CN108132291B - Utilize the method for impedance spectrum calibration oxygen concentration - Google Patents

Utilize the method for impedance spectrum calibration oxygen concentration Download PDF

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CN108132291B
CN108132291B CN201711408178.XA CN201711408178A CN108132291B CN 108132291 B CN108132291 B CN 108132291B CN 201711408178 A CN201711408178 A CN 201711408178A CN 108132291 B CN108132291 B CN 108132291B
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oxygen concentration
impedance spectrum
biscuit
electrode
powder
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CN108132291A (en
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刘涛
王相南
于景坤
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Northeastern University China
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/409—Oxygen concentration cells
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4071—Cells and probes with solid electrolytes for investigating or analysing gases using sensor elements of laminated structure
    • G01N27/4072—Cells and probes with solid electrolytes for investigating or analysing gases using sensor elements of laminated structure characterized by the diffusion barrier
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4073—Composition or fabrication of the solid electrolyte

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Abstract

The present invention relates to the technical fields more particularly to a kind of method using impedance spectrum calibration oxygen concentration using electrochemical method test oxygen concentration.In method using impedance spectrum calibration oxygen concentration of the invention, first lambda sensor is placed in furnace and connects electrochemical workstation, lambda sensor is heated to set temperature again, then it is filled with detection gas known to oxygen concentration into furnace, impedance spectrum is finally obtained using ac impedance spectroscopy detection pattern using electrochemical workstation.Impedance spectrum is mapped with oxygen concentration as a result, provides a kind of novel oxygen concentration scaling method.

Description

Utilize the method for impedance spectrum calibration oxygen concentration
Technical field
The present invention relates to the technical field of use electrochemical method test oxygen concentration more particularly to a kind of utilization impedance spectrum marks Determine the method for oxygen concentration.
Background technique
The each process such as coking, sintering, ironmaking, steel-making, steel rolling use miscellaneous heating furnace in ferrous metallurgical industry, disappear Consume mass energy.Make heating furnace optimization burning, air-fuel ratio is highly important thermal parameter, and only air-fuel ratio is reasonable, ability Reach ideal ignition temperature.If air supply amount is excessive, oxidizing atmosphere is presented in furnace, furnace temperature reduces, workpiece combustion Consumption increases.Otherwise fuel gas supply amount is excessive, equally furnace temperature is caused to reduce, and incomplete combustion, has not only wasted combustion gas but also polluted environment. Therefore, the proportion (O of air and combustion gas is accurately controlled2: CO), instructing operator's reasonable operation is a vital task.
Oxygen concentration using oxygen sensor in real time, in on-line checking furnace gas is a kind of directly effective method.Electricity Chemical lambda sensor is divided into concentration cell type and two kinds of limit-current type.Both sensors are respectively in electromotive force mode and the limit It works under current-mode, has obtained electromotive force signal and current signal, oxygen concentration then can be obtained according to Nernst equation.
Oxygen concentration either is obtained using electromotive force signal or current signal, sensitivity is to be improved, therefore, for Lambda sensor also needs further to study, can more delicately detect oxygen concentration.
Summary of the invention
(1) technical problems to be solved
The purpose of the present invention is to provide a kind of methods using impedance spectrum calibration oxygen concentration, for studying sensitivity more High Novel oxygen method for measurement of concentration.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses include:
The present invention provides a kind of method using impedance spectrum calibration oxygen concentration, includes the following steps: S1, sets lambda sensor In furnace, wherein the lambda sensor includes double-layer structure, the Yi Jilian formed by dense diffusion barrier and solid electrolyte layer The first electrode and second electrode at double-layer structure both ends are connect, connects electrochemical operation between the first electrode and the second electrode It stands；S2, the lambda sensor being located in furnace is heated to set temperature；S3, detection gas known to oxygen concentration are filled with into furnace； S4, using electrochemical workstation, impedance spectrum is obtained using ac impedance spectroscopy detection pattern.
