CN105203611A - Combustion gas transmission and distribution apparatus and making method thereof - Google Patents
Combustion gas transmission and distribution apparatus and making method thereof Download PDFInfo
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Landscapes
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention discloses a combustion gas transmission and distribution apparatus and a making method thereof. The outer wall of the combustion gas transmission and distribution is provided with solid electrolyte gas sensors every 2Km. Unexpected sensitivity and ultrafast response recovery speed of detection of easy-leakage dangerous gases of the apparatus are realized, and the flammable and explosive dangers of the combustion gas transmission and distribution apparatus in the use process can be timely found, so the combustion gas transmission and distribution apparatus has very large market prospect.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a fuel gas transmission and distribution device and a manufacturing method thereof.
Background
The gas distribution equipment is usually composed of gas valve station, gas storage and distribution station, distribution pipe network, etc., and the liquefied petroleum gas is usually transported from the production place to the storage and distribution station by various transportation means and equipment, and then supplied to the user in various ways.
The gas transmission and distribution device generally transports flammable and explosive gases such as natural gas, and the like, so that gas leakage is easily caused due to corrosion and the like, and the safety coefficient of the gas can be improved by detecting the gas.
Disclosure of Invention
The invention provides a gas transmission and distribution device and a manufacturing method thereof, aiming at the problems in the background technology.
The invention provides the following technical scheme:
a gas transmission and distribution device is characterized in that solid electrolyte type gas sensors are arranged on the outer wall of the gas transmission and distribution device every 2Km and comprise a heating plate, a Yttrium Stabilized Zirconia (YSZ) substrate (1) arranged on the heating plate, a platinum (Pt) reference electrode (4) arranged on the YSZ substrate, a sensitive electrode A (3) and a sensitive electrode B (5), wherein the sensitive electrode A and the sensitive electrode B are respectively arranged on two sides of the Pt reference electrode, the sensitive electrode A is made of tungsten oxide nanoparticles doped with nano nickel oxide powder, and the sensitive electrode B is made of nano SnO2And (3) pulverizing.
Preferably, the YSZ substrate is doped with 8 mol% of Y2O3The physical size is 6mm 4mm 0.2mm, and two nano porous structures with 1 x 2mm areas are corroded by an electrochemical method and are respectively used for placing a sensitive electrode A and a sensitive electrode B; manufacturing platinum dots with the diameter of 0.1-0.3mm on the nano porous area of the YSZ substrate to be used as the connection between the YSZ substrate and the electrode; the thickness of the sensitive electrode A and the sensitive electrode B is 0.5mm, and SnO in the sensitive electrode B2The particle size of the nano powder is 15-22 nm.
A manufacturing method of a gas transmission and distribution device is characterized in that solid electrolyte type gas sensors are arranged on the outer wall of the gas transmission and distribution device at intervals of 2Km, each solid electrolyte type gas sensor comprises a porous Yttrium Stabilized Zirconia (YSZ) substrate, and a platinum (Pt) reference electrode, a sensitive electrode A and a sensitive electrode B which are arranged on the YSZ substrate, wherein the sensitive electrode A and the sensitive electrode B are respectively arranged on two sides of the Pt reference electrode; wherein,
a. ultrasonically cleaning a YSZ substrate with water and absolute ethyl alcohol successively for multiple times, and drying for later use;
b. taking platinum paste, manufacturing a 1-by-2 mm thin strip-shaped platinum paste strip in the middle of the cleaned YSZ substrate, respectively manufacturing a small platinum paste circular point in a porous area of the YSZ, and adopting a screen printing process during mass production;
c. respectively sticking three sections of platinum wires to the areas of the YSZ sheet, which are just coated with the platinum slurry, and then placing the YSZ substrate under an infrared lamp for baking for several hours;
d. taking a proper amount of sensitive electrode materials A, B, respectively putting the sensitive electrode materials A, B into agate mortar, fully grinding the sensitive electrode materials, adding a small amount of deionized water, preparing into viscous slurry A, B, and respectively coating the slurry A, B on the porous structure of the substrate to form two sensitive electrodes A, B of the sensor, wherein the thickness of the two sensitive electrodes A, B is 0.5 mm;
e. putting the substrate obtained in the previous step into a muffle furnace, and sintering at the high temperature of 800 ℃ for two hours;
f. and (3) uniformly coating a layer of inorganic adhesive on the surface of the n-shaped Pt heating plate printed with the Pt electrode, then adhering the heating plate and the substrate obtained in the previous step together, sintering in a muffle furnace at 200 ℃ for 20 minutes, and taking out to obtain the prototype device of the sensor.
Preferably, the first and second liquid crystal materials are,
(1) porous yttria-stabilized zirconia (YSZ) (2) preparation:
preparing porous structure YSZ by adopting a double-groove electrochemical corrosion method;
a. taking YSZ plate (8 mol% Y)2O3Doping, 6mm by 4mm by 0.2mm), sequentially performing multiple ultrasonic cleaning with water and absolute ethyl alcohol, and drying;
b. preparing a pretreatment solution: according to the mass portion, 1-1.8% of tea saponin, 2% of malic acid and the balance of purified water are added, then YSZ flat plates are put into the YSZ flat plates and are completely immersed, the YSZ flat plates are treated for 20-28min at the temperature of 50-58 ℃, then the YSZ flat plates are treated for 2min by microwave, and the YSZ flat plates are cleaned and naturally dried for standby;
the microwave treatment parameters are as follows: 2450MHz and 65W, irradiating for 2-5s at an interval of 10min for 3-5 times;
c. preparing an etching solution, mixing HF (40% by volume) and deionized water according to a volume ratio of 1:5, adding potassium permanganate in a proper amount, placing the mixture into a double-electric-tank electrochemical device, wherein the etching tank and a clamp are both made of corrosion-resistant polytetrafluoroethylene materials, an electrode is columnar metal Pt, the clamp divides the etching tank into two non-communicated areas, and the center of the clamp is provided with two holes with a specific shape of 1 x 2 mm;
d. the corrosion process is carried out under dark condition, the power supply used by the device is a constant current source, and the density of the applied corrosion current is 40mA/cm2After 30min, forming two porous structures (2) with the area of 1 x 2mm on a YSZ flat plate, and after the preparation is finished and cleaned, storing the porous structures in absolute ethyl alcohol;
(2) preparing a sensitive electrode material A:
a. synthesizing tungsten oxide nanoparticles: weighing 1.5g of Na2WO4, dissolving in 45mL of deionized water, and dropwise adding an HCl solution with the concentration of 3mol/L under the condition of stirring until tungstic acid is completely precipitated; then centrifugally separating, putting the precipitate into a small beaker, adding 30mL of deionized water, adding 75g of KNO3, violently stirring to form a paste, carrying out hydrothermal reaction at 180 ℃ for 12h, and naturally cooling to room temperature; fully washing the reactant (precipitate) with deionized water, then washing with ethanol, filtering, dehydrating and drying at 80 ℃ to obtain a product, namely tungsten oxide nano-particles;
b. tungsten oxide nanoparticles doped with nickel oxide: taking the mass ratio of 3: 1, putting the tungsten oxide nano particles and the nano nickel powder into a stirrer to be fully mixed; then putting the mixed material into a vacuum tube furnace, heating to 300 ℃, preserving heat for 4 hours to fully oxidize the nickel powder, and finally naturally cooling to room temperature;
(3) preparing a sensitive electrode material B:
a. firstly, SnO with the grain diameter of 15-22nm2Drying the nanometer powder in a vacuum drying oven at 80 ℃ for 12 hours;
b. weighing dried SnO22.0g of nano powder, then adding 4.0ml of chloroplatinic acid solution with the concentration of 10mmol/L, and carrying out ultrasonic treatment for 15min after complete impregnation to uniformly mix the nano powder;
c. and standing the mixture for 6h, then drying the mixture in a vacuum drying oven at 80 ℃ for 12h, sintering the mixture at 500 ℃ for 12h after drying, and naturally cooling to room temperature to obtain the sensitive electrode B.
