CN202770799U - Current-mode NO2 sensor of solid electrolyte - Google Patents
Current-mode NO2 sensor of solid electrolyte Download PDFInfo
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- CN202770799U CN202770799U CN 201220405136 CN201220405136U CN202770799U CN 202770799 U CN202770799 U CN 202770799U CN 201220405136 CN201220405136 CN 201220405136 CN 201220405136 U CN201220405136 U CN 201220405136U CN 202770799 U CN202770799 U CN 202770799U
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- solid electrolyte
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Abstract
The utility model discloses a current-mode NO2 sensor of solid electrolyte. The sensor comprises a La1-xSrxGa1-yMgyO3-delta (LSGM) solid electrolyte base layer which is formed by sintering an La1-xSrxGa1-yMgyO3-delta material and is of a compact ceramic wafer body structure, a porous positive collector layer and a porous negative collector layer, wherein the porous positive collector layer and the porous negative collector layer are respectively arranged on the upper surface and the lower surface of the LSGM solid electrolyte base layer, an appropriate amount of platinum paste layer for collecting electric charge is coated at the central position of the upper surface of the porous positive collector layer, and positive electrode leads for being connected with a power supply positive electrode are respectively led out from the porous positive collector layer from the platinum paste layer and the porous negative collector layer. The LSGM solid electrolyte is prepared by means of a tape casting technology, and a NiO sensitive electrode and a Pt reference electrode are printed and formed by means of a thick film screen printing technology and form a fixed whole in a sintering mode. The current-mode NO2 sensor of the solid electrolyte has the advantages of being simple in structure, small in volume, stable in performance, high in measuring accuracy and sensitive in response and further achieving the purpose of reducing the operation temperature.
Description
Technical field
The utility model relates to a kind of NO
2Sensor is especially for NO
2A kind of current mode NO of measurement of concetration control
2Sensor, specifically a kind of current mode NO of solid electrolyte
2Sensor.
Background technology
The chemical classes NO of current solid electrolyte
xSensor can be finished NO in the vehicle exhaust owing to easily matching with other parts of engine electronic control system fuel injection system
xSo the detection that content is easy, quick, real-time is such NO
xSensor has become automobile-used NO
xThe first-selection of sensor.
In recent years, based on zirconia base NO
xThe development research of the various electrode materials of sensor is very active, and multiple device prototype is produced out, has demonstrated a lot of desirable advantages.But traditional YSZ material will just have larger oxygen ionic conductivity under very high temperature, and along with the reduction of temperature, resistance sharply increases, and has therefore determined that sensors with auxiliary electrode were must at high temperature move, and its working temperature is generally at 1000 ℃ or higher.And the hot environment operation can bring the thermal expansivity aging, each parts of sensor such as the adverse reaction between electrode-electric solution matter interface, electrode to be difficult to the problems such as coupling, difficult sealing, power consumption height.Therefore people in the urgent need to develop a kind of in, replace traditional YSZ material with regard to the electrolyte with higher oxygen ionic conductivity in the low temperature range, to guarantee NO
2Sensor has higher performance, satisfies the needs of people's production and construction.
Summary of the invention
Technical problem to be solved in the utility model is for above-mentioned prior art present situation, can realize NO and be provided in the middle low temperature environment
2Gas concentration detects, and highly sensitive, the current mode NO of a kind of solid electrolyte easy to use
2Sensor.Simple, the low in energy consumption characteristics with stable performance and long service life of this sensor preparation technology, and can reach the purpose that reduces the sensor operating temperature.
The utility model solves the problems of the technologies described above the technical scheme that adopts: a kind of current mode NO of solid electrolyte
2Sensor, this sensor comprises by La
1-xSr
xGa
1-yMg
yO
3-δThe LSGM solid electrolyte basic unit of the ceramic of compact sheet body structure that the material sintering is made and the positive collector layer of porous and the negative collector layer of porous that are separately positioned on this LSGM solid electrolyte basic unit's upper surface and lower surface, the upper surface center of the positive collector layer of porous scribbles an amount of platinum slurry layer that is used for collecting electric charge, and the positive collector layer of porous leads to respectively for the positive and negative electrode lead-in wire that connects power positive cathode through platinum slurry layer and the negative collector layer of porous.
