CN109115857A - Humidity detection sensor and its preparation method and application under a kind of high temperature - Google Patents

Humidity detection sensor and its preparation method and application under a kind of high temperature Download PDF

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CN109115857A
CN109115857A CN201811072120.7A CN201811072120A CN109115857A CN 109115857 A CN109115857 A CN 109115857A CN 201811072120 A CN201811072120 A CN 201811072120A CN 109115857 A CN109115857 A CN 109115857A
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solid electrolyte
cavity
conductor solid
oxygen ion
proton conductor
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刘涛
王相南
于景坤
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Northeastern University China
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4073—Composition or fabrication of the solid electrolyte
    • G01N27/4074—Composition or fabrication of the solid electrolyte for detection of gases other than oxygen
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4075—Composition or fabrication of the electrodes and coatings thereon, e.g. catalysts
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4078—Means for sealing the sensor element in a housing

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  • Measuring Oxygen Concentration In Cells (AREA)

Abstract

The present invention relates to humidity detection sensors under a kind of high temperature comprising: oxygen ion conductor solid electrolyte and proton conductor solid electrolyte, wherein the proton conductor solid electrolyte is with CaZr1‑ xMxO3For substrate, wherein M be selected from In, Ga and Sc at least one, 0 x≤0.05 <.Oxygen ion conductor solid electrolyte and proton conductor solid electrolyte group unify a cavity, and the one side of described two solid electrolytes towards cavity covers porous platinum/Silver Electrode and is electrically conducted, described two solid electrolytes cover electrode in contrast to the one side of cavity, and draw guiding respectively for being electrically connected with electrochemical workstation.The cavity is also inserted into a conduit, and cavity is inserted into one end of conduit, and the other end extends to the direction far from the cavity, and the conduit is as diffusion barrier and tested gas connection.The invention further relates to the preparation method and application of humidity detection sensor under the high temperature.The present invention can be used for monitoring the humidity of mixed gas at 600~800 DEG C.

Description

Humidity detection sensor and its preparation method and application under a kind of high temperature
Technical field
It is especially a kind of for measuring the electrochemical sensor of nitrogen content the present invention relates to electrochemical sensor technology field And preparation method thereof.
Background technique
Online accurate monitoring humidity is an important task in industrial processes.The humidity of country's independent research at present Electrochemical sensor is considerably less, and main part still comes from foreign countries.European patent EP 2275806B1 discloses a kind of humidity biography Sensor, including the PSS:H of the first Ti membrane electrode and Ti film second electrode and sandwiched between the first electrode and the second electrode are solid The solid electrolyte of body electrolyte and the Si/SiO2 except the 2nd Ti membrane electrode.The electrochemical sensor is to rely on folder Poly- (styrene sulfonic acid) acid of thickness about 80nm between two Ti membrane electrodes) or the polyanions polyelectrolyte such as PSS:H, shape At vertical capacitor structure or impedance variety structure, with Impedance Analysis in relative humidity.In use, by the electrochemical sensor Other capacitors and inductor are connected to form resonance circuit, read humidity level by monitoring resonance frequency.But this is wet Spending sensor is usually the humidity detection being used under room temperature, and the polyanions polyelectrolyte such as PSS:H decomposes at high temperature, thus Humidity detection under temperature contour for several Baidu, then can not be applicable in.
Summary of the invention
(1) technical problems to be solved
In order to overcome the above technical problems, it the object of the present invention is to provide humidity detection sensor under a kind of high temperature, is used for Monitor under high temperature, usually at 600~800 DEG C water vapour content electrochemical sensor, the electrochemical sensor structure is simple, Its cell reaction process is simpler, stable working performance and accuracy height.Moreover, it relates to which humidity is supervised under a kind of high temperature Survey the preparation method and application of sensor.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses include:
Humidity detection sensor under a kind of high temperature comprising: oxygen ion conductor solid electrolyte and proton conductor solid electricity Xie Zhi, wherein the proton conductor solid electrolyte is with CaZr1-xMxO3For substrate, wherein M is selected from In, Ga and Sc at least within One of, 0 x≤0.05 <；
The oxygen ion conductor solid electrolyte and the proton conductor solid electrolyte group unify a cavity, the oxygen from The one side of sub- conductor solid electrolyte towards the cavity is first surface, and the one side in contrast to the cavity is second surface；
The one side of the proton conductor solid electrolyte towards the cavity is third surface, in contrast to the one of the cavity Face is the 4th surface；
Wherein, the first surface and third surface are all covered with porous platinum/Silver Electrode and to be electrically connected；Described Two surfaces and the 4th surface are all covered with external electrode；
The cavity is inserted into a conduit, and the cavity is inserted into one end of the conduit, and the other end is to far from the cavity Direction extend, the conduit is as diffusion barrier and tested gas connection.Wherein it is preferred to which the conduit is a capillary.
