CN107903057A - The preparation method of lambda sensor dielectric substrate and fine and close diffusion layer double-decker - Google Patents

The preparation method of lambda sensor dielectric substrate and fine and close diffusion layer double-decker Download PDF

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CN107903057A
CN107903057A CN201711192886.4A CN201711192886A CN107903057A CN 107903057 A CN107903057 A CN 107903057A CN 201711192886 A CN201711192886 A CN 201711192886A CN 107903057 A CN107903057 A CN 107903057A
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diffusion layer
dielectric substrate
fine
biscuit
close diffusion
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CN107903057B (en
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刘涛
王相南
莫扬成
易茂义
李静云
于景坤
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Northeastern University China
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Abstract

The present invention relates to oxygen sensor technical field, more particularly to the preparation method of lambda sensor dielectric substrate and fine and close diffusion layer double-decker.Preparation method provided by the present invention, is to form fine and close diffusion layer using electrostatic spray on dielectric substrate biscuit, or forms dielectric substrate using electrostatic spray on fine and close diffusion layer biscuit.The dielectric substrate that the preparation method is prepared and the bond strength of dielectric substrate and fine and close diffusion layer in fine and close diffusion layer double-decker are high, and preparation speed is fast, suitable for large-scale production.

Description

The preparation method of lambda sensor dielectric substrate and fine and close diffusion layer double-decker
Technical field
The present invention relates to oxygen sensor technical field, more particularly to lambda sensor dielectric substrate and fine and close diffusion The preparation method of layer double-decker.
Background technology
In the industry such as automobile, metallurgy, energy, using oxygen sensor is online, monitoring oxygen concentration is a kind of in real time Effective method, has been to be concerned by more and more people, and oxygen sensor mainly includes concentration potential type lambda sensor and pole Flow pattern of rationing the power supply lambda sensor.Wherein, concentration potential type lambda sensor there are fuel-poor region control it is insensitive the shortcomings of, therefore, application Wider, sensitiveer, longer life expectancy the limit-current type oxygen sensor of response receives much concern.
Limit-current type oxygen sensor is divided into pinhole type, porous type and dense diffusion barrier type, wherein, pinhole type and more Pass, which exists, to involve great expense, the defects of pore deformation and solid particle blocking often occurs.Compare, dense diffusion barrier type As a result of oxonium ion-electron mixed conductor as dense diffusion barrier, the problem of pore plugging can be overcome, workability Can more it stablize, the response time is sensitiveer, longer life expectancy.The cross-section structure of dense diffusion barrier limit-current type oxygen sensor Schematic diagram is as shown in Figure 1, such a lambda sensor generally includes positive and negative platinum electrode, dense diffusion barrier (referred to as fine and close diffusion Layer), solid electrolyte layer (abbreviation dielectric substrate) and elevated-temperature seal glass glaze.
Dense diffusion barrier limit-current type oxygen sensor can utilize discharge plasma sintering, Co-sintering and tile It is prepared by the methods of compound.Wherein, using discharge plasma sintering (SPS) technology, in sintering process easily because of fine and close diffusion layer The material of material and dielectric substrate mismatches and causes sintered body to split, therefore influences oxygen determination performance.Using Co-sintering method, Because fine and close diffusion layer material and dielectric substrate material thermal coefficient of expansion and sintering shrinkage mismatch, and be easy to cause Sintered body is cracked during co-sintering, influences the diffusion of oxonium ion in the sensor.Utilize tile composite algorithm, oxygen determination Can be good, but the method long preparation period, process are cumbersome, and also the fine and close diffusion layer prepared in normal sintering contains more gas Hole, is unfavorable for mass producing.
The content of the invention
(1) technical problems to be solved
It is an object of the invention to provide the preparation of a kind of lambda sensor dielectric substrate and fine and close diffusion layer double-decker Dielectric substrate and fine and close diffusion layer in method, the dielectric substrate prepared by the preparation method and fine and close diffusion layer double-decker Bond strength is high, and preparation speed is fast, suitable for large-scale production.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses include：
One aspect of the present invention provides the preparation method of a kind of lambda sensor dielectric substrate and fine and close diffusion layer double-decker, Include the following steps：S1, prepare dielectric substrate biscuit；S2, using electrostatic spraying will include the fine and close diffusion layer mixed The mixed solution of powder and diluent is sprayed on dielectric substrate biscuit, and fine and close diffusion laminin is formed on dielectric substrate biscuit Base；S3, be dried the obtained dielectric substrate biscuit with fine and close diffusion layer biscuit in step S2；S4, to dried Dielectric substrate biscuit with fine and close diffusion layer biscuit is sintered；S5, by the electricity with fine and close diffusion layer biscuit after sintering Solution matter laminin base is cooled to room temperature, and densification diffusion layer biscuit after cooling forms fine and close diffusion layer, electrolyte laminin after cooling Base forms dielectric substrate, and fine and close diffusion layer is stacked on top of each other with dielectric substrate and is connected, and forms double-decker.
According to the present invention, in step s 2, the process conditions of electrostatic spraying are：The voltage of electrostatic field is 25-30kV, spray gun Distance with dielectric substrate biscuit is 5-10cm.
According to the present invention, diluent is absolute ethyl alcohol, butanol, acetone, toluene, dimethylbenzene, styrene, ethyl acetate, vinegar One or more combinations in acid butyl ester, dimethylformamide, polyalcohol or phenmethylol.
According to the present invention, diluent is made of following component by mass percentage：Absolute ethyl alcohol 37.5%；Butanol 12%；Toluene 13.5%；Ethyl acetate 19%；Butyl acetate 18%.
According to the present invention, in step s 2, the particle diameter of fine and close diffusion layer powder is 40-60nm, fine and close in mixed solution to expand The concentration for dissipating layer powder is 2-4g/mL；In step s3, drying temperature is 100-120 DEG C；In step s 4, sintering temperature is 1000-1600℃。
Another aspect of the present invention provides the preparation side of a kind of lambda sensor dielectric substrate and fine and close diffusion layer double-decker Method, includes the following steps：S1, prepare fine and close diffusion layer biscuit；S2, using electrostatic spraying will include the electrolyte mixed The mixed solution of layer powder and diluent is sprayed on fine and close diffusion layer biscuit, and dielectric substrate is formed on fine and close diffusion layer biscuit Biscuit；S3, be dried the obtained fine and close diffusion layer biscuit with dielectric substrate biscuit in step S2；S4, to drying after The fine and close diffusion layer biscuit with dielectric substrate biscuit be sintered；S5, by the cause with dielectric substrate biscuit after sintering Close diffusion layer biscuit is cooled to room temperature, and densification diffusion layer biscuit after cooling forms fine and close diffusion layer, dielectric substrate after cooling Biscuit forms dielectric substrate, and fine and close diffusion layer is stacked on top of each other with dielectric substrate and is connected, and forms double-decker.
According to the present invention, in step s 2, the process conditions of electrostatic spraying are：The voltage of electrostatic field is 25-30kV, spray gun Distance with dielectric substrate biscuit is 5-10cm.
