CN201594086U - All solid state mixed potential type NOx sensor - Google Patents
All solid state mixed potential type NOx sensor Download PDFInfo
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- CN201594086U CN201594086U CN2009201999900U CN200920199990U CN201594086U CN 201594086 U CN201594086 U CN 201594086U CN 2009201999900 U CN2009201999900 U CN 2009201999900U CN 200920199990 U CN200920199990 U CN 200920199990U CN 201594086 U CN201594086 U CN 201594086U
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Abstract
The utility model provides a all solid state mixed potential type NOx sensor, which is prepared based on the sintering technology of spark plasma, and comprises an electrolyte layer, a sensitive electrode layer, a reference electrode and a working electrode, wherein a plurality of layers of composite materials of the electrolyte layer and the sensitive electrode layer are directly sintered through the sintering technology of spark plasma, and the reference electrode and a working electrode layer of screen holes are directly printed on the center of the upper and the lower surfaces of the composite materials through screen printing. Because the all solid state mixed potential type NOx sensor is made by the sintering technology of spark plasma, the sensitive electrode layer and the electrolyte layer of an obtained sensor are not excellently combined, the sensor does not exist the problems of tilting and cracking and the like, and has the characteristics of excellent repeatability, steady performance, simple making process, short making period, small volume and rapid response and the like. The NOx concentration detection range of the all solid state mixed potential type NOx sensor can be from 1 percent to 75 percent, the response time is less than 2min, and the all solid state mixed potential type NOx sensor is suitable for detecting wider range of NOx concentration.
Description
Technical field
The utility model relates to a kind of all-solid mixed-potential NOx sensor, is applicable in the rugged surroundings such as vehicle exhaust the NOx (NO+NO of (400 ℃～900 ℃) in the large-temperature range
2) detection of concentration.
Background technology
Oxides of nitrogen (NOx) is typical atmosphere pollution, can cause acid rain, photochemical fog etc.Reasons such as the use of mineral fuel, emission of automobile wastes all can cause airborne nitrogen dioxide to increase, the too high meeting of content of nitrogen dioxide causes diseases such as respiratory system, injury of lungs in the air, ozonosphere in the atmospheric envelope is also had certain destruction, and the serious harm people are healthy.Therefore the NOx sensor application that is used for the detection of NOx concentration is very extensive; except that being used for detecting the NOx noxious emission material, also they are used for the multinomial purposes such as control, industrial safety guarantee, craft sanitary, environmental protection and prevention and cure of pollution of production process in fields such as environmental protection, medical treatment, metallurgy, traffic.Traditional NOx detection method (as Saltzman method, chemoluminescence method, chromatography etc.) is highly sensitive, detection limit is low, but install complexity, cost an arm and a leg, and owing to its under the motor exhaust harsh and unforgiving environments permanance and thermotolerance is lower, can not realize the reasons such as on-the-spot continuous monitoring of NOx, be unsuitable for being installed on the automobile.Comparatively speaking, full curing chemistry class NOx sensor then can satisfy in the vehicle exhaust requirements such as easy, quick, the on-the-spot detection of NOx content.Full curing chemistry class NOx sensor mainly is divided three classes by its principle of work: semi-conductor type, concentration potential type and mixed potential type, semiconductor type sensor poor selectivity wherein, the detectable gas of concentration potential type sensor is less, and has the problem of elevated-temperature seal.Mixed potential type sensor is that semi-conductor type and concentration potential type combine and the novel sensor that grows up, both had the semiconductor type sensor plane, need not reference gas, without advantages such as encapsulants, have also simultaneously that concentration potential type sensor test gas scope is big, an output potential signal, advantage such as test easily.The nearly more than ten years are discovered mixed potential type NOx sensor that selective oxidation zirconium base is made into as electrolyte in a large number under harsh working environments such as motor exhaust, have higher chemical stability and thermotolerance, sensitivity higher, can obtain bigger signal output.Traditional preparation method and means are to adopt high temperature sintering to obtain the zirconium oxide base electrolyte sheet, again the sensitive electrode coated materials are carried out co-sintering on electrolyte matrix.In this preparation method, because shrinkage factor is inconsistent in two kinds of material sintering processes, electrolyte and sensitive electrode are easily peeled off, produce ftracture, warp, phenomenon such as separation, significantly reduced three-phase reaction interface (gas, zirconium oxide base electrolyte, sensitive electrode), make catalytic activity, the oxidation of electrode surface, the reduction reaction speed of sensitive electrode reduce, finally influence the detection sensitivity of sensor at high temperature section (＞700 ℃).
