CN104749235A - High-selectivity compensation type CO sensor and preparation method thereof - Google Patents
High-selectivity compensation type CO sensor and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a compensation type CO sensor for measuring the concentration of CO. The compensation type CO sensor comprises solid electrolyte, a sensing electrode, a reference electrode and an electrode lead wire, wherein the electrode lead wire is led out from the sensing electrode and the reference electrode respectively, the solid electrolyte is tubular YSZ, the sensing electrode and the reference electrode are both arranged outside the solid electrolyte, the sensing electrode is an In2O3 doped ZnO composite sensing electrode, and the reference electrode is a Cr2O3 reference electrode with columnar morphology. The invention also discloses a preparation method of the CO sensor. According to the compensation type CO sensor, the response to interfering gases such as a hydrocarbon compound, particularly for C3H6 gas, is inhibited under a condition that the CO gas response value is not damaged basically, and the selectivity of the sensor is improved greatly.
Description
Technical field
The present invention relates to a kind of CO sensor for CO measurement of concetration, be specifically related to a kind of based on In
2o
3doping ZnO composite sensing electrode (Sensing Electrode, SE) and column pattern Cr
2o
3the high sensitivity, high selectivity setoff type CO sensor and preparation method thereof of tubular type yttrium stable zirconium oxide (Yttria-StabilizedZirconia, the YSZ) base of sensitive electrode.
Background technology
Galvanochemistry class CO sensor based on YSZ easily matches with other parts of engine electronic control system fuel injection system, can to the content of CO in vehicle exhaust carry out easy, quick, detect in real time, become the first-selection of automobile-used CO sensor.
In prior art, a kind of Type C O sensor many employings liquid electrolyte liquid is as ion transmission medium, the detection mechanism of this kind of sensor is: when CO gas is diffused on working electrode surface through ventilated membrane by the pore on shell, under the catalytic action of working electrode, CO gas is oxidized on the working electrode (s.Its chemical equation is: CO+H
2o → CO
2+ 2H
++ 2e
-there is the H that oxidation reaction produces on the working electrode (s
+ion and electronics, by electrolytic solution transfer to keep with working electrode certain intervals on electrode, with the oxygen generation reduction reaction in water.Its chemical equation is: 1/2O
2+ 2H
++ 2e
-→ H
2o, therefore, sensor internal just there occurs the reversible reaction of oxidation-reduction, and its chemical equation is: 2CO+2O
2→ 2CO
2, the reversible reaction of this oxidation-reduction working electrode and to electrode between occur all the time, and produce potential difference (PD) between electrode.But because the reaction occurred on two electrodes all can make electrode polarization, this makes electrode potential be difficult to remain constant, thus also limit the detectable scope of carbonomonoxide concentration.
The CO sensor of another kind of type adopts solid electrolyte, and as membrane type or chip YSZ, material corresponding on YSZ both sides are printed respectively, as sensitive electrode and reference electrode, shows much desirable advantage.But when test, because sensitive electrode and reference electrode are exposed in CO gas simultaneously, if contrast electrode exists response to CO, then can have an impact to the sensitivity of sensor, this just proposes high requirement to choosing of reference electrode.To this, disclose a kind of electric potential type CO sensor in Chinese patent application file (publication number: CN104237334A), it is by adopting based on In
2o
3doping ZnO composite sensing electrode is placed in outside solid electrolyte, with reference to electrodes inside solid electrolyte, sensitive electrode is separated completely with reference electrode.The principle of work of this sensor: sensor is put into proving installation, respectively the contact conductor that sensitive electrode and reference electrode are drawn is connected to positive pole and the negative pole of digital multimeter, pass into a certain amount of CO gas, then sensitive electrode will produce the reaction of following mixed potential: CO+O
2-→ CO
2+ 2e
-, 1/2O
2+ 2e
-→ O
2-.Therefore, sensor internal just there occurs the reversible reaction of oxidation-reduction, and its chemical equation is: 2CO+2O
2→ 2CO
2, the reversible reaction of this oxidation-reduction occurs all the time between working electrode and reference electrode, and produces potential difference (PD) between electrode.The oxonium ion produced by the electrochemical reaction on sensitive electrode, the constantly mobile change producing electric charge, gathers output electromotive force by digital multimeter on the solid electrolyte, and then detects CO harmful gas content.Although this patent reduces the requirement to reference electrode, improve the sensitivity of sensor to CO to a certain extent, but still the interference existed by other gases (particularly hydrocarbon), still need the CO sensor researching and developing high sensitivity, high selectivity.