For optimizing technique scheme, Adopts measure also comprises:
The thickness of above-mentioned LSGM solid electrolyte basic unit is 0.6mm.
The positive collector layer of above-mentioned porous is sensitive electrode, and the negative collector layer of porous is reference electrode.
Compared with prior art, sensor of the present utility model has adopted novel middle temperature solid oxygen ion conductor material La
1-xSr
xGa
1-yMg
yO
3-δAs NO
2The solid electrolyte of sensor has replaced traditional zirconia material, thereby has reduced NO
2The working temperature of sensor has guaranteed that sensor can work under lower temperature, greatly prolonged the serviceable life of product.And product of the present utility model adds 0.6V～1.2V operating voltage when work, adopting the large I sensing range of measuring circuit current signal is 0～600ppm NO
2Gas concentration.The utility model has the advantages that: simple in structure, volume is little, stable performance, measuring accuracy is high and be quick on the draw, and can also reach the purpose that reduces the sensor operating temperature simultaneously.
Description of drawings
Fig. 1 is cross-sectional view of the present utility model;
Fig. 2 is fundamental diagram of the present utility model;
Fig. 3 is the I-V characteristic working curve figure of the utility model in the time of 450 ℃;
Fig. 4 is the utility model output current I and NO in the time of 450 ℃
2The graph of relation of concentration;
Fig. 5 is curve map time response of the present utility model.
Embodiment
Below in conjunction with accompanying drawing embodiment of the present utility model is described in further detail.
Reference numeral wherein is: LSGM solid electrolyte basic unit 1, the positive collector layer 2 of porous, the negative collector layer 3 of porous, platinum slurry layer 4, contact conductor 5, power supply 6, wire 7.
Fig. 1 to Fig. 5 is structure of the present utility model and principle of work characteristic, curve synoptic diagram.
Shown in Figure 1, the current mode NO of a kind of solid electrolyte of the present utility model
2Sensor, this sensor comprises by La
1-xSr
xGa
1-yMg
yO
3-δThe LSGM solid electrolyte basic unit 1 of the ceramic of compact sheet body structure that the material sintering is made and the positive collector layer 2 of porous and the negative collector layer 3 of porous that are separately positioned on this LSGM solid electrolyte basic unit 1 upper surface and lower surface, the upper surface center of the positive collector layer 2 of porous scribbles an amount of platinum slurry layer 4 that is used for collecting electric charge, and the positive collector layer 2 of porous leads to respectively for the positive and negative electrode lead-in wire 5 that connects power supply 6 both positive and negative polarities through platinum slurry layer 4 and the negative collector layer 3 of porous.Compare with conventional art, solid electrolyte of the present utility model adopts La
1-xSr
xGa
1-yMg
yO
3-δMaterial is made, La
1-xSr
xGa
1-yMg
yO
3-δBe abbreviated as LSGM, La
1-xSr
xGa
1-yMg
yO
3-δMaterial has very high pure oxygen ion electric conductivity under 600 ℃～800 ℃ conditions of middle low temperature, ionic conductivity is about 4 times of YSZ solid electrolyte, and in very wide partial pressure of oxygen scope (10
-20~ be pure oxygen ion conductor in 1atm), itself and many mixed conductor materials not only have good chemical compatibility in addition, and also have good thermal expansion matching performance, therefore are optimal materials in the low-temperature solid oxygen ion conductor material in the conduct.La
1-xSr
xGa
1-yMg
yO
3-δMaterial has guaranteed that sensor of the present utility model can operate in lower working temperature, thereby has avoided traditional sensors to move the defective of bringing, the serviceable life of greatly having improved this product under hot environment.This product adds 0.6V～1.2V operating voltage when work, adopting the large I sensing range of measuring circuit current signal is 0～600ppm NO
2Gas concentration.The utility model has the advantages that: adopted La
1-xSr
xGa
1-yMg
yO
3-δMaterial is as NO
2The solid electrolyte of sensor has replaced traditional zirconia material, has reduced NO
2The working temperature of sensor, it is simple in structure, volume is little, highly sensitive and easy for operation, is suitable for batch production.
