technical Field
The invention relates to the technical field of nitrogen-oxygen sensors, in particular to a ceramic core of a nitrogen-oxygen sensor.
Background
The nitrogen-oxygen sensor is a gas sensor for detecting nitrogen oxides in tail gas of diesel vehicles. With the increasing emphasis of the country on environmental protection, NO is treated in the discharge regulationxEmissions limits are also becoming more and more tightly controlled. For reducing NO in diesel vehiclesxAnd (4) emission, wherein a Selective Catalytic Reduction (SCR) system is added to an engine emission system. The principle is that when the tail gas of the engine is discharged, the sprayed urea is mixed with the tail gas, and NH is utilized on the surface of the SCR system catalyst3Reduction of NOxReacting to harmless N2. Nitrogen oxygen sensor is used for monitoring NO in the systemxContent to control the effect of urea injection quantity.
The chip type nitrogen-oxygen sensor ceramic core is a core component of the nitrogen-oxygen sensor and is made by utilizing the principle that zirconia ceramic has oxygen ion conductivity at high temperature. The ceramic core of the nitrogen-oxygen sensor generally consists of six or more layers of yttrium-stabilized zirconia ceramics, and cavities, platinum electrodes, alumina diffusion barriers, alumina insulating layers and the like are respectively arranged at different positions according to functional requirements. The processing technology of the nitrogen-oxygen sensor core is a multilayer ceramic co-firing technology, specifically, punching, filling, screen printing, laminating, isostatic pressing, cutting, sintering and the like are carried out on raw ceramics, and finally, a functional ceramic core is formed. The common cavity making technology in the multilayer ceramic co-firing process is to punch holes on the green ceramic, then fill volatile materials before isostatic pressing, and finally remove the volatile materials by sintering to form the cavity. Because the design size of the cavity is difficult to maintain during the manufacturing of the cavity, the defects are easy to cause during the sintering removal of the volatile materials, and the like, the cavity manufacturing is always a big difficulty in the multilayer ceramic co-firing process, so that the excessive cavity is reasonably avoided, and the great significance is realized on reducing the process difficulty.
A conventional NI sensor ceramic chip core (similar structural function can refer to a NI sensor ceramic chip patent application with publication No. CN 109298057A) as shown in FIGS. 1 and 2 contains NOxThe tail gas enters from the first cavity 1-1, the concentration is reduced in an equal proportion through the first diffusion barrier 1-2, the concentration is reduced in an equal proportion through the second cavity 1-3 and the second diffusion barrier 1-4, the tail gas enters into the third cavity, namely the first detection cavity 1-5, oxygen in the tail gas is pumped out by the power of the first-stage pump electrode 1-6, the concentration is further reduced through the third diffusion barrier 1-7, the tail gas enters into the fourth cavity, namely the second detection cavity 1-8, the tail gas passes through the second-stage pump electrode 1-1-9 pumping out the residual oxygen and finally carrying out NO decomposition reaction at the measuring electrodes 1-10 to decompose NO into N2And O2Decomposed O2Pumping out from the measuring electrode 1-10, and calculating NO in the tail gas according to the pump current between the measuring electrode 1-10 and the outer electrode 1-11xAnd meanwhile, the rear part of the tablet core is also provided with reference air passages 1-12 which are used for communicating with the external atmospheric environment and storing reference air, and the air can enter the porous protection layers 1-14 on the reference electrodes 1-13 and diffuse to the reference electrodes 1-13. In the actual production process, the ceramic core sheet has more cavity structures, so that the complexity of the production process is increased, the defect is easy to occur in the production process of the excessive cavities, the product rejection rate is high, and in addition, due to the arrangement of the reference air passages 1-12, when the reference air passages 1-12 enter the reference air passages 1-12 due to tail gas leakage or other pollution, and the air oxygen partial pressure is reduced, the nitrogen oxygen sensor fails.
Disclosure of Invention
Aiming at the problems that the traditional ceramic chip core has more hollow cavities and is provided with a reference air passage to possibly cause sensor failure, the invention provides the ceramic chip core of the nitrogen-oxygen sensor, which reduces the cavity structure to simplify the processing technology, reduces the possibility of product defects caused by excessive cavities needing to be processed, simultaneously omits the reference air passage and avoids the problem of sensor failure caused by reference air passage pollution.
The technical scheme is as follows: the utility model provides a nitrogen oxygen sensor ceramic core, its includes first substrate, second substrate, third substrate, fourth substrate, fifth substrate and the sixth substrate that sets up from top to bottom, the outer electrode is installed to the first substrate outside, the third substrate with install reference electrode, its characterized in that between the fourth substrate: a tail gas treatment cavity, a first detection cavity and a second detection cavity are sequentially arranged in the middle of the second substrate, diffusion barriers are arranged among the tail gas treatment cavity, the first detection cavity and the second detection cavity, and the front parts of two sides of the tail gas treatment cavity are provided with the diffusion barriers; and only an installation cavity used for installing the reference electrode is arranged between the third substrate and the fourth substrate, and the oxygen in the tail gas is pumped into the installation cavity by applying current between the outer electrode and the reference electrode, so that the oxygen partial pressure in the installation cavity is consistent with the oxygen partial pressure in the atmosphere.
