CN102608183A - Nitrogen-oxygen sensor - Google Patents
Nitrogen-oxygen sensor Download PDFInfo
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- CN102608183A CN102608183A CN2012100651075A CN201210065107A CN102608183A CN 102608183 A CN102608183 A CN 102608183A CN 2012100651075 A CN2012100651075 A CN 2012100651075A CN 201210065107 A CN201210065107 A CN 201210065107A CN 102608183 A CN102608183 A CN 102608183A
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Abstract
The invention discloses a nitrogen-oxygen sensor, which comprises a zirconium oxide substrate, two sensitive electrodes and a reference electrode, wherein the zirconium oxide substrate is made of yttrium-oxide-stabilized zirconium oxide, both the two sensitive electrodes are positioned on the zirconium oxide substrate and used for contacting with detected gas, one sensitive electrode is sensitive to NO (nitrogen monoxide) gas, the other sensitive electrode is sensitive to NO2 (nitrogen dioxide) gas, the reference electrode is positioned on the other side of the zirconium oxide substrate and used for contacting with air, and the two sensitive electrodes are respectively electrically connected with the reference electrode. The operating range of the nitrogen-oxygen sensor ranges from 350 DEG C to 800 DEG C, the concentration range of detected nitrogen oxides ranges from 5ppm to 3000ppm, and the response time can reach 1.2 seconds. The nitrogen-oxygen sensor is simple in structure and high in response speed and has the advantages of stable performance, simple manufacture process and wide measurement range.
Description
Technical field
The invention belongs to sensor technology, be specifically related to a kind of survey sensor of oxides of nitrogen gas, be applicable to the measurement of vehicle exhaust, metallurgy industry oxides of nitrogen gas.
Background technology
Oxides of nitrogen (NOx) is meant NO and NO
2Potpourri, be the harmful gas that produces acid deposition thing one of the main reasons such as acid rain, it damages human health and environment.Along with the continuous increase of automobile, the discharging of its tail gas has increased the NOx gas content in the atmosphere, is the amount of nitrogen oxides in the control atmosphere, needs to detect the content of oxides of nitrogen, the oxides of nitrogen of dischargings such as monitoring automobile.
Nitrogen oxide sensor mainly contains at present: semi-conductor type, concentration potential type and compound electromotive force type.Semiconductor type sensor is relatively poor relatively to the selectivity of gas, stability is also relatively poor relatively; The concentration potential type is higher to seal request; Compound electromotive force type sensor construction is complicated, be easy to lose efficacy, and these sensors all can not be distinguished measuring N O and NO at present
2Gas, thereby limited its range of application.
Summary of the invention
The invention provides a kind of nitrogen oxide sensor, this sensor can be measured NO and NO in the tail gas simultaneously
2Content, can obtain simultaneously the content of NOx.
A kind of nitrogen oxide sensor provided by the invention is characterized in that it comprises the zirconia matrix, two sensitive electrodes and a reference electrode; The material of zirconia matrix is a yttria-stabilized zirconia, and two sensitive electrodes all are positioned on the zirconia matrix, is used for contacting with tested gas, and one of them sensitive electrode is responsive to NO gas, and another sensitive electrode is to NO
2Gas is responsive, and reference electrode is positioned at the another side of zirconia matrix, is used for contacting with air, and two sensitive electrodes are electrically connected with reference electrode respectively.
As the improvement of technique scheme, the more sensitive sensitive electrode of NO gas is processed by NiO, perhaps to process by the compound substance of NiO and YSZ, the percent by volume of YSZ is 5～30Vol% in the compound substance; To NO
2The more sensitive sensitive electrode of gas is made up of CuO layer and overlayer, and overlayer is processed by the spinel that contains Mn element 0～10Vol%.
As the further improvement of technique scheme, the zirconia matrix is that the zirconia ceramics material of 5～8mole% is processed for yttria content.
As further improving again of technique scheme; This sensor also comprises well heater; Well heater is made up of zone of heating and the heating resistor that is arranged in the zone of heating; Insulate between heating resistor and the zone of heating, be provided with the air duct that for reference electrode contacts with air between well heater and the zirconia matrix.
As the further improvement of technique scheme, heating resistor is processed by metal Pt; Zone of heating is identical with the material of zirconia matrix, is that the zirconia ceramics material of 5～8 moles of % is processed by yttria content.
Matrix can adopt ceramic curtain coating or roll film and method manufacturing such as injection moulding, NO sensitive electrode and NO
2Sensitive electrode can adopt the method for printing screen preparation.