According to the present invention, step S1-S4 is repeated with the different set temperature of multiple groups respectively, by all set temperature institutes Corresponding impedance spectrum set is depicted as temperature comparisons' figure.
According to the present invention, the different set temperature of multiple groups is respectively positioned in the range of 650 DEG C -850 DEG C.
According to the present invention, with multiple groups there are the detection gas of different oxygen concentrations to repeat step S1-S4 respectively, will owns Impedance spectrum set corresponding to detection gas is depicted as an oxygen concentration comparison diagram.
According to the present invention, the oxygen concentration of multiple groups detection gas is greater than 0 and is less than or equal to 21%.
According to the present invention, it is connected with the first platinum filament on the first electrode, is connected with the second platinum filament on the second electrode, first Electrode passes through the first platinum filament with second electrode respectively and the second platinum filament connects electrochemical workstation.
According to the present invention, the material of dense diffusion barrier is LSM, LSC or LSF；The material of solid electrolyte layer is LSGM。
(3) beneficial effect
The beneficial effects of the present invention are:
In method using impedance spectrum calibration oxygen concentration of the invention, first lambda sensor is placed in furnace and connects electrochemistry Work station, then lambda sensor is heated to set temperature, it is then filled with detection gas known to oxygen concentration into furnace, finally utilizes Electrochemical workstation obtains impedance spectrum using ac impedance spectroscopy detection pattern.Impedance spectrum is mapped with oxygen concentration as a result, is mentioned A kind of novel oxygen concentration scaling method is supplied, for studying the higher Novel oxygen method for measurement of concentration of sensitivity.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the lambda sensor used in following examples one；
Fig. 2 is the impedance spectrum obtained of method provided by embodiment one in following specific embodiment；
Fig. 3 is the temperature comparisons' figure obtained of method provided by embodiment two in following specific embodiment；
Fig. 4 is the oxygen concentration comparison diagram obtained of method provided by embodiment three in following specific embodiment.
[appended drawing reference]
1: the first platinum filament；2: first electrode；3: dense diffusion barrier；4: solid electrolyte layer；5: second electrode；6: the Two platinum filaments；7: electrochemical workstation.
Specific embodiment
In order to preferably explain the present invention, in order to understand, with reference to the accompanying drawing, by specific embodiment, to this hair It is bright to be described in detail.
Embodiment one
A kind of method using impedance spectrum calibration oxygen concentration is provided in the present embodiment, and this method comprises the following steps:
S1, lambda sensor as shown in Figure 1 is placed in furnace, wherein the lambda sensor includes by dense diffusion barrier 3 The double-layer structure that is formed with solid electrolyte layer 4 and it is connected to the first electrode 2 and second electrode 5 at double-layer structure both ends, Electrochemical workstation 7 is connected between first electrode 2 and second electrode 5.
S2, the lambda sensor being located in furnace is heated to set temperature, in the present embodiment, set temperature is 650 DEG C, i.e., Lambda sensor is heated to 650 DEG C.
S3, it is filled with detection gas known to oxygen concentration into furnace, is filled with the detection that oxygen concentration is 5.3% in the present embodiment Gas, oxygen concentration mentioned by this paper are volumetric concentration.
S4, using electrochemical workstation 7, impedance spectrum, such as Fig. 2 are obtained using ac impedance spectroscopy detection pattern.
In the above process, lambda sensor, set temperature, electrochemical workstation 7 running parameter determine after, impedance spectrum and inspection It is determining for surveying the relationship of the oxygen concentration of gas, that is to say, that in lambda sensor, the work of set temperature, electrochemical workstation 7 In the case that parameter is fixed, a kind of detection gas of oxygen concentration correspond essentially to an impedance spectrum.In this way, homogeneous in above-mentioned condition Deng in the case where, the oxygen concentration of detection gas can be demarcated by impedance spectrum, as long as it is dense to obtain unknown oxygen at the standard conditions later The impedance spectrum of the gas of degree, you can learn that the oxygen concentration of the gas.
