CN106770583A - The method that rotary coating prepares limit-current type oxygen sensor dense diffusion barrier - Google Patents
The method that rotary coating prepares limit-current type oxygen sensor dense diffusion barrier Download PDFInfo
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Abstract
A kind of method that rotary coating prepares limit-current type oxygen sensor dense diffusion barrier, belongs to sensor of chemical gas technical field.The method includes：Dissolve the binder in solvent, constitute organic carrier, LSM is dispersed in organic carrier, dense diffusion barrier slurry LSM is obtained；Wherein, in mass ratio, LSM: solvent: binding agent=(2~6): (5~10): (0.01~0.05)；1~10min is rotated with 1000~10000r/min with rotary coating instrument, dense diffusion barrier slurry is coated uniformly on YSZ surfaces, then dried, obtain dry surface with one layer of solid electrolyte of dense diffusion barrier；5~7h, prepared coating limit-current type oxygen sensor dense diffusion barrier on the solid electrolyte are sintered at 1000~1600 DEG C.Dense diffusion barrier prepared by the method, its dense structure is uniform, fine and close, and pore-free, diffusion barrier layer is high with the bond strength of matrix, and thickness is accurately controlled, and the manufacturing cycle is short.
Description
Technical field
The present invention relates to sensor of chemical gas technical field, specially a kind of rotary coating prepares limit-current type oxygen biography
The method of sensor dense diffusion barrier.
Background technology
In the industry such as automobile, metallurgy, energy, using electrochemical sensor is online, real-time monitoring oxygen concentration is that one kind has
The method of effect.Electrochemical sensor can be divided into two kinds of concentration cell type and limit-current type according to the difference of operation principle, compare
For, limit-current type compensate for the concentration cell type deficiency low to fuel-poor region low-response, sensitivity, with the response time it is short,
Sensitivity is high, long lifespan, without reference gas the advantages of.Limit-current type oxygen sensor is divided into pinhole type, porous type and densification
Diffusion Barrier stratotype, wherein, pinhole type is involved great expense, and the phenomenon that aperture clogs deformation occurs is used for a long time；Though porous type
So prepare relatively easy, but porosity is difficult to control to, and long-term use can be led because of the pollution of the particulate matter such as dust in atmosphere to be measured
Gas permeability is caused to deteriorate, so that the performance and used life of lambda sensor is influenceed, therefore pinhole type and porous type limit-current type oxygen
Sensor is restricted in actual applications.Can be overcome as dense diffusion barrier using oxonium ion-electron mixed conductor
The shortcoming of pinhole type and porous type, is not in use the problem of pore plugging, and service behaviour is more stablized, used
Time is longer.In recent years, the research of dense diffusion barrier limit-current type oxygen sensor becomes new focus, its cross-section structure
Schematic diagram is as shown in figure 1, its composition includes positive and negative electrode layer, dense diffusion barrier, solid electrolyte layer and elevated-temperature seal glass
Glass glaze.
Domestic and international research worker is carried out to the preparation method of the dense diffusion barrier in limit-current type oxygen sensor
Many research work, respectively with Y2O3The ZrO of stabilization2(abbreviation YSZ) is solid electrolyte, by using magnetron sputtering, silk screen
Printing film forming (thick film coating), Co-sintering, discharge plasma sintering and ceramics the method such as are combined and are prepared for limit-current type
Lambda sensor dense diffusion barrier.Garzom et al. is respectively with La0.84Sr0.16MnO3And La (LSM)0.8Sr0.2CoO3(LSC)
As dense diffusion barrier, lambda sensor is prepared for using magnetron sputtering and silk-screen printing film technique.Because oxonium ion is moved
Shifting rate is higher, and dense diffusion barrier thickness prepared by magnetron sputtering method is again very thin, causes lambda sensor oxygen determination scope narrower；And
Though the silk-screen printing film technique of use increased the thickness of dense diffusion barrier, in slurry in high-temperature sintering process
Organic matter can cause many micropores, cause the consistency of dense diffusion barrier and reduce.Xia Hui et al. is with LSM as dense diffusion barrier
Hinder layer, lambda sensor is prepared for using Co-sintering method.Thermal coefficient of expansion, sintering shrinkage mismatch because of LSM and YSZ,
And cause sintered body to occur crackle during co-sintering, influence the diffusion of oxonium ion.Zou Jie et al. respectively with LSM,
La0.75Sr0.25Cr0.5Mn0.5O3Etc. (LSCM) it is dense diffusion barrier, is prepared for using discharge plasma sintering (SPS) technology
Lambda sensor.Because LSM is easily reduced in SPS sintering engineerings by C, the thermal coefficient of expansion of LSCM and YSZ is mismatched and causes sintering
Body ftractures, therefore oxygen determination performance is undesirable.Liu Tao et al. is with Sr1-xYxCoO3-δIt is dense diffusion barrier, with
La0.8Sr0.2Ga0.83Mg0.17O2.815(LSGM) be solid electrolyte, lambda sensor be prepared for using ceramics composite algorithm, obtain compared with
Good oxygen determination characteristic, but the method preparation process is cumbersome, the cycle is long, and also dense diffusion barrier prepared by conventional sintering contains
There is increased number of stomata.