The invention has the advantages that:
according to the invention, the solid electrolyte type gas sensors are arranged on the outer wall of the gas transmission and distribution device at intervals of 2Km, so that unexpected sensitivity and ultra-fast response recovery speed are achieved for detection of dangerous gas which is easy to leak, flammable and explosive dangerous situations can be found in the using process in time, and the gas transmission and distribution device has a great market prospect.
Drawings
FIG. 1 is a schematic view of a dual cell electrochemical device;
FIG. 2 is a schematic structural view of the gas distribution apparatus of the present invention;
FIG. 3 is a schematic diagram of the porous structure of a YSZ plate;
fig. 4 is a schematic structural view of the gas sensor of the present invention.
Detailed Description
The technical invention is mainly designed by considering the following points:
gas sensor
The gas sensor is a device or apparatus capable of converting the type, concentration, etc. of a target gas into a detectable signal according to a certain rule in air or an environment with certain characteristics. The detection modes mainly comprise test current, resistance, potential, heat, temperature and the like. The gas sensor is mainly classified into a semiconductor type, a solid electrolyte type, and the like according to its operating characteristics.
Solid electrolyte
Solid electrolyte type gas sensors are generally electrochemical sensors, mainly composed of electrolytes, sensitive electrodes and reference electrodes, and the electrolytes are important components of the sensors. Conductors are classified into electronic conductors and ionic conductors according to the difference of carriers, the latter being electrolytes, and some ionic crystals having high ionic conductivity in addition to general liquid electrolytes, such solid conductors being called solid electrolytes (solid electrolytes) including ceramics, glass, inorganic metal salts and some organic polymer materials.
The conductive ions in the solid electrolyte may be either cations or anions, which are mainly determined by defects of the material itself.
Yttrium Stabilized Zirconia (YSZ)
Stabilized zirconia/Yttria Stabilized Zirconia (YSZ) is one of the most useful solid electrolytes, zirconia (ZrO) at ambient temperatures2) Is a monoclinic crystal, has low ionic conductivity, and can be doped with proper amount of divalent or trivalent cubic symmetric oxide (Y)2O3、MgO、CaO、Sc2O3) It is treated to exhibit ion conductivity, has high oxygen ion conductivity, excellent chemical stability, and thermal and mechanical stability, and has been widely used in the fields of solid oxide fuel cells and gas sensors.
Porous structure YSZ
The porous structure YSZ is still composed of originally interconnected atoms in terms of elemental composition, but has a unique porous and loose structure. The specific surface area is large, gas can react on a three-phase interface (zirconium oxide, electrode and gas) conveniently, and the sensitivity is improved. The porous region of YSZ is prepared by adopting a double-groove electrochemical corrosion method, the preparation process is simple, and the appearance of the porous region is easy to control.
Gas-sensitive properties of tungsten oxide
Tungsten oxide is an n-type metal oxide semiconductor, and is a surface resistance control type gas sensitive material. The atomic property of the surface of the tungsten oxide crystal is active, gas molecules are easy to adsorb, and when the gas molecules are adsorbed on the surface of the crystal, the concentration of carriers in the tungsten oxide crystal is correspondingly changed, which is expressed as the resistance change of the sensor. The mechanism of resistance change generated by gas absorption and desorption of the tungsten oxide gas sensor, namely the gas-sensitive mechanism, is very complex, and researchers have not been uniformly known so far. Research shows that tungsten oxide is coupled with NO2、HS2、SO2And various gases have better gas-sensitive characteristics. However, the sensitivity, selectivity and the like of a pure tungsten oxide film are mostly insufficient, the tungsten oxide nanoparticles prepared by the method can increase the contact area of the material and the gas to be detected, and improve the sensitivity, and in addition, nickel oxide particles with catalytic action or selectivity on gas adsorption are compounded, so that the selectivity of the sensitive electrode on nitrogen oxide gas is improved.
SnO2Gas-sensitive nature
SnO2Belongs to an n-type semiconductor, and has obvious gas-sensitive effect due to the existence of oxygen vacancies or tin ions, and the gas-sensitive mechanism is generally considered to be a surface adsorption control type mechanism. When heated to a certain temperature in clean air, O2Will be in SnO2Surface adsorption to form multiple adsorbed oxygen species, with electrons from SnO2The crystal grains are transferred to adsorbed oxygen, a depletion layer is formed on the surface of SnO2 crystal grains, the conductivity of sensitive materials is reduced, and the sensitive materials are exposed to a reducing detection atmosphere (H)2CO, hydrocarbon gas), the detected gas reacts with the adsorbed oxygen species, SnO2The adsorbed oxygen on the surface of the crystal grains or on the grain boundary is desorbed, the depletion layer becomes thinner, the conductivity is increased, and the gas is detected through the change of the material conductivity. In the present invention at SnO2Pt is added for modification on the basis of the nano film, so that the detection sensitivity of the nano film to CO is greatly improved.
For the sensitive mechanism of the yttrium-stabilized zirconia-based NOx sensor, when the sensor is placed in a gas detection environment, a series of chemical reactions occur on a three-phase interface (zirconia, an electrode and gas), because the catalytic rates of the sensitive electrode and the reference electrode are different, a potential difference is formed between the sensitive electrode and the reference electrode, and the magnitude of the potential difference reflects the concentration of the gas to be detected, so that the purposes of detecting the gas and the concentration of the gas are achieved. Therefore, the electrochemical and chemical catalytic activity of the electrode material, the electrode microstructure and the like are main factors considered by the sensitive electrode.
Fig. 2 is a schematic structural diagram of the gas distribution device of the present invention, and gas sensors 1 are disposed at every 2Km on the outer wall of the gas distribution device 10.