Summary of the invention
Technical problem to be solved in the utility model is the present situation at prior art, and a kind of measuring ability with large-temperature range (400 ℃～900 ℃) is provided, and sensing range is wide, good reproducibility, the all-solid mixed-potential NOx sensor that fabrication cycle is short.
The utility model solves the problems of the technologies described above the technical scheme that is adopted: a kind of all-solid mixed-potential NOx sensor, comprise dielectric substrate, it is characterized in that: the one side of dielectric substrate is provided with the sensitive electrode layer, the inner face of this sensitive electrode layer and the one side of dielectric substrate are combined into one, the another side of dielectric substrate is provided with reference electrode, the outside of sensitive electrode layer is provided with working electrode, is connected with first lead-in wire on the reference electrode, is connected with second lead-in wire on the working electrode.
The measure of taking also comprises:
In above-mentioned a kind of all-solid mixed-potential NOx sensor, working electrode adopts the thick film screen printing technique to be produced on the upper surface center of sensitive electrode layer, and reference electrode adopts the thick film screen printing technique to be produced on the lower surface center of dielectric substrate.
In above-mentioned a kind of all-solid mixed-potential NOx sensor, the area of working electrode accounts for 50～80% of sensitive electrode layer upper surface area, the area of reference electrode accounts for 50～80% of dielectric substrate lower surface area, the thickness of dielectric substrate is 0.3mm～1mm, the thickness of sensitive electrode layer is 0.1mm～0.8mm, the area of sensitive electrode layer account for dielectric substrate top surface area 50～80%.
In above-mentioned a kind of all-solid mixed-potential NOx sensor, all be shaped on sieve screen apertures on working electrode and the reference electrode.
In above-mentioned a kind of all-solid mixed-potential NOx sensor, dielectric substrate is that the zirconia ceramics material of 8%mol is made by yttrium content, and the sensitive electrode layer is made by NiO or NiO+Ni composite ceramic material, and wherein the Ni volume content is 0～50%.
In above-mentioned a kind of all-solid mixed-potential NOx sensor, working electrode and reference electrode are made by platinum metal material.
In above-mentioned a kind of all-solid mixed-potential NOx sensor, this NOx working sensor temperature range is 400 ℃～900 ℃, and can detect the nitric oxide concentration scope is 1%～75%, and the response time is less than 2min.
Compared with prior art, advantage of the present utility model is to adopt novel discharge plasma sintering (SPS, SparkPlasma Sintering) technology, add the pressure of 50MPa during by discharge sintering at two ends up and down of material, make dielectric substrate and the once sintered moulding of sensitive electrode layer, not only can solve dielectric substrate and the sensitive electrode layer is peeled off problem, simultaneously can also obtain the zirconium oxide base electrolyte sheet of density more than 99.9%, and shortened the sintering period greatly, at high temperature working signal is stable with the NOx sensor for this all-solid mixed-potential type automobile, measuring ability with large-temperature range, but the theory detectable concentration is 1%～75% (stagnation pressure is an atmospheric pressure), response time is less than 2min, and technology success ratio height, fabrication cycle is short, the sensitive element density height that is made into, and sensitive electrode layer and dielectric substrate are combined, do not warp, not easy to crack, air tight.
Description of drawings
Fig. 1 is the front view of NOx sensor;
Fig. 2 is the vertical view of NOx sensor;
Fig. 3 is the upward view of NOx sensor;
Fig. 4 is the fundamental diagram of NOx sensor;
Fig. 5 is NOx concentration and output potential graph of relation;
Fig. 6 is curve time response of NOx sensor.
Embodiment
Below be specific embodiment of the utility model and in conjunction with the accompanying drawings, the technical solution of the utility model is further described, but the utility model be not limited to these embodiment.
Extremely shown in Figure 6 as Fig. 1, among the figure, dielectric substrate 11; Sensitive electrode layer 12; Reference electrode 13; Working electrode 14; First lead-in wire 2; Second lead-in wire 3; Sieve screen apertures 4.
As shown in Figures 1 to 4, the utility model is a kind of all-solid mixed-potential NOx sensor, mainly comprise dielectric substrate 11, sensitive electrode layer 12, reference electrode 13, working electrode 14, the one side of dielectric substrate 11 is provided with sensitive electrode layer 12, the inner face of the one side of dielectric substrate 11 and sensitive electrode layer 12 is in the same place by discharge plasma sintering technique is sintered combined, here discharge plasma sintering technique is under the environment of vacuum, powder is contained in the mould of graphite making, promote blood circulation towards electric current, pressurization is with a kind of technological means of the rapid densified sintering product of powder.