According to the present invention, diluent is absolute ethyl alcohol, butanol, acetone, toluene, dimethylbenzene, styrene, ethyl acetate, vinegar One or more combinations in acid butyl ester, dimethylformamide, polyalcohol or phenmethylol.
According to the present invention, diluent is made of following component by mass percentage：Absolute ethyl alcohol 61.7%；Dimethylbenzene 28%；Butyl acetate 10.3%.
According to the present invention, in step s 2, the particle diameter of dielectric substrate powder is 40-60nm, dielectric substrate in mixed solution The concentration of powder is 2-4g/mL；In step s3, drying temperature is 100-120 DEG C；In step s 4, sintering temperature 1000- 1600℃。
(3) beneficial effect
The beneficial effects of the invention are as follows：
In the preparation method of the lambda sensor dielectric substrate of the present invention and fine and close diffusion layer double-decker, using electrostatic Coating forms fine and close diffusion layer biscuit on dielectric substrate biscuit, or dielectric substrate biscuit is formed on fine and close diffusion layer biscuit, In spraying, spraying is uniformly and bonding force is strong for this method, makes the bond strength of fine and close diffusion layer and dielectric substrate high, prepares at the same time Speed is especially fast, greatly improves labor productivity, so that considerable economic results in society are obtained, suitable for large-scale production.
Brief description of the drawings
Fig. 1 is the structure diagram of dense diffusion barrier limit-current type oxygen sensor in the prior art；
Fig. 2 is the preparation side of the lambda sensor dielectric substrate that following examples 1 provide and fine and close diffusion layer double-decker The flow chart of method；
Lambda sensor dielectric substrate and fine and close diffusion layer prepared by the preparation method that Fig. 3 is provided by following examples 1 The local SEM figures of double-decker；
Fig. 4 is that the SEM in the section of double-decker made from conventional sintering technique schemes；
Fig. 5 be a dense diffusion barrier limit-current type oxygen sensor oxygen determination I-V curve, the dense diffusion barrier Limit-current type oxygen sensor includes lambda sensor dielectric substrate and cause prepared by the preparation method that following examples 1 are provided Close diffusion layer double-decker.
Fig. 6 is the preparation method of the lambda sensor dielectric substrate that embodiment 3 provides and fine and close diffusion layer double-decker Flow chart.
【Description of reference numerals】
1：Anode；2：Fine and close diffusion layer；3：Dielectric substrate；4：Cathode；5：Elevated-temperature seal glass glaze.
Embodiment
In order to preferably explain the present invention, in order to understand, below in conjunction with the accompanying drawings, by embodiment, to this hair It is bright to be described in detail.
Embodiment 1
With reference to Fig. 2, the present embodiment provides the preparation of a kind of lambda sensor dielectric substrate and fine and close diffusion layer double-decker Method, specifically comprises the following steps：
S1, prepare dielectric substrate biscuit, and the main component of the electrolyte biscuit is YSZ, and the thickness of electrolyte biscuit is located at 4.91mm, electrolyte biscuit are the disk of a diameter of 9.82mm.
S2, using electrostatic spraying by mixed solution (mixed solution include the fine and close diffusion layer powder that mixes and Diluent) it is sprayed on above-mentioned dielectric substrate biscuit, fine and close diffusion layer biscuit is formed on dielectric substrate biscuit.
Further, step S2 includes following sub-step in the present embodiment：
S2.1, by particle diameter be 40-60nm fine and close diffusion layer powder ultrasonic be scattered in diluent, ultrasonic 1h so that cause Close diffusion layer powder is evenly distributed in diluent, and the concentration for obtaining fine and close diffusion layer powder is the mixed solution of 3g/mL.Its In, selected diluent can be absolute ethyl alcohol, butanol, acetone, toluene, dimethylbenzene, styrene, ethyl acetate, butyl acetate, diformazan One or more combinations in base formamide, polyalcohol or phenmethylol.
S2.2, sprayed using electrostatic spray：Specifically, obtained mixed solution in step S2.1 is loaded into injection In device, the electrostatic spray in the case where voltage is the electrostatic field of 25kV, the distance of spray gun to dielectric substrate biscuit is 5cm, formation of spraying Droplet forms fine and close diffusion layer biscuit on dielectric substrate biscuit, and the thickness position of the fine and close diffusion layer biscuit of formation is 1mm, causes Close diffusion layer biscuit is the disk of a diameter of 9.82mm.
Specifically, electrostatic spray refers to make electronegative paint particles (in the present embodiment using high-pressure electrostatic electric field Coating refers to fine and close diffusion layer powder) along electric field opposite direction directed movement, and by paint particles absorption workpiece surface ( Workpiece refers to dielectric substrate biscuit in the present embodiment) a kind of spraying method, the operation principle of electrostatic spraying is by outer power-up Field causes spray solution to carry a certain amount of electric charge, will overcome solution under the action of Coulomb repulsion between extra electric field power and electric charge Surface tension so that electrospray solution atomization, in workpiece surface curing molding.Therefore, it is coated using electrostatic spray, It can make the bond strength higher of fine and close diffusion layer biscuit and dielectric substrate biscuit.
In the present embodiment, selected diluent is to be made of following component by mass percentage：Absolute ethyl alcohol 37.5%, Butanol 12%, toluene 13.5%, ethyl acetate 19% and butyl acetate 18%.Wherein, absolute ethyl alcohol, butanol, toluene, acetic acid Ethyl ester and butyl acetate are non-activated thinner, do not contain active group in its molecule, are all atent solvents, in dilution In do not participate in reaction, simply play the purpose for the viscosity for reducing mixed solution, and then ensure the fluency of spraying and with enough Speed.Meanwhile mentioned component is in addition to playing diluting effect, to mechanical performance, thermal change temperature, media-resistant and aging damage etc. The influence having had.In addition, the ability that coating particle carries electric charge in the electric field is inevitable electrical related with coating, wherein main Parameter be exactly coating dielectric constant.In general, the polarity of common coating is very low, impedance commonly greater than 100M Ω, in order to Coating is set to can adapt to electrostatic spraying, it is necessary to adjust the impedance of coating with the higher diluent of dielectric constant, be allowed in 25- Between 30M Ω.And ethyl acetate and/or butyl acetate can then play the role of strengthening the electric conductivity of mixed solution so that mixed Close solution and more can adapt to electrostatic spraying.And when selecting the proportioning of diluent, it is necessary in view of mixing the dilution formed afterwards The evaporation rate of agent, if evaporation rate is too slow, easily leads in fine and close diffusion layer biscuit and produces bubble, and then cause fine and close diffusion layer Stomata is excessive in biscuit；If evaporation rate is too fast, do not reach diluted purpose, fine and close diffusion layer biscuit and electrolyte can be influenced The bond strength of laminin base.Therefore the solvent of different boiling has been selected to mix in the proportioning of each component in selecting diluent The evaporation rate of diluent is adjusted, and the proportioning provided in the present embodiment is drawn by theory analysis and lot of experiment validation , it is directed to coordinates with fine and close diffusion layer powder, possesses suitable evaporation rate, can reach certain dilution purpose, at the same time The preferred solution of the electric conductivity of mixed solution can be improved again.