Preferably, the oxygen ion conductor solid electrolyte is Y2O3, CaO or MgO doping ZrO2Based solid electrolyte； Or it is
Y2O3The ThO of doping2Based solid electrolyte；Or it is
Sm2O3Or Pr2O3The CeO of doping2Based solid electrolyte.
Preferably, external electrode set by the second surface and the 4th surface is platinum film electrode or Silver Electrode.
Preferably, the second surface passes through platinum conducting wire with external electrode set by the 4th surface respectively or silver wire is connect At the both ends of electrochemical workstation.
Preferably, porous platinum/Silver Electrode that the first surface is covered with third surface is led using platinum conducting wire or silver Line is electrically connected.
Preferably, the cavity that the oxygen ion conductor solid electrolyte and proton conductor solid electrolyte are composed, institute The seam crossing stated on cavity is sealed with ceramic glaze.
Preferably, proton conductor solid electrolyte is CaZr1-xInxO3, wherein 0 x≤0.05 <, it is highly preferred that the x =0.05.
The present invention also provides a kind of preparation methods of humidity detection sensor under high temperature, which comprises
S1: pressing step: by oxygen ion conductor solid electrolyte powder substrate and proton conductor solid electrolyte powder base Material compacting, obtains oxygen ion conductor solid electrolyte green body and proton conductor solid electrolyte green body, wherein proton conductor solid Electrolyte substrate is CaZr1-xMxO3, wherein M be selected from In, Ga and Sc at least one, 0 x≤0.05 <；
S2: sinter molding step: the S1 green body suppressed is sintered at high temperature, respectively obtains oxygen ion conductor solid electrolysis Matter and proton conductor solid electrolyte；
S3: coating platinum slurry or silver paste: by oxygen ion conductor solid electrolyte made from step S2 and proton conductor solid electricity The interior lateral surface of solution matter is coated with platinum slurry or silver paste, and the platinum slurry or silver paste are mixed by platinum powder, silver powder with film forming polymer lotion Slurrying；
S4: high-temperature calcinations step: under aerobic environment, by the obtained oxygen ion conductor solid electrolyte of step S3 and proton Conductor solid electrolyte is calcined at high temperature, leaves hole, platinum slurry or silver after making the film forming polymer oxidation in platinum slurry or silver paste Slurry becomes the porous platinum/Silver Electrode combined closely with oxygen ion conductor solid electrolyte and proton conductor solid electrolyte；
S5: assembling steps: being combined into a cavity for oxygen ion conductor solid electrolyte and proton conductor solid electrolyte, will The oxygen ion conductor solid electrolyte and proton conductor solid electrolyte towards the cavity side porous platinum/Silver Electrode into Row is electrically connected；A conduit is inserted on the cavity, the cavity is inserted into one end of the conduit, and the other end is to far from institute The direction for stating cavity extends.By the conduit as diffusion barrier and tested gas connection, diffusion barrier can prevent the cavity Tested gas constantly spreads mobile and causes measured value unstable in tested process.
Preferably, in step S1, proton conductor solid electrolyte is CaZr1-xInxO3, wherein 0 x≤0.05 <, more preferably Ground, the x=0.05, the proton conductor solid electrolyte powder substrate are to be prepared as follows:
According to CaZr1-xInxO3In each metallic element molar ratio weighing Ca (NO3)2、ZrO(NO3)2With In (NO3)3, 80 It is soluble in water at~95 DEG C, glycine and glycerol is then added, makes cation complex, ammonium hydroxide is added and is adjusted to neutrality, 190~ Violent evaporation at 210 DEG C reaches spontaneous combustion moment, forms the white powder of high degree of dispersion, collects white powder grinding, and 650 It is calcined at~750 DEG C to decompose organic matter therein, increasing calcining temperature to 900~1000 DEG C of decomposition CaCO therein3, decompose Fine powder is ground into after complete.Alternatively, according to CaZr1-xInxO3In each metallic element molar ratio weighing CaCO3、ZrO2And In2O3, will The CaCO of weighing3、ZrO2And In2O3It grinds and is uniformly mixed, in the case where there is oxygen atmosphere in 1000~1200 DEG C of 4~7h of calcining, obtain CaZr1-xInxO3Solid solution is ground into fine powder.