Summary of the invention
The object of the invention is for the above-mentioned problems in the prior art, propose a kind of high sensitivity, high selectivity setoff type CO sensor and preparation method thereof, this sensor can realize detecting in real time the high selectivity of CO gas concentration in high temperature environments.
Object of the present invention realizes by following technical proposal: a kind of high selectivity setoff type CO sensor, comprise solid electrolyte, sensitive electrode, reference electrode and contact conductor, described contact conductor is drawn respectively by sensitive electrode and reference electrode, described solid electrolyte is tubular type YSZ, described sensitive electrode and reference electrode are all arranged on outside solid electrolyte, and described sensitive electrode is based on In
2o
3doping ZnO composite sensing electrode, described reference electrode is column pattern Cr
2o
3reference electrode.
The reaction mechanism of plane mixed potential formula gas sensor: under the effect of catalyzer, before entering three phase boundary, can there is a gas-phase reaction in gas to be measured (for CO), this reaction is CO CO gaseous oxidation
2; After gas arrives three phase boundary place, there are following two reactions simultaneously, be respectively:
CO+O
2-→CO
2+2e
-
1/2O
2+2e
-→O
2-
As anodic current density and the O of CO generation
2time the cathode-current density produced is equal, can produce an equilibrium potential, this equilibrium potential is just called mixed potential.And according to bibliographical information, mixed potential E
mix=E
0+ A (plnC
o2-qlnC
cO), (wherein E
0, p, q, A value is constant), infer thus, when oxygen concentration one timing, usually used as the mixed potential of response signal and the logarithm of CO gas concentration linear.
The present invention by constantly testing discovery, is doped with 10-50wt.%In selecting
2o
3znO do on the basis of sensitive electrode, coupling column pattern Cr
2o
3electrode material for referencial use composition setoff type CO sensor, when substantially not damaging CO gas response, inhibit widely to interference gas (as hydrocarbon, especially C
3h
6gas) response, thus significantly improve selectivity and the sensitivity of sensor.Its reason is, column pattern Cr
2o
3to the response of object gas substantially lower than 10mV, to the response of interference gas be doped with 10-50wt.%In
2o
3the sensitive electrode of ZnO consistent, basic difference is not more than 10mV, is doped with 10-50wt.%In
2o
3znO sensitive electrode and column pattern Cr
2o
3the response characteristic of reference electrode is all the principle of work meeting mixed potential type sensor, and the logarithm of their mixed potential and gas concentrations is separately linear.When coupling is doped with 10-50wt.%In
2o
3znO sensitive electrode and column pattern Cr
2o
3when reference electrode forms setoff type sensor, total mixed potential is also linear with the logarithm of gas concentration, meets the principle of work of mixed potential, that is, mutual interelectrode characteristic can carry out compensating for (or being referred to as to offset), is similar to mathematical subtraction.
In addition, in prior art, original Pt reference electrode does not respond substantially to object gas, only and O
2concentration be correlated with, only play an effect with reference to contrast, and two electrodes that setoff type sensor of the present invention adopts are all the principle of work meeting mixed potential type sensor, so Pt reference electrode can be omitted in sensor of the present invention, by the column pattern Cr be coupled
2o
3bear the effect with reference to contrast, on the basis not damaging object gas response, suppress the response of interference gas, that is, under the highly sensitive prerequisite of maintenance, improve the selectivity of sensor.
In above-mentioned high selectivity setoff type CO sensor, as preferably, the width of described sensitive electrode and reference electrode is 2-4mm.If electrode width is long, increase cost (In on the one hand
2o
3not very cheap), can add Production Time on the other hand, in addition, the actual induction section length of YSZ pipe is limited, if the width of electrode is long, just may not apply so much electrode.If width is narrow, limited induction area is too small, and the difficulty of collecting electric charge strengthens.Therefore, the width of sensitive electrode and reference electrode all controls at 2-4mm by the present invention.Further preferably, the width of described sensitive electrode and reference electrode is 3mm.
In above-mentioned high selectivity setoff type CO sensor, as preferably, described sensitive electrode is 10-50wt.% (In
2o
3account for the proportion of ZnO quality) In
2o
3doping ZnO composite sensing electrode.Further preferably, described sensitive electrode is 30wt.% (In
2o
3account for the proportion of ZnO quality) In
2o
3doping ZnO composite sensing electrode.