The obtained dielectric substrate biscuit with fine and close diffusion layer biscuit in step S2, be placed in drying box and done by S3 Dry, drying temperature is 115 DEG C, drying time 18h.During this, diluent is sufficiently volatilized.
The dried dielectric substrate biscuit with fine and close diffusion layer biscuit, be placed in high temperature furnace and be sintered by S4, burns Junction temperature is 1500 DEG C.
In the present embodiment, 1000 DEG C first are warming up to by the heating rate of 10 DEG C/min in sintering, then by 5 DEG C/min Heating rate be warming up to 1500 DEG C, persistently sinter 8h at this temperature afterwards.Because of the biscuit formed using electrostatic painting process Very high and double-decker combination power is also very big for consistency after drying, thus using it is this be first rapidly heated again it is slow The staged of speed heating is sintered to substitute original Isothermal sinter mode, the burning needed in the case where reaching identical sintering effect Junction temperature is lower, saves the energy, reduces cost.
S5, cool to the dielectric substrate biscuit with fine and close diffusion layer biscuit after sintering with the furnace room temperature, after cooling Fine and close diffusion layer biscuit forms fine and close diffusion layer 2, and dielectric substrate biscuit after cooling forms dielectric substrate 3, fine and close 2 He of diffusion layer Dielectric substrate 3 is stacked on top of each other and connected, forms double-decker, the wherein thickness of dielectric substrate 3 is 4.89mm, a diameter of 9.77mm, the thickness of fine and close diffusion layer 2 is 0.96mm, a diameter of 9.77mm.
Further, above-mentioned steps S1 includes following sub-step in the present embodiment：
S1.1, by dielectric substrate material powder (being in the present embodiment YSZ powder) be squeezed into circular electrolyte synusia Shape matrix；
Dielectric substrate flaky matrix, be placed in high temperature furnace by S1.2, and dielectric substrate flaky matrix is sintered, sintering temperature Spend for 1300 DEG C, sintering time 6h；
Dielectric substrate flaky matrix after sintering, is cooled to the furnace room temperature by S1.3, forms dielectric substrate biscuit.
Since the mixed solution comprising fine and close diffusion layer powder is being sprayed on dielectric substrate biscuit using electrostatic spraying When, mixed solution can produce powerful impact force to dielectric substrate biscuit, and (this impact is due to that electronegative paint particles exist Produced between extra electric field power and electric charge under the action of Coulomb repulsion), therefore, the intensity of dielectric substrate biscuit is had to Ask, the destroying infection spraying effect of dielectric substrate biscuit is otherwise easily caused in spraying.So when preparing dielectric substrate biscuit First carry out once sintered, spraying can be received to ensure that dielectric substrate biscuit possesses enough intensity.
Wherein, the YSZ powder employed in step S1.1 is made by following steps：
A1, in molar ratio, Y (NO3)3·6H2O ﹕ ZrOCl2·8H2O=(6.5-10) ﹕ (93.5-90) carry out dispensing, its In, Y (NO3)3·6H2The molar concentration of O is 7-9mol%；
A2, by Y (NO3)3·6H2O and Y (NO3)3·6H2O is dissolved separately in deionized water, is filtered to remove insoluble miscellaneous Y (NO are made after matter3)3Aqueous solution and ZrOCl2Aqueous solution, wherein, the addition of deionized water so that raw material fully dissolves subject to；
A3, by Y (NO3)3Aqueous solution and ZrOCl2Aqueous solution mixes, and mixed solution, the molar concentration position of mixed solution is made In the range of 0.6-1.1mol/L；
A4, ammonium hydroxide is added dropwise into mixed solution while stirring, until the pH value of mixed solution stops that ammonia is added dropwise when reaching 9 Water, is made presoma sediment, wherein, the concentration of ammonium hydroxide is located at 25-28wt%；
Presoma sediment, be placed in drying box by a5, presoma sediment is dried, drying temperature is located at 60- In the range of 80 DEG C, drying time is in more than 20h；
Presoma sediment after drying, be placed in high temperature furnace by a6, and dried presoma sediment is calcined, is forged Temperature is burnt in the range of 600-1600 DEG C, and solid-solution powder is made in the range of 6-7h in calcination time；
Solid-solution powder, be ground by a7 in agate mortar, and milling time is located in the range of 2-4h, and YSZ is made Powder, granularity≤100nm of YSZ powder.
Certainly, not limited to this, the dielectric substrate material powder employed in step S1.1 can also be commercial 8YSZ.
Further, the preparation of above-mentioned YSZ powder preferably includes following steps：
A1, in molar ratio, Y (NO3)3·6H2O ﹕ ZrOCl2·8H2O=(8) ﹕ (92) carry out dispensing, wherein, Y (NO3)3· 6H2The molar concentration of O is 8mol%；
A2, by Y (NO3)3·6H2O and Y (NO3)3·6H2O is dissolved separately in deionized water, is filtered to remove insoluble miscellaneous Y (NO are made after matter3)3Aqueous solution and ZrOCl2Aqueous solution, wherein, the addition of deionized water so that raw material fully dissolves subject to；
A3, by Y (NO3)3Aqueous solution and ZrOCl2Aqueous solution mixes, and mixed solution, the molar concentration position of mixed solution is made In the range of 0.8mol/L；
A4, ammonium hydroxide is added dropwise into mixed solution while stirring, until the pH value of mixed solution stops that ammonia is added dropwise when reaching 9 Water, is made presoma sediment, wherein, the concentration of ammonium hydroxide is located at 27wt%；
Presoma sediment, be placed in drying box by a5, and presoma sediment is dried, and drying temperature is located at 70 DEG C In the range of, drying time 24h；
Presoma sediment after drying, be placed in high temperature furnace by a6, and dried presoma sediment is calcined, is forged Temperature is burnt in the range of 1100 DEG C, and solid-solution powder is made in the range of 6h in calcination time；
Solid-solution powder, be ground, milling time 3h by a7 in agate mortar, and YSZ powder, YSZ powder is made Granularity≤100nm.
Drawn by theory analysis and lot of experiment validation, when YSZ powder is prepared by above-mentioned optimum condition, with spray The fine and close diffusion layer powder applied on it combines combination that is more preferable, and then increasing dielectric substrate biscuit and fine and close diffusion layer biscuit Intensity, make combine it is even closer, the double-decker for making to prepare possesses more excellent performance.