Specifically, in the present embodiment, in step sl, the material of solid electrolyte layer 4 is LSGM, solid electrolyte layer 4 Diameter be 10mm, with a thickness of 2mm.The material of dense diffusion barrier 3 is LSM, and the diameter of dense diffusion barrier 3 is 10mm, with a thickness of 1mm.Solid electrolyte layer 4 and dense diffusion barrier 3 are fixed together to form double-layer structure.First Electrode 2 and second electrode 5 are connected on two circular end faces of double-layer structure, and first electrode 2 and second electrode 5 are Circular electrode, the diameter of the two are 9mm.It is connected with the first platinum filament 1 on the first electrode 2, is connected in second electrode 5 Second platinum filament 6 connects electrochemical workstation 7, the electrochemistry work that the present embodiment uses between the first platinum filament 1 and the second platinum filament 6 Make the electrochemical workstation 7 that station 7 leads to (Metrohm Autolab) production for Switzerland ten thousand, model PGSTAT204, voltage is 100-240V。
More specifically, the manufacturing process of lambda sensor used in the present embodiment are as follows: the first step, using electrostatic spray Form double-layer structure；Second step, in the two sides of double-layer structure, electrode coated material (diameter 9mm) is to be used to form first electrode 2 and second electrode 5, platinum filament is separately connected on the electrode material of two sides, 800 DEG C are heat-treated 1 hour, form lambda sensor.
Wherein, above-mentioned electrode material can be the common electrode materials such as the noble metals such as platinum, gold, silver, adopt in the present embodiment Electrode is made with platinum；First platinum filament 1 and the second platinum filament 6 also could alternatively be the conducting wire of other materials.
Wherein, forming double-layer structure using electrostatic spray in the first step includes following sub-step:
First sub-step prepares electrolyte layer biscuit, and the main component of the electrolyte biscuit is LSGM.
Second sub-step, by partial size be 40-60nm fine and close diffusion layer powder (main component LSM) ultrasonic disperse in dilute Agent is released (to be made of following component by mass percentage: dehydrated alcohol 37.5%, butanol 12%, toluene 13.5%, ethyl acetate 19% and butyl acetate 18%) in, ultrasonic 1h obtains densification so that fine and close diffusion layer powder is evenly distributed in diluent The concentration of diffusion layer powder is the mixed solution of 3g/mL.Then mixed solution obtained is fitted into syringe, is in voltage The distance of electrostatic spray under the electrostatic field of 25kV, spray gun to electrolyte layer biscuit is 5cm, and the droplet formed by spraying is in electrolyte Fine and close diffusion layer biscuit is formed on laminin base.
Third sub-step, the electrolyte layer biscuit obtained in the second sub-step with fine and close diffusion layer biscuit is placed in it is dry It is dried in dry case, drying temperature is 115 DEG C, drying time 18h.During this, diluent is adequately volatilized.
Electrolyte layer biscuit with fine and close diffusion layer biscuit after drying is placed in high temperature furnace and carries out by the 4th sub-step Sintering is first warming up to 1000 DEG C by the heating rate of 10 DEG C/min in sintering, is then warming up to by the heating rate of 5 DEG C/min 1500 DEG C, persistently it is sintered 8h at this temperature later.
The double-layer structure formed using above-mentioned electrostatic spray, dense structure is uniform, stomata is few, and consistency is improved, So that the oxygen determination performance and oxygen determination range of lambda sensor are improved, it is particularly suited for calibration oxygen concentration.