It is further characterized in that:
a constant current is loaded between the outer electrode and the reference electrode;
and a porous protective layer is arranged in the mounting cavity.
Compared with the traditional ceramic core, the ceramic core can omit a first cavity and a reference air passage, can ensure normal use and reduce the number of cavities to be processed, can avoid the problem of sensor failure caused by the pollution of the reference air passage, and can improve the strength and reliability of the core while reducing the difficulty of the manufacturing process and the manufacturing cost.
Drawings
FIG. 1 is a diagram of a conventional tablet core;
FIG. 2 is a sectional view taken along line A-A of FIG. 1;
FIG. 3 is a block diagram of the present invention;
FIG. 4 is a sectional view taken along line B-B of FIG. 3;
fig. 5 is a graph of the measurement accuracy of a sensor using the present invention.
Detailed Description
As shown in fig. 3 and 4, the ceramic core of the oxynitride sensor comprises a first substrate 1, a second substrate 2, a third substrate 3, a fourth substrate 4, a fifth substrate 5 and a sixth substrate 6 which are arranged up and down, wherein outer electrodes 1-11 are arranged on the outer side of the first substrate 1, reference electrodes 1-13 are arranged between the third substrate 3 and the fourth substrate 4, a tail gas treatment cavity 7, a first detection cavity 1-5 and a second detection cavity 1-8 are sequentially arranged in the middle of the second substrate 2, a gas diffusion barrier 8 is arranged among the tail gas treatment cavity 7, the first detection cavity 1-7 and the second detection cavity 1-8, and the front parts of the two sides of the tail gas treatment cavity 7 are provided with the gas diffusion barrier 8 and the front ends are sealed; only an installation cavity 9 used for installing reference electrodes 1-13 is arranged between the third substrate 3 and the fourth substrate 4, a porous protection layer is arranged in the installation cavity 9, a power supply is connected between the external electrodes 1-11 and the reference electrodes 1-13, constant current is applied between the external electrodes 1-11 and the reference electrodes 1-13, oxygen in tail gas is pumped into the installation cavity 9, and the oxygen partial pressure in the installation cavity 9 is consistent with the oxygen partial pressure in atmospheric air.
Two porous gas diffusion barriers 8 are additionally arranged on the side surface of the tail gas treatment cavity 7, and tail gas enters the cavity from the diffusion barriers on the side surface. The diffusion barriers are arranged on the two sides of the cavity simultaneously, so that local nonuniformity of entering tail gas is avoided to the maximum extent, and simultaneously, the tail gas in the cavity is mixed more uniformly due to the opposite impact effect of the entering tail gas.
A plurality of oxygen vacancies exist in the crystal structure of the zirconia, and the oxygen vacancies can freely migrate at high temperature (more than 300 ℃), namely oxygen ions can be conducted in the crystal structure. Under the high temperature condition, if there is oxygen partial pressure differential in zirconia pottery both sides, oxygen will ionize into oxygen ion, and spontaneous one side that moves from the oxygen partial pressure is high to the oxygen partial pressure is low, simultaneously, because the removal of oxygen ion, zirconia pottery will have certain potential difference, and the size of potential difference depends on the oxygen partial pressure ratio of zirconia pottery both sides. After the reference gas channels 1-12 are eliminated, under high temperature, if the partial pressure difference of oxygen is not existed on two sides of the zirconia ceramics, the migration of oxygen ions does not occur spontaneously between the zirconia crystals, but if a voltage is applied on two sides, the oxygen/oxygen ions will migrate passively under the action of the voltage. As shown in FIG. 3, the reference electrodes 1-13 are covered with a porous protective layer, i.e., a small space is created for the reference electrodes 1-13. When a constant current of about 10uA is applied between the external electrodes 1-11 and the reference electrodes 1-13, the external electrodes 1-11 pump a very small amount of oxygen in the exhaust gas into the porous protective layers at the reference electrodes 1-13, and the oxygen partial pressure value in the air can be achieved only by little oxygen because of the very small space in the porous protective layers. In this way, similar effects to those of the air reference channels 1-12 can be simulated at the reference electrodes 1-13.
