CN106168598B - One kind being based on YSZ and CoTa2O6Sensitive electrode blendes together electric potential type NO2Sensor, preparation method and applications - Google Patents

One kind being based on YSZ and CoTa2O6Sensitive electrode blendes together electric potential type NO2Sensor, preparation method and applications Download PDF

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CN106168598B
CN106168598B CN201610555727.5A CN201610555727A CN106168598B CN 106168598 B CN106168598 B CN 106168598B CN 201610555727 A CN201610555727 A CN 201610555727A CN 106168598 B CN106168598 B CN 106168598B
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卢革宇
刘方猛
梁喜双
孙鹏
刘凤敏
孙彦峰
马健
高原
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Jilin University
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Abstract

One kind being based on YSZ and CoTa2O6Sensitive electrode blendes together electric potential type high temperature NO2Sensor, preparation method and its application in vehicle exhaust monitoring.Sensor is successively by the Al with Pt heating electrodes2O3Ceramic wafer, YSZ substrates, Pt reference electrodes and sensitive electrode composition；Reference electrode and sensitive electrode are separate and symmetrically prepare at the both ends of YSZ upper surface of base plate, YSZ base lower surfaces and the Al with Pt heating electrodes2O3Ceramic wafer is bonded together；The material of sensitive electrode is CoTa2O6.The present invention utilizes the CoTa with high electrochemical catalytic activity using YSZ as ion conductive layer2O6Composite oxide material is sensitive electrode, changes the microscopic appearance of sensitive electrode by different calcination temperatures (800 DEG C~1200 DEG C), and be built into senser element respectively, by comparing at high temperature to NO2Response size, obtain with higher sensitive property device.

Description

One kind being based on YSZ and CoTa2O6Sensitive electrode blendes together electric potential type NO2Sensor, system Preparation Method and its application
Technical field
The invention belongs to gas sensor technical fields, and in particular to one kind being based on YSZ and CoTa2O6Sensitive electrode mixes At electric potential type high temperature NO2Sensor, preparation method and its application in vehicle exhaust monitoring.
Background technology
With being continuously increased for car ownership, environmental pollution caused by motor vehicle exhaust emission and increasingly deficient resource are asked Topic has become two significant challenges that auto industry sustainable development is faced.Therefore, in order to cope with challenges, countries in the world land It is continuous to propose tightened up vehicular emission standards to limit the discharge of poisonous and harmful tail gas.In addition, in order to improve the burning of fuel Efficiency reduces the discharge of carbon dioxide, and NO is installed on lean burn or direct fuel-injection enginexType of attracting deposit catalysis system passes to make up The low NO of the three-phase catalytic system of systemxElimination ability.However, when catalyst is to NOxThe ability of attracting deposit when reaching saturation, need by The hydrocarbon of high concentration supplies catalyst to realize the recovery for the ability of attracting deposit.Therefore, low cost, high stable, high intensity and The NO of hypersensitivity energyxThe rear and front end that sensor should be installed in catalyst monitors NO in real timexConcentration, so as to adjust The regeneration opportunity of catalyst.Since vehicle mounted tail gas after-treatment system is usually under the harsh state of high temperature and humidity, so It is required that sensor should be able to bear the environment of high temperature and humidity.Very fortunately, YSZ and metal oxide sensitive electrical are based on Pole blendes together electric potential type gas sensor and can meet requirements above.
Stabilizing zirconia base blendes together electric potential type NO2The sensitive mechanism of sensor is：NO in atmosphere2By sensitive electrode layer to Three-phase reaction interface is spread, due to react (1), NO in diffusion process2Concentration can continuously decrease, sensitive oxide electricity The porosity of pole can determine NO2The reduction degree of concentration.At the three phase boundary of gas/sensitive electrode/YSZ, while NO occurs2 Electrochemical reducting reaction and oxygen electrochemical oxidation reactions, reaction (2) and (3) constitute a local cell, when the two reaction When rate is equal, reaction reaches balance, is formed on sensitive electrode and blendes together current potential, its potential difference with reference electrode is as sensing The detection signal of device.Detection signal magnitude is determined by electrochemical reaction (2) and the rate of (3), and reaction rate is depending on quick Electrochemistry and the chemical catalysis activity of sense electrode material, electrode material microstructure (such as the porosity of material, granularity, pattern Deng).