Wherein, the component of diluent is arranged, dehydrated alcohol, butanol, toluene, ethyl acetate and butyl acetate are non- Reactive diluent does not contain active group in molecule, is all atent solvent, does not participate in reaction in dilution, only rise To the purpose for the viscosity for reducing mixed solution, and then guarantees the fluency of spraying and there is enough speed.Meanwhile mentioned component Other than playing diluting effect, the influence that has had to mechanical performance, thermal change temperature, media-resistant and aging damage etc..In addition, coating The ability that particle carries charge in the electric field is inevitable related with the electrical property of coating, wherein most important parameter is exactly the dielectric of coating Constant.In general, the polarity of common coating is very low, and impedance is commonly greater than 100M Ω, in order to make coating can adapt to electrostatic It applies, it is necessary to which the impedance that coating is adjusted with the higher diluent of dielectric constant is allowed between 25-30M Ω.And ethyl acetate And/or butyl acetate can then play the role of enhancing the electric conductivity of mixed solution, so that mixed solution more can adapt to electrostatic Spraying.And when selecting the proportion of diluent, the evaporation rate of the diluent in view of being formed after mixing is needed, if volatilization speed Degree is too slow, easily leads in fine and close diffusion layer biscuit and generates bubble, and then causes stomata in fine and close diffusion layer biscuit excessive；If volatilization Speed is too fast, then diluted purpose is not achieved, and will affect the bond strength of fine and close diffusion layer biscuit and electrolyte layer biscuit.Therefore The solvent of different boiling has been selected to mix to adjust the evaporation rate of diluent when the proportion of each ingredient in selecting diluent, And the proportion provided in the present embodiment is obtained by theory analysis and lot of experiment validation, is directed to and fine and close diffusion layer Powder cooperation, has suitable evaporation rate, can reach certain dilution purpose, while the conduction of mixed solution can be improved again The preferred embodiment of property.Using this diluent, performance more preferably lambda sensor can be produced, delicately oxygen determination is more conducive to.
Specifically, in the first sub-step, electrolyte layer biscuit is prepared by following steps:
Electrolyte layer raw material powder (being in the present embodiment LSGM powder) is squeezed into circular electrolyte layer by step 1 Flaky matrix.
Electrolyte layer flaky matrix is placed in high temperature furnace by step 2, is sintered to electrolyte layer flaky matrix, sintering Temperature is 1250 DEG C, sintering time 7.5h.
Sintered electrolyte layer flaky matrix is cooled to the furnace room temperature by step 3, forms electrolyte layer biscuit.
Wherein, used LSGM powder is preferably made by following steps:
A1, La is calcined respectively2O3Powder and MgO powder, La2O3The calcination temperature of powder is 1050 DEG C, and calcination time is 10.5h；The calcination temperature of MgO powder is 1000 DEG C, calcination time 9h.
A2, La is weighed respectively2O3Powder, SrCO3Powder, Ga2O3Powder and MgO powder, wherein between the value of each raw material Relationship be according to 0.83 ﹕ of molar ratio La ﹕ Sr ﹕ Ga ﹕ Mg ﹕ O=0.8 0.2 ﹕ of ﹕, 0.17 ﹕ 2.815.In the present embodiment specifically, By balance preheating more than half an hour, the horizontal bead of adjustment keeps balance holding horizontal, uses calibration of weight.Specifically, in the present embodiment Middle selection La2O3Powder 10.4259g, SrCO3Powder 2.3621g, Ga2O3Powder 6.2232g, MgO powder 0.5539g.
A3, by load weighted La2O powder, SrCO3Powder, Ga2O3Powder and MgO powder are mixed to form mixed-powder Mixed-powder is ground to granularity≤100 μm by 19.5651g.In the present embodiment specifically, by load weighted La2O powder, SrCO3Powder, Ga2O3Powder and MgO powder are placed in agate pot, agate ball will be added by layer on it, the accumulation of agate ball is added Height is consistent with the height of above-mentioned powder, is subsequently poured into alcohol, and alcohol height is consistent with ball, seals up sealing ring, covers agate lid, After rocking, agate pot is placed in resin ball grinder, fills up paper between agate pot and resin ball milling, big lid is covered, uses screw It tightens and is placed on planetary ball mill, grinding is taken out after 8 hours, at this time granularity≤100 μm of mixed-powder.
A4, mixed-powder is dried.Specifically, agate pot is placed in baking oven, to the mixed-powder after grinding into Row drying, drying temperature are 90 DEG C, drying time 6h.