In above-mentioned high selectivity setoff type CO sensor, as preferably, described solid electrolyte is solid oxygen ion conductor material tubular type YSZ.
Another object of the present invention is the preparation method providing a kind of above-mentioned high selectivity setoff type CO sensor, and described preparation method comprises the following steps:
A adopt isostatic pressing technology make tubular type YSZ blank, then in air ambient after 500-900 DEG C of binder removal 2-4h, then put into high temperature furnace sinter at 1350-1550 DEG C 2-4h shaping solid electrolyte;
B obtains sensitive electrode slurry, and adopt cladding process to apply sensitive electrode slurry in solid electrolyte outer surface induction zone, prepare sensitive electrode, the width control system of sensitive electrode is at 2-4mm;
It is shaping in 1000-1300 DEG C of sintering 2-4h that high temperature furnace put into by step B gained sample by C;
D obtains reference electrode slurry, and adopt cladding process to apply reference electrode slurry in described tubular type YSZ outer surface induction zone, prepare reference electrode, the width control system of reference electrode is at 2-4mm;
It is shaping in 800-900 DEG C of sintering 2-4h that high temperature furnace put into by step D gained sample by E;
F draws high temperature electrode lead-in wire from sensitive electrode and reference electrode surface respectively, as platinum filament (through coiling or welding), obtains high selectivity setoff type CO sensor finished product.
The present invention is drawn by great many of experiments, In
2o
3the sintering temperature of doping ZnO composite sensing electrode, when 1000-1300 DEG C, has good response to CO gas; And the column pattern In that reference electrode adopts
2o
3material is nano material, its sintering temperature is unsuitable too high, within the scope of 800-900 DEG C, and performance improves gradually along with sintering temperature, but when sintering temperature will destroy its inner structure more than 900 DEG C, affect performance, so, further preferably, in step C, the sintering temperature of sample is 1200 DEG C, and in step e, the sintering temperature of sample is 900 DEG C.
Wherein, the preparation method of described induction zone is, the polishing of solid electrolyte blind end outside surface is obtained induction zone.
In the preparation method of above-mentioned high selectivity setoff type CO sensor, as preferably, the sample in step C and step e all dries 6-12h before sintering at 120-150 DEG C.
In the preparation method of above-mentioned high selectivity setoff type CO sensor, as preferably, in step D, the preparation method of sensitive electrode is: will be doped with 10-50wt.% (In
2o
3account for the proportion of ZnO quality) In
2o
3znO slurry adopt cladding process to be formed in induction zone, dry.Further preferably, the preparation method of sensitive electrode is: will be doped with 30wt.% (In
2o
3account for the proportion of ZnO quality) In
2o
3znO slurry adopt cladding process be formed in induction zone, at 120-150 DEG C, dry 6-12h in drying baker.
Compared with prior art, the invention has the advantages that employing is doped with 10-50wt.%In
2o
3znO as sensitive electrode material, be coupled column pattern Cr simultaneously
2o
3reference electrode composition setoff type CO sensor, when substantially not damaging CO gas response, inhibit to interference gas (as hydrocarbon, especially C
3h
6gas) response, drastically increase the selectivity of sensor.
Accompanying drawing explanation
Fig. 1 is that the present invention is coupled ZnO (+30wt.%In
2o
3)-SE and column pattern Cr
2o
3-SE forms the cross-sectional view of high selectivity setoff type CO sensor;
Fig. 2 is the fundamental diagram of high selectivity setoff type CO sensor of the present invention in Fig. 1;
Fig. 3 adopts single ZnO (+30wt.%In
2o
3)-SE or single column pattern Cr
2o
3-SE makes sensitive electrode, by the cross-sectional view of the CO sensor of Pt electrode for referencial use;
Fig. 4 adopts single ZnO (+30wt.%In in Fig. 3
2o
3)-SE makes sensitive electrode, improves figure at different temperatures with the CO sensor of Pt electrode for referencial use to the response of CO gas;
Fig. 5 adopts single ZnO (+30wt.%In in Fig. 3
2o
3)-SE makes sensitive electrode, with the CO sensor of Pt electrode for referencial use at different temperatures to the response diagram of each gas;
Fig. 6 adopts single column pattern Cr in Fig. 3
2o
3-SE makes sensitive electrode, with the CO sensor of Pt electrode for referencial use at different temperatures to the response diagram of each gas;
Fig. 7 is that CO sensor in Fig. 1 is at different temperatures to the response diagram of each gas;
Fig. 8 be CO sensor in Fig. 1 under fixed temperature to the step curve figure of the gas of variable concentrations;
Fig. 9 be in Fig. 1 high selectivity setoff type CO sensor of the present invention under fixed temperature, the variable concentrations of gas is taken the logarithm after linear diagram.