Nitrogen oxide sensor provided by the invention can be measured NO and NO in the tail gas simultaneously
2Content, can obtain simultaneously the content of NOx.Nitrogen oxide sensor provided by the invention, its working range are 350～800 ℃, and the concentration range that can detect oxides of nitrogen is 5～3000ppm, and the response time can reach 1.2 seconds.The present invention is simple in structure, and response speed is fast, and has stable performance, the characteristics that the simple measurement range of manufacture craft is wide.
Description of drawings
Fig. 1 is to be the structural representation of nitrogen oxide sensor provided by the invention.
Fig. 2 is the structural representation of a kind of instantiation provided by the invention.
Fig. 3 is for adopting device shown in Figure 2, and (5～30vol%YSZ), electrode 3 is the spinel that is coated with 5vol%Mn on the CuO to YSZ content difference in the electrode 2, and electrode 4 is the sensor that Pt formed, different N O
2Potential value E1 and E2 under the gas concentration condition.
Fig. 4 is for adopting device shown in Figure 2, NiO (+15wt%YSZ) electrode is at different N O
2The NO content that obtains under the gas concentration condition and the graph of a relation of electromotive force.
Fig. 5 is for adopting device shown in Figure 2, and the CuO electrode is at different N O
2The NO content that obtains under the gas concentration condition and the graph of a relation of electromotive force.
Fig. 6 is the NiO that obtained by the result of Fig. 4 and Fig. 5 (+15wt%YSZ) electrode and CuO electrode potential and NO and NO
2Graph of a relation between the content.
Embodiment
In order to make the object of the invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with accompanying drawing and embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
As shown in Figure 2, sensor is made up of 2,3 and reference electrodes of 1, two sensitive electrode of zirconia matrix 4.Zirconia matrix 1 is as solid electrolyte, and its material is yttria-stabilized zirconia (YSZ), and sensitive electrode 2 and 3 all is positioned on the zirconia matrix 1, is used for contacting with tested gas.Reference electrode 4 is positioned at the another side of zirconia matrix 1, and reference electrode 4 is used for contacting with air, and two sensitive electrodes 2,3 are electrically connected with reference electrode 4 respectively.
In order to shorten the initial working time of sensor, this sensor can also be provided with well heater 8, and well heater 8 is made up of zone of heating 8 and the heating resistor 5 that is arranged in the zone of heating 8, insulation between heating resistor 5 and the zone of heating 8.The function of well heater 8 mainly is that sensor is heated to uniform temperature, and as 500～650 ℃, heating resistor 5 can be to be processed by metallic resistance materials such as metal Pt.
Being provided with air duct reference electrode 4 between well heater 8 and the matrix 1 contacts with air.
Contiguous block between well heater 8 and the matrix 1 is processed by electrically non-conductive material and is got final product, and in order to simplify preparation technology, can adopt and well heater 8 or matrix 1 identical materials.In order to simplify preparation technology, zone of heating 8 can adopt with matrix 1 identical materials or other electrically non-conductive material and process.
Wherein 2 pairs of NO gases of sensitive electrode are responsive, 3 couples of NO of sensitive electrode
2Gas is responsive, and sensitive electrode 2 can be made by the compound substance of NiO or NiO+5～30Vol%YSZ.Sensitive electrode 3 is made by materials at two layers, and one deck is by the CuO material, and another layer is for containing the spinel of 0～10Vol% (preferred 5Vol%) Mn element, and this layer covers on the CuO electrode.The material of zirconia matrix 1 is that the zirconia ceramics material of 5～8mole% is processed for yttria content, and reference electrode 4 is made by precious metals pt.
Illustrate the manufacture craft of the sensor below:
Adopt the flow casting molding method to make cast sheet to contain 5mole% yttria zirconia material; Behind 1450 ℃ of 120 minutes sintering; Adopt method for printing screen to be printed on NiO+15Vol%YSZ slurry and CuO electrode slurry on the substrate respectively; And the magnesium aluminate spinel slurry that will contain 5Vol%Mn is printed on CuO electrode top layer it covered, and 1200 ℃ of sintering 20 minutes, adopts the Pt silk with four as shown in Figure 1 coupling together of electrode then.Form a battery comparatively responsive by electrode 2 and electrode 4, and form another to NO by electrode 3 and electrode 4 to NO
2Comparatively responsive battery.