Be the optimizing product performance, improve product market competitiveness, the positive collector layer 2 of porous of the present utility model is made for the NiO electrode slurry that contains terpinol and ethyl cellulose.
Among the embodiment, the material of the negative collector layer 3 of porous is platinum.
Among the embodiment, La
1-xSr
xGa
1-yMg
yO
3-δIn the material, the span of described x and y is respectively: 0.1≤x≤0.2,0.1≤y≤0.2.
Among the embodiment, the thickness of LSGM solid electrolyte of the present utility model basic unit 1 is 0.6mm.
Among the embodiment, the positive collector layer 2 of porous is sensitive electrode, and the negative collector layer 3 of porous is reference electrode.
Can not see from Fig. 1, the contact conductor 5 of the positive collector layer 2 of porous of the present utility model is the positive electrode lead-in wire, is used for being connected with the positive pole of power supply 8, correspondingly, the contact conductor 5 of the negative collector layer 3 of porous is the negative electrode lead-in wire, is used for being connected with the negative pole of power supply 8.
The utility model also provides a kind of current mode NO of solid electrolyte
2The preparation method of sensor, the method may further comprise the steps:
A, the known flow casting molding technology of employing are with La
1-xSr
xGa
1-yMg
yO
3-δMake the LSGM ceramic chips;
B, with above-mentioned LSGM ceramic chips at a certain temperature behind binder removal, put into the LSGM solid electrolyte basic unit that the high temperature sintering furnace sintering makes the ceramic of compact lamellar body;
C, employing thick film screen printing technique are printed on the homemade NiO electrode slurry that has added certain terpinol and ethyl cellulose the upper surface of above-mentioned LSGM solid electrolyte basic unit, print out the positive collector layer of porous;
D, the above-mentioned LSGM solid electrolyte basic unit that is printed with the positive collector layer of porous is put into drying box after dry a period of time, send into again sinter molding in the high temperature furnace, make the sensor semi-finished product blank;
E, employing thick film screen printing technique are printed out the negative collector layer of porous with the platinum pulp material at the LSGM of the sensor semi-finished product blank solid electrolyte basic unit lower surface, and draw the negative electrode lead-in wire from the negative collector layer of porous simultaneously;
F, at above-mentioned a little Pt slurry of the positive collector layer upper surface of porous centre spot printing that is printed with the sensor semi-finished product blank of the negative collector layer of porous, and draw simultaneously the positive electrode lead-in wire, be shaped with sensor finished product blank;
G, above-mentioned sensor finished product blank is sent in the high temperature furnace behind the sintering again, made this product.
LSGM ceramic chips among the above-mentioned step B is put into 1400 ℃ high temperature sintering furnace sintering 2h behind binder removal 22h under 360 ℃ the temperature.
The temperature of drying box is 80 ℃ sends into sintering 2h in 1400 ℃ of high temperature furnaces after 4h oven dry among the above-mentioned step D.
The sintering temperature of high temperature furnace is 1000 ℃ among the above-mentioned step G, and the time is 1h.
Principle of work of the present utility model as shown in Figure 2, power supply 6 is that the negative collector layer 3 of sensitive electrode and porous is the operating voltage that applies variation between reference electrode by wire 7 at the positive collector layer 2 of porous, sensitive electrode connects the positive pole of power supply 6, and reference electrode connects the negative pole of power supply 6.Under the effect of this operating voltage, will produce following electrochemical reaction on sensitive electrode and the reference electrode:
Sensitive electrode: NO
2+ 2e=NO+O
2-
Reference electrode: 2O
2--4e=O
2
By near the NO the sensitive electrode
2The oxonium ion that produces of electrochemical reaction, by LSGM solid electrolyte basic unit, constantly be pumped into the reference electrode side, and near reference electrode, lose electronics and form oxygen and be diffused in the outside air.This reaction shows as the generation of electric current I at circuit, this electric current increases along with the increase that applies operating voltage V.