Reaction equation is as follows：
NO2→NO+1/2O2 (1)
NO2+2e-→NO+O2- (2)
O2-→1/2O2+2e- (3)
Currently, in order to prepare the sensor of more high sensitivity characteristic, domestic and international most researchers are dedicated to sensitive electrode material The research of material.For example, this seminar make with Cr2O3-WO3Electric potential type NO is blended together for the YSZ bases of sensitive electrode material2Sensing Device is to 100ppm NO2Blend together potential value be 52mV (Quan Diao, Chengguo Yin, Yingwei Liu, Jianguo Li,Xun Gong,Xishuang Liang,Shiqi Yang, Hong Chen,Geyu Lu,Mixed-potential-type NO2sensor using stabilized zirconia and Cr2O3-WO3nanocomposites,Sensor and Actuators B 180(2013) 90-95).This NO2Although sensor has acceptable sensitive property, continual exploitation It can be used for NO2The sensitive electrode material of the high electrochemical catalytic activity of gas detection is still very necessary.
Invention content
The object of the present invention is to provide one kind being based on YSZ and CoTa2O6Sensitive electrode blendes together electric potential type high temperature NO2Sensing Device, preparation method and its application in vehicle exhaust monitoring.The obtained sensor of the present invention other than there is high sensitivity, Also there is lower Monitoring lower-cut, well selectivity, moisture-proof and stability.
NO according to the present invention2Sensor is to be based on solid electrolyte YSZ and high electrochemical catalytic performance CoTa2O6It is multiple It is the new type high temperature NO constructed by sensitive electrode to close oxide material2Sensor, YSZ (ZrO2(doping mass fraction 8% Y2O3)) it is used as ion conductive layer.
It is of the present invention a kind of based on YSZ and CoTa2O6Sensitive electrode blendes together electric potential type NO2Sensor, such as Fig. 1 institutes Show, successively by the Al with Pt heating electrodes2O3Ceramic wafer, YSZ substrates, Pt reference electrodes and sensitive electrode composition；Reference electrode Separate with sensitive electrode and symmetrically prepare at the both ends of YSZ upper surface of base plate, YSZ base lower surfaces are heated with Pt The Al of electrode2O3Ceramic wafer is bonded together；The material of sensitive electrode is CoTa2O6, it is prepared by the following method：
Weigh the Ta of 0.5~2mmol2O5, be dissolved in 30~60mL, mass fraction 40~50% hydrofluoric acid water In solution, stirred 12~24 hours at 60~90 DEG C；The ammonium hydroxide of 15~20mL, mass concentration 25~28% is added dropwise dropwise Into the above solution, the pH value for adjusting reaction system is 8~10, is aged 12~14 hours, through being filtered, washed neutrality, obtains White precipitate；The above white precipitate is dissolved in the aqueous solution of citric acid, continues stirring at 60~80 DEG C 1~2 hour, adds Enter CoCl2·6H2O aqueous solutions continue stirring to gel；It is small that obtained gel is dried under 80~90 DEG C of vacuum conditions to 12~24 When obtain xerogel, obtained xerogel is calcined 2~4 hours under the conditions of 800~1200 DEG C finally, obtains CoTa2O6It is sensitive Electrode material；Wherein CoCl2·6H2O and Ta2O5Dosage molar ratio be 1：1, citric acid and Ta2O5Dosage molar ratio be 2~ 5：1.