At a certain temperature (350～800 ℃) two batteries with the NOx gas (NO and the NO that obtain respectively in the tail gas
2Mixed gas) electromotive force E
1And E
2:
Electrode 2:
Electrode 3:
In the formula: E
1---the electromotive force that is produced between electrode 2 and the electrode 4
E
2---the electromotive force that is produced between electrode 3 and the electrode 4
P
NO---NO content
a
1, b
1, c
1, a
2, b
2, c
2Be respectively constant
Therefore two sensors measure two equations respectively, and we can obtain the P in this moment tail gas through finding the solution this system of equations then
NO(being NO content) and P
NO2(be NO
2Content) and total NOx content (both sums)
This sensor be except measuring the NOx content in the tail gas, also NO and NO among the measuring N Ox simultaneously
2Content.
As another aspect of the present invention, a kind of sensitive electrode material to nitrogen oxide sensor is provided also.Wherein a kind of for adding the YSZ ceramic powders of 5～25Vol% in the NiO powder, another kind of for the electrode surface of making at the CuO powder covers the spinel that contains Mn that one deck has pore texture, be printed on the Zirconia electrolytic matrix through method for printing screen.
Instance 1-3:
Instance 1-3 adopts structure shown in Figure 2, and the material of its matrix 1 is by containing 5moleY
2O
3Zirconia material make, electrode 3 constitutes (its potential value E1 is a curve D) by CuO layer 7 and overlayer 6, overlayer 6 is made by the spinel that contains 5vol%Mn, electrode 4 is made by Pt, heating resistor is made by Pt.The electrode 2 of instance 1 is made (its potential value E2 is a curve A) by NiO+15vol%YSZ, and the electrode 2 of instance 2 is made (its potential value E2 is a curve B) by NiO+5vol%YSZ, and the electrode 2 of instance 3 is made (its potential value E2 is a curve C) by NiO+30vol%YSZ.
The sensor of Fig. 3 for adopting device shown in Figure 2 to obtain, in the instance 1, the NO that obtains under the heterogeneity sensitive electrode condition
2The relation of gas concentration and electrode potential value.
Fig. 4 is for adopting device shown in Figure 2, in the instance 1, NiO (+15wt%YSZ) electrode is at different N O
2The NO content that obtains under the gas concentration condition and the graph of a relation of electromotive force.
Fig. 5 is for adopting device shown in Figure 2, and in the instance 1, the CuO electrode is at different N O
2The NO content that obtains under the gas concentration condition and the graph of a relation of electromotive force.
Fig. 6 is in the instance 1 that is obtained by the result of Fig. 4 and Fig. 5, NiO (+15wt%YSZ) electrode and CuO electrode potential and NO and NO
2Graph of a relation between the content.
Instance 4-6:
The material of each several part and component are as shown in the table among the instance 4-6
| |
|
|
|
|
| |
8moleYSZ | NiO+5vol％YSZ | | Pt |
| Instance | ||||
| 5 | 6moleYSZ | NiO+15vol％YSZ | The spinel of CuO+10vol% | Pt |
| Instance | ||||
| 6 | 7moleYSZ | NiO+30vol％YSZ | The spinel of CuO+8vol%Mn | Pt |
The resulting sensor of instance 4-6 can reach the technique effect that the present invention has equally.
Those skilled in the art will readily understand; The above is merely preferred embodiment of the present invention; Not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, be equal to and replace and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a nitrogen oxide sensor is characterized in that, it comprises the zirconia matrix, two sensitive electrodes and a reference electrode; The material of zirconia matrix is a yttria-stabilized zirconia, and two sensitive electrodes all are positioned on the zirconia matrix, is used for contacting with tested gas, and one of them sensitive electrode is responsive to NO gas, and another sensitive electrode is to NO
2Gas is responsive, and reference electrode is positioned at the another side of zirconia matrix, is used for contacting with air, and two sensitive electrodes are electrically connected with reference electrode respectively.
2. nitrogen oxide sensor according to claim 1; It is characterized in that; The more sensitive sensitive electrode of NO gas is processed by NiO; Perhaps processed by the compound substance of NiO and YSZ, the percent by volume of YSZ is 5～30Vol% in the compound substance, and YSZ is meant that yttria content is the zirconia ceramics material of 5～8mole%.
3. nitrogen oxide sensor according to claim 1 and 2 is characterized in that, to NO
2The more sensitive sensitive electrode of gas is made up of CuO layer and overlayer, and overlayer is processed by the spinel that contains Mn element 0～10Vol%.
4. nitrogen oxide sensor according to claim 1 and 2 is characterized in that, the zirconia matrix is that the zirconia ceramics material of 5～8mole% is processed for yttria content.
5. nitrogen oxide sensor according to claim 3 is characterized in that, the zirconia matrix is that the zirconia ceramics material of 5～8mole% is processed for yttria content.