Example 1:
a manufacturing method of a gas transmission and distribution device is characterized in that solid electrolyte type gas sensors are arranged on the outer wall of the gas transmission and distribution device at intervals of 2Km, each solid electrolyte type gas sensor comprises a porous Yttrium Stabilized Zirconia (YSZ) substrate, and a platinum (Pt) reference electrode, a sensitive electrode A and a sensitive electrode B which are arranged on the YSZ substrate, wherein the sensitive electrode A and the sensitive electrode B are respectively arranged on two sides of the Pt reference electrode;
the solid electrolyte type gas sensor is manufactured by the following method:
(1) preparation of porous yttrium-stabilized zirconia (YSZ):
preparing porous structure YSZ by adopting a double-groove electrochemical corrosion method;
a. taking YSZ plate (8 mol% Y)2O3Doping, 6mm by 4mm by 0.2mm), sequentially performing multiple ultrasonic cleaning with water and absolute ethyl alcohol, and drying;
b. preparing a pretreatment solution: according to the mass parts, 1% of tea saponin, 2% of malic acid and the balance of purified water are added, then YSZ flat plates are put into the pure water, completely immersed, treated for 20min at the temperature of 58 ℃, then treated for 2min by microwave, cleaned and naturally dried for standby;
the microwave treatment parameters are as follows: 2450MHz and 65W, irradiating for 5s at an interval of 10min for 3 times in total;
c. preparing an etching solution, mixing HF (40% by volume) and deionized water according to a volume ratio of 1:5, adding potassium permanganate in a proper amount, putting the mixture into a double-cell electrochemical device (shown in figure 1), wherein the etching cell and a clamp are both made of corrosion-resistant polytetrafluoroethylene materials, an electrode is columnar metal Pt, the clamp divides the etching cell into two regions which are not communicated with each other, and the center of the clamp is provided with two holes with a specific shape of 1 x 2 mm;
d. the corrosion process is carried out under dark condition, the power supply used by the device is a constant current source, and the density of the applied corrosion current is 40mA/cm2After 30min, forming two porous structures with the area of 1 x 2mm on a YSZ flat plate, and after the preparation is finished and cleaned, storing the porous structures in absolute ethyl alcohol;
(2) preparing a sensitive electrode material A:
a. synthesizing tungsten oxide nanoparticles: weighing 1.5g Na2WO4Dissolving in 45mL of deionized water, and dropwise adding an HCl solution with the concentration of 3mol/L under the stirring condition until tungstic acid is completely precipitated; then centrifugally separating, putting the precipitate into a small beaker, adding 30mL of deionized water, and then adding 75g of KNO3Violently stirring to form paste, carrying out hydrothermal reaction for 12h at 180 ℃, and naturally cooling to room temperature; fully washing the reactant (precipitate) with deionized water, then washing with ethanol, filtering, dehydrating and drying at 80 ℃ to obtain a product, namely tungsten oxide nano-particles;
b. tungsten oxide nanoparticles doped with nickel oxide: taking the mass ratio of 3: 1, putting the tungsten oxide nano particles and the nano nickel powder into a stirrer to be fully mixed; then putting the mixed material into a vacuum tube furnace, heating to 300 ℃, preserving heat for 4 hours to fully oxidize the nickel powder, and finally naturally cooling to room temperature;
(3) preparing a sensitive electrode material B:
a. firstly, SnO with the particle size of 22nm2Drying the nanometer powder in a vacuum drying oven at 80 ℃ for 12 hours;
b. weighing dried SnO22.0g of nano powder, then adding 4.0ml of chloroplatinic acid solution with the concentration of 10mmol/L, and carrying out ultrasonic treatment for 15min after complete impregnation to uniformly mix the nano powder;
c. standing the mixture for 6h, then drying the mixture in a vacuum drying oven at 80 ℃ for 12h, sintering the mixture at 500 ℃ for 12h after drying, and naturally cooling to room temperature to obtain a sensitive electrode B;
(4) gas sensor fabrication
The nitrogen oxide sensor is mainly composed of two parts: porous YSZ flat plate and Pt 'ji' shape electrode heating plate, the device preparation steps are as follows:
a. taking the YSZ substrate treated in the step (1), sequentially carrying out ultrasonic cleaning with water and absolute ethyl alcohol for multiple times, and drying for later use;
b. taking platinum paste, manufacturing a 1-by-2 mm thin strip-shaped platinum paste strip in the middle of the cleaned YSZ substrate, respectively manufacturing a small platinum paste circular point in a porous area of the YSZ, and adopting a screen printing process during mass production;
c. respectively sticking three sections of platinum wires to the areas of the YSZ sheet, which are just coated with the platinum slurry, and then placing the YSZ substrate under an infrared lamp for baking for several hours;
d. taking a proper amount of sensitive electrode materials A, B, respectively putting the sensitive electrode materials A, B into agate mortar, fully grinding the sensitive electrode materials, adding a small amount of deionized water, preparing into viscous slurry A, B, and respectively coating the slurry A, B on the porous structure of the substrate to form two sensitive electrodes A, B of the sensor, wherein the thickness of the two sensitive electrodes A, B is 0.5 mm;
e. putting the substrate obtained in the previous step into a muffle furnace, and sintering at the high temperature of 800 ℃ for two hours;
f. uniformly coating a layer of inorganic adhesive (water glass and Al) on the surface of the n-shaped Pt heating plate printed with the Pt electrode2O3Mixing to obtain) And then, adhering the heating plate and the substrate obtained in the previous step together, putting the substrate into a muffle furnace, sintering the substrate for 20 minutes at 200 ℃, and taking the substrate out to obtain the prototype device of the sensor.
The device of this example operates at 300 ℃ for 100ppm NO2The sensitivity can reach 21mV/decade, and the response recovery speed is higher and is about 18 s; for 200ppm CO, the sensitivity can reach 39mV/decade, and the response recovery speed is about 5 s.
In this embodiment, the YSZ substrate is doped with 8 mol% Y2O3The physical size is 6mm 4mm 0.2mm, and two nano porous structures with 1 x 2mm areas are corroded by an electrochemical method and are respectively used for placing a sensitive electrode A and a sensitive electrode B; manufacturing platinum dots with the diameter of 0.1-0.3mm on a nano porous area of the YSZ substrate to be used as the connection between the YSZ substrate and an electrode; the thickness of the sensitive electrode A and the sensitive electrode B is 0.5mm, and SnO in the sensitive electrode B2The particle size of the nano powder is 15-22 nm.