Spin coating technique refers to the addition dense diffusion barrier coating on solid electrolyte matrix surface, using rotation
The centrifugal force of generation is coated in the surface of matrix with making coating uniform, and dense diffusion barrier is made by technical process such as drying, sintering
Hinder the method that layer coating and solid electrolyte matrix are combined together, finally assembling forms dense diffusion barrier limit-current type
Lambda sensor.
The content of the invention
The present invention is proposed for the deficiency in the existing dense diffusion barrier technology for preparing limit-current type oxygen sensor
A kind of method that utilization spin coating method prepares limit-current type oxygen sensor dense diffusion barrier.Prepared by the method
Dense diffusion barrier, its dense structure is uniform, fine and close, pore-free, the combination of diffusion barrier layer and solid electrolyte matrix
Intensity is high, and thickness is accurately controlled, and the manufacturing cycle is short.
The method that a kind of rotary coating of the invention prepares limit-current type oxygen sensor dense diffusion barrier, including with
Lower step：
Step 1, gets the raw materials ready
Dissolve the binder in solvent, organic carrier is constituted, by La1-xSrxMnO3(LSM) it is dispersed in organic carrier
In, dense diffusion barrier slurry La is obtained1-xSrxMnO3, wherein, x is 0.16~0.3；Wherein, in mass ratio, fine and close diffusion
Barrier layer powder La1-xSrxMnO3: solvent: binding agent=(2~6): (5~10): (0.01~0.05)；
Described solvent is one or more in the saturating alcohol of turpentine oil, sec-octyl alcohol, ethylene glycol or acetone；
Described binding agent is one or more in ethyl cellulose, methylcellulose or hydroxyethyl cellulose.
Step 2, rotary coating
Dense diffusion barrier slurry rotary coating instrument is coated uniformly on Y2O3The ZrO of stabilization2(YSZ) solid electrolytic
Matter surface, obtains surface with one layer of solid electrolyte of dense diffusion barrier；Wherein, the rotary coating work of rotary coating instrument
Skill parameter is：Rotation revolution is 1000~10000r/min, and rotational time is 1~10min, and coating number of times is 1~5 time；
Step 3, dries
The solid electrolyte that surface has one layer of dense diffusion barrier is dried, after drying completely, drying is obtained
Surface afterwards has one layer of solid electrolyte of dense diffusion barrier；
Step 4, sintering
The solid electrolyte that dried surface has one layer of dense diffusion barrier is sintered, is cooled to after sintering
Room temperature, prepared coating limit-current type oxygen sensor dense diffusion barrier on the solid electrolyte.
In described step 1, described binding agent dissolving is dissolved using heating water bath in a solvent, and heating-up temperature is 70
~100 DEG C.
In described step 1, described dense diffusion barrier powder is prepared, the preparation method using sol-gal process
Obtained dense diffusion barrier powder purity is high, impurity content is few.
In described step 3, described dry drying equipment is drying box, and drying temperature is 70~90 DEG C, when drying
Between be more than 24h；
In described step 4, described sintering, agglomerating plant is high temperature furnace, and sintering temperature is 1000~1600 DEG C, sintering
Time is 5~7h；
In described step 4, described is cooled to room temperature to cool to room temperature with the furnace.
The coating of preparation limit-current type oxygen sensor dense diffusion barrier on the solid electrolyte, dense diffusion barrier
Hinder thickness≤50 μm of layer.
