CN102043007A - Nitrogen oxide sensor chip - Google Patents
Nitrogen oxide sensor chip Download PDFInfo
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- CN102043007A CN102043007A CN2010105257273A CN201010525727A CN102043007A CN 102043007 A CN102043007 A CN 102043007A CN 2010105257273 A CN2010105257273 A CN 2010105257273A CN 201010525727 A CN201010525727 A CN 201010525727A CN 102043007 A CN102043007 A CN 102043007A
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Abstract
The invention discloses a nitrogen oxide sensor chip. The nitrogen oxide sensor chip is formed by laminating six layers of substrates which are made of zirconium oxide, wherein the second layer of substrate comprises four cavities, namely a first cavity, a second cavity, a third cavity and a fourth cavity; three rows of diffusion barrier layers are respectively arranged among the four cavities in turn; a first electrode is arranged in the third cavity; a second electrode and a third electrode are arranged in the fourth cavity; the third layer of substrate is provided with a reference gas channel connected with atmosphere; a reference electrode is arranged between the third layer of substrate and the fourth layer of substrate; a porous aluminum oxide layer is covered on the reference electrode; the reference gas channel is communicated with the porous aluminum oxide layer through small holes; a heating electrode is arranged between the fourth layer of substrate and the fifth layer of substrate; an insulating layer is arranged on the upper part and the lower part of the heating electrode respectively; the first layer of substrate is provided with a fourth electrode; and a protective layer is covered on the fourth electrode. The nitrogen oxide sensor chip with the structure can prevent gold in a non-activated electrode from polluting an activated electrode due to volatilization during sintering, is not required to be sintered stepwise, and is formed by laminating the six layers of substrates and sintering at one time.
Description
Technical field
The present invention relates to a kind of NOx sensor chip, relating in particular to a kind of is electrolytical flat NOx sensor chip with the stabillzed with yttrium zirconium dioxide, belongs to vehicle exhaust control system field.。
Background technology
Along with the order of energy crisis in the world wide is acute increasingly, the increasingly stringent of Abgasgesetz, the fuel-economizing of internal combustion engine and emission problem more and more are subjected to people's attention.New vehicle fuel laws and regulations pertaining to the economy has all been reformulated in each countries and regions, discharging quantitative limitation to oxides of nitrogen in the vehicle exhaust etc. is also more and more stricter, NOx sensor is the research focus in the automobile sensor field always, because automobile-used NOx sensor must be worked in the engine operation environment, NOx sensor must have following 3 functions:
(1) because engine combustion and exhaust emissions temperature thereof are higher, NOx sensor must be worked under higher temperature;
(2) require the NOx sensor material can stand the impact of-20 ℃-900 ℃ regular temperature jump;
(3) the oxides of nitrogen dividing potential drop in the tail gas is changed to make respond fast and recover, and repeatability, stability to be got well.
Figure 1 shows that the sectional view of original NOx sensor chip, entire chip is by six layers of compact zirconia (ZrO
2) substrate of matter is formed by stacking, and is expressed as ZrO as shown in the figure from top to bottom respectively
2-1, ZrO
2-2, ZrO
2-3, ZrO
2-4, ZrO
2-5, ZrO
2-6.The principle of work of chip is: tail gas to be measured is entered among the cavity 2A by path 1A, at oxygen ejectment element (by electrode 3A, electrode 4A and substrate ZrO
2-1 composition) under the effect, outside the chamber, the oxygen photosensitive elements is (by electrode 5A, electrode 10A and substrate ZrO with the oxygen ejectment in the cavity 2A
2-3 form) detect the oxygen concentration feedback oxygen supply ejectment element in the chamber, the two coordination, the oxygen concentration in making cavity 2A is adjusted to a definite value.Gas in the cavity 2A enters among the cavity 8A through path 6A again, passes through detecting element this moment (by electrode 7A, electrode 12A and ZrO
2-3 form) can detect the concentration of the oxides of nitrogen among the cavity 8A.Cavity 11A is the calibrating gas chamber, is connected with air.Electrode 9A is a heating electrode.Wherein electrode 7A is the activated electrode that can make decompose nitrogen oxides, and electrode 4A and electrode 5A are the disactivation electrode that adds gold.