Example 2:
a manufacturing method of a gas transmission and distribution device is characterized in that solid electrolyte type gas sensors are arranged on the outer wall of the gas transmission and distribution device at intervals of 2Km, each solid electrolyte type gas sensor comprises a porous Yttrium Stabilized Zirconia (YSZ) substrate, and a platinum (Pt) reference electrode, a sensitive electrode A and a sensitive electrode B which are arranged on the YSZ substrate, wherein the sensitive electrode A and the sensitive electrode B are respectively arranged on two sides of the Pt reference electrode;
the solid electrolyte type gas sensor is manufactured by the following method:
(1) preparation of porous yttrium-stabilized zirconia (YSZ):
preparing porous structure YSZ by adopting a double-groove electrochemical corrosion method;
a. taking YSZ plate (8 mol% Y)2O3Doping, 7mm by 5mm by 0.2mm), sequentially performing multiple ultrasonic cleaning with water and absolute ethyl alcohol, and drying;
b. preparing a pretreatment solution: according to the mass portion, 1.8% of tea saponin, 2% of malic acid and the balance of purified water are added, then YSZ flat plates are put into the YSZ flat plates and are completely immersed, the YSZ flat plates are treated for 28min at the temperature of 50 ℃, then the YSZ flat plates are treated for 2min by microwave, and the YSZ flat plates are cleaned and naturally dried for standby;
the microwave treatment parameters are as follows: 2450MHz and 65W, irradiating for 2s at an interval of 10min for 5 times;
c. preparing an etching solution, mixing HF (40% by volume) and deionized water according to a volume ratio of 1:5, adding potassium permanganate in a proper amount, putting the mixture into a double-cell electrochemical device (shown in figure 1), wherein the etching cell and a clamp are both made of corrosion-resistant polytetrafluoroethylene materials, an electrode is columnar metal Pt, the clamp divides the etching cell into two regions which are not communicated with each other, and the center of the clamp is provided with two holes with a specific shape of 2 x 2 mm;
d. the corrosion process is carried out under dark condition, the power supply used by the device is a constant current source, and the density of the applied corrosion current is 40mA/cm2After 30min, forming two porous structures with 2 x 2mm areas on the YSZ flat plate, and after the preparation is finished, cleaning and storing the porous structures in absolute ethyl alcohol;
(2) preparing a sensitive electrode material A:
a. synthesizing tungsten oxide nanoparticles: weighing 1.5g Na2WO4Dissolving in 45mL of deionized water, and dropwise adding an HCl solution with the concentration of 3mol/L under the stirring condition until tungstic acid is completely precipitated; then centrifugally separating, putting the precipitate into a small beaker, adding 30mL of deionized water, and then adding 75g of KNO3Violently stirring to form paste, carrying out hydrothermal reaction for 12h at 180 ℃, and naturally cooling to room temperature; fully washing the reactant (precipitate) with deionized water, then washing with ethanol, filtering, dehydrating and drying at 80 ℃ to obtain a product, namely tungsten oxide nano-particles;
b. tungsten oxide nanoparticles doped with nickel oxide: taking the mass ratio of 3: 1, putting the tungsten oxide nano particles and the nano nickel powder into a stirrer to be fully mixed; then putting the mixed material into a vacuum tube furnace, heating to 300 ℃, preserving heat for 4 hours to fully oxidize the nickel powder, and finally naturally cooling to room temperature;
(3) preparing a sensitive electrode material B:
a. firstly SnO with the particle size of 15nm2Drying the nanometer powder in a vacuum drying oven at 80 ℃ for 12 hours;
b. weighing dried SnO22.0g of nano powder, then adding 4.0ml of chloroplatinic acid solution with the concentration of 10mmol/L, and carrying out ultrasonic treatment for 15min after complete impregnation to uniformly mix the nano powder;
c. standing the mixture for 6h, then drying the mixture in a vacuum drying oven at 80 ℃ for 12h, sintering the mixture at 500 ℃ for 12h after drying, and naturally cooling to room temperature to obtain a sensitive electrode B;
(4) gas sensor fabrication
The nitrogen oxide sensor is mainly composed of two parts: porous YSZ flat plate and Pt 'ji' shape electrode heating plate, the device preparation steps are as follows:
a. taking the YSZ substrate treated in the step (1), sequentially carrying out ultrasonic cleaning with water and absolute ethyl alcohol for multiple times, and drying for later use;
b. taking platinum paste, manufacturing a2 x 2 mm-sized thin strip-shaped platinum paste strip in the middle of the cleaned YSZ substrate, respectively manufacturing a small platinum paste circular point in a porous area of the YSZ, and adopting a screen printing process during mass production;
c. respectively sticking three sections of platinum wires to the areas of the YSZ sheet, which are just coated with the platinum slurry, and then placing the YSZ substrate under an infrared lamp for baking for several hours;
d. taking a proper amount of sensitive electrode materials A, B, respectively putting the sensitive electrode materials A, B into agate mortar, fully grinding the sensitive electrode materials, adding a small amount of deionized water, preparing into viscous slurry A, B, and respectively coating the slurry A, B on the porous structure of the substrate to form two sensitive electrodes A, B of the sensor, wherein the thickness of the two sensitive electrodes A, B is 0.5 mm;
e. putting the substrate obtained in the previous step into a muffle furnace, and sintering at the high temperature of 800 ℃ for two hours;
f. and (3) uniformly coating a layer of inorganic adhesive (prepared by mixing water glass and Al2O 3) on the surface of the n-shaped Pt heating plate printed with the Pt electrode, then adhering the heating plate and the substrate obtained in the previous step together, putting the substrate into a muffle furnace, sintering at 200 ℃ for 20 minutes, and taking out the substrate to obtain the prototype device of the sensor.
The device of this example operates at 300 ℃ for 100ppm NO2The sensitivity can reach 52mV/decade, and the response recovery speed is faster and is about 8 s; for 200ppm CO, the sensitivity can reach 62mV/decade, and the response recovery speed is about 3 s.
In this embodiment, the YSZ substrate is doped with 8 mol% Y2O3The physical size is 7mm x 5mm x 0.2mm, and a nano porous structure with two 2 x 2mm areas is formed by electrochemical corrosion and is respectively used for placing a sensitive electrode A and a sensitive electrode B; manufacturing platinum dots with the diameter of 0.1-0.3mm on a nano porous area of the YSZ substrate to be used as the connection between the YSZ substrate and an electrode; the thickness of the sensitive electrode A and the sensitive electrode B is 0.5mm, and SnO in the sensitive electrode B2The particle size of the nano powder is 15-22 nm.
By adjusting the size of the YSZ substrate and the porous nano structure and experimental parameters, the detection sensitivity of the YSZ substrate to the hazardous gas CO is improved to 62mV/decade, the response time is shortened to 3s, and an unexpected result is obtained.