The solid electrolyte for being coated with dense diffusion barrier is assembled into lambda sensor, after tested, oxygen determination scope be 0~
8.4vol%.
The method that rotary coating of the invention prepares limit-current type oxygen sensor dense diffusion barrier, compared to existing
Technology, its advantage is：
1. the dense diffusion barrier for being prepared using spin coating technique of the invention, its dense structure is uniform, pore-free,
Dense diffusion barrier is high with solid electrolyte substrate combinating strength, and width and thickness are accurately controlled, and can make solid electricity
The heat affected area scope and deformation for solving matter matrix are minimized by, and the manufacturing cycle is short.
2. the lambda sensor that the dense diffusion barrier for being prepared using the present invention is assembled with solid electrolyte, it is possible to increase oxygen
The oxygen determination scope of sensor and the stability and reappearance of transducing signal.
Brief description of the drawings
Fig. 1 is the structural representation of common dense diffusion barrier limit-current type oxygen sensor；
Wherein, 1 is negative electrode, and 2 is dense diffusion barrier, and 3 is solid electrolyte, and 4 is anode, and 5 is elevated-temperature seal glass
Glaze；
Fig. 2 cuts for limit-current type oxygen sensor dense diffusion barrier prepared by the rotary coating of the embodiment of the present invention 1
The SEM figures in face；
Fig. 3 is the SEM figures of dense diffusion barrier prepared by conventional sintering method；
Fig. 4 is the oxygen determination I-V curve of the lambda sensor of dense diffusion barrier composition prepared by the embodiment of the present invention 1.
Specific embodiment
With reference to embodiment, the present invention is described in further detail.
The structural representation of common dense diffusion barrier limit-current type oxygen sensor is shown in Fig. 1, wherein, 1 is negative electrode,
2 is dense diffusion barrier, and 3 is solid electrolyte, and 4 is anode, and 5 is elevated-temperature seal glass glaze.
In following examples, dense diffusion barrier raw powder's production technology specifically includes following steps：
(1) in molar ratio, La (NO3)3∶Sr(NO3)2∶Mn(NO3)2=(1-x): x: 1 carries out dispensing；
(2) by La (NO3)3、Sr(NO3)2With Mn (NO3)2It is dissolved separately in deionized water, filters, removes insoluble miscellaneous
Matter obtains La (NO3)3The aqueous solution, Sr (NO3)2The aqueous solution and Mn (NO3)2The aqueous solution；Wherein, the addition of deionized water is can fill
Point dissolve each raw material be defined；
Three kinds of aqueous solution are mixed, mixed solution is obtained；Wherein, the addition of water is defined by that can dissolve each raw material；
(3) in mixed solution, complexing agent citric acid solution is added while stirring, after stirring, ammonia spirit is added dropwise,
Ethylene glycol being added simultaneously, when solution ph is 8.0~9.5, stopping that ammoniacal liquor is added dropwise, sol-gel precursor is obtained；
Wherein, the mass concentration of citric acid solution is 10~15%, and the mass concentration of ammonia spirit is 25~28%；Massage
You compare, metal cation in mixing: citric acid: ethylene glycol=1: 4.8: 1.2；
(4) sol-gel precursor is placed in drying box, 75~85 DEG C, is dried completely, obtained dried colloidal sol and coagulate
Glue presoma；
(5) dried sol-gel precursor is put into high temperature furnace, at 500~1000 DEG C, calcines 5~7h, be obtained
Dense diffusion barrier powder La1-xSrxMnO3Solid-solution powder；
(6) by dense diffusion barrier powder La1-xSrxMnO3Solid-solution powder be placed in agate mortar and be ground, grind
It is 2~3h to consume time, and refines powder and is well mixed, and prepared granularity is≤100 μm, the fine and close diffusion that purity is 99.99%
Barrier layer powder La1-xSrxMnO3。
In following examples, Y2O3The ZrO of stabilization2(YSZ) for solid electrolyte can be commercial 8YSZ or self-control.