A5, the level-one biscuit that mixed-powder is pressed into disc.Specifically, preparing the mold that diameter is 20mm, wine is used Smart cotton rub wash clean keeps surface, inner wall clean；The mixed-powder that grinding has been dried is poured slowly into mold, shakes, makes powder Material keeps horizontal as far as possible in a mold, is put into compression bar, is placed in homemade pressure-like machine.The pressure of application 20MPa, pressure maintaining 5 minutes, Mixed-powder is suppressed, demoulding obtains the level-one biscuit that diameter is 20mm.Later, pressure-like mold is cleaned.
A6, level-one biscuit is sintered, is 40mm, is highly 45mm specifically, above-mentioned level-one biscuit is put into diameter Corundum crucible in, cover corundum lid, label is placed in high temperature reheating furnace and is sintered, and sintering temperature is 1100 DEG C, when sintering Between be 16h.
A7, after level-one biscuit is cooling, level-one biscuit is ground into the level-one powder of granularity≤100 μm.Specifically, by one Grade biscuit is placed in agate mortar, covers aluminium foil, and there are osculums, is allowed to crush with grinding rod pressure level-one biscuit, then, manually not It rests and grinds 2h, grind granularity≤100 μm of the powder of formation, form level-one powder.
A8, the second level biscuit that level-one powder is pressed into disc.Specifically, preparing the mold that diameter is 20mm, wine is used Smart cotton rub wash clean keeps surface, inner wall clean；The level-one powder that grinding has been dried is poured slowly into mold, shakes, makes one Grade powder keeps horizontal as far as possible in a mold, is put into compression bar, is placed in homemade pressure-like machine.Apply the pressure of 20MPa, pressure maintaining 5 Minute, mixed-powder is suppressed, demoulding obtains the second level biscuit that diameter is 20mm.Later, pressure-like mold is cleaned.
A9, second level biscuit is sintered, is 40mm, is highly 45mm specifically, second level biscuit is gently put into diameter Corundum crucible in, cover corundum lid, label is placed in high temperature reheating furnace and is sintered, and sintering temperature is 1300 DEG C, and sintering time is 16 hours.
A10, after second level biscuit is cooling, second level biscuit is ground into the second level powder of granularity≤100 μm.Specifically, will Second level biscuit is placed in agate mortar, covers aluminium foil, and there are osculums, is allowed to crush with grinding rod pressure second level biscuit, then, manually It does not rest and grinds 2h, grind granularity≤100 μm of the powder of formation, form second level powder.
A11, the three-level powder that second level powder is further ground into granularity≤80 μm.Specifically, weighing several pieces about The second level powder of 0.4g, the second patent flour feed powder material of several pieces 2g are placed in clean mortar, every part of one drop glycerine of powder supplying (glycerol), is dipped with tweezers, is instilled in mortar.It mixes second level powder with glycerine (glycerol), does not rest manually and grind 15 points Clock.
A12, compacting three-level powder, are formed as the three-level biscuit of disc.Specifically, least disadvantage shifts mixed powder Expect that on template, slowly pouring into the diameter that alcohol swab scrubs be gently to shake in the mold of 10mm, makes mixed Powder surfacing, is put into pressure-like bar, continuous compressed minitablets, applies 20MPa pressure, and pressure maintaining 5 minutes.
A13, three-level biscuit is sintered, is 40mm, is highly 45mm specifically, three-level biscuit is gently put into diameter Corundum crucible in, cover corundum lid, label is placed in high temperature reheating furnace and is sintered, and sintering temperature is 1500 DEG C, and sintering time is 16h。
A14, the LSGM powder that three-level biscuit is ground into granularity≤100 μm.Specifically, after three-level biscuit is cooling, it will Three-level biscuit is placed in agate mortar, is ground to sintered three-level biscuit, until the granularity for the powder that grinding is formed≤ 100 μm, obtain LSGM powder.