Though this NOx sensor can realize measuring the function of nitrous oxides concentration, because the fusing point of gold is 1064 ℃, and the sintering temperature of zirconium oxide substrate is up to 1400-1600 ℃, and golden volatilization can make active electrode be polluted in sintering process like this.
The patent No. is that the summary of the invention of JP09171015 is: in order to prevent in the sintering process that activated electrode is polluted in the gold volatilization in the disactivation electrode, main part and ejectment element portion separately made, and sinter molding separately, and then unite two into one.Figure 2 shows that the STRUCTURE DECOMPOSITION figure of this invention, ZrO among the figure
2-1, ZrO
2-2, ZrO
2-3, ZrO
2-4, ZrO
2-5, ZrO
2-7 the expression be to be numbered 1,2,3,4,5,7 compact zirconia (ZrO
2) substrate; Al
2O
3-6 the expression be to be numbered 6 compact aluminum oxide (Al
2O
3) substrate of matter.
This NOx sensor by with calibrating gas chamber 7B, gas sampled chamber 5B, the detecting element (ZrO of air communication
2-4, electrode 6B and with 6B electrode of opposite 6 ' B), ejectment element 1.1B and heating element (Al
2O
3-6 and ZrO
2-7) constitute.In all matrixes except Al
2O
3-6 is outside the compact aluminum oxide matter, and remaining material is compact zirconia matter.Tail gas to be measured diffuses into sensor by gas sampled diffusion resistive layer 3B, and ejectment element 1.1B is discharged to the sensor outside with the oxygen in the gas.Gas enters sampling gas gas compartment 5B through small holes 4B again, the indoor gas of electrode 6B and gas sample contacts, the indoor gas of electrode 6 ' B and calibrating gas contacts, and electrode 6B and electrode 6 ' B are connected the concentration that the size of current that flows through circuit by measurement can reflect oxides of nitrogen gas in the tail gas with lead.
Electrode 6B is an activated electrode in this NOx sensor, and electrode 2 ' B is the inactive electrode that contains gold.Because the fusing point of gold is 1064 ℃, and the zirconic sintering temperature of solid electrolyte is up to 1400-1600 ℃, for the volatilization that prevents gold in the sintering process pollutes activated electrode, earlier with ejectment part 1.1B and the independent sintering of main part (except that other parts of ejectment part), and then with adhesive 1B with two parts sinter molding that is bonded into one.
This method can avoid the gold in the disactivation electrode that activated electrode is polluted really, but complex manufacturing technology, and main body and ejectment partially sinter in the all-in-one-piece process, and the connection of lead-in wire is very difficult.Though this method possible in theory is not suitable for large-scale production.
Summary of the invention
Technical matters to be solved by this invention provides a kind of can accurately the measurement nitrous oxides concentration in the vehicle exhaust, does not have pollution and the manufacture craft simple NOx sensor chip of the volatilization of gold to activated electrode in the sintering process.
Technical scheme of the present invention is as follows:
A kind of NOx sensor chip; be overrided to form by six layers of substrate ground floor to layer 6 substrate; the material of six layers of substrate is zirconia; comprise four cavitys on the second layer substrate; first cavity; second cavity; the 3rd cavity; the 4th cavity; be respectively arranged with three row diffusion barrier layers between four cavitys successively; be provided with first electrode in the 3rd cavity; be provided with second electrode and third electrode in the 4th cavity; the 3rd layer of substrate is provided with the reference gas passage that links to each other with atmosphere; be provided with contrast electrode between the 3rd layer of substrate and the 4th layer of substrate; be coated with porous alumina layer on the contrast electrode; the reference gas passage is communicated with porous alumina layer by aperture; the 4th layer of substrate and and the layer 5 substrate between be provided with heating electrode, heating electrode a layer insulating respectively arranged up and down, the ground floor substrate is provided with the 4th electrode; be coated with matcoveredn on the 4th electrode, be coated with the rete of one deck Woelm Alumina matter on the described third electrode.