Wherein, Y2O3The ZrO of stabilization2(YSZ) it is the synthetic method of solid electrolyte, comprises the following steps：
(1) in molar ratio, Y (NO3)3·6H2O∶ZrOCl2·8H2O=(7.5~10): (92.5~90) carry out dispensing,
Wherein, Y (NO3)3·6H2The molar concentration of O is 8-9mol%；
(2) by Y (NO3)3·6H2O and ZrOCl2·8H2O is dissolved separately in deionized water, filtering, is removed insoluble miscellaneous
Matter, is obtained Y (NO3)3The aqueous solution and ZrOCl2The aqueous solution；Wherein, the addition of deionized water is so that raw material fully dissolves is defined；
Two kinds of aqueous solution are mixed, mixed solution is obtained；The molar concentration of mixed solution is preferably 0.5~1.0mol/L；
(3) in mixed solution, ammonia spirit is added while stirring, when solution ph is 9, stop that ammoniacal liquor, system is added dropwise
Obtain presoma sediment；
Wherein, the concentration of ammoniacal liquor is 25~28wt.%；
(4) presoma sediment is placed in drying box, at 65~75 DEG C, dries more than 24h, after drying completely, be obtained dry
Presoma sediment after dry；
(5) dried presoma sediment is put into high temperature furnace, 5~7h is calcined at 500~1600 DEG C, electricity is obtained
Solve the solid-solution powder of matter；
(6) solid-solution powder of electrolyte is ground, milling time is 2~3h, refines powder and be well mixed it,
The YSZ powders of granularity≤100 μm are obtained；
Described grinding is carried out in agate mortar；
(7) by YSZ pressed by powder into diameter 8~12mm disks, 5~7h is sintered at 1000~1600 DEG C, solid electricity is obtained
Xie Zhi.
Embodiment 1
A kind of method that rotary coating prepares limit-current type oxygen sensor dense diffusion barrier, comprises the following steps：
Step 1, gets the raw materials ready
(1) ethyl cellulose and the saturating alcohol of turpentine oil are mixed, heating water bath is dissolved to 80 DEG C, after dissolving completely, is obtained
To organic carrier, by La0.84Sr0.16MnO3(LSM) it is dispersed in organic carrier, dense diffusion barrier slurry is obtained
La0.84Sr0.16MnO3；Wherein, in mass ratio, dense diffusion barrier powder La0.84Sr0.16MnO3: the saturating alcohol of turpentine oil: ethyl is fine
Dimension element=4: 7: 0.04；
Step 2, rotary coating
Dense diffusion barrier slurry rotary coating instrument is coated uniformly on 8YSZ solid electrolytes surface purchased in market, is obtained
Surface has one layer of solid electrolyte of dense diffusion barrier；Wherein, the spin coating process parameter of rotary coating instrument is：Rotation
Number walk around for 3000r/min, rotational time is 5min, coating number of times is 3 times, prefabricated thickness is 40 μm；
Step 3, dries
The solid electrolyte that surface has one layer of dense diffusion barrier is placed in drying box, is dried at 80 DEG C
24h, after drying completely, obtains dried surface with one layer of solid electrolyte of dense diffusion barrier；
Step 4, sintering
The solid electrolyte that dried surface has one layer of dense diffusion barrier is placed in high temperature furnace, is heated to
1200 DEG C of heat preservation sintering 6h, cool to room temperature with the furnace, and prepared coating limit-current type oxygen sensor on the solid electrolyte is caused
Close diffusion barrier layer, the thickness of dense diffusion barrier is 30 μm.Limit-current type oxygen sensor prepared by rotary coating is fine and close
Diffusion barrier layer, the SEM figures in its section are as shown in Figure 2, it can be seen that dense diffusion barrier dense structure is uniform, pore-free,
It is high with solid electrolyte substrate combinating strength, and it is fuzzy to demarcate between dense diffusion barrier and solid electrolyte；And it is traditional
Sinter the dense diffusion barrier for preparing as shown in Figure 3, it can be seen that have many stomatas, dense diffusion barrier and solid electrolytic
Demarcate between matter obvious.
The solid electrolyte for being coated with dense diffusion barrier is assembled into lambda sensor, after tested, oxygen determination scope be 0~
6.4vol%, test sample result is as shown in Figure 4.