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 ﹕ carries out ingredient；
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 additional amount of deionized water is so that original Subject to material sufficiently dissolution；
B3, by La (NO3)3Aqueous solution, Sr (NO3)2Aqueous solution and Mn (NO3)2Aqueous solution mixing, is made mixed solution；
B4, citric acid solution citric acid is added while stirring into mixed solution, after mixing evenly, ethylene glycol is added, 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% range Interior, in molar ratio, Jin belongs to Yang Li ﹕ Ning Meng Suan ﹕ ethylene glycol=1 ﹕, 4.8 ﹕ 1.2 in mixed solution；
B5, sol-gel precursor is placed in drying oven, sol-gel precursor is dried, drying temperature is located at In the range of 90 DEG C；
B6, the sol-gel precursor after drying is placed in high temperature furnace, to by the sol-gel precursor after drying into Row calcining, calcination temperature are located in the range of 850 DEG C, and calcination time is located at 5.5h, and solid-solution powder is made；
B7, solid-solution powder is placed in agate mortar, 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.
Certainly, the present invention is not limited to this, and the material of fine and close diffusion layer can also be LSC or LSF.Above-mentioned set temperature not office It is limited to 650 DEG C, is preferably chosen in the range of 650 DEG C -850 DEG C；The oxygen concentration for the detection gas being filled with is also not limited to 5.3%, preferably chosen in the range of being greater than 0 and being less than or equal to 21%.
Embodiment two
In the present embodiment, it is based on embodiment one, repeats step S1-S4 respectively with 6 groups of different set temperatures and (changes Yan Zhi is repeated 6 times step S1 to step S4, every time in set temperature only in step S2 change), obtain 6 impedance spectrums, will Impedance spectrum set corresponding to all set temperatures is depicted as temperature comparisons and schemes (referring to Fig. 3).Wherein, 6 groups of different setting temperature Degree includes 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 820 DEG C and 850 DEG C.
Wherein, what the large icons in Fig. 3 went out is that impedance spectrum set corresponding to all set temperatures is depicted as temperature comparisons Figure, and the small figure in Fig. 3 is the amplification in region corresponding to 700 DEG C, 750 DEG C, 800 DEG C, 820 DEG C and 850 DEG C in big figure, namely It is clearer show 700 DEG C, 750 DEG C, 800 DEG C, 820 DEG C and 850 DEG C corresponding to impedance spectrum comparison.
As can be seen from Figure 3, in the Ohmic resistance that the intercept of high frequency region and real axis intersection point is sensor, including solid electrolytic Matter resistance, electrode resistance and lead resistance.In the Ohmic resistance and polarization electricity that the intercept of low frequency range and real axis intersection point is sensor The sum of resistance.And under different temperatures, the difference of impedance spectrum is apparent and there are certain rules, and therefore, impedance spectrum is for temperature Sensitivity is very high, is conducive to the oxygen concentration for sensitively measuring unknown gas.
Certainly, in other embodiments, set temperature is not limited to 6 groups, and the value of each set temperature is also not limited to 6 values are stated, are preferably chosen in the range of 650 DEG C -850 DEG C.
Embodiment three
In the present embodiment, it is based on embodiment one, is repeated respectively with 12 groups of detection gas with different oxygen concentrations Step S1-S4 (in other words, be repeated 12 times step S1 to step S4, every time in the oxygen concentrations of only detection gas change), obtain Then impedance spectrum set corresponding to all detection gas is depicted as an oxygen concentration comparison diagram (referring to figure by 12 impedance spectrums 4).Wherein, the oxygen concentration of 12 groups of detection gas be respectively 0.2%, 1.2%, 3.0%, 5.2%, 6.8%, 9.1%, 10.9%, 13.1%, 15.0%, 17.1%, 19.0%, 20.9%.
Figure 4, it is seen that the intercept (Ohmic resistance) of high frequency region and real axis intersection point is almost unchanged, low frequency range and high frequency The difference (polarization resistance) of the intercept of area and real axis intersection point increases with the increase of oxygen content.Also, in oxygen concentration minor change When (such as comparison 19.0% and 20.9%), the difference of impedance spectrum is all very big, therefore, impedance spectrum for oxygen concentration sensitivity very Height is conducive to the oxygen concentration for sensitively measuring unknown gas.