Fine and close diffusion layer powder employed in step S2.1 is LSM powder, and specific preparation method is as follows：
B1, in molar ratio, La (NO3)3·Sr(NO3)2·Mn(NO3)20.2 ﹕ 1 of=0.8 ﹕ carry out dispensing；
B2, by La (NO3)3、Sr(NO3)2With Mn (NO3)2It is dissolved separately in deionized water, is filtered to remove insoluble impurities After obtain La (NO3)3Aqueous solution, Sr (NO3)2Aqueous solution and Mn (NO3)2Aqueous solution, wherein, the addition of deionized water is so that original Material is fully subject to dissolving；
B3, by La (NO3)3Aqueous solution, Sr (NO3)2Aqueous solution and Mn (NO3)2Aqueous solution mixes, and mixed solution is made；
B4, add citric acid solution citric acid into mixed solution while stirring, after stirring evenly, adds ethylene glycol, stirs Ammonium hydroxide is added dropwise after mixing uniformly, until the pH value of mixed solution stops that ammonium hydroxide is added dropwise when being located at 8.0-9.5, collosol and gel forerunner is made Body, wherein, the mass concentration of citric acid solution citric acid is located in the range of 10-20%, and the mass concentration of ammonium hydroxide is located at 20- In the range of 30%, in molar ratio, Jin belongs to Yang Li ﹕ Ning Meng Suan ﹕ ethylene glycol=1 ﹕, 4.8 ﹕ 1.2 in mixed solution；
Sol-gel precursor, be placed in drying oven by b5, sol-gel precursor is dried, drying temperature is located at In the range of 70-90 DEG C；
Dried sol-gel precursor, be placed in high temperature furnace by b6, to by dried sol-gel precursor into Row calcining, calcining heat are located in the range of 500-1000 DEG C, and calcination time is located at 5-6h, and solid-solution powder is made；
Solid-solution powder, be placed in agate mortar by b7, solid-solution powder is ground, milling time is located at 2-3h's In the range of, LSM powder, the granularity 40-60nm of LSM powder, purity 99.99% is made.
Further, the preparation of above-mentioned LSM powder preferably includes following steps：
B1, in molar ratio, La (NO3)3·Sr(NO3)2·Mn(NO3)20.2 ﹕ 1 of=0.8 ﹕ carry out dispensing；
B2, by La (NO3)3、Sr(NO3)2With Mn (NO3)2It is dissolved separately in deionized water, is filtered to remove insoluble impurities After obtain La (NO3)3Aqueous solution, Sr (NO3)2Aqueous solution and Mn (NO3)2Aqueous solution, wherein, the addition of deionized water is so that original Material is fully subject to dissolving；
B3, by La (NO3)3Aqueous solution, Sr (NO3)2Aqueous solution and Mn (NO3)2Aqueous solution mixes, and mixed solution is made；
B4, add citric acid solution citric acid into mixed solution while stirring, after stirring evenly, adds ethylene glycol, stirs Ammonium hydroxide is added dropwise after mixing uniformly, until the pH value of mixed solution stops that ammonium hydroxide is added dropwise when being located at 9.0, sol-gel precursor is made, Wherein, the mass concentration of citric acid solution citric acid is located in the range of 15%, and the mass concentration of ammonium hydroxide is located at 25% scope Interior, in molar ratio, Jin belongs to Yang Li ﹕ Ning Meng Suan ﹕ ethylene glycol=1 ﹕, 4.8 ﹕ 1.2 in mixed solution；
Sol-gel precursor, be placed in drying oven by b5, sol-gel precursor is dried, drying temperature is located at In the range of 80 DEG C；
Dried sol-gel precursor, be placed in high temperature furnace by b6, to by dried sol-gel precursor into Row calcining, calcining heat are located in the range of 800 DEG C, and calcination time is located at 6h, and solid-solution powder is made；
Solid-solution powder, be placed in agate mortar by b7, solid-solution powder is ground, milling time is located at the model of 3h In enclosing, LSM powder, the granularity 40-60nm of LSM powder, purity 99.99% is made.
Drawn by theory analysis and lot of experiment validation, can be with when LSM powder is prepared by above-mentioned optimum condition It is easier to be combined with mixed solution when using electrostatic spraying and is capable of the ejection of more smooth smoothness, speed is prepared so as to improve Degree, greatly improves labor productivity, so that considerable economic results in society are obtained, suitable for large-scale production.
It is lambda sensor dielectric substrate prepared by the preparation method provided in the present embodiment with reference to Fig. 3 and Fig. 4, Fig. 3 Scheme with the local SEM of fine and close diffusion layer double-decker, which is in accelerating potential (EHT)=15.00kV, secondary electron detection letter Obtained under conditions of number SignalA=SE2, operating distance (WD)=8.1mm, amplification factor (Mag)=2.00KX, in Fig. 3 Downside is dielectric substrate 3, and upside is fine and close diffusion layer 2.Fig. 4 is the SEM in the section of double-decker made from conventional sintering technique Figure, the figure be accelerating potential (EHT)=15.00kV, secondary electron detectable signal SignalA=SE2, operating distance (WD)= Obtained under conditions of 9.0mm, amplification factor (Mag)=5.00KX, downside is dielectric substrate 3 in Fig. 4, and upside is spread to be fine and close Layer 2.
Comparison diagram 3 and Fig. 4 can be seen that the fine and close diffusion layer 2 formed using above-mentioned electrostatic spray, compared to existing skill The fine and close diffusion layer prepared in art using conventional sintering method, dense structure is uniform, stomata is few, and consistency is improved, and can The heat affected area scope and deformation for making dielectric substrate 3 are minimized by, and the width of fine and close diffusion layer 2 and thickness can essences Really control, wherein, the thickness of fine and close diffusion layer 2 can be controlled by limiting the spray time of electrostatic spraying, and then include the cause The oxygen determination performance of the lambda sensor of close diffusion layer 2 is improved.It should be noted that Fig. 3 is to break obtained double-decker into two with one's hands The Local map shot afterwards, the pit on fine and close diffusion layer 2 in Fig. 3 are formed when double-decker is broken into two with one's hands, are not to spray Formed during painting.
Further, with reference to Fig. 5, lambda sensor will be fabricated to by double-decker made of above-mentioned preparation method, i.e., such as Fig. 1 In include anode 1, dense diffusion barrier (referred to as fine and close diffusion layer 2), solid electrolyte layer (abbreviation dielectric substrate 3), cathode 4 With elevated-temperature seal glass glaze 5.After tested, oxygen determination scope is 0-17.69vol%.
Thus, fine and close diffusion layer is formed using electrostatic spray, its dense structure is uniform, stomata is few, and consistency is carried Height, and then the oxygen determination performance of the lambda sensor comprising the densification diffusion layer is improved.Secondly, fine and close expansion is made using electrostatic spraying It is high to dissipate the bond strength of layer and dielectric substrate, and is not easy cracked, further increases comprising the densification diffusion layer The oxygen determination performance of lambda sensor.Again, the process of the preparation method is simple, and preparation speed is fast, is adapted to produce in enormous quantities.In addition, The oxygen determination scope for the lambda sensor that the double-decker formed by the preparation method of the present invention is formed is improved.Thus, this reality Apply the preparation method that example provides a kind of new beneficial lambda sensor dielectric substrate and fine and close diffusion layer double-decker.
Embodiment 2
The present embodiment provides the preparation method of a kind of lambda sensor dielectric substrate and fine and close diffusion layer double-decker, specifically Include the following steps：
S1, prepare dielectric substrate biscuit, and the main component of the electrolyte biscuit is YSZ, and the thickness of electrolyte biscuit is 2.92mm, electrolyte biscuit are the disk of a diameter of 9.8mm.
S2, using electrostatic spraying will include the mixed solution of fine and close the diffusion layer powder and diluent mixed spray On dielectric substrate biscuit, fine and close diffusion layer biscuit is formed on dielectric substrate biscuit.