6. nitrogen oxide sensor according to claim 1 and 2; It is characterized in that; This sensor also comprises well heater; Well heater is made up of zone of heating and the heating resistor that is arranged in the zone of heating, insulate between heating resistor and the zone of heating, is provided with the air duct that for reference electrode contacts with air between well heater and the zirconia matrix.
7. nitrogen oxide sensor according to claim 3; It is characterized in that; This sensor also comprises well heater; Well heater is made up of zone of heating and the heating resistor that is arranged in the zone of heating, insulate between heating resistor and the zone of heating, is provided with the air duct that for reference electrode contacts with air between well heater and the zirconia matrix.
8. nitrogen oxide sensor according to claim 5; It is characterized in that; This sensor also comprises well heater; Well heater is made up of zone of heating and the heating resistor that is arranged in the zone of heating, insulate between heating resistor and the zone of heating, is provided with the air duct that for reference electrode contacts with air between well heater and the zirconia matrix.
9. nitrogen oxide sensor according to claim 8 is characterized in that heating resistor is processed by metal Pt.
10. nitrogen oxide sensor according to claim 7 is characterized in that, zone of heating is identical with the material of zirconia matrix.
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|---|---|---|---|
| CN201210065107.5A CN102608183B (en) | 2012-03-13 | 2012-03-13 | Nitrogen-oxygen sensor |
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|---|---|---|---|
| CN201210065107.5A CN102608183B (en) | 2012-03-13 | 2012-03-13 | Nitrogen-oxygen sensor |
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| CN102608183A true CN102608183A (en) | 2012-07-25 |
| CN102608183B CN102608183B (en) | 2014-03-12 |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103399042A (en) * | 2013-08-07 | 2013-11-20 | 无锡隆盛科技股份有限公司 | NOx sensor chip detection circuit |
| CN103728359A (en) * | 2014-01-20 | 2014-04-16 | 中国科学院上海硅酸盐研究所 | NOx sensor and preparation method thereof |
| CN103808785A (en) * | 2014-03-12 | 2014-05-21 | 江苏埃尔贝勒汽车电子有限公司 | Special rapid heating oxygen sensor for monitoring automobile exhaust |
| CN104267139A (en) * | 2014-09-15 | 2015-01-07 | 金坛鸿鑫电子科技有限公司 | Ammonia sensor |
| CN104374818A (en) * | 2014-08-08 | 2015-02-25 | 杭州纳瑙新材料科技有限公司 | Planar oxygen sensor |
| CN104819998A (en) * | 2015-04-23 | 2015-08-05 | 福州大学 | Impedance spectroscopy type NOx (Nitric Oxide) sensor and preparation method of solid electrolyte material thereof |
| CN104897763A (en) * | 2015-04-30 | 2015-09-09 | 武汉爱德威科技有限责任公司 | Nitrogen-oxygen sensor and tail gas NOx content measurement method |
| CN105014769A (en) * | 2015-06-25 | 2015-11-04 | 武汉大学 | 3D printing preparation method based on nanosecond-picosecond-femtosecond laser compound technology for NOx sensor |
| CN105044187A (en) * | 2015-09-08 | 2015-11-11 | 无锡百灵传感技术有限公司 | Sensor for detecting nitrogen oxide content in car exhaust |
| CN105244520A (en) * | 2015-10-28 | 2016-01-13 | 杨炳 | Air battery pack and manufacturing method thereof |
| US9671351B2 (en) | 2014-04-24 | 2017-06-06 | Stmicroelectronics S.R.L. | Multi-sensor optical device for detecting chemical species and manufacturing method thereof |
| CN107174926A (en) * | 2017-06-28 | 2017-09-19 | 苏州华商新能源有限公司 | A kind of desulfuring and denitrifying apparatus automatically controlled |
| CN107335326A (en) * | 2017-06-28 | 2017-11-10 | 苏州华商新能源有限公司 | A kind of desulfuring and denitrifying apparatus |
| CN108375618A (en) * | 2018-02-11 | 2018-08-07 | 常州联德电子有限公司 | Intelligent nitrogen oxide sensor and its detection method |