Certainly, in other embodiments, oxygen concentration is not limited to above-mentioned 12 values, can also be greater than 0 and be less than or equal to It is chosen in the range of 21% such as 18.6%, 19.2%.
Based on the above embodiments two with embodiment three it will be evident that because of the area different oxygen concentrations corresponding impedance spectrum You Hen great Not, it after demarcating oxygen concentration using impedance spectrum, when detecting unknown gas, is worked, is passed through under impedance mode using lambda sensor Its impedance spectrum is obtained, can be obtained its oxygen content, this method has higher sensitivity.
The above is only a preferred embodiment of the present invention, for those of ordinary skill in the art, according to the present invention Thought, there will be changes in the specific implementation manner and application range, and the content of the present specification should not be construed as to the present invention Limitation.

Claims (4)

1. a kind of method using impedance spectrum calibration oxygen concentration, which comprises the steps of:
S1, lambda sensor is placed in furnace, wherein the lambda sensor includes by dense diffusion barrier and solid electrolyte layer shape At double-layer structure and be connected to the first electrode and second electrode at the double-layer structure both ends, in the first electrode and Electrochemical workstation is connected between the second electrode；
S2, the lambda sensor being located in the furnace is heated to set temperature；
Detection gas known to oxygen concentration are filled in S3, Xiang Suoshu furnace；
S4, using the electrochemical workstation, impedance spectrum is obtained using ac impedance spectroscopy detection pattern；
Step S1-S4 is repeated with the different set temperature of multiple groups respectively, by impedance spectrum collection corresponding to all set temperatures Conjunction is depicted as temperature comparisons' figure, and the different set temperature of multiple groups is respectively positioned in the range of 650 DEG C -850 DEG C；
Wherein, double-layer structure, including following sub-step are formed using electrostatic spray in the first step:
First sub-step prepares electrolyte layer biscuit；
Second sub-step, by partial size be 40-60nm fine and close diffusion layer powder ultrasonic be scattered in diluent, ultrasonic 1h so that Fine and 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, so Mixed solution obtained is fitted into syringe afterwards, the electrostatic spray in the case where voltage is the electrostatic field of 25kV, spray gun to electrolyte layer The distance of biscuit is 5cm, and the droplet formed by spraying forms fine and close diffusion layer biscuit on electrolyte layer biscuit, wherein dilution Agent is made of following component by mass percentage: dehydrated alcohol 37.5%, butanol 12%, toluene 13.5%, ethyl acetate 19% and butyl acetate 18%；
Electrolyte layer biscuit obtained in second sub-step with fine and close diffusion layer biscuit is placed in drying box by third sub-step In be dried, drying temperature be 115 DEG C, drying time 18h；
The electrolyte layer biscuit with fine and close diffusion layer biscuit after drying is placed in high temperature furnace and burns by the 4th sub-step Knot is first warming up to 1000 DEG C by the heating rate of 10 DEG C/min in sintering, is then warming up to by the heating rate of 5 DEG C/min 1500 DEG C, persistently it is sintered 8h at this temperature later.
2. the method according to claim 1 using impedance spectrum calibration oxygen concentration, which is characterized in that
With multiple groups there are the detection gas of different oxygen concentrations to repeat step S1-S4 respectively, it will be corresponding to all detection gas Impedance spectrum set be depicted as an oxygen concentration comparison diagram.
3. the method according to claim 2 using impedance spectrum calibration oxygen concentration, which is characterized in that
The oxygen concentration of multiple groups detection gas is greater than 0 and is less than or equal to 21%.
4. the method according to claim 1 using impedance spectrum calibration oxygen concentration, which is characterized in that
It is connected with the first platinum filament on the first electrode, is connected with the second platinum filament, first electricity in the second electrode Pole passes through first platinum filament with the second electrode respectively and connects the electrochemical workstation with second platinum filament.
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