Further, step S2 includes following sub-step in the present embodiment：
S2.1, by particle diameter be 40-60nm fine and close diffusion layer powder ultrasonic be scattered in diluent (component is same as above), ultrasound 1h, the concentration for obtaining fine and close diffusion layer powder is the mixed solution of 4g/mL.
S2.2, sprayed using electrostatic spray：Specifically, obtained mixed solution in step S2.1 is loaded into injection In device, the electrostatic spray in the case where voltage is the electrostatic field of 30kV, the distance of spray gun to dielectric substrate biscuit is 8cm, formation of spraying Covered with fine and close diffusion layer biscuit is formed on dielectric substrate biscuit, the thickness position of the fine and close diffusion layer biscuit of formation is droplet 2mm, fine and close diffusion layer biscuit are the disk of diameter 9.8mm.It is coated using electrostatic spray, fine and close diffusion layer biscuit can be made With the bond strength higher of dielectric substrate biscuit.
The obtained dielectric substrate biscuit with fine and close diffusion layer biscuit in step S2, be placed in drying box and done by S3 Dry, drying temperature is 120 DEG C, drying time 17h.
The dried dielectric substrate biscuit with fine and close diffusion layer biscuit, be placed in high temperature furnace and be sintered by S4, burns Junction temperature is 1050 DEG C.
In the present embodiment, first carry out being warming up to 950 DEG C by the heating rate of 10 DEG C/min in sintering, then by 5 DEG C/ The heating rate of min is warming up to 1050 DEG C, sintering time 10h.Using this staged for being first rapidly heated and heating up at a slow speed again Sintering, the sintering temperature needed in the case where reaching identical sintering effect is lower, saves the energy, reduces cost.
S5, cool to the dielectric substrate biscuit with fine and close diffusion layer biscuit after sintering with the furnace room temperature, after cooling Fine and close diffusion layer biscuit forms fine and close diffusion layer 2, and dielectric substrate biscuit after cooling forms dielectric substrate 3, fine and close 2 He of diffusion layer Dielectric substrate 3 is stacked on top of each other and connected, forms double-decker, the wherein thickness of dielectric substrate 3 is 2.91mm, a diameter of 9.76mm, the thickness of fine and close diffusion layer 2 is 1.96mm, a diameter of 9.76mm.
Further, above-mentioned steps S1 includes following sub-step in the present embodiment：
S1.1, by dielectric substrate material powder (being in the present embodiment YSZ powder) be squeezed into circular electrolyte synusia Shape matrix；
Dielectric substrate flaky matrix, be placed in high temperature furnace by S1.2, and dielectric substrate flaky matrix is sintered, sintering temperature Spend in the range of 1500 DEG C, sintering time 4h；
Dielectric substrate flaky matrix after sintering, is cooled to the furnace room temperature by S1.3, forms dielectric substrate biscuit.
Wherein, in step S1.1 the preparation method of YSZ powder such as embodiment 1 narration, details are not described herein.In step Fine and close diffusion layer powder employed in S2.1 is LSM powder, the narration of the preparation method such as embodiment 1 of LSM powder, herein not Repeat again.
Lambda sensor will be fabricated to made of above-mentioned preparation method by double-decker, i.e., as included anode 1, densification in Fig. 1 Diffusion barrier layer (referred to as fine and close diffusion layer 2), solid electrolyte layer (abbreviation dielectric substrate 3), cathode 4 and elevated-temperature seal glass glaze 5.After tested, oxygen determination scope is 0-20.34vol%.
Certainly the present invention forms fine and close diffusion layer biscuit on dielectric substrate biscuit, and then sintering is cooled into double-decker Preparation method in be not limited to above-described embodiment, in step sl, the main component of electrolyte biscuit is is not limited only to YSZ powder or LSGM powder；The step of preparing dielectric substrate biscuit is also not limited to step S1.1 to S1.3, also may be used With using other modes；Prepare YSZ powder the step of be also not limited to a1 to a7, can also use other modes or directly with Buying pattern obtains；The thickness of dielectric substrate flaky matrix is preferably any value in 3-5mm in step S1.1, and diameter is preferred For any value in 10-15mm；In step s 2, fine and close diffusion layer powder be also not limited to only LSM powder or LSC powder or LSF powder；Any value of the particle diameter of fine and close diffusion layer powder preferably in 40-60nm, it is fine and close in mixed solution Any value of the concentration of diffusion layer powder preferably in for 2-4g/mL；Since the particle size of fine and close diffusion layer powder is dense with its Spend and very big influence is played to the effect of electrostatic spraying, by experimental results demonstrate when the particle diameter of fine and close diffusion layer powder is more than It during 60nm, can cause to spray uneven, the compactness of the fine and close diffusion layer biscuit of formation is affected, and when particle diameter is less than 40nm Shi Zehui increases the process such as difficulty of processing, increase grinding, and then reduces productivity, and therefore, the particle diameter of fine and close diffusion layer powder is excellent Any value being selected in 40-60nm；When the concentration of fine and close diffusion layer powder in mixed solution is less than 2g/mL, formed after spraying Fine and close diffusion layer biscuit there are excessive bubble stomata in fine and close diffusion layer biscuit can be caused excessive, and in the mixed solution When the concentration of fine and close diffusion layer powder is more than 4g/mL, since mixed solution concentration is excessive, it is not easy to spray in spraying, makes production Efficiency substantially reduces, while also reduces preparation speed, and waste product substandard products are more, therefore fine and close diffusion layer powder in mixed solution Any value of the concentration preferably in for 2-4g/mL；Diluent is also not limited to above-mentioned implementation into subassembly and proportioning There is provided in example, as long as certain evaporation rate can be reached；In step S2.2, the voltage of electrostatic field is preferably in 25- Any value in 30kV；Distance any value preferably among 5-10cms of the spray gun to dielectric substrate biscuit；The fine and close diffusion of formation The thickness of laminin base can voluntarily control coating thickness as needed, and the thickness of general densification diffusion layer biscuit is preferably in 1-2mm In any value；In step s3, any value of the drying temperature preferably in 100-120 DEG C；In step s 4, sintering temperature is excellent Any value being selected in 1000-1600 DEG C；Further, it is preferable to the staged sintering side heated up at a slow speed again using being first rapidly heated Method, is preferably：Any value that is warming up in 950-1000 DEG C first is carried out by the heating rate of 10 DEG C/min during sintering, then by 5 DEG C/heating rate of min is warming up to any value in 1000-1600 DEG C, then sinter 8-10h.
Meanwhile in the preparation method of lambda sensor dielectric substrate of the invention and fine and close diffusion layer double-decker, use Electrostatic spray, this method can make the preparation process mechanization, serialization, reduction waste product of fine and close diffusion layer and dielectric substrate Rate, obtains excellent coating performance, and then obtains well stable electric property, and preparation speed is especially fast, greatly improves work Productivity, so that considerable economic results in society are obtained, suitable for large-scale production.In spraying, spraying is uniform at the same time and bonds Power is strong, makes the bond strength of fine and close diffusion layer and dielectric substrate high, and the deformation of dielectric substrate and fine and close diffusion layer is decreased to minimum Degree, be less prone to crackle, and the dense structure of final obtained fine and close diffusion layer and dielectric substrate is uniform, stomata significantly subtracts It is few, the performance of the lambda sensor comprising the double-decker can be improved.