Heating electrode insulation course material up and down is a compact aluminum oxide matter; The material of first electrode and second electrode is to the insensitive metallic ceramics of oxides of nitrogen; The material of first electrode and second electrode is that noble metal platinum and low catalytically-active materials are formed; The material of third electrode is that noble metal platinum and high catalytic activity material are formed; The protective seam material that covers on the 4th electrode is a Woelm Alumina matter.
Beneficial effect: in the time of can avoiding sintering on the structure of the present invention in the disactivation electrode volatilization of gold the pollution of activated electrode and be need not the substep sintering, only need six layers of superimposed once sintered moulding in back of substrates are got final product.
Among the present invention, third electrode surface coverage protective seam, in the time of can preventing sintering in disactivation electrode second electrode volatilization of gold to the pollution of activated electrode third electrode, thereby the catalytic activity that has guaranteed the activated electrode third electrode is unaffected.Therefore need not disactivation electrode and activated electrode are separated sintering, only need once sintered can finishing.Thereby simplified manufacturing process, reduced manufacture difficulty.
Description of drawings
Fig. 1 is the sectional view of original NOx sensor chip;
Fig. 2 is depicted as the sensor construction exploded view of patent JP09171015;
Fig. 3 is the sandwich construction sectional view of NOx sensor chip of the present invention;
Fig. 4 is a NOx sensor chip second layer structure vertical view among Fig. 3;
Fig. 5 is a NOx sensor heating plate structure vertical view among Fig. 3.
Embodiment
Below in conjunction with accompanying drawing the specific embodiment of the invention is described further.
A kind of NOx sensor chip; be overrided to form by six layers of substrate ground floor to layer 6 substrate 1-6; the material of six layers of substrate is zirconia; comprise four cavitys on the second layer substrate 2; first cavity 7; second cavity 9; the 3rd cavity 13; the 4th cavity 16; be respectively arranged with three row diffusion barrier layers 8 between four cavitys successively; 10; 14; be provided with first electrode 12 in the 3rd cavity 13; be provided with second electrode 15 and third electrode 18 in the 4th cavity 16; the 3rd layer of substrate 3 is provided with the reference gas passage 22 that links to each other with atmosphere; be provided with contrast electrode 19 between the 3rd layer of substrate 3 and the 4th layer of substrate 4; be coated with porous alumina layer 20 on the contrast electrode 19; reference gas passage 22 is communicated with porous alumina layer 20 by aperture 21; be provided with heating electrode 23 between the 4th layer of substrate 4 and the layer 5 substrate 5; heating electrode 23 a layer insulating 24 respectively arranged up and down, the ground floor substrate is provided with on the 4th electrode 11, the four electrodes 11 and is coated with protective seam 25.
Be coated with the rete 17 of one deck Woelm Alumina matter on the third electrode 18.
The material of first electrode 12 and second electrode 15 is to the insensitive metallic ceramics of oxides of nitrogen.
The material of first electrode 12 and second electrode 15 is that noble metal platinum and low catalytically-active materials are formed.
The material of third electrode 18 is that noble metal platinum and high catalytic activity material are formed.
The control area is just realized the ejectment function in the 3rd cavity 13 by the following method:
The 4th electrode 11, first electrode 12 and ground floor substrate 1 just dielectric substrate constitute main oxygen pump, in the NOx sensor course of work, main oxygen pump the two poles of the earth apply an adjustable power of direct current, with the control area promptly the oxygen pump in the 3rd cavity 13 to the outside or with the oxygen pump of outside to the control area promptly in the 3rd cavity 13, with this make the control area promptly the partial pressure of oxygen in the 3rd cavity 13 be fixed on some specific values.
The interior electrode of main oxygen pump promptly first electrode 12 and external electrode promptly the material of the 4th electrode 11 all be the metallic ceramics of porous.Wherein interior electrode i.e. first electrode 12 must be to the insensitive disactivation electrode of oxides of nitrogen, the ability that does not promptly possess decomposing nitrogen oxide, can adopt noble metal platinum, zirconia and other low catalytic activity, for example the gold or other have the metallic ceramics of the material of similar functions to make.