Description of reference numerals:
1, solid electrolyte; 2, sensitive electrode; 3, reference electrode; 4, contact conductor; 5, Pt reference electrode.
Embodiment
Be below specific embodiments of the invention and by reference to the accompanying drawings, technical scheme of the present invention is further described, but the present invention be not limited to these embodiments.
As shown in Figure 1, high selectivity setoff type CO sensor disclosed by the invention comprises solid electrolyte 1, sensitive electrode 2, reference electrode 3 and contact conductor 4, contact conductor 4 is drawn respectively by sensitive electrode 2 and reference electrode 3, solid electrolyte 1 is tubular type YSZ, sensitive electrode 2 and reference electrode 3 are all arranged on outside solid electrolyte 1, and sensitive electrode 2 is based on In
2o
3doping ZnO composite sensing electrode, reference electrode 3 is column pattern Cr
2o
3reference electrode.
As shown in Figure 2, the principle of work of high selectivity setoff type CO sensor of the present invention is: CO sensor is put into proving installation, the contact conductor of drawing from sensitive electrode 2 and reference electrode 3 is linked to built-up circuit on the positive pole and negative pole of digital multimeter, pass into a certain amount of CO gas, then sensitive electrode 2, reference electrode 3 will produce the reaction of following mixed potential:
CO+O
2-→CO
2+2e
-
1/2O
2+2e
-→O
2-
The oxonium ion produced by the electrochemical reaction on sensitive electrode 2, reference electrode 3, on solid electrolyte 1, the constantly mobile change producing electric charge, exports by digital multimeter collection the size that electromotive force carrys out perception electric charge.Column pattern Cr
2o
3to the response of object gas substantially lower than 10mV, to the response of interference gas be doped with 10-50wt.%In
2o
3the sensitive electrode of ZnO consistent, basic difference is not more than 10mV, is doped with 10-50wt.%In
2o
3znO sensitive electrode and column pattern Cr
2o
3the response characteristic of reference electrode all meets the principle of work of mixed potential type sensor, and the logarithm of their mixed potential and gas concentrations is separately linear.When coupling is doped with 10-50wt.%In
2o
3znO sensitive electrode and column pattern Cr
2o
3when reference electrode forms setoff type sensor, total mixed potential is also linear with the logarithm of gas concentration, meets the principle of work of mixed potential, when substantially not damaging CO gas response, inhibit widely to interference gas (as hydrocarbon, especially C
3h
6gas) response, thus significantly improve selectivity and the sensitivity of sensor.
In addition, as preferably, the width of described sensitive electrode and reference electrode is 2-4mm.Further preferably, the width of described sensitive electrode and reference electrode is 3mm.
As preferably, described sensitive electrode is 10-50wt.% (In
2o
3account for the proportion of ZnO quality) In
2o
3doping ZnO composite sensing electrode.Further preferably, described sensitive electrode is 30wt.% (In
2o
3account for the proportion of ZnO quality) In
2o
3doping ZnO composite sensing electrode.
As preferably, described solid electrolyte is solid oxygen ion conductor material tubular type YSZ.
The invention discloses the preparation method of above-mentioned high selectivity setoff type CO sensor, described preparation method comprises the following steps:
A adopt isostatic pressing technology make tubular type YSZ blank, then in air ambient after 500-900 DEG C of binder removal 2-4h, then put into high temperature furnace sinter at 1350-1550 DEG C 2-4h shaping solid electrolyte;
B obtains sensitive electrode slurry, and adopt cladding process to apply sensitive electrode slurry in solid electrolyte outer surface induction zone, prepare sensitive electrode, the width control system of sensitive electrode is at 2-4mm;
It is shaping in 1000-1300 DEG C of sintering 2-4h that high temperature furnace put into by step B gained sample by C;
D obtains column pattern Cr
2o
3reference electrode slurry, adopt cladding process to apply reference electrode slurry in described tubular type YSZ outer surface induction zone, prepare reference electrode, the width control system of reference electrode is at 2-4mm;
It is shaping in 800-900 DEG C of sintering 2-4h that high temperature furnace put into by step D gained sample by E;
F draws high temperature electrode lead-in wire at sensitive electrode and reference electrode surface Pt silk respectively, obtains high selectivity setoff type CO sensor finished product.