Embodiment 3
In the present embodiment, the difference with embodiment 1 and embodiment 2 is, embodiment 1 and embodiment 2 are in electricity Solve and fine and close diffusion layer biscuit is formed on matter laminin base, then sintering is cooled into double-decker, and the present embodiment is expanded in densification Dissipate and dielectric substrate biscuit is formed on laminin base, then sintering is cooled into double-decker.
With reference to Fig. 6, specifically, lambda sensor is specifically walked with the preparation method of dielectric substrate and fine and close diffusion layer double-decker It is rapid as follows：
S1, prepare fine and close diffusion layer biscuit, and the main component of the densification diffusion layer biscuit is LSM, fine and close diffusion layer biscuit Thickness be 0.96mm, a diameter of 9.82mm.
S2, using electrostatic spraying, by mixed solution, (mixed solution includes the dielectric substrate powder that mixes and dilute Release agent) it is sprayed on fine and close diffusion layer biscuit, dielectric substrate biscuit is formed on fine and close diffusion layer biscuit.
Further, step S2 includes following sub-step in the present embodiment：
S2.1, by particle diameter be 40-60nm dielectric substrate powder ultrasonic be scattered in diluent, ultrasonic 1h, is electrolysed The concentration of matter layer powder is the mixed solution of 2g/mL.Wherein, selected diluent is absolute ethyl alcohol, butanol, acetone, toluene, diformazan One or more combinations in benzene, styrene, ethyl acetate, butyl acetate, dimethylformamide, polyalcohol or phenmethylol. Preferably diluent is made of following component by mass percentage：Absolute ethyl alcohol 61.7%, dimethylbenzene 28% and acetic acid fourth Ester 10.3%, absolute ethyl alcohol, toluene, butyl acetate are non-activated thinner, do not contain active group in its molecule, are all inertia Solvent, does not participate in reaction in dilution, simply plays the purpose for the viscosity for reducing mixed solution, and then ensure the stream of spraying Smooth property and there is enough speed.Meanwhile mentioned component is in addition to playing diluting effect, to mechanical performance, thermal change temperature, resistance to Jie The influence that matter and aging damage etc. have had.In addition, the ability that coating particle carries electric charge in the electric field is inevitable electrical with coating It is related, wherein most important parameter is exactly the dielectric constant of coating.In general, the polarity of common coating is very low, and impedance is often More than 100M Ω, in order to make coating can adapt to electrostatic spraying, it is necessary to adjust coating with the higher diluent of dielectric constant Impedance, is allowed between 25-30M Ω.And butyl acetate can then play the role of strengthening the electric conductivity of mixed solution so that mixed Close solution and more can adapt to electrostatic spraying.And when selecting the proportioning of diluent, it is necessary in view of mixing the dilution formed afterwards The evaporation rate of agent, if evaporation rate is too slow, easily leads in fine and close diffusion layer biscuit and produces bubble, and then cause fine and close diffusion layer Stomata is excessive in biscuit；If evaporation rate is too fast, do not reach diluted purpose, fine and close diffusion layer biscuit and electrolyte can be influenced The bond strength of laminin base.Therefore the solvent of different boiling has been selected to mix in the proportioning of each component in selecting diluent The evaporation rate of diluent is adjusted, and the proportioning provided in the present embodiment is drawn by theory analysis and lot of experiment validation , it is directed to coordinates with dielectric substrate powder, possesses suitable evaporation rate, can reach certain dilution purpose, while again The preferred solution of the electric conductivity of mixed solution can be improved.
S2.2, sprayed using electrostatic spray：Specifically, obtained mixed solution in step S2.1 is loaded into injection In device, the electrostatic spray in the case where voltage is the electrostatic field of 30kV, the distance of spray gun to fine and close diffusion layer biscuit is 6cm, and spraying is formed Droplet dielectric substrate biscuit is formed on fine and close diffusion layer biscuit, the thickness position of the dielectric substrate biscuit of formation is 2mm, directly Footpath is 9.82mm.It is coated using electrostatic spray, the bond strength of fine and close diffusion layer biscuit and dielectric substrate biscuit can be made Higher.
S3, be placed in drying box the obtained fine and close diffusion layer biscuit with dielectric substrate biscuit in step S2 and do Dry, drying temperature is 100 DEG C, drying time 20h.
S4, be placed in high temperature furnace to the dried fine and close diffusion layer biscuit with dielectric substrate biscuit and be sintered, and sinters Temperature is 1200 DEG C.
It is further preferred that first carry out being warming up to 1100 DEG C by the heating rate of 10 DEG C/min in sintering, then by 5 DEG C/heating rate of min is warming up to 1200 DEG C, sintering time is 9.5h afterwards.Heated up at a slow speed again using this be first rapidly heated Staged sintering, in the case where reaching identical sintering effect needed for sintering temperature it is lower, save the energy, reduce into This.
The fine and close diffusion layer biscuit with dielectric substrate biscuit after sintering, be cooled to room temperature, densification after cooling by S5 Diffusion layer biscuit forms fine and close diffusion layer 2, and dielectric substrate biscuit after cooling forms dielectric substrate 3, fine and close diffusion layer 2 and electrolysis Matter layer 3 is stacked on top of each other and connected, forms double-decker, wherein the thickness of fine and close diffusion layer 2 is 0.96mm, a diameter of 9.78mm； The thickness of dielectric substrate 3 is 1.96mm, a diameter of 9.78mm.
Further, above-mentioned steps S1 includes following sub-step in the present embodiment：
S1.1, by LSM powder be squeezed into LSM flaky matrix；
LSM flaky matrix, be placed in high temperature furnace by S1.2, LSM flaky matrix is sintered, 1350 DEG C of sintering temperature, Sintering time is 6h；
LSM flaky matrix after sintering, is cooled to the furnace room temperature by S1.3, forms fine and close diffusion layer biscuit.
Since the mixed solution comprising dielectric substrate powder is being sprayed on fine and close diffusion layer biscuit using electrostatic spraying When, mixed solution can produce powerful impact force to fine and close diffusion layer biscuit, and (this impact is due to electronegative paint particles Produced between extra electric field power and electric charge under the action of Coulomb repulsion), therefore, have necessarily to the intensity of fine and close diffusion layer biscuit It is required that the destroying infection spraying effect of fine and close diffusion layer biscuit is otherwise easily caused in spraying.So preparing fine and close diffusion layer First carry out once sintered during biscuit, spraying can be received to ensure that fine and close diffusion layer biscuit possesses enough intensity.
Wherein, in step S1.1 the preparation method of LSM powder such as embodiment 1 narration, simply final LSM powder mulls extremely Granularity≤100nm, without being limited to 40-60nm.Dielectric substrate powder employed in step S2.1 is YSZ powder, The narration of the preparation method of YSZ powder such as embodiment 1, simply most YSZ powder mulls to granularity is 40-60nm at last.
Lambda sensor will be fabricated to made of above-mentioned preparation method by double-decker, i.e., as included anode 1, densification in Fig. 1 Diffusion barrier layer (referred to as fine and close diffusion layer 2), solid electrolyte layer (abbreviation dielectric substrate 3), cathode 4 and elevated-temperature seal glass glaze 5.After tested, oxygen determination scope is 0-18.7vol%.