External electrode promptly covers the protective seam 25 that one deck contains Woelm Alumina matter above the 4th electrode 11, and its effect is to prevent the oily matter pollution in the tail gas or damage i.e. the 4th electrode 11 of external electrode.
The principle of work of measured zone part:
External electrode i.e. the 4th electrode 11, solid electrolyte layer is that the ground floor substrate 1 and second electrode 15 constitute auxiliary oxygen pump.In the NOx sensor course of work, apply at the two poles of the earth of auxiliary oxygen pump the direct current adjustable voltage until make measured zone promptly the oxygen concentration in the 4th cavity 16 be fixed on a constant extremely low value, oxides of nitrogen generation decomposition reaction decompose nitrogen oxides becomes nitrogen and oxygen under this low oxygen concentration.
The interior electrode of auxiliary oxygen pump i.e. second electrode 15 and the interior electrode of main oxygen pump is that the material of first electrode 12 is the same, is the insensitive disactivation electrode material of oxides of nitrogen.Can adopt the metallic ceramics of same composition to make.
The interior electrode of measuring pump is that third electrode 18 must be the activated electrode that can make decompose nitrogen oxides, can adopt noble metal platinum, other strong active materials of zirconia, and for example rhodium or other have the metallic ceramics of the metal of similar functions to make.Be coated with the rete 17 of one deck Woelm Alumina matter simultaneously on the third electrode 18, be used for preventing measured zone promptly in the 4th cavity 16 the interior electrode of auxiliary oxygen pump promptly inert metal such as the gold in second electrode 15 be shed on the third electrode 18, thereby the catalytic activity that has guaranteed third electrode 18 is unaffected.Therefore need not disactivation electrode and activated electrode are separated sintering, only need once sintered can finishing, thereby simplified manufacturing process, reduced manufacture difficulty.
The NOx sensor chip also is provided with contrast electrode 19, its surface coverage one deck porous alumina layer 20.Be provided with reference gas passage 22 in the 3rd layer of substrate 3 simultaneously, reference gas passage 22 communicates with atmosphere, have aperture 21 on the 4th layer of substrate 4, reference gas passage 22 and porous alumina layer 20 are connected, thereby guarantee that contrast electrode 19 contacts with the reference air all the time.
The control area promptly the 3rd cavity 13 and measured zone promptly the oxygen concentration in the 4th cavity 16 measure by contrast electrode 19, concrete grammar is: with the control area promptly first electrode 12 on the 3rd cavity 13 surfaces be connected with contrast electrode 19 usefulness leads, measure the voltage between two electrodes, can reflect that the control area is the oxygen concentration in the 3rd cavity 13, this value also reflects the air-fuel ratio of engine; With measured zone promptly the 4th cavity 16 surfaces electrode promptly second electrode 15 be connected with contrast electrode 19 usefulness leads, measure the voltage between two electrodes, can reflect the i.e. oxygen concentration in the 4th cavity 16 of measured zone, can according to this be worth judge measured zone promptly the oxygen concentration in the 4th cavity 16 whether reached and be enough to make the required concentration of oxides of nitrogen gas generation decomposition reaction.
The layer 5 substrate 5 of NOx sensor chip is a heating plate, and the effect of heating plate is to whole NOx sensor chip heating, makes it reach working temperature (being that solid electrolyte has higher conductivity) at short notice.Print heating electrode 23 on the layer 5 substrate 5 and between the 4th layer of substrate 4 surface, the upper and lower surface of heating electrode 23 all covers one deck compact aluminum oxide matter insulation course 24.The shape of heating electrode 23 is seen Fig. 5, because the groundwork position of NOx sensor is at the head of chip, for making its temperature can rise to optimum working temperature rapidly, the header pattern of heating electrode 23 is designed to thinner bending shown in Figure 5, and upside head 23a and lower head 23b are rotational symmetry, last lead-in wire 23c, go between 23d also axisymmetricly down, its width is upside head 23a and lower head 23b width 5-20 times.Subsidiary electrode 23e plays the determination sensor working temperature.Also be provided with pressure diffusion aperture 21 on the 4th layer of substrate 4, this aperture penetrates the 4th layer of substrate 4, and layer 5 substrate 5 is a heating plate, links to each other with reference gas passage 22 by pressure diffusion aperture 21, alleviates the inner ever-increasing internal stress of zone of heating in the heating process.