Example 3:
a manufacturing method of a gas transmission and distribution device is characterized in that solid electrolyte type gas sensors are arranged on the outer wall of the gas transmission and distribution device at intervals of 2Km, each solid electrolyte type gas sensor comprises a porous Yttrium Stabilized Zirconia (YSZ) substrate, and a platinum (Pt) reference electrode, a sensitive electrode A and a sensitive electrode B which are arranged on the YSZ substrate, wherein the sensitive electrode A and the sensitive electrode B are respectively arranged on two sides of the Pt reference electrode;
the solid electrolyte type gas sensor is manufactured by the following method:
(1) preparation of porous yttrium-stabilized zirconia (YSZ):
preparing porous structure YSZ by adopting a double-groove electrochemical corrosion method;
a. taking YSZ plate (8 mol% Y)2O3Doping, 8mm by 4mm by 0.2mm), sequentially performing multiple ultrasonic cleaning by using water and absolute ethyl alcohol, and drying;
b. preparing a pretreatment solution: according to the mass parts, 1.3% of tea saponin, 2% of malic acid and the balance of purified water are added, then YSZ flat plates are put into the YSZ flat plates and are completely immersed, the YSZ flat plates are treated for 21min at the temperature of 57 ℃, then the YSZ flat plates are treated for 2min by microwave, and the YSZ flat plates are cleaned and naturally dried for standby;
the microwave treatment parameters are as follows: 2450MHz, 65W, 3s irradiation, 10min interval, 4 total irradiation
c. Preparing an etching solution, mixing HF (40% by volume) and deionized water according to a volume ratio of 1:5, adding potassium permanganate in a proper amount, putting the mixture into a double-cell electrochemical device (shown in figure 1), wherein the etching cell and a clamp are both made of corrosion-resistant polytetrafluoroethylene materials, an electrode is columnar metal Pt, the clamp divides the etching cell into two regions which are not communicated with each other, and the center of the clamp is provided with two holes with a specific shape of 1 x 2 mm;
d. the corrosion process is carried out under dark condition, the power supply used by the device is a constant current source, and the density of the applied corrosion current is 40mA/cm2After 30min, forming two porous structures with the area of 1 x 2mm on a YSZ flat plate, and after the preparation is finished and cleaned, storing the porous structures in absolute ethyl alcohol;
(2) preparing a sensitive electrode material A:
a. synthesizing tungsten oxide nanoparticles: weighing 1.5g Na2WO4Dissolving in 45mL of deionized water, and dropwise adding an HCl solution with the concentration of 3mol/L under the stirring condition until tungstic acid is completely precipitated; then centrifugally separating, putting the precipitate into a small beaker, adding 30mL of deionized water, and then adding 75g of KNO3Stirring vigorously to form a paste, reacting hydrothermally at 180 deg.C for 12h, and reactingThen cooling to room temperature; fully washing the reactant (precipitate) with deionized water, then washing with ethanol, filtering, dehydrating and drying at 80 ℃ to obtain a product, namely tungsten oxide nano-particles;
b. tungsten oxide nanoparticles doped with nickel oxide: taking the mass ratio of 3: 1, putting the tungsten oxide nano particles and the nano nickel powder into a stirrer to be fully mixed; then putting the mixed material into a vacuum tube furnace, heating to 300 ℃, preserving heat for 4 hours to fully oxidize the nickel powder, and finally naturally cooling to room temperature;
(3) preparing a sensitive electrode material B:
a. firstly, SnO with the particle size of 20nm2Drying the nanometer powder in a vacuum drying oven at 80 ℃ for 12 hours;
b. weighing dried SnO22.0g of nano powder, then adding 4.0ml of chloroplatinic acid solution with the concentration of 10mmol/L, and carrying out ultrasonic treatment for 15min after complete impregnation to uniformly mix the nano powder;
c. standing the mixture for 6h, then drying the mixture in a vacuum drying oven at 80 ℃ for 12h, sintering the mixture at 500 ℃ for 12h after drying, and naturally cooling to room temperature to obtain a sensitive electrode B;
(4) gas sensor fabrication
The nitrogen oxide sensor is mainly composed of two parts: porous YSZ flat plate and Pt 'ji' shape electrode heating plate, the device preparation steps are as follows:
a. taking the YSZ substrate treated in the step (1), sequentially carrying out ultrasonic cleaning with water and absolute ethyl alcohol for multiple times, and drying for later use;
b. taking platinum paste, manufacturing a 1-by-2 mm thin strip-shaped platinum paste strip in the middle of the cleaned YSZ substrate, respectively manufacturing a small platinum paste circular point in a porous area of the YSZ, and adopting a screen printing process during mass production;
c. respectively sticking three sections of platinum wires to the areas of the YSZ sheet, which are just coated with the platinum slurry, and then placing the YSZ substrate under an infrared lamp for baking for several hours;
d. taking a proper amount of sensitive electrode materials A, B, respectively putting the sensitive electrode materials A, B into agate mortar, fully grinding the sensitive electrode materials, adding a small amount of deionized water, preparing into viscous slurry A, B, and respectively coating the slurry A, B on the porous structure of the substrate to form two sensitive electrodes A, B of the sensor, wherein the thickness of the two sensitive electrodes A, B is 0.5 mm;
e. putting the substrate obtained in the previous step into a muffle furnace, and sintering at the high temperature of 800 ℃ for two hours;
f. and (3) uniformly coating a layer of inorganic adhesive (prepared by mixing water glass and Al2O 3) on the surface of the n-shaped Pt heating plate printed with the Pt electrode, then adhering the heating plate and the substrate obtained in the previous step together, putting the substrate into a muffle furnace, sintering at 200 ℃ for 20 minutes, and taking out the substrate to obtain the prototype device of the sensor.
The device of this example operates at 300 ℃ for 100ppm NO2The sensitivity can reach 30mV/decade, and the response recovery speed is faster and is about 17 s; for 200ppm CO, the sensitivity can reach 45mV/decade, and the response recovery speed is about 4 s.
The YSZ substrate is doped with 8 mol% of Y2O3The physical size is 8mm x 4mm x 0.2mm, and a nano porous structure with two 1 x 2mm areas is formed by electrochemical corrosion and is respectively used for placing a sensitive electrode A and a sensitive electrode B; manufacturing platinum dots with the diameter of 0.1-0.3mm on the nano porous area of the YSZ substrate to be used as the connection between the YSZ substrate and the electrode; the thickness of the sensitive electrode A and the sensitive electrode B is 0.5mm, and SnO in the sensitive electrode B2The particle size of the nano powder is 15-22 nm.
By adjusting the size and experimental parameters of the YSZ substrate and the porous nano structure, the hazardous gas NO is treated2The detection sensitivity of the method is improved to 30mV/decade, and the response time to CO is shortened to 4s, thereby obtaining an unexpected result.