Preferably, in step S1, the oxygen ion conductor solid electrolyte substrate is Y2O3, CaO or MgO doping ZrO2 Based solid electrolyte；It or is Y2O3The ThO of doping2Based solid electrolyte；It or is Sm2O3Or Pr2O3The CeO of doping2Base solid electrolytic Matter.
Wherein it is preferred to which the oxygen ion conductor solid electrolyte substrate is Y2O3The zirconium oxide ZrO of doping2(YSZ), YSZ can be commercial goods or be prepared as follows:
According to the molar ratio weighing Y (NO of metallic element each in YSZ3)3·6H2O and ZrOCl2·8H2O is dissolved in water respectively In, ammonium hydroxide adjusting pH=9~10 are added under stiring and are co-precipitated, the sediment of presoma, sediment separate out, difference are obtained With distilled water and ethanol washing, colloidal presoma sediment is obtained, it is small that sediment is calcined to 1~10 at 700~850 DEG C When, obtain Y2O3The zirconia solid electrolyte YSZ of doping, grind into powder.Distilled water and ethanol washing, effect are mainly Remove Cl-Equal foreign ions, while reducing the agglomeration between sediment.
Preferably, in step S1, the pressing step is to lead oxygen ion conductor solid electrolyte powder substrate and proton For body solid electrolyte powder substrate in pressing mold, green body is made in 200~300Mpa of axial pressure.
Preferably, in step S2, the sinter molding step is sintered 5~10 hours at 1500 DEG C~1700 DEG C.By The solid electrolyte of sinter molding has ceramic performance, has very high intensity, and compactness is good.
Preferably, in step S3, the film forming polymer is PE, PP, CMC, PVC, PVA, PET, PVDF or PTFE.
Preferably, in step S4, the calcination temperature is 1000~1100 DEG C, and the time is 0.5h~2h.
Preferably, in step S5, processing is sealed using glass glaze or ceramic glaze to whole seams on the cavity.
The present invention also provides humidity detection sensors under a kind of high temperature in test high-temperature gas answering in water vapour content With comprising:
(1) the sensor external electrode is connected to the chem workstation comprising additional power source, to the cavity of sensor Inside be passed through the gas of multiple groups temperature and different humidity, applied voltage value be continuously improved, until the current value of sensor not with Voltage value is increased and is increased, this is carrying current；
(2) it draws under the temperature, carrying current-moisture curve；
(3) it is connected to tested gas with the conduit of the sensor, applied voltage value is continuously improved, until the electric current of sensor Value is not increased with voltage value and is increased, and current value at this time is the tested corresponding carrying current of gas, further according to step (2) Carrying current-moisture curve relationship obtains the humidity of tested gas.
In this application, carrying current defines: electric current no longer increases with the increase of applied voltage, and by ion/proton The rate for reaching electrode surface from bulk diffusion is controlled, and reaches a limiting value.
(3) beneficial effect
The beneficial effects of the present invention are:
Humidity detection sensor at a high temperature of the present invention, for measuring the humidity of gas under high temperature, and obtained limit electricity Stream-humidity matched curve is straight line, it is thus possible to which Accurate Determining is tested the humidity of gas.Its proton conductor solid electrolyte For CaZr1-xMxO3For substrate, wherein M be selected from In, Ga and Sc at least one, oxygen ion conductor solid electrolyte is preferably Y2O3The zirconium oxide ZrO of equal doping2, two kinds of solid electrolytes all have excellent thermal shock resistance, heat-resisting quantity, furthermore of the invention Sensor interfacial electrochemistry react very simple, fabulous job stability can be shown, therefore at a high temperature of the present invention Humidity detection sensor is that one kind has excellent performance humidity sensor, is existed particularly suitable in superhigh temperature production technology route to humidity Line monitoring.
Detailed description of the invention
Fig. 1 is the structure and schematic illustration of humidity detection sensor under a kind of high temperature of the invention.
Fig. 2 is the preparation method flow chart of humidity detection sensor under a kind of high temperature of the invention.
Fig. 3 is In2O3The CaZrO of doping3Proton conductor solid electrolyte SEM figure.
Fig. 4 is Y2O3Stable ZrO2Oxygen ion conductor solid electrolyte SEM figure.
Fig. 5 be 750 DEG C at the embodiment of the present invention sensor six different humidities (steam partial pressure 0.002atm, 0.030atm, 0.049atm, 0.101atm, 0.134atm, 0.168atm) under current-voltage relation curve figure.
Fig. 6 is to be fitted to obtain carrying current-humidity (steam partial pressure) graph of relation according to the test result of Fig. 5.