The another side of dielectric substrate 11 is provided with reference electrode 13, sensitive electrode layer 12 outside are provided with working electrode 14, being specially reference electrode 13 adopts the thick film screen printing technique to make the lower surface center that is connected in dielectric substrate 11, working electrode 14 adopts the thick film screen printing technique to make the upper surface center that is connected in sensitive electrode layer 12, working electrode 14 and reference electrode 13 are made by platinum metal material, all be shaped on sieve screen apertures 4 on working electrode 14 and the reference electrode 13, be connected with first lead-in wire 2 on the reference electrode 13, be connected with second lead-in wire 3 on the working electrode 14, dielectric substrate 11 is that the zirconia ceramics material of 8%mol is made by yttrium content, sensitive electrode layer 12 is made by the NiO+Ni composite ceramic material, and wherein the Ni volume content is 0～50%.
When the preparation all-solid mixed-potential NOx sensor, be to adopt the manufacturing of discharge plasma sintering technique technology, but because discharge plasma sintering technique Fast Sintering, therefore pressurization can make two kinds of materials combine closely in sintering process, can not occur because shrinkage factor is inconsistent warping, phenomenon such as cracking.Being specially step 1 and being is earlier that the zirconia powder of 8%mol is evenly put into the light compacting of graphite jig and made dielectric substrate 11 with yttrium content, step 2 is put into the zirconia powder upper surface center making sensitive electrode layer 12 that yttrium content is 8%mol with the NiO or the NiO+Ni powder that mix again, step 3 is that the graphite jig that installs powder is put into discharging plasma sintering equipment at 1150 ℃～1350 ℃ sintering, be incubated 3～5 minutes, sintering is finished, after stove pressurize cooling, take out the demoulding, re-using abrasive paper for metallograph burnishes and fabricates dielectric substrate 11 and sensitive electrode layer 12 and is combined into one, step 4 adopts the thick film screen printing technique to make the working electrode 14 with sieve screen apertures 4 alloy platinum materials at the upper surface center of sensitive electrode layer 12, adopt the thick film screen printing technique to make the reference electrode 13 with sieve screen apertures 4 alloy platinum materials at the lower surface center of dielectric substrate 11, step 6 is at a certain temperature with working electrode 14 then, reference electrode 13 sinter moldings.
The area of making back working electrode 14 accounts for 50～80% of sensitive electrode layer 12 upper surface area, the area of reference electrode 13 accounts for 50～80% of dielectric substrate 11 lower surface areas, thickness is 0.3mm～1mm behind the sintering of dielectric substrate 11, thickness is 0.1mm～80.8mm behind the sintering of sensitive electrode layer 12, the area of sensitive electrode layer 12 account for dielectric substrate 11 top surface area 50～80%, and NOx working sensor temperature range is 400 ℃～900 ℃, can detect the nitric oxide concentration scope is 1%～75%, and the response time is less than 2min.
The all-solid mixed-potential NOx sensor that uses method of the present utility model to produce, its principle of work be as shown in Figure 4:
Two electrodes that have a full curing NOx sensor of platinum electrode are respectively reference electrode 13 and working electrode 14 is in the same atmosphere of oxygen and tested mixed gas NOx (NO+NO2 gas), a plurality of electrochemical reactions take place on electrode, the electrode potential that is produced when each reaction is reached balance is referred to as mixed potential, and the response of electromotive force device is exactly a mixed potential difference between two electrodes.Because NO and the difference of NO2 in the three phase boundary place of two electrodes with different catalytic action redox reaction speed can produce different mixed potentials at two electrode places, the size of mixed potential is relevant with the concentration of reducing gas.
Reference electrode 13 (anode) and working electrode 14 (negative electrode) two electrodes place the tested mixed gas of being made up of oxygen and reducibility gas or oxidizing gas during work, need not reference gas.For NO, following reaction takes place respectively in anode and negative electrode:
2NO+2O
2-→2NO
2+4e
-
O
2+4e→2O
2-
And for NO
2, anode and cathode reaction are:
2O
2-→O
2+4e
NO
2+2e→NO+O
2-
Because above two electrochemical reactions are reversible reaction, the dynamic oxidation rate of reduction difference of each electrode, the different mixed potential that causes electrode to produce.With NO
2Be example, according to the Nernst theory, mixed potential can be expressed as:
In the formula: R is gas law constant (8.314J/ (molK)); T is working temperature (K); F is a Faraday constant; K is the electrochemical reaction speed constant.By the mixed potential that produces on the battery, thereby can determine NO
2Concentration.
When Figure 5 shows that 700 ℃, the NOx concentration of NOx sensor and the graph of relation of output potential Es.As can be seen, the relation of NOx concentration and Es and the height of above-mentioned theory meet among the figure.Fig. 6 is curve time response of NOx sensor, shows good repeatability and less than the quick response of 2min.