Wherein, the preparation method of described induction zone is, the polishing of solid electrolyte blind end outside surface is obtained induction zone.
As preferably, the sample in step C and step e all dries 6-12h before sintering at 120-150 DEG C.
As preferably, in step C, the sintering temperature of sample is 1200 DEG C, and in step e, the sintering temperature of sample is 900 DEG C.
As preferably, in step D, the preparation method of sensitive electrode is: will be doped with 10-50wt.% (In
2o
3account for the proportion of ZnO quality) In
2o
3znO slurry adopt cladding process to be formed in induction zone, dry.Further preferably, the preparation method of sensitive electrode is: will be doped with 30wt.% (In
2o
3account for the proportion of ZnO quality) In
2o
3znO slurry adopt cladding process be formed in induction zone, at 120-150 DEG C, dry 6-12h in drying baker.
The optimum configurations table of table 1: embodiment 1-5
In view of the present invention program's embodiment is numerous, each embodiment experimental data is huge numerous, be not suitable for particularize explanation herein, but the content of the required checking of each embodiment is all close with the final conclusion obtained, so do not illustrate one by one the checking content of each embodiment, only with embodiment 1, the excellent part of the present patent application is representatively described herein.
Be described in detail with embodiment 1 below, in the present embodiment, by YSZ pipe from top (solid section) to down about 3cm region sand papering is smooth, will 30wt.%In be doped with
2o
3the ZnO powder of powder and terpinol slurry (being prepared by 70% terpinol+30% ethyl cellulose) mix according to the proportioning of proper proportion (as 1:1) and grind evenly in agate mortar, cladding process is adopted to be prepared in the surface in region that solid electrolyte 1 polishes, width is 3mm, put into drying box and dry 8h at 140 DEG C, be placed in high temperature furnace more shaping in 1200 DEG C of sintering 2h, obtain sensitive electrode 2.By synthetic column pattern Cr
2o
3powder and terpinol slurry (being prepared by 70% terpinol+30% ethyl cellulose) mix according to the proportioning of proper proportion (as 1:1) and grind evenly in agate mortar, cladding process is adopted to be prepared in the surface in region that solid electrolyte 1 polishes, width is 3mm, put into drying box and dry 8h at 140 DEG C, be placed in high temperature furnace more shaping in 900 DEG C of sintering 2h, obtain reference electrode 3.Finally draw high temperature electrode lead-in wire 4 from the surface of sensitive electrode 2 and reference electrode 3, as platinum filament (through coiling or welding), high selectivity setoff type CO sensor can be obtained.
With the 30wt.%In that adulterates
2o
3znO sensitive electrode material prepare sensitive electrode 2, coupling column pattern Cr
2o
3it is that example carries out dependence test experiment that-SE prepares the CO sensor that reference electrode 3 obtains, and the present invention will be described, as shown in the figure.
Fig. 3 adopts single ZnO (+30wt.%In
2o
3)-SE or single column pattern Cr
2o
3-SE makes sensitive electrode, by the cross-sectional view of the CO sensor of Pt electrode for referencial use.
Figure 4 shows that Fig. 3 adopts single ZnO (+30wt.%In
2o
3)-SE makes sensitive electrode, with the CO sensor of Pt electrode for referencial use at 450-550 DEG C, the O of 5vol.%
2under, for the response of the CO gas of 200ppm.As seen from the figure, 500 DEG C time, response is maximum, and ZnO (+30wt.%In of the present invention
2o
3)-SE response than doping before single ZnO, In
2o
3all want large.Therefore, doping improves the response of sensor to CO gas, and ZnO (+30wt.%In is described
2o
3) sensitivity of-SE is higher.
Fig. 5 adopts single ZnO (+30wt.%In in Fig. 3
2o
3)-SE makes sensitive electrode, with the CO sensor of Pt electrode for referencial use at 450-550 DEG C, the O of 5vol.%
2under, for the response comparison diagram of the gas with various of 200ppm.As seen from the figure, 500 DEG C time, the response of each gas reaches maximum, and CO, C
3h
6the response of gas is bigger than normal compared with other gases.