The sensor of the embodiment of the present invention is in four different temperatures (660 when Fig. 7 is humidity 0.063atm (steam partial pressure) DEG C, 690 DEG C, 720 DEG C, 750 DEG C) under current-voltage relation curve figure.
Fig. 8 is to be fitted to obtain carrying current-temperature curve figure according to the test result of Fig. 7.
Label symbol explanation:
10- sensor, 1- proton conductor solid electrolyte, 2- oxygen ion conductor solid electrolyte, 11- cavity, 5- are porous Platinum film electrode, 51- cavity inside conductor, 4- ceramic glaze, 3- conduit, 6- voltmeter, 7- ammeter, 8- additional power source, 9- external electrical Pole, 91- cavity outer conductor, first surface, second surface, third surface and the 4th surface of A, B, C, D- solid electrolyte.
Specific embodiment
In order to preferably explain the present invention, in order to understand, with reference to the accompanying drawing, by specific embodiment, to this hair It is bright to be described in detail.
It is shown in Figure 1, for the structure and work of humidity detection sensor under a kind of high temperature of present pre-ferred embodiments Schematic illustration.Humidity detection sensor 100 includes proton conductor solid electrolyte 1, oxygen ion conductor solid under its high temperature Electrolyte 2, porous platinum membrane electrode 5, capillary 3 and ceramic glaze 4.Wherein, proton conductor solid electrolyte 1 and oxygen ion conductor are solid Body electrolyte 2 is fired into half bowl-type respectively, is mutually butted into a cavity 11, and seam crossing is resistance to using ceramic glaze or glass glaze 4 etc. The sealed material of high temperature seals, and makes cavity 11 in addition to capillary 3, rest part is airtight.Proton conductor solid electrolyte 1 with CaZr1-xMxO3For substrate, wherein M be selected from In, Ga and Sc at least one, 0 x≤0.05 <, preferably CaZr1-xInxO3, It is highly preferred that x=0.05.Oxygen ion conductor solid electrolyte 2 is Y2O3, CaO or MgO doping ZrO2Based solid electrolyte or For Y2O3The ThO of doping2Based solid electrolyte is Sm2O3Or Pr2O3The CeO of doping2Based solid electrolyte；Preferably, oxonium ion Conductor solid electrolyte 2 is Y2O3The ZrO of doping2Based solid electrolyte YSZ.Oxygen ion conductor solid electrolyte 2 is towards cavity 11 One side be first surface A, the one side in contrast to the cavity is second surface B, and proton conductor solid electrolyte 1 is towards cavity 11 one side is third surface C, and the one side in contrast to cavity 11 is the 4th surface D.It is covered on first surface A and third surface C It is stamped porous platinum membrane electrode 5, covering is equipped with external electrode 9 on second surface B and the 4th surface D.Wherein porous platinum membrane electrode 5 It can be replaced porous Silver Electrode, external electrode 9 equally can be platinum film layer/silver external electrode, and two external electrodes 9 pass through extraction Cavity outer conductor 91 can be electrically connected with the both ends of electrochemical workstation.First surface A and the porous platinum of third surface C electricity Conducting wire 51 is electrically connected in transit chamber body between pole 5, which is platinum conducting wire or silver wire.Capillary 3 is inserted by a perforation Enter in the cavity 11, and the seam crossing of the capillary 3 and the cavity 11 also uses glass glaze or ceramic glaze 4 to seal.In cavity 11 The porous platinum electrode 5 covered in first surface A and third surface C or porous silver electrode surface have several apertures, into cavity Tested gas in 11 can directly be contacted with proton conductor solid electrolyte 1, oxygen ion conductor solid electrolyte 2, and in height Electrochemical reaction is occurred for catalyst with the silver in the platinum or porous Silver Electrode in porous platinum electrode 5 under temperature.
Electrochemical workstation includes voltmeter 6, ammeter 7 and additional power source 8, and the positive transit chamber of additional power source 8 is external Conducting wire 91 is connected to 2 external electrode 9 of oxygen ion conductor solid electrolyte, and the external conducting wire 91 of the cathode transit chamber of additional power source 8 connects It is connected to 1 external electrode 9 of proton conductor solid electrolyte.