NO of the present invention2The preparation process of sensor is as follows：
(1) Pt reference electrodes are made：The Pt ginsengs of 15~20 μm thick of making are starched using Pt in one end of YSZ upper surface of base plate Electrode is examined, while will be sticked to after a Pt doublings on reference electrode centre position and being used as contact conductor, then YSZ substrates exist It is toasted 1~2 hour under the conditions of 90~120 DEG C, then YSZ substrates is calcined 1~2 hour at 1000~1200 DEG C, exclude platinum slurry In terpinol, be finally down to room temperature；
(2) CoTa is made2O6Sensitive electrode：By CoTa2O6Sensitive electrode material is slurred material with deionized water, and quality is dense Degree is 2~20%；The slurry is made on the platinum point for connecting platinum filament with the other end of the symmetrical YSZ upper surface of base plate of reference electrode The sensitive electrode of standby 20~30 μ m-thicks；
(3) to have the YSZ substrates of reference electrode and sensitive electrode to calcine 1~3 at 800~1000 DEG C above-mentioned preparation small When；Heating rate when preferred high-temperature calcination is 1~2 DEG C/min；
(4) inorganic bond is prepared：Measure waterglass (Na2SiO3·9H2O) 2~4mL, and weigh Al2O3Powder 0.7~ 1.0g, by waterglass and Al2O3Powder is mixed and stirred for uniformly, required inorganic bond being made；
(5) inorganic bond is used to heat the Al of electrode by YSZ base lower surfaces and with Pt2O3Ceramic wafer is bonded in one It rises；
Wherein, the Al of Pt heating electrodes is carried2O3Ceramic wafer is in Al2O3It is obtained by silk-screen printing Pt on ceramic wafer, The Al of electrode is heated with Pt2O3Ceramic wafer is used as the heating plate of device together；
(6) device bonded welded, encapsulated, to be prepared it is of the present invention based on YSZ and CoTa2O6Sensitive electrode blendes together electric potential type NO2Sensor.
The present invention utilizes the CoTa with high electrochemical catalytic activity using YSZ as ion conductive layer2O6Composite oxides Material is sensitive electrode, changes the microscopic appearance of sensitive electrode by different calcination temperatures (800 DEG C~1200 DEG C), and respectively It is built into senser element, by comparing at high temperature to NO2Response size, obtain with higher sensitive property device.
Advantages of the present invention：
(1) sensor utilize typical solid electrolyte --- stabilizing zirconia (YSZ), have good thermal stability and Chemical stability can detect NO in harsh environment2；
(2) high-performance composite oxide CoTa is prepared using sol-gel method2O6As sensor sensing electrode, preparation side Method is simple, is conducive to the industrialized production of mass.
(3) by changing different calcination temperatures (800 DEG C~1200 DEG C), the sensitive electrical with different pore passage structures is obtained Pole layer, to optimize the microstructure of sensitive electrode, the sensor performance constructed by different calcination temperature sensitive electrode materials Comparison finds that 1000 DEG C are calcined CoTa2O6Electric potential type device is blended together at high temperature to NO for the YSZ bases of sensitive electrode2It shows Highest response, and there is lower Monitoring lower-cut, good sensitivity, selectivity, repeatability, moisture-proof and stability, There is potential application prospect in terms of vehicle exhaust monitoring.
Description of the drawings
Fig. 1：YSZ bases of the present invention blend together electric potential type NO2The structural schematic diagram of sensor (a) and heating plate (b).
Each section title：CoTa2O6Sensitive electrode 1, Pt reference electrodes 3, Pt silks 4, Pt points 5, adds with Pt YSZ substrates 2 The Al of thermode2O3Ceramic wafer 6, inorganic bond 7.
Fig. 2：The XRD diagram of three kinds of sensitive electrode materials obtained by the present invention.(wherein, abscissa is angle, and ordinate is Intensity)
As shown in Fig. 2, for CoTa under different calcination temperatures2O6The XRD diagram of sensitive electrode material, by with standard spectrogram pair Than, synthesis three kinds of sensitive electrode materials with standard card JCPDS (File No. 84-2063) unanimously, be tetragonal crystal system three Rutile structure composite oxides.Show that the sensitive electrode material that we invent preparation is CoTa2O6Material.
Fig. 3：The SEM of the sensitive electrode material under different calcination temperatures prepared by the present invention schemes.
As shown in figure 3, a：800 DEG C, b：1000 DEG C, c：The CoTa of 1200 DEG C of calcinings2O6The SEM of sensitive electrode material schemes, from It can be seen from the figure that, with the raising of calcination temperature, granular size and duct size gradually increase, it can thus be seen that changing The calcination temperature of sensitive material can change the microscopic appearance of sensitive electrode, and the porosity of electrode is conducive to the diffusion of gas.
Fig. 4：It is utilized respectively the CoTa of 800,1000 and 1200 DEG C of calcinings2O6The sensor constructed as sensitive electrode material To 100ppm NO2Response size comparison.(wherein, abscissa is potential difference values, and ordinate is different electrode materials, work It is 650 degree to make temperature)
The sensitive property test of device uses static test (detailed process is as shown in the examples), the sound of sensor It should be worth with Δ V=VNO2-VAirIt indicates.As shown in figure 4, being the device made by embodiment 1,2,3 to 100ppm NO2Response It is worth comparison diagram, it can be seen from the figure that the device obtained by embodiment 1,2,3 is to 100ppm NO2Response be respectively 93, 62 and 54mV.It can be seen that the CoTa of 1000 DEG C of calcinings2O6YSZ bases as sensitive electrode material blend together electric potential type NO2Sensing Utensil has highest response.