Embodiment 2
A kind of method that rotary coating prepares limit-current type oxygen sensor dense diffusion barrier, comprises the following steps：
Step 1, gets the raw materials ready
(1) ethyl cellulose and the saturating alcohol of turpentine oil are mixed, heating water bath is dissolved to 70 DEG C, after dissolving completely, is obtained
To organic carrier, by La0.7Sr0.3MnO3It is dispersed in organic carrier, dense diffusion barrier slurry is obtained
La0.7Sr0.3MnO3；Wherein, in mass ratio, dense diffusion barrier powder La0.7Sr0.3MnO3: the saturating alcohol of turpentine oil: ethyl cellulose
Element=2: 5: 0.01；
Step 2, rotary coating
Dense diffusion barrier slurry rotary coating instrument is coated uniformly on 8YSZ solid electrolytes surface purchased in market, is obtained
Surface has one layer of solid electrolyte of dense diffusion barrier；Wherein, the spin coating process parameter of rotary coating instrument is：Rotation
Number walk around for 4000r/min, rotational time is 5min, coating number of times is 2 times, prefabricated thickness is 35 μm；
Step 3, dries
The solid electrolyte that surface has one layer of dense diffusion barrier is placed in drying box, is dried at 80 DEG C
24h, after drying completely, obtains dried surface with one layer of solid electrolyte of dense diffusion barrier；
Step 4, sintering
The solid electrolyte that dried surface has one layer of dense diffusion barrier is placed in high temperature furnace, is heated to
1500 DEG C of heat preservation sintering 5.5h, cool to room temperature, prepared coating limit-current type oxygen sensor on the solid electrolyte with the furnace
Dense diffusion barrier, the thickness of dense diffusion barrier is 30 μm.
The solid electrolyte for being coated with dense diffusion barrier is assembled into lambda sensor, after tested, oxygen determination scope be 0~
7.3vol%.
Embodiment 3
A kind of method that rotary coating prepares limit-current type oxygen sensor dense diffusion barrier, comprises the following steps：
Step 1, gets the raw materials ready
(1) ethyl cellulose and ethylene glycol are mixed, heating water bath is dissolved to 90 DEG C, after dissolving completely, is had
Airborne body, by La0.8Sr0.2MnO3It is dispersed in organic carrier, dense diffusion barrier slurry La is obtained0.8Sr0.2MnO3；
Wherein, in mass ratio, dense diffusion barrier powder La0.8Sr0.2MnO3: ethylene glycol: ethyl cellulose=3: 6: 0.02；
Step 2, rotary coating
Dense diffusion barrier slurry rotary coating instrument is coated uniformly on 8YSZ solid electrolytes surface purchased in market, is obtained
Surface has one layer of solid electrolyte of dense diffusion barrier；Wherein, the spin coating process parameter of rotary coating instrument is：Rotation
Number walk around for 5000r/min, rotational time is 5min, coating number of times is 5 times, prefabricated thickness is 60 μm；
Step 3, dries
The solid electrolyte that surface has one layer of dense diffusion barrier is placed in drying box, is dried at 80 DEG C
24h, after drying completely, obtains dried surface with one layer of solid electrolyte of dense diffusion barrier；
Step 4, sintering
The solid electrolyte that dried surface has one layer of dense diffusion barrier is placed in high temperature furnace, is heated to
1400 DEG C of heat preservation sintering 6h, cool to room temperature with the furnace, and prepared coating limit-current type oxygen sensor on the solid electrolyte is caused
Close diffusion barrier layer, the thickness of dense diffusion barrier is 50 μm.
The solid electrolyte for being coated with dense diffusion barrier is assembled into lambda sensor, after tested, oxygen determination scope be 0~
7.6vol%.
Embodiment 4
A kind of method that rotary coating prepares limit-current type oxygen sensor dense diffusion barrier, comprises the following steps：
Step 1, gets the raw materials ready
(1) ethyl cellulose and acetone are mixed, heating water bath is dissolved to 100 DEG C, after dissolving completely, obtains organic
Carrier, by La0.8Sr0.2MnO3It is dispersed in organic carrier, dense diffusion barrier slurry La is obtained0.8Sr0.2MnO3；Its
In, in mass ratio, dense diffusion barrier powder La0.8Sr0.2MnO3: acetone: ethyl cellulose=4: 8: 0.03；
Step 2, rotary coating
Dense diffusion barrier slurry rotary coating instrument is coated uniformly on 8YSZ solid electrolytes surface purchased in market, is obtained
Surface has one layer of solid electrolyte of dense diffusion barrier；Wherein, the spin coating process parameter of rotary coating instrument is：Rotation
Number walk around for 6000r/min, rotational time is 5min, coating number of times is 5 times, prefabricated thickness is 60 μm；
Step 3, dries
The solid electrolyte that surface has one layer of dense diffusion barrier is placed in drying box, is dried at 90 DEG C
24h, after drying completely, obtains dried surface with one layer of solid electrolyte of dense diffusion barrier；
Step 4, sintering
The solid electrolyte that dried surface has one layer of dense diffusion barrier is placed in high temperature furnace, is heated to
1600 DEG C of heat preservation sintering 5h, cool to room temperature with the furnace, and prepared coating limit-current type oxygen sensor on the solid electrolyte is caused
Close diffusion barrier layer, the thickness of dense diffusion barrier is 50 μm.