Fig. 6 adopts single column pattern Cr in Fig. 3
2o
3-SE makes sensitive electrode, with the CO sensor of Pt electrode for referencial use at 450-550 DEG C, the O of 5vol.%
2under, for the response comparison diagram of the gas with various of 200ppm.As seen from the figure, for other gases, C
3h
6response maximum and reach the highest 500 DEG C time, other gases do not respond substantially.Column pattern Cr is described simultaneously
2o
3-SE is to C
3h
6the response of gas and ZnO (+30wt.%In
2o
3) being more or less the same of-SE, meet the preparation requirement of setoff type sensor.
Fig. 7 is that in Fig. 1, the present invention is coupled ZnO (+30wt.%In
2o
3)-SE and column pattern Cr
2o
3-SE forms high selectivity setoff type CO sensor at 450-550 DEG C, the O of 5vol.%
2under, for the response comparison diagram of the gas with various of 200ppm.As seen from the figure, the response of CO gas is maximum and reach the highest 500 DEG C time, and compare with Fig. 4, Fig. 5, Fig. 6, the present invention only decreases-12mV to CO response, and C
3h
6the response of gas is suppressed.Therefore visible, setoff type CO sensor of the present invention, substantially not damaging on the basis of CO response, greatly inhibits C
3h
6response, drastically increase the selectivity of sensor.
Fig. 8 is that in Fig. 1, the present invention is coupled ZnO (+30wt.%In
2o
3)-SE and column pattern Cr
2o
3-SE forms high selectivity setoff type CO sensor at 500 DEG C, the O of 5vol.%
2under, CO, C
3h
6the response diagram when concentration of gas changes from 0-500ppm.As seen from the figure, setoff type CO sensor of the present invention steps fabulous, declines and recovery rate is consistent, substantially even and if under the large concentration of 500ppm, sensor is to C
3h
6gas does not also respond substantially, and on the contrary, the response of CO increases step by step.As can be seen here, compared with CO sensor of the prior art, setoff type CO sensor of the present invention drastically increases sensitivity and selectivity, is the CO sensor of high sensitivity, high selectivity.
Fig. 9 is that in Fig. 1, the present invention is coupled ZnO (+30wt.%In
2o
3)-SE and column pattern Cr
2o
3-SE forms high selectivity setoff type CO sensor at 500 DEG C, the O of 5vol.%
2under, CO, C
3h
6when the concentration of gas changes from 0-500ppm, the response diagram of the sensor obtained after concentration is taken the logarithm.As seen from the figure, setoff type CO sensor of the present invention linearly fabulous, substantially point-blank, namely there is obvious linear relationship in the response of sensor and the logarithm value of gas concentration to all points, proves the electrochemical sensor of electric potential type.
Specific embodiment described herein is only to the explanation for example of the present invention's spirit.Those skilled in the art can make various amendment or supplement or adopt similar mode to substitute to described specific embodiment, but can't depart from spirit of the present invention or surmount the scope that appended claims defines.
Claims (8)
1. a high selectivity setoff type CO sensor, comprise solid electrolyte, sensitive electrode, reference electrode and contact conductor, described contact conductor is drawn respectively by sensitive electrode and reference electrode, it is characterized in that, described solid electrolyte is tubular type YSZ, described sensitive electrode and reference electrode are all arranged on outside solid electrolyte, and described sensitive electrode is based on In
2o
3doping ZnO composite sensing electrode, described reference electrode is column pattern Cr
2o
3reference electrode.
2. high selectivity setoff type CO sensor according to claim 1, it is characterized in that, the width of described sensitive electrode and reference electrode is 2-4mm.
3. high selectivity setoff type CO sensor according to claim 1, it is characterized in that, described sensitive electrode is 10-50wt.% (In
2o
3account for the proportion of ZnO quality) In
2o
3doping ZnO composite sensing electrode.
4. high selectivity setoff type CO sensor according to claim 1, it is characterized in that, described sensitive electrode is 30wt.% (In
2o
3account for the proportion of ZnO quality) In
2o
3doping ZnO composite sensing electrode.
5. high selectivity setoff type CO sensor according to claim 1, is characterized in that, described solid electrolyte is solid oxygen ion conductor material tubular type YSZ.