Example 4:
a manufacturing method of a gas transmission and distribution device is characterized in that solid electrolyte type gas sensors are arranged on the outer wall of the gas transmission and distribution device at intervals of 2Km, each solid electrolyte type gas sensor comprises a porous Yttrium Stabilized Zirconia (YSZ) substrate, and a platinum (Pt) reference electrode, a sensitive electrode A and a sensitive electrode B which are arranged on the YSZ substrate, wherein the sensitive electrode A and the sensitive electrode B are respectively arranged on two sides of the Pt reference electrode;
the solid electrolyte type gas sensor is manufactured by the following method:
(1) preparation of porous yttrium-stabilized zirconia (YSZ):
preparing porous structure YSZ by adopting a double-groove electrochemical corrosion method;
a. taking YSZ plate (8 mol% Y)2O3Doping, 9mm by 5mm by 0.2mm), sequentially performing multiple ultrasonic cleaning with water and absolute ethyl alcohol, and drying;
b. preparing a pretreatment solution: according to the mass parts, 1.7% of tea saponin, 2% of malic acid and the balance of purified water are added, then YSZ flat plates are put into the YSZ flat plates and are completely immersed, the YSZ flat plates are treated for 27min at the temperature of 51 ℃, then the YSZ flat plates are treated for 2min by microwave, and the YSZ flat plates are cleaned and naturally dried for standby;
the microwave treatment parameters are as follows: 2450MHz and 65W, irradiating for 4s at an interval of 10min for 3 times in total;
c. preparing an etching solution, mixing HF (40% by volume) and deionized water according to a volume ratio of 1:5, adding potassium permanganate in a proper amount, putting the mixture into a double-cell electrochemical device (shown in figure 1), wherein the etching cell and a clamp are both made of corrosion-resistant polytetrafluoroethylene materials, an electrode is columnar metal Pt, the clamp divides the etching cell into two regions which are not communicated with each other, and the center of the clamp is provided with two holes with a specific shape of 3 x 2 mm;
d. the corrosion process is carried out under dark condition, the power supply used by the device is a constant current source, and the density of the applied corrosion current is 40mA/cm2After 30min, forming two porous structures with the area of 3 x 2mm on a YSZ flat plate, and after the preparation is finished and cleaned, storing the porous structures in absolute ethyl alcohol;
(2) preparing a sensitive electrode material A:
a. synthesizing tungsten oxide nanoparticles: weighing 1.5g Na2WO4Dissolving in 45mL of deionized water, and dropwise adding an HCl solution with the concentration of 3mol/L under the stirring condition until tungstic acid is completely precipitated; then centrifugally separating, putting the precipitate into a small beaker, adding 30mL of deionized water, and then adding 75g of KNO3Violently stirring to form paste, carrying out hydrothermal reaction for 12h at 180 ℃, and naturally cooling to room temperature; fully washing the reactant (precipitate) with deionized water, then washing with ethanol, filtering, dehydrating and drying at 80 ℃ to obtain a product, namely tungsten oxide nano-particles;
b. tungsten oxide nanoparticles doped with nickel oxide: taking the mass ratio of 3: 1, putting the tungsten oxide nano particles and the nano nickel powder into a stirrer to be fully mixed; then putting the mixed material into a vacuum tube furnace, heating to 300 ℃, preserving heat for 4 hours to fully oxidize the nickel powder, and finally naturally cooling to room temperature;
(3) preparing a sensitive electrode material B:
a. firstly SnO with the particle size of 16nm2Drying the nanometer powder in a vacuum drying oven at 80 ℃ for 12 hours;
b. weighing dried SnO22.0g of nano powder, then adding 4.0ml of chloroplatinic acid solution with the concentration of 10mmol/L, and carrying out ultrasonic treatment for 15min after complete impregnation to uniformly mix the nano powder;
c. standing the mixture for 6h, then drying the mixture in a vacuum drying oven at 80 ℃ for 12h, sintering the mixture at 500 ℃ for 12h after drying, and naturally cooling to room temperature to obtain a sensitive electrode B;
(4) gas sensor fabrication
The nitrogen oxide sensor is mainly composed of two parts: porous YSZ flat plate and Pt 'ji' shape electrode heating plate, the device preparation steps are as follows:
a. taking the YSZ substrate treated in the step (1), sequentially carrying out ultrasonic cleaning with water and absolute ethyl alcohol for multiple times, and drying for later use;
b. taking platinum paste, manufacturing a thin strip-shaped platinum paste belt with the size of 3 x 2mm in the middle of the cleaned YSZ substrate, respectively manufacturing a small platinum paste circular point in a porous area of the YSZ, and adopting a screen printing process during mass production;
c. respectively sticking three sections of platinum wires to the areas of the YSZ sheet, which are just coated with the platinum slurry, and then placing the YSZ substrate under an infrared lamp for baking for several hours;
d. taking a proper amount of sensitive electrode materials A, B, respectively putting the sensitive electrode materials A, B into agate mortar, fully grinding the sensitive electrode materials, adding a small amount of deionized water, preparing into viscous slurry A, B, and respectively coating the slurry A, B on the porous structure of the substrate to form two sensitive electrodes A, B of the sensor, wherein the thickness of the two sensitive electrodes A, B is 0.5 mm;
e. putting the substrate obtained in the previous step into a muffle furnace, and sintering at the high temperature of 800 ℃ for two hours;
f. and (3) uniformly coating a layer of inorganic adhesive (prepared by mixing water glass and Al2O 3) on the surface of the n-shaped Pt heating plate printed with the Pt electrode, then adhering the heating plate and the substrate obtained in the previous step together, putting the substrate into a muffle furnace, sintering at 200 ℃ for 20 minutes, and taking out the substrate to obtain the prototype device of the sensor.
The device of this example operates at 300 ℃ for 100ppm NO2The sensitivity can reach 40mV/decade, and the response recovery speed is higher and is about 10 s; for 200ppm CO, the sensitivity can reach 53mV/decade, and the response recovery speed is about 5 s.
In this embodiment, the YSZ substrate is doped with 8 mol% Y2O3The physical size is 9mm x 5mm x 0.2mm, and a nano porous structure with two 3 x 2mm areas is formed by electrochemical corrosion and is respectively used for placing a sensitive electrode A and a sensitive electrode B; manufacturing platinum dots with the diameter of 0.1-0.3mm on a nano porous area of the YSZ substrate to be used as the connection between the YSZ substrate and an electrode; the thickness of the sensitive electrode A and the sensitive electrode B is 0.5mm, and SnO in the sensitive electrode B2The particle size of the nano powder is 15-22 nm.
By adjusting the size of the YSZ substrate and the porous nano structure and experimental parameters, the detection sensitivity of the YSZ substrate to the hazardous gas CO is improved to 53mV/decade, and the response time is shortened to 5s, so that an unexpected result is obtained.