The Zirconium powder that described NOx sensor adopted refers to the zirconia powder of handling through the 5mol% yttria-stabilized.
Claims (6)
1. NOx sensor chip; be overrided to form by six layers of substrate ground floor to layer 6 substrate (1-6); it is characterized in that: the material of six layers of substrate is zirconia; comprise four cavitys on the second layer substrate (2); first cavity (7); second cavity (9); the 3rd cavity (13); the 4th cavity (16); be respectively arranged with three row diffusion barrier layers (8 between four cavitys successively; 10; 14); be provided with first electrode (12) in the 3rd cavity (13); be provided with second electrode (15) and third electrode (18) in the 4th cavity (16); the 3rd layer of substrate (3) is provided with the reference gas passage (22) that links to each other with atmosphere; be provided with contrast electrode (19) between the 3rd layer of substrate (3) and the 4th layer of substrate (4); be coated with porous alumina layer (20) on the contrast electrode (19); reference gas passage (22) is communicated with porous alumina layer (20) by aperture (21); the 4th layer of substrate (4) and and layer 5 substrate (5) between be provided with heating electrode (23); heating electrode (23) a layer insulating (24) respectively arranged up and down; the ground floor substrate is provided with the 4th electrode (11); be coated with protective seam (25) on the 4th electrode (11), be coated with the rete (17) of one deck Woelm Alumina matter on the described third electrode (18).
2. NOx sensor chip according to claim 1 is characterized in that: described heating electrode (23) insulation course (24) material up and down is a compact aluminum oxide matter.
3. NOx sensor chip according to claim 1 is characterized in that: the material of described first electrode (12) and second electrode (15) is to the insensitive metallic ceramics of oxides of nitrogen.
4. NOx sensor chip according to claim 4 is characterized in that: the material of described first electrode (12) and second electrode (15) is that noble metal platinum and low catalytically-active materials are formed.
5. NOx sensor chip according to claim 1 is characterized in that: the material of described third electrode (18) is that noble metal platinum and high catalytic activity material are formed.
6. NOx sensor chip according to claim 1 is characterized in that: it is Woelm Alumina matter that described the 4th electrode (11) is gone up protective seam (25) material that covers.
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| CN2010105257273A CN102043007A (en) | 2010-10-30 | 2010-10-30 | Nitrogen oxide sensor chip |
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|---|---|---|---|---|
| CN102842902A (en) * | 2012-09-08 | 2012-12-26 | 无锡隆盛科技股份有限公司 | Oxygen pump protection circuit of nitrogen-oxygen sensor |
| CN103645221A (en) * | 2013-11-26 | 2014-03-19 | 武汉锆元传感技术有限公司 | Slurry for slits in zirconia base electrochemical NOx sensor chip, and manufacturing method thereof |
| CN104034781A (en) * | 2014-06-16 | 2014-09-10 | 深圳市普利斯通传感科技有限公司 | Manufacturing method of piece-type wide-domain oxygen sensor chip |
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| CN104049018A (en) * | 2014-06-30 | 2014-09-17 | 东风电子科技股份有限公司 | Nox sensor chip |
| CN106770578A (en) * | 2016-12-27 | 2017-05-31 | 东风电子科技股份有限公司 | For the chip of NOx sensor |
| CN106908505A (en) * | 2017-03-07 | 2017-06-30 | 东风电子科技股份有限公司 | For the novel chip of NOx sensor |