6. a preparation method for high selectivity setoff type CO sensor, is characterized in that, described preparation method comprises the following steps:
A adopt isostatic pressing technology make tubular type YSZ blank, then in air ambient after 500-900 DEG C of binder removal 2-4h, then put into high temperature furnace sinter at 1350-1550 DEG C 2-4h shaping solid electrolyte;
B obtains sensitive electrode slurry, and adopt cladding process to apply sensitive electrode slurry in tubular type YSZ outer surface induction zone, prepare sensitive electrode, the width control system of sensitive electrode is at 2-4mm;
It is shaping in 1000-1300 DEG C of sintering 2-4h that high temperature furnace put into by step B gained sample by C;
D obtains reference electrode slurry, and adopt cladding process to apply reference electrode slurry in described tubular type YSZ outer surface induction zone, prepare reference electrode, the width control system of reference electrode is at 2-4mm;
It is shaping in 800-900 DEG C of sintering 2-4h that high temperature furnace put into by step D gained sample by E;
F from sensitive electrode and reference electrode surface extraction electrode lead-in wire, obtains high selectivity setoff type CO sensor finished product respectively.
7. the preparation method of high selectivity setoff type CO sensor according to claim 6, is characterized in that, the sample in step C and step e all dries 6-12h before sintering at 120-150 DEG C.
8. the preparation method of high selectivity setoff type CO sensor according to claim 6, it is characterized in that, in step D, the preparation method of sensitive electrode is: will be doped with 10-50wt.% (In
2o
3account for the proportion of ZnO quality) In
2o
3znO slurry adopt cladding process to be formed in induction zone, dry.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105334256A (en) * | 2015-10-29 | 2016-02-17 | 宁波大学 | Potentiometric CO sensor based on Ni-doped PdO sensitive electrode and preparation method of potentiometric CO sensor |
| WO2020172805A1 (en) * | 2019-02-27 | 2020-09-03 | Qi Diagnostics Limited | Sensing material for high sensitivity and selectivity |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000329734A (en) * | 1999-05-20 | 2000-11-30 | Akebono Brake Res & Dev Center Ltd | Solid-electrolyte-type gas sensor |
| US20070144237A1 (en) * | 2005-12-20 | 2007-06-28 | Moseley Patrick T | Air quality monitor |
| CN104215673A (en) * | 2014-08-28 | 2014-12-17 | 宁波大学 | Preparation method of Zr-based nitric oxide sensor with high selectivity |
| CN104237334A (en) * | 2014-08-07 | 2014-12-24 | 宁波市鄞州永林电子电器有限公司 | Potential type CO sensor and preparation method thereof |
| CN104391010A (en) * | 2014-11-19 | 2015-03-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Cr2O3-ZnO composite nano material as well as preparation method and application thereof |
-
2015
- 2015-03-12 CN CN201510108513.9A patent/CN104749235B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000329734A (en) * | 1999-05-20 | 2000-11-30 | Akebono Brake Res & Dev Center Ltd | Solid-electrolyte-type gas sensor |
| US20070144237A1 (en) * | 2005-12-20 | 2007-06-28 | Moseley Patrick T | Air quality monitor |
| CN104237334A (en) * | 2014-08-07 | 2014-12-24 | 宁波市鄞州永林电子电器有限公司 | Potential type CO sensor and preparation method thereof |
| CN104215673A (en) * | 2014-08-28 | 2014-12-17 | 宁波大学 | Preparation method of Zr-based nitric oxide sensor with high selectivity |
| CN104391010A (en) * | 2014-11-19 | 2015-03-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Cr2O3-ZnO composite nano material as well as preparation method and application thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105334256A (en) * | 2015-10-29 | 2016-02-17 | 宁波大学 | Potentiometric CO sensor based on Ni-doped PdO sensitive electrode and preparation method of potentiometric CO sensor |
| WO2020172805A1 (en) * | 2019-02-27 | 2020-09-03 | Qi Diagnostics Limited | Sensing material for high sensitivity and selectivity |
| TWI732461B (en) * | 2019-02-27 | 2021-07-01 | 香港商氣葩科技有限公司 | Sensing material for high sensitivity and selectivity |
| CN114144667A (en) * | 2019-02-27 | 2022-03-04 | 气传感科技有限公司 | High sensitivity and selectivity sensing materials |
| EP3942286A4 (en) * | 2019-02-27 | 2022-12-28 | QI Sensor Technologies Limited | Sensing material for high sensitivity and selectivity |
| CN114144667B (en) * | 2019-02-27 | 2024-03-26 | 气传感科技有限公司 | High sensitivity and selectivity sensing material |
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