Example 5 comparative example:
a manufacturing method of a gas transmission and distribution device is characterized in that solid electrolyte type gas sensors are arranged on the outer wall of the gas transmission and distribution device at intervals of 2Km, each solid electrolyte type gas sensor comprises a porous Yttrium Stabilized Zirconia (YSZ) substrate, and a platinum (Pt) reference electrode, a sensitive electrode A and a sensitive electrode B which are arranged on the YSZ substrate, wherein the sensitive electrode A and the sensitive electrode B are respectively arranged on two sides of the Pt reference electrode;
the solid electrolyte type gas sensor is manufactured by the following method:
(1) preparation of porous yttrium-stabilized zirconia (YSZ):
preparing porous structure YSZ by adopting a double-groove electrochemical corrosion method;
a. taking YSZ plate (8 mol% Y)2O3Doping, 10mm by 5mm by 0.2mm), sequentially performing multiple ultrasonic cleaning with water and absolute ethyl alcohol, and drying;
b. preparing a pretreatment solution: soaking in purified water for 10min, cleaning, and naturally drying;
the microwave treatment parameters are as follows: 2450MHz and 65W, irradiating for 2s at an interval of 10min for 5 times;
b. preparing an etching solution, mixing HF (40% by volume) and deionized water according to a volume ratio of 1:5, adding potassium permanganate in a proper amount, putting the mixture into a double-cell electrochemical device (shown in figure 1), wherein the etching cell and a clamp are both made of corrosion-resistant polytetrafluoroethylene materials, an electrode is columnar metal Pt, the clamp divides the etching cell into two regions which are not communicated with each other, and the center of the clamp is provided with two holes with a specific shape of 2 x 4 mm;
c. the corrosion process is in the dark stripThe corrosion treatment is carried out under the condition that a power supply used by the device is a constant current source and the density of the applied corrosion current is 40mA/cm2After 30min, forming two porous structures with 2 x 4mm areas on the YSZ flat plate, and after the preparation is finished, cleaning and storing the porous structures in absolute ethyl alcohol;
(2) preparing a sensitive electrode material A:
a. synthesizing tungsten oxide nanoparticles: weighing 1.5g Na2WO4Dissolving in 45mL of deionized water, and dropwise adding an HCl solution with the concentration of 3mol/L under the stirring condition until tungstic acid is completely precipitated; then centrifugally separating, putting the precipitate into a small beaker, adding 30mL of deionized water, and then adding 75g of KNO3Violently stirring to form paste, carrying out hydrothermal reaction for 12h at 180 ℃, and naturally cooling to room temperature; fully washing the reactant (precipitate) with deionized water, then washing with ethanol, filtering, dehydrating and drying at 80 ℃ to obtain a product, namely tungsten oxide nano-particles;
b. tungsten oxide nanoparticles doped with nickel oxide: taking the mass ratio of 3: 1, putting the tungsten oxide nano particles and the nano nickel powder into a stirrer to be fully mixed; then putting the mixed material into a vacuum tube furnace, heating to 300 ℃, preserving heat for 4 hours to fully oxidize the nickel powder, and finally naturally cooling to room temperature;
(3) preparing a sensitive electrode material B:
a. firstly SnO with the particle size of 5nm2Drying the nanometer powder in a vacuum drying oven at 80 ℃ for 12 hours;
b. weighing dried SnO22.0g of nano powder, then adding 4.0ml of chloroplatinic acid solution with the concentration of 10mmol/L, and carrying out ultrasonic treatment for 15min after complete impregnation to uniformly mix the nano powder;
c. standing the mixture for 6h, then drying the mixture in a vacuum drying oven at 80 ℃ for 12h, sintering the mixture at 500 ℃ for 12h after drying, and naturally cooling to room temperature to obtain a sensitive electrode B;
(4) gas sensor fabrication
The nitrogen oxide sensor is mainly composed of two parts: porous YSZ flat plate and Pt 'ji' shape electrode heating plate, the device preparation steps are as follows:
a. taking the YSZ substrate treated in the step (1), sequentially carrying out ultrasonic cleaning with water and absolute ethyl alcohol for multiple times, and drying for later use;
b. taking platinum paste, manufacturing a2 x 4 mm-sized thin strip-shaped platinum paste strip in the middle of the cleaned YSZ substrate, respectively manufacturing a small platinum paste circular point in a porous area of the YSZ, and adopting a screen printing process during mass production;
c. respectively sticking three sections of platinum wires to the areas of the YSZ sheet, which are just coated with the platinum slurry, and then placing the YSZ substrate under an infrared lamp for baking for several hours;
d. taking a proper amount of sensitive electrode materials A, B, respectively putting the sensitive electrode materials A, B into agate mortar, fully grinding the sensitive electrode materials, adding a small amount of deionized water, preparing into viscous slurry A, B, and respectively coating the slurry A, B on the porous structure of the substrate to form two sensitive electrodes A, B of the sensor, wherein the thickness of the two sensitive electrodes A, B is 0.5 mm;
e. putting the substrate obtained in the previous step into a muffle furnace, and sintering at the high temperature of 800 ℃ for two hours;
f. and (3) uniformly coating a layer of inorganic adhesive (prepared by mixing water glass and Al2O 3) on the surface of the n-shaped Pt heating plate printed with the Pt electrode, then adhering the heating plate and the substrate obtained in the previous step together, putting the substrate into a muffle furnace, sintering at 200 ℃ for 20 minutes, and taking out the substrate to obtain the prototype device of the sensor.
The device of this example operates at 300 ℃ for 100ppm NO2The sensitivity can reach 50mV/decade, and the response recovery speed is faster and is about 15 s; for 200ppm CO, the sensitivity can reach 60mV/decade, and the response recovery speed is about 3 s.
At the working temperature of 300 ℃, the device is used for 100ppm of NO2The sensitivity can reach 79mV/decade, and the response recovery speed is faster and is about 20 s; for 200ppm CO, the sensitivity can reach 125mV/decade, and the response recovery speed is about 9 s.
In this embodiment, the YSZ substrate is doped with 8 mol% Y2O3The physical size is 10mm x 5mm x 0.2mm, and a nano porous structure with two 2 x 4mm areas is formed by electrochemical corrosion and is used for placing a sensitive electrode A and a sensitive electrode B respectively; manufacturing platinum dots with the diameter of 0.1-0.3mm on a nano porous area of the YSZ substrate to be used as the connection between the YSZ substrate and an electrode; the thickness of the sensitive electrode A and the sensitive electrode B is 0.5mm, and SnO in the sensitive electrode B2The particle size of the nano powder is 15-22 nm.
Through adjustment of YSZ substrate, size of porous nanostructure and experimental parameters, the composite material can be used for treating CO and NO in hazardous gases2The detection sensitivity is respectively improved to 125mV/decade and 79mV/decade, and the response time is respectively shortened to 9s and 20s, thereby obtaining unexpected results.
Therefore, the solid electrolyte type gas sensors are arranged on the outer wall of the gas transmission and distribution device at intervals of 2Km, the optimal sensitivity and response time are obtained by comparing the performances of the sensors under different experimental process parameters, unexpected effects are obtained, the flammable and combustible dangerous situations of the gas transmission and distribution device in the using process can be found in time, and the gas transmission and distribution device has a great market prospect.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical invention and the inventive concept thereof are equivalent to or changed within the technical scope of the present invention.