Embodiment 4
In the present embodiment, the difference with embodiment 1 and embodiment 2 is, embodiment 1 and embodiment 2 are in electricity Solve and fine and close diffusion layer biscuit is formed on matter laminin base, then sintering is cooled into double-decker, and the present embodiment is expanded in densification Dissipate and dielectric substrate biscuit is formed on laminin base, then sintering is cooled into double-decker.
Specifically, lambda sensor is comprised the following steps that with the preparation method of dielectric substrate and fine and close diffusion layer double-decker：
S1, prepare fine and close diffusion layer biscuit, and the main component of the densification diffusion layer biscuit is LSM, fine and close diffusion layer biscuit Thickness be 1.96mm, a diameter of 9.84mm.
Mixed solution comprising the dielectric substrate powder mixed and diluent, be sprayed on using electrostatic spraying by S2 On fine and close diffusion layer biscuit, dielectric substrate biscuit is formed on fine and close diffusion layer biscuit.
Further, step S2 includes following sub-step in the present embodiment：
S2.1, by particle diameter be 40-60nm dielectric substrate powder ultrasonic be scattered in diluent, ultrasonic 1h, is electrolysed The concentration of matter layer powder is the mixed solution of 3.5g/mL.Wherein, selected diluent is absolute ethyl alcohol, butanol, acetone, toluene, two One or more combinations in toluene, styrene, ethyl acetate, butyl acetate, dimethylformamide, polyalcohol or phenmethylol. Preferably diluent is made of following component by mass percentage：Absolute ethyl alcohol 61.7%, dimethylbenzene 28% and acetic acid fourth Ester 10.3%.
S2.2, sprayed using electrostatic spray：Specifically, obtained mixed solution in step S2.1 is loaded into injection In device, the electrostatic spray in the case where voltage is the electrostatic field of 25kV, the distance of spray gun to fine and close diffusion layer biscuit is 9cm, and spraying is formed Droplet form dielectric substrate biscuit on fine and close diffusion layer biscuit, the thickness of the dielectric substrate biscuit of formation is 3mm, diameter For 9.84mm.It is coated using electrostatic spray, the bond strength of fine and close diffusion layer biscuit and dielectric substrate biscuit can be made more It is high.
S3, be placed in drying box the obtained fine and close diffusion layer biscuit with dielectric substrate biscuit in step S2 and do Dry, drying temperature is 100 DEG C, drying time 21h.
S4, be placed in high temperature furnace to the dried fine and close diffusion layer biscuit with dielectric substrate biscuit and be sintered, and sinters Temperature is 1150 DEG C.
Further, first carry out being warming up to 900 DEG C by the heating rate of 10 DEG C/min in sintering, then by 5 DEG C/min's Heating rate is warming up to 1150 DEG C, maintains this temperature to sinter 11.5h afterwards.Using this rank for being first rapidly heated and heating up at a slow speed again Ladder type sinters, and the sintering temperature needed in the case where reaching identical sintering effect is lower, saves the energy, reduces cost.
The fine and close diffusion layer biscuit with dielectric substrate biscuit after sintering, be cooled to room temperature, densification after cooling by S5 Diffusion layer biscuit forms fine and close diffusion layer 2, and dielectric substrate biscuit after cooling forms dielectric substrate 3, fine and close diffusion layer 2 and electrolysis Matter layer 3 is stacked on top of each other and connected, forms double-decker, wherein the thickness of fine and close diffusion layer 2 is 1.98mm, a diameter of 9.79mm, The thickness of dielectric substrate 3 is 2.96mm, a diameter of 9.79mm.
Further, above-mentioned steps S1 includes following sub-step in the present embodiment：
S1.1, by LSM powder be squeezed into LSM flaky matrix；
LSM flaky matrix, be placed in high temperature furnace by S1.2, LSM flaky matrix is sintered, 1380 DEG C of sintering temperature, Sintering time is 6h；
LSM flaky matrix after sintering, is cooled to the furnace room temperature by S1.3, forms fine and close diffusion layer biscuit；
Wherein, the LSM powder employed in step S1.1 and the method for embodiment 1 are essentially identical, and difference is, presses Molar ratio, La (NO3)3·Sr(NO3)2·Mn(NO3)20.3 ﹕ 1 of=0.7 ﹕, and final LSM powder mulls are to granularity≤100nm .Dielectric substrate powder employed in step S2.1 is YSZ powder, and the preparation method such as embodiment 1 of YSZ powder is chatted State, wherein it is 40-60nm that final YSZ powder, which needs to be ground to granularity,.
Lambda sensor will be fabricated to made of above-mentioned preparation method by double-decker, i.e., as included anode 1, densification in Fig. 1 Diffusion barrier layer (referred to as fine and close diffusion layer 2), solid electrolyte layer (abbreviation dielectric substrate 3), cathode 4 and elevated-temperature seal glass glaze 5.After tested, oxygen determination scope is 0-17.8vol%.
Certainly the present invention forms dielectric substrate biscuit on fine and close diffusion layer biscuit, and then sintering is cooled into double-decker Preparation method in be not limited to above-described embodiment, in step sl, the main component of fine and close diffusion layer biscuit is is not limited to Only LSM powder or LSC powder or LSF powder；The step of preparing fine and close diffusion layer biscuit is also not limited to step S1.1 to S1.3, can also use other modes；The step of preparing LSM powder is also not limited to b1 to b7, can also use it His mode is directly obtained with buying pattern.
In step s 2, specifically, in step S2.1, dielectric substrate powder is also not limited to only YSZ powder, also may be used To be LSGM powder；Any value of the concentration of dielectric substrate powder preferably in for 2-4g/mL in mixed solution；Diluent into Subassembly and proportioning are also not limited to what is provided in above-described embodiment, as long as certain evaporation rate can be reached； In step S2.2, any value of the voltage of electrostatic field preferably in 25-30kV；The distance of spray gun to fine and close diffusion layer biscuit is preferred Any value in 5-10cm；The thickness of the dielectric substrate biscuit of formation can voluntarily control coating thickness as needed, generally Any value of the thickness of dielectric substrate biscuit preferably in 3-5mm.
In step s3, any value of the drying temperature preferably in 100-120 DEG C.
In step s 4, any value of the sintering temperature preferably in 1000-1600 DEG C；It is it is preferred that slow using being first rapidly heated again The staged sintering of speed heating, wherein：900-1100 DEG C first is warming up to by the heating rate of 10 DEG C/min during sintering, then by 5 DEG C/heating rate of min is warming up to 1000-1200 DEG C, keep the temperature to sinter 8-12h afterwards.