Fig. 5：The CoTa calcined using 1000 DEG C2O6Sensor as sensitive electrode material is to NO2Sensitivity curve. (wherein, abscissa NO2Concentration, ordinate are potential difference values, and operating temperature is 650 degree, and illustration is current sensor pair 0.5 ~5ppm NO2Sensitivity curve figure).
The sensitivity of sensor is that sensor is centainly measuring response and corresponding log concentration in concentration range The slope of linear relationship.As shown in figure 5, for the CoTa calcined using 1000 DEG C2O6Sensor pair as sensitive electrode material NO2Sensitivity curve figure, it can be seen from the figure that 5~500ppm of device pair NO2Sensitivity be 80mV/decade, it is minimum The NO of 500ppb can be detected2, this sensor shows good sensitivity and very low Monitoring lower-cut.
Fig. 6：The CoTa calcined using 1000 DEG C2O6The selectivity of sensor as sensitive electrode material.It is (wherein, horizontal Coordinate is potential difference values, and ordinate is test gas, and illustration is the enlarged drawing to ethylene, methane and hydrogen)
As shown in fig. 6, for the CoTa of 1000 DEG C of calcinings2O6The selectivity of sensor as sensitive electrode material, from figure It can be seen that device pair 50 and 100ppm NO2Highest response is shown, it is relatively low to the response of other gases, by This is as it can be seen that device has selectivity well.
Fig. 7：The CoTa calcined with 1000 DEG C2O6The humidity of sensor as sensitive electrode material influences.It is (wherein, horizontal Coordinate is relative humidity, and ordinate is potential difference values)
Sensor humidity measurement refer to device under different humidity (in 20~98% humidity ranges) to 100ppm NO2's Response changes.As shown in fig. 7, for the CoTa calcined with 1000 DEG C2O6Device as sensitive electrode material is under different humidity To 100ppm NO2Response, it can be seen from the figure that device is in 20~98% humidity range, to 100ppm NO2Sound It should change less than 10.7%, showing sensor has good moisture-proof.
Fig. 8：The CoTa calcined with 1000 DEG C2O6The stability of sensor as sensitive electrode material.(wherein, abscissa For the time, ordinate is respectively potential difference values and potential difference knots modification)
The stability test of device was maintained at sensor under 650 degree of operating temperature, by 20 days continuous high temperature items Test is to 50,100 and 200ppm NO under part2Response as standard, a point is taken every three days in test process, to remember Record the variation in 20 days.As shown in figure 8, for the CoTa calcined with 1000 DEG C2O6Device as sensitive electrode material was at 20 days Interior stability test, it can be seen from the figure that device is in 20 days, 50,100 and 200ppm of device pair NO2The wave of response Dynamic range is less than 10.2%, shows that device has good stability.
Specific implementation mode
Embodiment 1：
CoTa is prepared with sol-gel method2O6Material, by CoTa obtained2O6It carries out 1000 DEG C of calcinings and is used as sensitive electrode Material makes YSZ bases and blendes together Copper diethlydithiocarbamate, and tests sensor to NO2Air-sensitive performance, detailed process is as follows：
1. making Pt reference electrodes：It is starched using Pt in one end of the YSZ upper surface of base plate of 2 × 2mm of length and width, thickness 0.2mm Make one layer of 0.5mm × 2mm size, 15 μ m-thicks Pt reference electrodes, while with being sticked in reference electrode after a Pt doublings Between extraction electrode lead on position；Then YSZ substrates are toasted 1.5 hours under the conditions of 100 DEG C, then by YSZ substrates 1000 It is calcined 1 hour at DEG C, to exclude the terpinol in platinum slurry, is finally down to room temperature.