Claims (4)
1. A gas transmission and distribution device is characterized in that solid electrolyte type gas sensors are arranged on the outer wall of the gas transmission and distribution device at intervals of 2Km and comprise a heating plate, a Yttrium Stabilized Zirconia (YSZ) substrate arranged on the heating plate, a platinum (Pt) reference electrode arranged on the YSZ substrate, a sensitive electrode A and a sensitive electrode B, wherein the sensitive electrode A and the sensitive electrode B are respectively arranged on two sides of the Pt reference electrode, the sensitive electrode A is made of tungsten oxide nanoparticles doped with nano nickel oxide powder, and the sensitive electrode B is made of nano SnO2And (3) pulverizing.
2. The gas distribution apparatus of claim 1, wherein the YSZ substrate is doped with 8 mol% Y2O3The physical size is 6mm 4mm 0.2mm, and two nano porous structures with 1 x 2mm areas are corroded by an electrochemical method and are respectively used for placing a sensitive electrode A and a sensitive electrode B; manufacturing platinum dots with the diameter of 0.1-0.3mm on a nano porous area of the YSZ substrate, and connecting the YSZ substrate and the electrode; the thickness of the sensitive electrode A and the sensitive electrode B is 0.5mm, and SnO in the sensitive electrode B2The particle size of the nano powder is 15-22 nm.
3. The implementation method of the gas transmission and distribution device is characterized in that solid electrolyte type gas sensors are arranged on the outer wall of the gas transmission and distribution device at intervals of 2Km, each solid electrolyte type gas sensor comprises a porous Yttrium Stabilized Zirconia (YSZ) substrate, and a platinum (Pt) reference electrode, a sensitive electrode A and a sensitive electrode B which are arranged on the YSZ substrate, wherein the sensitive electrode A and the sensitive electrode B are respectively arranged on two sides of the Pt reference electrode; wherein,
a. ultrasonically cleaning a YSZ substrate with water and absolute ethyl alcohol successively for multiple times, and drying for later use;
b. taking platinum paste, manufacturing a 1-2 mm-sized thin strip-shaped platinum paste strip in the middle of the cleaned YSZ substrate, respectively manufacturing a platinum paste round point with the diameter of 0.1-0.3mm in a porous area of the YSZ, and adopting a screen printing process during mass production;
c. respectively sticking three sections of platinum wires to the areas of the YSZ sheet, which are just coated with the platinum slurry, and then placing the YSZ substrate under an infrared lamp for baking for several hours;
d. taking a proper amount of sensitive electrode materials A, B, respectively putting the sensitive electrode materials A, B into agate mortar, fully grinding the sensitive electrode materials, adding a small amount of deionized water, preparing into viscous slurry A, B, and respectively coating the slurry A, B on the porous structure of the substrate to form two sensitive electrodes A, B of the sensor, wherein the thickness of the two sensitive electrodes A, B is 0.5 mm;
e. putting the substrate obtained in the previous step into a muffle furnace, and sintering at the high temperature of 800 ℃ for two hours;
f. and (3) uniformly coating a layer of inorganic adhesive on the surface of the n-shaped Pt heating plate printed with the Pt electrode, then adhering the heating plate and the substrate obtained in the previous step together, sintering in a muffle furnace at 200 ℃ for 20 minutes, and taking out to obtain the prototype device of the sensor.
4. The implementation method of claim 3,
(1) preparation of porous yttrium-stabilized zirconia (YSZ):
preparing porous structure YSZ by adopting a double-groove electrochemical corrosion method;
a. taking YSZ plate (8 mol% Y)2O3Doping, 6mm by 4mm by 0.2mm), sequentially performing multiple ultrasonic cleaning with water and absolute ethyl alcohol, and drying;
b. preparing a pretreatment solution: according to the mass portion, 1-1.8% of tea saponin, 2% of malic acid and the balance of purified water are added, then YSZ flat plates are put into the YSZ flat plates and are completely immersed, the YSZ flat plates are treated for 20-28min at the temperature of 50-58 ℃, then the YSZ flat plates are treated for 2min by microwave, and the YSZ flat plates are cleaned and naturally dried for standby;
the microwave treatment parameters are as follows: 2450MHz and 65W, irradiating for 2-5s at an interval of 10min for 3-5 times;
c. preparing an etching solution, mixing HF (40% by volume) and deionized water according to a volume ratio of 1:5, adding potassium permanganate in a proper amount, placing the mixture into a double-electric-tank electrochemical device, wherein the etching tank and a clamp are both made of corrosion-resistant polytetrafluoroethylene materials, an electrode is columnar metal Pt, the clamp divides the etching tank into two non-communicated areas, and the center of the clamp is provided with two holes with a specific shape of 1 x 2 mm;
d. the corrosion process is carried out under dark condition, the power supply used by the device is a constant current source, and the density of the applied corrosion current is 40mA/cm2After 30min, forming two porous structures with the area of 1 x 2mm on a YSZ flat plate, and after the preparation is finished and cleaned, storing the porous structures in absolute ethyl alcohol;
(2) preparing a sensitive electrode material A:
a. synthesizing tungsten oxide nanoparticles: weighing 1.5g of Na2WO4, dissolving in 45mL of deionized water, and dropwise adding an HCl solution with the concentration of 3mol/L under the condition of stirring until tungstic acid is completely precipitated; then centrifugally separating, putting the precipitate into a small beaker, adding 30mL of deionized water, adding 75g of KNO3, violently stirring to form a paste, carrying out hydrothermal reaction at 180 ℃ for 12h, and naturally cooling to room temperature; fully washing the reactant (precipitate) with deionized water, then washing with ethanol, filtering, dehydrating and drying at 80 ℃ to obtain a product, namely tungsten oxide nano-particles;
b. tungsten oxide nanoparticles doped with nickel oxide: taking the mass ratio of 3: 1, putting the tungsten oxide nano particles and the nano nickel powder into a stirrer to be fully mixed; then putting the mixed material into a vacuum tube furnace, heating to 300 ℃, preserving heat for 4 hours to fully oxidize the nickel powder, and finally naturally cooling to room temperature;
(3) preparing a sensitive electrode material B:
a. firstly, SnO with the grain diameter of 15-22nm2Drying the nanometer powder in a vacuum drying oven at 80 ℃ for 12 hours;
b. weighing dried SnO22.0g of nano powder, then adding 4.0ml of chloroplatinic acid solution with the concentration of 10mmol/L, and carrying out ultrasonic treatment for 15min after complete impregnation to uniformly mix the nano powder;
c. and standing the mixture for 6h, then drying the mixture in a vacuum drying oven at 80 ℃ for 12h, sintering the mixture at 500 ℃ for 12h after drying, and naturally cooling to room temperature to obtain the sensitive electrode B.
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