The solid electrolyte for being coated with dense diffusion barrier is assembled into lambda sensor, after tested, oxygen determination scope be 0~
8.0vol%.
Embodiment 5
A kind of method that rotary coating prepares limit-current type oxygen sensor dense diffusion barrier, comprises the following steps：
Step 1, gets the raw materials ready
(1) methylcellulose and sec-octyl alcohol are mixed, heating water bath is dissolved to 70 DEG C, after dissolving completely, is had
Airborne body, by La0.8Sr0.2MnO3It is dispersed in organic carrier, dense diffusion barrier slurry La is obtained0.8Sr0.2MnO3；
Wherein, in mass ratio, dense diffusion barrier powder La0.8Sr0.2MnO3: sec-octyl alcohol: methylcellulose=5: 8: 0.04；
Step 2, rotary coating
Dense diffusion barrier slurry rotary coating instrument is coated uniformly on 8YSZ solid electrolytes surface purchased in market, is obtained
Surface has one layer of solid electrolyte of dense diffusion barrier；Wherein, the spin coating process parameter of rotary coating instrument is：Rotation
Number walk around for 10000r/min, rotational time is 1min, coating number of times is 1 time, prefabricated thickness is 30 μm；
Step 3, dries
The solid electrolyte that surface has one layer of dense diffusion barrier is placed in drying box, is dried at 70 DEG C
24h, after drying completely, obtains dried surface with one layer of solid electrolyte of dense diffusion barrier；
Step 4, sintering
The solid electrolyte that dried surface has one layer of dense diffusion barrier is placed in high temperature furnace, is heated to
1300 DEG C of heat preservation sintering 6h, cool to room temperature with the furnace, and prepared coating limit-current type oxygen sensor on the solid electrolyte is caused
Close diffusion barrier layer, the thickness of dense diffusion barrier is 28 μm.
The solid electrolyte for being coated with dense diffusion barrier is assembled into lambda sensor, after tested, oxygen determination scope be 0~
8.4vol%.
Embodiment 6
A kind of method that rotary coating prepares limit-current type oxygen sensor dense diffusion barrier, comprises the following steps：
Step 1, gets the raw materials ready
(1) hydroxyethyl cellulose and the saturating alcohol of turpentine oil are mixed, heating water bath is dissolved to 70 DEG C, after dissolving completely,
Organic carrier is obtained, by La0.8Sr0.2MnO3It is dispersed in organic carrier, dense diffusion barrier slurry is obtained
La0.8Sr0.2MnO3；Wherein, in mass ratio, dense diffusion barrier powder La0.8Sr0.2MnO3: the saturating alcohol of turpentine oil: ethoxy is fine
Dimension element=6: 10: 0.05；
Step 2, rotary coating
Dense diffusion barrier slurry rotary coating instrument is coated uniformly on self-control 9YSZ solid electrolytes surface, is obtained
Surface has one layer of solid electrolyte of dense diffusion barrier；Wherein, the spin coating process parameter of rotary coating instrument is：Rotation
Number walk around for 1000r/min, rotational time is 10min, coating number of times is 3 times, prefabricated thickness is 55 μm；
Step 3, dries
The solid electrolyte that surface has one layer of dense diffusion barrier is placed in drying box, is dried at 80 DEG C
24h, after drying completely, obtains dried surface with one layer of solid electrolyte of dense diffusion barrier；
Step 4, sintering
The solid electrolyte that dried surface has one layer of dense diffusion barrier is placed in high temperature furnace, is heated to
1000 DEG C of heat preservation sintering 7h, cool to room temperature with the furnace, and prepared coating limit-current type oxygen sensor on the solid electrolyte is caused
Close diffusion barrier layer, the thickness of dense diffusion barrier is 50 μm.