Water vapour into cavity 11 connects through the hole on porous platinum electrode 5 with proton conductor solid electrolyte 1 Touching, is catalyst with platinum/silver, and electrochemical reaction occurs:
H2O→2H++2e+1/2O2；(Formulas I)
Water vapour in cavity 11 is contacted through the hole of porous platinum electrode 5 with oxygen ion conductor solid electrolyte 2, with Platinum/silver is catalyst, and electrochemical reaction occurs:
H2O+2e→O2-+H2；(Formula II)
Since proton conductor solid electrolyte 1 connects the cathode of additional power source 8, the proton (2H of generation+) led across proton Body solid electrolyte 1 is moved to the 4th surface D from third surface C, then the external conducting wire 91 of transit chamber returns to the negative of additional power source 8 Pole, the electronics (2e) that the electrochemical reaction on 1 surface of proton conductor solid electrolyte generates pass through under the action of additional power source 8 Cavity inside conductor 51 is supplied to oxygen ion conductor solid electrolyte 2 (Formulas I).
Oxygen ion conductor solid electrolyte 2 receives the electronics (2e) from proton conductor solid electrolyte 1, generates negatively charged O2-.Since oxygen ion conductor solid electrolyte 2 connects the anode of additional power source 8, the O generated2-In the work of additional power source 8 It is moved to second surface B from first surface A across oxygen ion conductor solid electrolyte 2 with lower, then the external conducting wire 91 of transit chamber returns To the anode of additional power source 8, it is thusly-formed circuit loop (Formula II).
It is shown in Figure 2, for the preparation method stream of humidity detection sensor under a kind of high temperature of present pre-ferred embodiments Cheng Tu.
S1: pressing step: by oxygen ion conductor solid electrolyte powder substrate and proton conductor solid electrolyte powder base Material compacting, obtains oxygen ion conductor solid electrolyte green body and proton conductor solid electrolyte green body, wherein proton conductor solid Electrolyte substrate is CaZr1-xMxO3, wherein M be selected from In, Ga and Sc at least one, 0 x≤0.05 <.
Compacting is to press oxygen ion conductor solid electrolyte powder substrate and proton conductor solid electrolyte powder substrate In mould, green body is made in 200~300Mpa of axial pressure.
Wherein, proton conductor solid electrolyte powder substrate is preferably CaZr1-xInxO3, wherein 0 x≤0.05 <, more preferably Ground, the x=0.05 are made according to the optional one of the following two kinds mode:
First method, glycine-nitroglycerin combustion synthesis method: according to CaZr1-xInxO3In each metallic element mole Than weighing Ca (NO3)2、ZrO(NO3)2With In (NO3) 3, it is soluble in water (at about 80~95 DEG C) in the hot water, sweet ammonia is then added Acid and glycerol make cation complex, and ammonium hydroxide is added and is adjusted to neutrality, is heated to violent evaporation at 190~210 DEG C, reaches spontaneous combustion Moment forms the white powder of high degree of dispersion after burning, collect white powder grinding, and calcine at 650~750 DEG C to decompose Organic matter therein, increasing calcining temperature to 900~1000 DEG C of decomposition CaCO therein3, fine powder is ground into after having decomposed.
Second method, high temperature solid phase synthesis: according to CaZr1-xInxO3In each metallic element molar ratio weighing CaCO3、ZrO2And In2O3, by the CaCO of weighing3、ZrO2And In2O3Grind and be uniformly mixed, in the case where there is oxygen atmosphere in 1000~ 1200 DEG C of 4~7h of calcining, obtain CaZr1-xInxO3Solid solution is ground into fine powder.
In there is experiment, according to above-mentioned the first or second of synthetic method, determines x=0.05, calculate each raw material CaZr is made in molar ratio0.95In0.05O3Solid electrolyte powder material, SEM figure are shown in Figure 3.
Wherein, oxygen ion conductor solid electrolyte substrate is Y2O3, CaO or MgO doping ZrO2Based solid electrolyte；Or For Y2O3The ThO of doping2Based solid electrolyte；It or is Sm2O3Or Pr2O3The CeO of doping2Based solid electrolyte.Preferably, oxygen from Sub- conductor solid electrolyte substrate is YSZ, and YSZ can be commercial goods or be prepared as follows:
According to the molar ratio weighing Y (NO of metallic element each in YSZ3)3·6H2O and ZrOCl2·8H2O is dissolved in water respectively In, ammonium hydroxide adjusting pH=9~10 are added under stiring and are co-precipitated, the sediment of presoma, sediment separate out, difference are obtained With distilled water and ethanol washing, colloidal presoma sediment is obtained, it is small that sediment is calcined to 1~10 at 700~850 DEG C When, proper electrolyte YSZ is ground into powder.
In there is experiment, according to above-mentioned preparation process, make Y element and the molar ratio 8:92, Y obtained of Zr2O3Stablize ZrO2YSZ solid electrolyte powder material, SEM is shown in Figure 4.