Advantage of the present utility model is to adopt novel discharge plasma sintering (SPS, Spark Plasma Sintering) technology, add the pressure of 50MPa during by discharge sintering at two ends up and down of material, make dielectric substrate and the once sintered moulding of sensitive electrode layer, not only can solve dielectric substrate and the sensitive electrode layer is peeled off problem, simultaneously can also obtain the zirconium oxide base electrolyte sheet of density more than 99.9%, and shortened the sintering period greatly, at high temperature working signal is stable with the NOx sensor for this all-solid mixed-potential type automobile, measuring ability with large-temperature range, but the theory detectable concentration is 1%～75% (stagnation pressure is an atmospheric pressure), response time is less than 2min, and technology success ratio height, fabrication cycle is short, the sensitive element density height that is made into, sensitive electrode layer and dielectric substrate are combined, do not warp, not easy to crack, air tight.
Specific embodiment described herein only is that the utility model spirit is illustrated.The utility model person of ordinary skill in the field can make various modifications or replenishes or adopt similar mode to substitute described specific embodiment, but can't depart from the defined scope of spirit of the present utility model.
Claims (4)
1. all-solid mixed-potential NOx sensor, comprise dielectric substrate (11), it is characterized in that: the one side of described dielectric substrate (11) is provided with sensitive electrode layer (12), the one side of the inner face of this sensitive electrode layer (12) and dielectric substrate (11) is combined into one, the another side of described dielectric substrate (11) is provided with reference electrode (13), the outside of sensitive electrode layer (11) is provided with working electrode (14), be connected with first lead-in wire (2) on the described reference electrode (13), be connected with second lead-in wire (3) on the working electrode (14).
2. a kind of all-solid mixed-potential NOx sensor according to claim 1, it is characterized in that: described working electrode (14) adopts the thick film screen printing technique to be produced on the upper surface center of sensitive electrode layer (12), and described reference electrode (13) adopts the thick film screen printing technique to be produced on the lower surface center of dielectric substrate (11).
3. a kind of all-solid mixed-potential NOx sensor according to claim 2, it is characterized in that: the area of described working electrode (14) accounts for 50～80% of sensitive electrode layer (12) upper surface area, the area of described reference electrode (13) accounts for 50～80% of dielectric substrate (11) lower surface area, the thickness of dielectric substrate (11) is 0.3mm～1mm, the thickness of described sensitive electrode layer (12) is 0.1mm～0.8mm, the area of sensitive electrode layer (12) account for dielectric substrate (11) top surface area 50～80%.
4. a kind of all-solid mixed-potential NOx sensor according to claim 3 is characterized in that: all be shaped on sieve screen apertures (4) on described working electrode (14) and the reference electrode (13).
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| CN2009201999900U CN201594086U (en) | 2009-11-13 | 2009-11-13 | All solid state mixed potential type NOx sensor |
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| CN2009201999900U CN201594086U (en) | 2009-11-13 | 2009-11-13 | All solid state mixed potential type NOx sensor |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102495122A (en) * | 2011-12-14 | 2012-06-13 | 吉林大学 | Mixed-potential nitrogen dioxide sensor based on porous YSZ (yttria stabilization zirconia) substrate and preparation method for sensor |
| CN101706470B (en) * | 2009-11-13 | 2012-06-27 | 宁波工程学院 | All-solid mixed-potential NOx sensor and preparation method thereof |
| 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 |
| CN108562630A (en) * | 2018-06-11 | 2018-09-21 | 遵义师范学院 | Carbon dioxide in-situ measurement device and production method in a kind of hydrothermal system |
-
2009
- 2009-11-13 CN CN2009201999900U patent/CN201594086U/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101706470B (en) * | 2009-11-13 | 2012-06-27 | 宁波工程学院 | All-solid mixed-potential NOx sensor and preparation method thereof |
| CN102495122A (en) * | 2011-12-14 | 2012-06-13 | 吉林大学 | Mixed-potential nitrogen dioxide sensor based on porous YSZ (yttria stabilization zirconia) substrate and preparation method for sensor |
| CN102495122B (en) * | 2011-12-14 | 2013-08-14 | 吉林大学 | Mixed-potential nitrogen dioxide sensor based on porous YSZ (yttria stabilization zirconia) substrate and preparation method for sensor |
| 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 |
| CN108562630A (en) * | 2018-06-11 | 2018-09-21 | 遵义师范学院 | Carbon dioxide in-situ measurement device and production method in a kind of hydrothermal system |
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Granted publication date: 20100929 Termination date: 20121113 |