The solid electrolyte for being coated with dense diffusion barrier is assembled into lambda sensor, after tested, oxygen determination scope be 0~
7.8vol%.
Claims (8)
1. a kind of method that rotary coating prepares limit-current type oxygen sensor dense diffusion barrier, it is characterised in that the party
Method is comprised the following steps：
Step 1, gets the raw materials ready
Dissolve the binder in solvent, organic carrier is constituted, by La1-xSrxMnO3It is dispersed in organic carrier, is obtained and causes
Close diffusion barrier layer slurry La1-xSrxMnO3, wherein, x is 0.16~0.3；Wherein, in mass ratio, dense diffusion barrier powder
La1-xSrxMnO3: solvent: binding agent=(2~6): (5~10): (0.01~0.05)；
Described solvent is one or more in the saturating alcohol of turpentine oil, sec-octyl alcohol, ethylene glycol or acetone；
Described binding agent is one or more in ethyl cellulose, methylcellulose or hydroxyethyl cellulose；
Step 2, rotary coating
Dense diffusion barrier slurry rotary coating instrument is coated uniformly on Y2O3The ZrO of stabilization2Solid electrolyte surface, obtains
There is one layer of solid electrolyte of dense diffusion barrier to surface；Wherein, the spin coating process parameter of rotary coating instrument is：
Rotation revolution is 1000~10000r/min, and rotational time is 1~10min, and coating number of times is 1~5 time；
Step 3, dries
The solid electrolyte that surface has one layer of dense diffusion barrier is dried, after drying completely, obtains dried
Surface has one layer of solid electrolyte of dense diffusion barrier；
Step 4, sintering
The solid electrolyte that dried surface has one layer of dense diffusion barrier is sintered, room is cooled to after sintering
Temperature, prepared coating limit-current type oxygen sensor dense diffusion barrier on the solid electrolyte.
2. the method that rotary coating as claimed in claim 1 prepares limit-current type oxygen sensor dense diffusion barrier, its
It is characterised by, in described step 1, described binding agent dissolving is dissolved using heating water bath in a solvent, and heating-up temperature is 70
~100 DEG C.
3. the method that rotary coating as claimed in claim 1 prepares limit-current type oxygen sensor dense diffusion barrier, its
It is characterised by, in described step 1, described dense diffusion barrier powder is obtained using sol-gal process.
4. the method that rotary coating as claimed in claim 1 prepares limit-current type oxygen sensor dense diffusion barrier, its
It is characterised by, in described step 3, described dry drying equipment is drying box, and drying temperature is 70~90 DEG C, when drying
Between be more than 24h.
5. the method that rotary coating as claimed in claim 1 prepares limit-current type oxygen sensor dense diffusion barrier, its
It is characterised by, in described step 4, described sintering, agglomerating plant is high temperature furnace, and sintering temperature is 1000~1600 DEG C, is burnt
The knot time is 5~7h.
6. the method that rotary coating as claimed in claim 1 prepares limit-current type oxygen sensor dense diffusion barrier, its
It is characterised by, in described step 4, described is cooled to room temperature to cool to room temperature with the furnace.
7. the method that rotary coating as claimed in claim 1 prepares limit-current type oxygen sensor dense diffusion barrier, its
It is characterised by, the limit-current type oxygen sensor dense diffusion barrier for coating on the solid electrolyte of preparation, densification diffusion
Thickness≤50 μm of barrier layer.
8. the method that rotary coating as claimed in claim 1 prepares limit-current type oxygen sensor dense diffusion barrier, its
It is characterised by, the solid electrolyte for being coated with dense diffusion barrier is assembled into lambda sensor, after tested, oxygen determination scope is 0
~8.4vol%.
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| CN108132291A (en) * | 2017-12-22 | 2018-06-08 | 东北大学 | Utilize the method for impedance spectrum calibration oxygen concentration |
| CN108982634A (en) * | 2018-08-10 | 2018-12-11 | 东北大学 | A kind of limit-current type oxygen sensor |
| CN113063832A (en) * | 2021-03-29 | 2021-07-02 | 山东科技大学 | Preparation method of compact diffusion layer limiting current type oxygen sensor |
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