| CN107561142A (en) * | 2017-07-25 | 2018-01-09 | 深圳安培龙科技股份有限公司 | A kind of independent segmented alive nitrogen oxide sensor |
| CN107643330A (en) * | 2017-06-28 | 2018-01-30 | 陈强 | A kind of oxides of nitrogen gas sensors |
| CN108469463A (en) * | 2018-03-22 | 2018-08-31 | 首凯汽车零部件（江苏）有限公司 | A kind of novel nitrogen oxide sensor chip and preparation method thereof |
| CN108490058A (en) * | 2018-04-09 | 2018-09-04 | 江苏奥力威传感高科股份有限公司 | A kind of NOx sensor towards vehicle energy saving environmental protection |
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| CN109001284A (en) * | 2018-06-15 | 2018-12-14 | 西安创联电气科技（集团）有限责任公司 | A kind of NOx sensor ceramic chip |
| 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 |
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| CN102842902B (en) * | 2012-09-08 | 2016-05-18 | 无锡隆盛科技股份有限公司 | Nitrogen oxide sensor oxygen pump holding circuit |
| CN102842902A (en) * | 2012-09-08 | 2012-12-26 | 无锡隆盛科技股份有限公司 | Oxygen pump protection circuit of nitrogen-oxygen sensor |
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| CN104034781A (en) * | 2014-06-16 | 2014-09-10 | 深圳市普利斯通传感科技有限公司 | Manufacturing method of piece-type wide-domain oxygen sensor chip |
| CN104049018A (en) * | 2014-06-30 | 2014-09-17 | 东风电子科技股份有限公司 | Nox sensor chip |
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| CN106908505A (en) * | 2017-03-07 | 2017-06-30 | 东风电子科技股份有限公司 | For the novel chip of NOx sensor |
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| CN107643330A (en) * | 2017-06-28 | 2018-01-30 | 陈强 | A kind of oxides of nitrogen gas sensors |
| CN107561142A (en) * | 2017-07-25 | 2018-01-09 | 深圳安培龙科技股份有限公司 | A kind of independent segmented alive nitrogen oxide sensor |
| CN108469463B (en) * | 2018-03-22 | 2020-07-28 | 首凯汽车零部件（江苏）有限公司 | Novel nitrogen oxide sensor chip and preparation method thereof |
| CN108469463A (en) * | 2018-03-22 | 2018-08-31 | 首凯汽车零部件（江苏）有限公司 | A kind of novel nitrogen oxide sensor chip and preparation method thereof |
| CN108490058A (en) * | 2018-04-09 | 2018-09-04 | 江苏奥力威传感高科股份有限公司 | A kind of NOx sensor towards vehicle energy saving environmental protection |
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| 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 |
| WO2020048300A1 (en) * | 2018-09-03 | 2020-03-12 | 上海长园维安电子线路保护有限公司 | Nitrogen oxide sensor ceramic chip |
| CN109507262A (en) * | 2018-11-21 | 2019-03-22 | 温州百岸汽车零部件有限公司 | A kind of NOx sensor chip pumping current adjustment |
| CN110297033A (en) * | 2019-08-08 | 2019-10-01 | 厦门海赛米克新材料科技有限公司 | A kind of civilian air-fuel ratio sensor chip and preparation method thereof |
| CN111141803A (en) * | 2020-01-14 | 2020-05-12 | 浙江百岸科技有限公司 | Nitrogen-oxygen sensor |
| CN111141800A (en) * | 2020-02-19 | 2020-05-12 | 浙江百岸科技有限公司 | Sensor chip |
| CN111474230A (en) * | 2020-05-21 | 2020-07-31 | 江苏惟哲新材料有限公司 | Nitrogen oxygen sensor ceramic chip |
| CN112834594A (en) * | 2021-02-22 | 2021-05-25 | 成都能斯特新材料科技有限公司 | Porous alumina film for nitrogen-oxygen sensor |
| CN113125542A (en) * | 2021-04-19 | 2021-07-16 | 连云港感瓷电子科技有限公司 | Nitrogen oxygen sensor ceramic chip with low concentration and high measurement precision |
| CN113267552A (en) * | 2021-05-14 | 2021-08-17 | 高鑫环保科技(苏州)有限公司 | Novel nitrogen oxygen sensor ceramic chip |
| CN113267552B (en) * | 2021-05-14 | 2023-12-22 | 高鑫环保科技(苏州)有限公司 | Nitrogen oxygen sensor ceramic chip |
| CN115684297A (en) * | 2022-10-08 | 2023-02-03 | 浙江百岸科技有限公司 | Nitrogen oxygen sensor chip with independently designed pump unit |
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