2. making CoTa2O6Sensitive electrode：First CoTa is prepared with sol-gel method2O6Material.Weigh 1mmol Ta2O5, it is dissolved in the aqueous solution of the hydrofluoric acid of 50mL in (mass fraction 40%), is stirred 24 hours at 80 DEG C；It will Ammonium hydroxide (mass concentration 25%) is added drop-wise to dropwise in the above solution, is adjusted pH value to 9, is aged 14 hours, through being filtered, washed Neutrality obtains white precipitate；The above white precipitate is dissolved in the aqueous solution that 0.6304g citric acids and 10mL water are made into, Continue stirring 2 hours at 80 DEG C, 0.2379g CoCl are added2·6H2O continues stirring to gel.Obtained spawn is existed It is dried 12 hours in 80 DEG C of vacuum drying chambers and obtains xerogel, finally calcined 2 hours, obtain under the conditions of 1000 DEG C in Muffle furnace 0.465g CoTa2O6Sensitive electrode material.
Take 5mg CoTa2O6Powder is tuned into slurry with 100mg deionized waters, by CoTa2O6Slurry is symmetrical with reference electrode YSZ upper surface of base plate the other end connection platinum filament platinum point on coating one layer of 0.5mm × 2mm size, the sensitive electrical of 20 μ m-thicks Pole, it is same with being sticked to extraction electrode lead on sensitive electrode after a platinum filament doubling.
The YSZ substrates with reference electrode and sensitive electrode made are warming up to 800 with the heating rate of 2 DEG C/min DEG C and be down to room temperature after keeping 2h.
3. bonding has the ceramic wafer of heating electrode.Use inorganic bond (Al2O3With waterglass Na2SiO3·9H2O, Quality is about than 5：1 prepares) Pt that carries of the lower surface (side of uncoated electrode) of YSZ substrates and same size is heated into electrode Al2O3Ceramic wafer (2 × 2mm of length and width, thickness 0.2mm) is bonded；
4. device welding, encapsulation.Device is welded on hexagonal tube socket, protective cover is put on, completes and blendes together electric potential type NO2Sensor.
Embodiment 2：
The CoTa calcined with 800 DEG C2O6Composite material makes NO as sensitive electrode material2Sensor, manufacturing process For：
The CoTa of 800 DEG C of calcinings2O6Sensitive electrode material preparation process and device fabrication processes are identical as embodiment 1.
Embodiment 3：
The CoTa calcined with 1200 DEG C2O6Composite material makes NO as sensitive electrode material2Sensor, manufacturing process For：
The CoTa of 1200 DEG C of calcinings2O6Sensitive electrode material preparation process and device fabrication processes are identical as embodiment 1.
Sensor is connected on Rigol signal testers, sensor is placed in air, 500ppb NO2、 1ppm NO2、 2ppm NO2、5ppm NO2、10ppm NO2、20ppm NO2、50ppm NO2、 100ppm NO2、200ppm NO2、300ppm NO2With 500ppm NO2Atmosphere in carry out voltage signal test.The test method of device uses traditional static testing, tool Body process is as follows：
1. sensor is connected on Rigol signal testers, in the test bottle that it is 1L full of air volume that device, which is placed in, Reach stable, as the aerial electromotive force value (V of deviceAir)。
2. sensor is transferred quickly to concentration NO to be measured is housed2In the test bottle of gas, until response signal reaches steady Fixed, as device is in NO2In electromotive force value (VNO2)。
3. device is transferred back in air bottle again, stable until reaching, device completes a secondary response recovery process.Device In NO2With electromotive force difference (the Δ V=V in airNO2-VAir) it is device to concentration NO2Response.Sensor is one Response in location survey amount concentration range and the sensitivity that the slope of the linear relationship of corresponding log concentration is the sensor.
The CoTa calcined respectively with 800,1000 and 1200 DEG C is listed in table 12O6Electricity is blended together for the YSZ bases of sensitive electrode Bit-type sensor is to 100ppm NO2Response.As can be seen from the table, the CoTa calcined with 1000 DEG C2O6For sensitive electrode Device show highest response, be 93mV.
The CoTa calcined with 1000 DEG C is listed in table 22O6Electric potential type is blended together for the YSZ bases that sensitive electrode material makes to pass Sensor is in various concentration NO2The difference of electromotive force and aerial electromotive force in atmosphere is with NO2The changing value of concentration.From table In it can be seen that, the sensitivity (slope) of device is 80mV/decade.It can be seen that 1000 DEG C of calcinings that we develop is new Type CoTa2O6The device that sensitive electrode material is constituted is to NO2Good sensitivity characteristic is shown, has obtained that there is high sensitivity YSZ bases blend together electric potential type NO2Sensor.