S2: sinter molding step: the S1 green body suppressed is sintered at high temperature, respectively obtains oxygen ion conductor solid electrolysis Matter and proton conductor solid electrolyte.
Wherein, sinter molding is sintered 5~10 hours at 1500 DEG C~1700 DEG C.Solid electrolyte tool by sinter molding Standby ceramic performance, has very high intensity, and compactness is good.
S3: coating platinum slurry or silver paste: by oxygen ion conductor solid electrolyte made from step S2 and proton conductor solid electricity The interior lateral surface of solution matter is coated with platinum slurry or silver paste, and the platinum slurry or silver paste are mixed by platinum powder, silver powder with film forming polymer lotion Slurrying.Wherein, film forming polymer PE, PP, CMC, PVC, PVA, PET, PVDF or PTFE.
S4: high-temperature calcinations step: under aerobic environment, by the obtained oxygen ion conductor solid electrolyte of step S3 and proton Conductor solid electrolyte is calcined at high temperature, leaves hole, platinum slurry or silver after making the film forming polymer oxidation in platinum slurry or silver paste Slurry becomes the porous platinum/Silver Electrode combined closely with oxygen ion conductor solid electrolyte 2 and proton conductor solid electrolyte 1, As shown in Figure 1, including porous platinum/Silver Electrode 9 outside the porous platinum/Silver Electrode 5 and cavity 11 in cavity 11.Its In, calcination temperature is 1000~1100 DEG C in this step, and the time is 0.5h~2h.
S5: the assembling steps (in conjunction with Fig. 1) of sensor 10: by oxygen ion conductor solid electrolyte 2 and proton conductor solid Electrolyte 1 is combined into a cavity 11, by oxygen ion conductor solid electrolyte 2 and proton conductor solid electrolyte 1 towards the cavity Porous platinum/Silver Electrode 5 of 11 sides is electrically connected using cavity inside conductor 51 (preferably platinum conducting wire), inserts on cavity 11 Enter a capillary 3, one end of capillary 3 is inserted into cavity 11, and the other end of conduit extends to the direction far from cavity 11.? Diffusion barrier and tested gas connection of the capillary 3 as gas, diffusion barrier can prevent tested gas in tested process It constantly spreads mobile and causes measured value unstable.Wherein, to whole seams on cavity 11 using glass glaze or ceramic glaze 4 into Row encapsulation process, seam crossing and capillary 3 including oxygen ion conductor solid electrolyte 2 and proton conductor solid electrolyte 1 exist The splicing position of cavity 11 is all sealed with ceramic glaze etc..Ceramic glaze has high temperature resistant and good airproof performance, with oxygen ion conductor solid electricity The characteristics of solution matter 2 and proton conductor solid electrolyte 1 can be consolidated closely.Wherein porous platinum/Silver Electrode 9 outside cavity 11 draws Two cavity outer conductors 91 out, for being connected to the both ends of additional power source 8 or electrochemical workstation.
The following are concrete application examples
Application examples 1
According to aforementioned preparation process, sensor 10 as shown in Figure 1 is assembled, wherein proton conductor solid electrolyte 1 is CaZr 0.95In0.05O3, oxygen ion conductor solid electrolyte 2 is YSZ (yttrium oxide Y2O3Stable zirconium oxide ZrO2, wherein Y:Zr Molar ratio=8:92).
The sensor 10 prepared is placed in furnace, is heated to predetermined temperature (750 DEG C), and with difference in air atmosphere Steam partial pressure 0.002atm, 0.030atm, 0.049atm, 0.101atm, 0.134atm, 0.168atm tested.
In experimentation, dry air atmosphere (steam partial pressure=10-4It atm is) that air is generated by zeolite column.It is wet Air atmosphere (steam partial pressure=0.025~0.110atm atmospheric pressure) bypasses air through water bubbler and is formed, the water Bubbler carries out temperature adjusting under assigned temperature.Finally, dry and wet air (steam partial pressure=0.025atm) is mixed, consider Corresponding flow velocity obtains air medium humidity (steam partial pressure=3*10-3atm).Feed tube heats and thorough at 110 DEG C Bottom isolation, to prevent water from condensing in test macro.