As shown in FIG. 5, the upper limit line in the figure is the required capability of the industry for the product, and the nitrogen oxygen sensor adopting the scheme measures NO with the concentration of 50ppm, 100ppm, 200ppm, 300ppm and 500ppm respectivelyxIn the range of 0-100 ppm, the error is less than 10ppm, in the range of 100-500 ppm, the error is less than 15%, and the requirement of diesel tail gas treatment industry on the error can be metAnd the measurement precision of the nitrogen oxygen sensor is required.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (3)

1. The utility model provides a nitrogen oxygen sensor ceramic core, its includes first substrate, second substrate, third substrate, fourth substrate, fifth substrate and the sixth substrate that sets up from top to bottom, the outer electrode is installed to the first substrate outside, the third substrate with install reference electrode, its characterized in that between the fourth substrate: a tail gas treatment cavity, a first detection cavity and a second detection cavity are sequentially arranged in the middle of the second substrate, diffusion barriers are arranged among the tail gas treatment cavity, the first detection cavity and the second detection cavity, and the front parts of two sides of the tail gas treatment cavity are provided with the diffusion barriers; and only an installation cavity used for installing the reference electrode is arranged between the third substrate and the fourth substrate, and the oxygen in the tail gas is pumped into the installation cavity by applying current between the outer electrode and the reference electrode, so that the oxygen partial pressure in the installation cavity is consistent with the oxygen partial pressure in the atmosphere.
2. The ceramic core of claim 1, wherein: and a constant current is loaded between the outer electrode and the reference electrode.
3. A ceramic core for a nitroxide sensor according to claim 1 or 2, characterized in that: and a porous protective layer is arranged in the mounting cavity.
CN202010433518.XA 2020-05-21 2020-05-21 Nitrogen oxygen sensor ceramic chip Active CN111474230B (en)

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1493876A (en) * 2002-11-01 2004-05-05 日本特殊陶业株式会社 Gas sensor having laminate comprising solid electrolyte layer and alumina substrate
US20070246358A1 (en) * 2004-06-05 2007-10-25 Robert Bosch Gmbh Sensor Element for Determining a Physical Property of a Measuring Gas
CN102043007A (en) * 2010-10-30 2011-05-04 无锡隆盛科技有限公司 Nitrogen oxide sensor chip
CN203929705U (en) * 2014-06-30 2014-11-05 东风电子科技股份有限公司 Nox sensor chip
US20150268188A1 (en) * 2012-12-10 2015-09-24 Ngk Insulators, Ltd. Sensor element and gas sensor
CN107748191A (en) * 2017-10-11 2018-03-02 上海交通大学 Automobile-used nitrogen oxides ammonia integrated sensor
CN207488226U (en) * 2017-07-26 2018-06-12 深圳安培龙科技股份有限公司 A kind of nitrogen oxide sensor into gas shielded
CN109298057A (en) * 2018-09-03 2019-02-01 上海长园维安电子线路保护有限公司 A kind of nitrogen oxide sensor ceramic chip
CN208953480U (en) * 2018-09-30 2019-06-07 江苏惟哲新材料有限公司 A kind of chip oxygen sensor
CN209148594U (en) * 2018-11-21 2019-07-23 温州百岸汽车零部件有限公司 A kind of NOx sensor chip pumping current adjustment
CN111141803A (en) * 2020-01-14 2020-05-12 浙江百岸科技有限公司 Nitrogen-oxygen sensor

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1493876A (en) * 2002-11-01 2004-05-05 日本特殊陶业株式会社 Gas sensor having laminate comprising solid electrolyte layer and alumina substrate
US20070246358A1 (en) * 2004-06-05 2007-10-25 Robert Bosch Gmbh Sensor Element for Determining a Physical Property of a Measuring Gas
CN102043007A (en) * 2010-10-30 2011-05-04 无锡隆盛科技有限公司 Nitrogen oxide sensor chip
US20150268188A1 (en) * 2012-12-10 2015-09-24 Ngk Insulators, Ltd. Sensor element and gas sensor
CN203929705U (en) * 2014-06-30 2014-11-05 东风电子科技股份有限公司 Nox sensor chip
CN207488226U (en) * 2017-07-26 2018-06-12 深圳安培龙科技股份有限公司 A kind of nitrogen oxide sensor into gas shielded
CN107748191A (en) * 2017-10-11 2018-03-02 上海交通大学 Automobile-used nitrogen oxides ammonia integrated sensor
CN109298057A (en) * 2018-09-03 2019-02-01 上海长园维安电子线路保护有限公司 A kind of nitrogen oxide sensor ceramic chip
CN208953480U (en) * 2018-09-30 2019-06-07 江苏惟哲新材料有限公司 A kind of chip oxygen sensor
CN209148594U (en) * 2018-11-21 2019-07-23 温州百岸汽车零部件有限公司 A kind of NOx sensor chip pumping current adjustment
CN111141803A (en) * 2020-01-14 2020-05-12 浙江百岸科技有限公司 Nitrogen-oxygen sensor

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