The CoTa that table 1 is calcined with 800,1000 and 1200 DEG C2O6For sensitive electrode material sensor to 100ppm NO2's Response compares
The CoTa that table 2 is calcined with 1000 DEG C2O6For sensitive electrode device Δ V with NO2The variation of concentration

Claims (5)

1. one kind being based on YSZ and CoTa2O6Sensitive electrode blendes together electric potential type NO2Sensor, successively by heating electrode with Pt Al2O3Ceramic wafer, YSZ substrates, Pt reference electrodes and sensitive electrode composition；Reference electrode and sensitive electrode are separate and symmetrical Ground is prepared in the both ends of YSZ upper surface of base plate, YSZ base lower surfaces and the Al with Pt heating electrodes2O3Ceramic wafer is bonded in one It rises；It is characterized in that：The material of sensitive electrode is CoTa2O6, it is prepared by the following method,
Weigh the Ta of 0.5~2mmol2O5, be dissolved in 30~60mL, mass fraction 40~50% hydrofluoric acid aqueous solution In, it is stirred 12~24 hours at 60~90 DEG C；The ammonium hydroxide of 15~20mL, mass concentration 25~28% are added drop-wise to dropwise above In solution, the pH value for adjusting reaction system is 8~10, is aged 12~14 hours, and through being filtered, washed neutrality, it is heavy to obtain white It forms sediment；The above white precipitate is dissolved in the aqueous solution of citric acid, continues stirring at 60~80 DEG C 1~2 hour, is added CoCl2·6H2O aqueous solutions continue stirring to gel；Obtained gel is dried 12~24 hours under 80~90 DEG C of vacuum conditions Xerogel is obtained, obtained xerogel is calcined 2~4 hours under the conditions of 800~1200 DEG C finally, obtains CoTa2O6Sensitive electrical Pole material；Wherein CoCl2·6H2O and Ta2O5Dosage molar ratio be 1：1, citric acid and Ta2O5Dosage molar ratio be 2~5： 1。
2. described in claim 1 a kind of based on YSZ and CoTa2O6Sensitive electrode blendes together electric potential type NO2The preparation side of sensor Method, its step are as follows：
(1) Pt reference electrodes are made：The Pt of 15~20 μ m-thicks is made with reference to electricity using Pt slurries in one end of YSZ upper surface of base plate Pole, while will be sticked to after a Pt doublings on reference electrode centre position and being used as contact conductor, then by YSZ substrates 90~ It is toasted 1~2 hour under the conditions of 120 DEG C, then YSZ substrates is calcined 1~2 hour at 1000~1200 DEG C, excluded in platinum slurry Terpinol is finally down to room temperature；
(2) CoTa is made2O6Sensitive electrode：By CoTa2O6Sensitive electrode material is slurred material, mass concentration 2 with deionized water ~20%；The slurry is prepared 20 on the platinum point for connecting platinum filament with the other end of the symmetrical YSZ upper surface of base plate of reference electrode The sensitive electrode of~30 μ m-thicks；
(3) the YSZ substrates of reference electrode and sensitive electrode are calcined 1~3 hour at 800~1000 DEG C preparation；
(4) inorganic bond is used to heat the Al of electrode by YSZ base lower surfaces and with Pt2O3Ceramic wafer is bonded together；
(5) device bonded welded, encapsulated, YSZ and CoTa is based on to be prepared2O6Sensitive electrode blendes together Electric potential type NO2Sensor.
3. as claimed in claim 2 a kind of based on YSZ and CoTa2O6Sensitive electrode blendes together electric potential type NO2The preparation of sensor Method, it is characterised in that：Heating rate when calcining described in step (3) is 1~2 DEG C/min.
4. as claimed in claim 2 a kind of based on YSZ and CoTa2O6Sensitive electrode blendes together electric potential type NO2The preparation of sensor Method, it is characterised in that：It is to measure 2~4mL of waterglass, and weigh Al2O30.7~1.0g of powder, by waterglass and Al2O3Powder Body is mixed and stirred for uniformly, required inorganic bond being made.
5. described in claim 1 a kind of based on YSZ and CoTa2O6Sensitive electrode blendes together electric potential type NO2Sensor is in car tail Application in gas monitoring.
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