When sensor 10 is in defined T and pH2When (~1 hour) balance of O, start to measure.More precisely, constant is straight Galvanic electricity pressure (being provided by additional power source 8) is applied to the outer external electrode 9 of cavity of sensor 10 (see Fig. 1).At this point, electric current is in electricity Occur in road, causes one group of electrochemical reaction.The applied voltage and current value applied is by 2550 constant currents of AMEL/constant potential Instrument control system, according to the voltage and current value measured, drafting obtains at as shown in Figure 5 750 DEG C, steam partial pressure 0.002atm, Current-voltage relation curve figure under 0.030atm, 0.049atm, 0.101atm, 0.134atm, 0.168atm is distinguished from Fig. 5 6 carrying current values for obtaining under six groups of difference steam partial pressures (gently locate, and electric current no longer increases with applied voltage by the upper right of curve Carrying current is corresponded to when adding and increasing).
With the increase of additional power source voltage value, then electric current, which starts to increase, gradually to be tended to stablize, and reaches a stationary value, That is carrying current (Ilim), carrying current indicates the stable condition for having reached the complete electrochemical decomposition of water vapour.In steam partial pressure When less than 0.1atm, carrying current (Ilim) it is as follows with the relationship of external parameter T:
Wherein, pH2O indicates steam partial pressure, wherein S, and L indicates that the internal diameter and length of capillary 3, T indicate absolute temperature (determining value), F is Faraday constant, and R is universal gas constant, D0(H2O) indicate water vapour in T0=273.15K, P0=1atm When diffusion coefficient, n is the empirical coefficient changed in 1.5~2 ranges.
Above-mentioned equation expression, steam partial pressure pH2O can be by drawing carrying current (Ilim) with the mark of steam partial pressure Directrix curve determines.
The 6 carrying current values obtained according to Fig. 5 draw carrying current-humidity (steam partial pressure) line as shown in FIG. 6 Sexual intercourse figure.Using Fig. 6 as standard curve, makes to be passed through the tested gas of analysis in 10 cavity 11 of sensor, increase outer power-up step by step Pressure, reads carrying current value, and steam partial pressure can be analyzed to obtain by linear dependence.
In conclusion the operating process that sensor of the invention is used to measure the humidity of gas under certain high temperature is as follows:
(1) the sensor external electrode is connected to the chem workstation comprising additional power source, to the cavity of sensor Inside be passed through the gas of multiple groups temperature and different humidity, applied voltage value be continuously improved, until the current value of sensor not with Voltage value is increased and is increased, this is carrying current；
(2) it draws under the temperature, carrying current-moisture curve；
(3) it is connected to tested gas with the conduit of the sensor, applied voltage value is continuously improved, until the electric current of sensor Value is not increased with voltage value and is increased, and current value at this time is the tested corresponding carrying current of gas, further according to step (2) Carrying current-moisture curve relationship obtains the humidity of tested gas.
Application examples 2
As shown in fig. 7, being passed through known humidity mixed gas, steam partial pressure pH in 10 cavity 11 of sensor2O= 0.063atm (steam partial pressure) sensor 10 is added in furnace respectively to 660 DEG C, 690 DEG C, 720 DEG C, 750 DEG C, each It under a temperature, gradually adjusts and additional power source voltage value (being provided by DC power supply 8) is provided, electric current starts to increase then gradually Tend to stablize, reaches a stationary value, i.e. carrying current (Ilim), it is completely electrochemical that carrying current expression has reached water vapour at this time The stable condition of credit solution.Test voltage and current value, draw sensor four different temperatures (660 DEG C, 690 DEG C, 720 DEG C, 750 DEG C) current-voltage relation curve figure, by obtaining corresponding current value when curve tends towards stability in figure, i.e. limit electricity Flow (Ilim)。
Carrying current (I under four different temperatures (660 DEG C, 690 DEG C, 720 DEG C, 750 DEG C) obtained according to Fig. 7lim), Draw carrying current as shown in Figure 8-temperature linearity relational graph.Using Fig. 8 as standard curve, make to be passed through in 10 cavity 11 of sensor The tested gas of analysis, increases applied voltage step by step, and reading carrying current value can be led in the case that steam partial pressure determines Linear dependence is crossed to analyze to obtain temperature.

Claims (10)

1. humidity detection sensor under a kind of high temperature, characterized in that it comprises:
Oxygen ion conductor solid electrolyte and proton conductor solid electrolyte, wherein the proton conductor solid electrolyte be with CaZr1-xMxO3For substrate, wherein M be selected from In, Ga and Sc at least one, 0 x≤0.05 <；
The oxygen ion conductor solid electrolyte and the proton conductor solid electrolyte group unify a cavity, and the oxonium ion is led The one side of body solid electrolyte towards the cavity is first surface, and the one side in contrast to the cavity is second surface；
The one side of the proton conductor solid electrolyte towards the cavity is third surface, and the one side in contrast to the cavity is 4th surface；
Wherein, the first surface and third surface are all covered with porous platinum/Silver Electrode and to be electrically connected；Second table Face and the 4th surface are all covered with external electrode；
The cavity is inserted into a conduit, and the cavity is inserted into one end of the conduit, and the other end is to the side far from the cavity To extension, the conduit is as diffusion barrier and tested gas connection.