Meanwhile in the preparation method of lambda sensor dielectric substrate of the invention and fine and close diffusion layer double-decker, use Prepared by electrostatic spray, this method can make the preparation process mechanization, serialization, reduction of fine and close diffusion layer and dielectric substrate useless Product rate, obtains excellent coating performance, and then obtains well stable electric property, and preparation speed is especially fast, greatly improves labor Dynamic productivity, so that considerable economic results in society are obtained, suitable for large-scale production.Sprayed at the same time in spraying uniform and viscous It is strong with joint efforts, make the bond strength of fine and close diffusion layer and dielectric substrate high, the deformation of dielectric substrate and fine and close diffusion layer is decreased to most Low degree, be less prone to crackle, and the dense structure of final obtained fine and close diffusion layer and dielectric substrate is uniform, stomata significantly subtracts It is few, the performance of the lambda sensor comprising the double-decker can be improved.
To sum up, the preparation method of above two lambda sensor dielectric substrate and fine and close diffusion layer double-decker, two kinds of sides Method is to form dielectric substrate and fine and close diffusion layer double-decker using electrostatic spray, and is to be initially formed dielectric substrate 3 With the biscuit of one in fine and close diffusion layer 2, then another layer of electrostatic spraying on this biscuit.
No matter above-mentioned any method, the combination of the dielectric substrate that can be prepared and fine and close diffusion layer double-decker is strong Degree is high, while it is especially fast to prepare speed, greatly improves labor productivity, so as to obtain considerable economic results in society, is suitable for Large-scale production.Specifically, by above two method, prepared using electrostatic spray, fine and close diffusion layer and electricity can be made The preparation process mechanization, serialization, reduction rejection rate of matter layer are solved, obtains excellent coating performance, and then obtain good stablize Electric property, it is especially fast to prepare speed, greatly improves labor productivity, so as to obtain considerable economic results in society, is applicable in In large-scale production.In spraying, spraying is uniformly at the same time and bonding force is strong, makes the bond strength of fine and close diffusion layer and dielectric substrate Height, the deformation of dielectric substrate and fine and close diffusion layer are decreased to minimum level, are less prone to crackle, and final obtained fine and close diffusion The dense structure of layer and dielectric substrate is uniform, stomata substantially reduces, and can improve the performance of the lambda sensor comprising the double-decker.
More than, only it is presently preferred embodiments of the present invention, is not the limitation that other forms are done to invention, it is any to be familiar with Professional and technical personnel is changed or is modified as the equivalence enforcement of equivalent variations possibly also with the technology contents of the disclosure above Example.But it is every without departing from technical solution of the present invention content, what the technical spirit according to the present invention made above example appoints What simple modification, equivalent variations and remodeling, still falls within the protection domain of technical solution of the present invention.

Claims (10)

1. the preparation method of a kind of lambda sensor dielectric substrate and fine and close diffusion layer double-decker, it is characterised in that including such as Lower step：
S1, prepare dielectric substrate biscuit；
S2, using electrostatic spraying be sprayed on institute by the mixed solution comprising fine and close the diffusion layer powder and diluent mixed State on dielectric substrate biscuit, fine and close diffusion layer biscuit is formed on the dielectric substrate biscuit；
S3, be dried the obtained dielectric substrate biscuit with fine and close diffusion layer biscuit in step S2；
S4, be sintered the dried dielectric substrate biscuit with fine and close diffusion layer biscuit；
Dielectric substrate biscuit with fine and close diffusion layer biscuit after the sintering, be cooled to room temperature, densification after cooling by S5 Diffusion layer biscuit forms fine and close diffusion layer, and dielectric substrate biscuit after cooling forms dielectric substrate, the densification diffusion layer and institute It is stacked on top of each other and connected to state dielectric substrate, forms double-decker.
2. the preparation method of lambda sensor dielectric substrate according to claim 1 and fine and close diffusion layer double-decker, its It is characterized in that,
In step s 2, the process conditions of electrostatic spraying are：
The voltage of electrostatic field is 25-30kV, and the distance of spray gun and the dielectric substrate biscuit is 5-10cm.
3. the preparation method of lambda sensor dielectric substrate according to claim 1 and fine and close diffusion layer double-decker, its It is characterized in that,
The diluent is absolute ethyl alcohol, butanol, acetone, toluene, dimethylbenzene, styrene, ethyl acetate, butyl acetate, diformazan One or more combinations in base formamide, polyalcohol or phenmethylol.
4. the preparation method of lambda sensor dielectric substrate according to claim 3 and fine and close diffusion layer double-decker, its It is characterized in that,
The diluent is made of following component by mass percentage：
Absolute ethyl alcohol 37.5%；
Butanol 12%；
Toluene 13.5%；
Ethyl acetate 19%；
Butyl acetate 18%.
5. lambda sensor dielectric substrate according to any one of claim 1 to 4 and fine and close diffusion layer double-decker Preparation method, it is characterised in that
In step s 2, the particle diameter of the fine and close diffusion layer powder be 40-60nm, densification diffusion layer powder in the mixed solution Concentration be 2-4g/mL；
In step s3, the drying temperature is 100-120 DEG C；
In step s 4, the sintering temperature is 1000-1600 DEG C.
6. the preparation method of a kind of lambda sensor dielectric substrate and fine and close diffusion layer double-decker, it is characterised in that including such as Lower step：
S1, prepare fine and close diffusion layer biscuit；
S2, using electrostatic spraying the mixed solution comprising the dielectric substrate powder mixed and diluent is sprayed on it is described On fine and close diffusion layer biscuit, dielectric substrate biscuit is formed on the fine and close diffusion layer biscuit；
S3, be dried the obtained fine and close diffusion layer biscuit with dielectric substrate biscuit in step S2；
S4, be sintered the dried fine and close diffusion layer biscuit with dielectric substrate biscuit；
The fine and close diffusion layer biscuit with dielectric substrate biscuit after the sintering, be cooled to room temperature, densification after cooling by S5 Diffusion layer biscuit forms fine and close diffusion layer, and dielectric substrate biscuit after cooling forms dielectric substrate, the densification diffusion layer and institute It is stacked on top of each other and connected to state dielectric substrate, forms double-decker.
7. the preparation method of lambda sensor dielectric substrate according to claim 6 and fine and close diffusion layer double-decker, its It is characterized in that,
In step s 2, the process conditions of electrostatic spraying are：
The voltage of electrostatic field is 25-30kV, and the distance of spray gun and the dielectric substrate biscuit is 5-10cm.
8. the preparation method of lambda sensor dielectric substrate according to claim 6 and fine and close diffusion layer double-decker, its It is characterized in that,
The diluent is absolute ethyl alcohol, butanol, acetone, toluene, dimethylbenzene, styrene, ethyl acetate, butyl acetate, diformazan One or more combinations in base formamide, polyalcohol or phenmethylol.
9. the preparation method of lambda sensor dielectric substrate according to claim 8 and fine and close diffusion layer double-decker, its It is characterized in that,
The diluent is made of following component by mass percentage：
Absolute ethyl alcohol 61.7%；
Dimethylbenzene 28%；
Butyl acetate 10.3%.
10. lambda sensor dielectric substrate and fine and close diffusion layer double-decker according to any one of claim 6 to 9 Preparation method, it is characterised in that
In step s 2, the particle diameter of the dielectric substrate powder is 40-60nm, and dielectric substrate powder is dense in the mixed solution Spend for 2-4g/mL；
In step s3, the drying temperature is 100-120 DEG C；
In step s 4, the sintering temperature is 1000-1600 DEG C.
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