The utility model NO when Figure 3 shows that 450 ℃
2The I-V characteristic working curve of sensor.Can see among the figure: the output current I of sensor increases with the increase of operating voltage, and after operating voltage was greater than 600mV, output current I presented with NO
2The increase of concentration and increasing.The utility model NO when Fig. 4 is 450 ℃
2Sensor is under the 900mV in operating voltage, output current I and NO
2The relation curve of concentration, can obviously see: the output current I of sensor is with NO
2The increase of concentration and increasing.Fig. 5 is the utility model NO
2Curve time response of sensor, as seen this sensor sheet reveals preferably repeatability, and response recovery time is also shorter, be respectively about 50s and 90s about.
Claims (3)
1. the current mode NO of a solid electrolyte
2Sensor is characterized in that: this sensor comprises by La
1-xSr
xGa
1-yMg
yO
3-δThe LSGM solid electrolyte basic unit (1) of the ceramic of compact sheet body structure that the material sintering is made and the positive collector layer of porous (2) and the negative collector layer (3) of porous that are separately positioned on this LSGM solid electrolyte basic unit (1) upper surface and lower surface, the upper surface center of the positive collector layer of described porous (2) scribbles an amount of platinum slurry layer (4) that is used for collecting electric charge, and the positive collector layer of described porous (2) leads to respectively for just connecting power supply (6) both positive and negative polarity through platinum slurry layer (4) and the negative collector layer (3) of porous, negative electrode lead-in wire (5).
2. the current mode NO of a kind of solid electrolyte according to claim 1
2Sensor is characterized in that: the thickness of described LSGM solid electrolyte basic unit (1) is 0.6mm.
3. the current mode NO of a kind of solid electrolyte according to claim 2
2Sensor is characterized in that: the positive collector layer of described porous (2) is sensitive electrode, and it is reference electrode that described porous is born collector layer (3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201220405136 CN202770799U (en) | 2012-08-16 | 2012-08-16 | Current-mode NO2 sensor of solid electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201220405136 CN202770799U (en) | 2012-08-16 | 2012-08-16 | Current-mode NO2 sensor of solid electrolyte |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN202770799U true CN202770799U (en) | 2013-03-06 |
Family
ID=47777363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201220405136 Expired - Fee Related CN202770799U (en) | 2012-08-16 | 2012-08-16 | Current-mode NO2 sensor of solid electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN202770799U (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102866192A (en) * | 2012-08-16 | 2013-01-09 | 宁波大学 | Current-type nitrogen dioxide (NO2) sensor of solid electrolyte and preparation method thereof |
| CN108828034A (en) * | 2018-04-28 | 2018-11-16 | 中原工学院 | A kind of preparation method of solid electrolytic sensor porous electrode |
-
2012
- 2012-08-16 CN CN 201220405136 patent/CN202770799U/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102866192A (en) * | 2012-08-16 | 2013-01-09 | 宁波大学 | Current-type nitrogen dioxide (NO2) sensor of solid electrolyte and preparation method thereof |
| CN102866192B (en) * | 2012-08-16 | 2015-08-26 | 宁波大学 | A kind of current mode NO of solid electrolyte 2sensor and preparation method thereof |
| CN108828034A (en) * | 2018-04-28 | 2018-11-16 | 中原工学院 | A kind of preparation method of solid electrolytic sensor porous electrode |
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| Date | Code | Title | Description |
|---|---|---|---|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130306 Termination date: 20150816 |
|
| EXPY | Termination of patent right or utility model |