2. humidity detection sensor under high temperature according to claim 1, which is characterized in that the oxygen ion conductor solid electricity Solution matter is Y2O3, CaO or MgO doping ZrO2Based solid electrolyte；It or is Y2O3The ThO of doping2Based solid electrolyte；Or it is Sm2O3Or Pr2O3The CeO of doping2Based solid electrolyte.
3. humidity detection sensor under high temperature according to claim 1 or 2, which is characterized in that the second surface and External electrode set by four surfaces is platinum film electrode or Silver Electrode.
4. humidity detection sensor under high temperature according to claim 3, which is characterized in that the second surface and the 4th table External electrode set by face passes through platinum conducting wire respectively or silver wire is connected to the both ends of electrochemical workstation.
5. humidity detection sensor under high temperature according to claim 1 or 2, which is characterized in that the first surface and Porous platinum/Silver Electrode that three surfaces are covered is electrically connected using platinum conducting wire or silver wire.
6. humidity detection sensor under high temperature according to claim 1, which is characterized in that the oxygen ion conductor solid electricity Solution matter and the cavity that is composed of proton conductor solid electrolyte, the seam crossing on the cavity are sealed with ceramic glaze.
7. the preparation method of humidity detection sensor under a kind of high temperature, which is characterized in that the described method includes:
S1: pressing step: by oxygen ion conductor solid electrolyte powder substrate and proton conductor solid electrolyte powder substrate pressure System, obtains oxygen ion conductor solid electrolyte green body and proton conductor solid electrolyte green body, wherein proton conductor solid electrolytic Matter substrate is CaZr1-xMxO3, wherein M be selected from In, Ga and Sc at least one, 0 x≤0.05 <；
S2: sinter molding step: by S1 suppress green body be sintered at high temperature, respectively obtain oxygen ion conductor solid electrolyte and Proton conductor solid electrolyte；
S3: coating platinum slurry or silver paste: by oxygen ion conductor solid electrolyte made from step S2 and proton conductor solid electrolyte Interior lateral surface be coated with platinum slurry or silver paste, platinum slurry or silver paste are by platinum powder, silver powder and film forming polymer lotion mixed pulp；
S4: high-temperature calcinations step: under aerobic environment, by the obtained oxygen ion conductor solid electrolyte of step S3 and proton conductor Solid electrolyte is calcined at high temperature, leaves hole after making the film forming polymer oxidation in platinum slurry or silver paste, platinum slurry or silver paste become At the porous platinum/Silver Electrode combined closely with oxygen ion conductor solid electrolyte and proton conductor solid electrolyte；
S5: assembling steps: being combined into a cavity for oxygen ion conductor solid electrolyte and proton conductor solid electrolyte, will be described Oxygen ion conductor solid electrolyte and porous platinum/Silver Electrode of proton conductor solid electrolyte towards the cavity side carry out electricity Property connection；A conduit is inserted on the cavity, the cavity is inserted into one end of the conduit, and the other end is to far from the chamber The direction of body extends.
8. preparation method according to claim 7, in step S1, proton conductor solid electrolyte is CaZr1-xInxO3, In 0 x≤0.05 <；The oxygen ion conductor solid electrolyte substrate is Y2O3The ZrO of doping2Based solid electrolyte YSZ.
9. preparation method according to claim 7, in step S5, to whole seams on the cavity using glass glaze or Ceramic glaze is sealed processing.
10. application of the humidity detection sensor in test high-temperature gas in water vapour content under a kind of high temperature, which is characterized in that Comprising steps of
(1) the sensor external electrode is connected to the chem workstation comprising additional power source, led into the cavity of sensor Enter the gas of multiple groups temperature and different humidity, applied voltage value is continuously improved, until the current value of sensor is not with voltage Value is increased and is increased, this is carrying current；
(2) it draws under the temperature, carrying current-moisture curve；
(3) be connected to tested gas with the conduit of the sensor, applied voltage value be continuously improved, until sensor current value not It increases and increases with voltage, current value at this time is the tested corresponding carrying current of gas, further according to the limit electricity of step (2) Stream-moisture curve relationship obtains the humidity of tested gas.
CN201811072120.7A 2018-09-14 2018-09-14 Humidity detection sensor and its preparation method and application under a kind of high temperature Pending CN109115857A (en)

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