| CN109239149A (en) * | 2018-09-12 | 2019-01-18 | 东北大学 | A kind of electrochemical sensor and preparation method thereof monitoring nitrogen content |
| CN112326751A (en) * | 2020-11-09 | 2021-02-05 | 中国南方电网有限责任公司超高压输电公司柳州局 | Nitrogen oxide sensor, preparation method thereof and nitrogen oxide detection device |
| CN114646673A (en) * | 2022-03-11 | 2022-06-21 | 浙江新瓷智能科技股份有限公司 | NO (nitric oxide)xGas sensor |
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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 |
| CN103399042A (en) * | 2013-08-07 | 2013-11-20 | 无锡隆盛科技股份有限公司 | NOx sensor chip detection circuit |
| CN103399042B (en) * | 2013-08-07 | 2015-09-02 | 无锡隆盛科技股份有限公司 | Nox sensor chip detecting circuit |
| CN103728359A (en) * | 2014-01-20 | 2014-04-16 | 中国科学院上海硅酸盐研究所 | NOx sensor and preparation method thereof |
| CN103808785B (en) * | 2014-03-12 | 2015-12-30 | 江苏埃尔贝勒汽车电子有限公司 | A kind of vehicle exhaust monitors special Fast Heating lambda sensor |
| CN103808785A (en) * | 2014-03-12 | 2014-05-21 | 江苏埃尔贝勒汽车电子有限公司 | Special rapid heating oxygen sensor for monitoring automobile exhaust |
| US10483298B2 (en) | 2014-04-24 | 2019-11-19 | Stmicroelectronics S.R.L. | Multi-sensor optical device for detecting chemical species and manufacturing method thereof |
| US11037965B2 (en) | 2014-04-24 | 2021-06-15 | Stmicroelectronics S.R.L. | Multi-sensor optical device for detecting chemical species and manufacturing method thereof |
| US9671351B2 (en) | 2014-04-24 | 2017-06-06 | Stmicroelectronics S.R.L. | Multi-sensor optical device for detecting chemical species and manufacturing method thereof |
| CN104374818A (en) * | 2014-08-08 | 2015-02-25 | 杭州纳瑙新材料科技有限公司 | Planar oxygen sensor |
| CN104267139A (en) * | 2014-09-15 | 2015-01-07 | 金坛鸿鑫电子科技有限公司 | Ammonia sensor |
| CN104267139B (en) * | 2014-09-15 | 2016-03-30 | 金坛鸿鑫电子科技有限公司 | Ammonia gas sensor |
| CN104819998A (en) * | 2015-04-23 | 2015-08-05 | 福州大学 | Impedance spectroscopy type NOx (Nitric Oxide) sensor and preparation method of solid electrolyte material thereof |
| CN104897763A (en) * | 2015-04-30 | 2015-09-09 | 武汉爱德威科技有限责任公司 | Nitrogen-oxygen sensor and tail gas NOx content measurement method |
| CN105014769A (en) * | 2015-06-25 | 2015-11-04 | 武汉大学 | 3D printing preparation method based on nanosecond-picosecond-femtosecond laser compound technology for NOx sensor |
| CN105044187A (en) * | 2015-09-08 | 2015-11-11 | 无锡百灵传感技术有限公司 | Sensor for detecting nitrogen oxide content in car exhaust |
| CN105044187B (en) * | 2015-09-08 | 2018-05-04 | 爱驰威汽车零部件（盐城）有限公司 | The sensor of amount of nitrogen oxides in a kind of detection vehicle exhaust |
| CN105244520A (en) * | 2015-10-28 | 2016-01-13 | 杨炳 | Air battery pack and manufacturing method thereof |
| CN107335326A (en) * | 2017-06-28 | 2017-11-10 | 苏州华商新能源有限公司 | A kind of desulfuring and denitrifying apparatus |
| CN107174926A (en) * | 2017-06-28 | 2017-09-19 | 苏州华商新能源有限公司 | A kind of desulfuring and denitrifying apparatus automatically controlled |
| CN108375618A (en) * | 2018-02-11 | 2018-08-07 | 常州联德电子有限公司 | Intelligent nitrogen oxide sensor and its detection method |
| WO2019154062A1 (en) * | 2018-02-11 | 2019-08-15 | 常州联德电子有限公司 | Intelligent nitrogen and oxygen sensor and detection method implemented by same |
| CN109239149A (en) * | 2018-09-12 | 2019-01-18 | 东北大学 | A kind of electrochemical sensor and preparation method thereof monitoring nitrogen content |
| CN109239149B (en) * | 2018-09-12 | 2019-09-24 | 东北大学 | A kind of electrochemical sensor and preparation method thereof monitoring Nitrogen in Hot Metal |
| CN112326751A (en) * | 2020-11-09 | 2021-02-05 | 中国南方电网有限责任公司超高压输电公司柳州局 | Nitrogen oxide sensor, preparation method thereof and nitrogen oxide detection device |
| CN114646673A (en) * | 2022-03-11 | 2022-06-21 | 浙江新瓷智能科技股份有限公司 | NO (nitric oxide)xGas sensor |
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