CN111189901B - Gd2Zr2O7Solid electrolyte type formaldehyde sensor and preparation method thereof - Google Patents

Gd2Zr2O7Solid electrolyte type formaldehyde sensor and preparation method thereof Download PDF

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CN111189901B
CN111189901B CN202010030188.XA CN202010030188A CN111189901B CN 111189901 B CN111189901 B CN 111189901B CN 202010030188 A CN202010030188 A CN 202010030188A CN 111189901 B CN111189901 B CN 111189901B
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刘方猛
蒋理
卢革宇
梁喜双
孙鹏
王晨光
刘晓敏
高原
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Jilin University
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Abstract

Ca-doped Gd taking rod-shaped ZnO as sensitive electrode2Zr2O7A solid electrolyte type formaldehyde (HCHO) sensor and a preparation method thereof belong to the technical field of gas sensors. Sequentially heating Al with Pt electrode2O3Ceramic heating plate, Ca-doped Gd2Zr2O7The reference electrode is arranged on the electrolyte substrate; the reference electrode and the ZnO sensitive electrode are respectively prepared at two ends of the upper surface of the electrolyte substrate in a strip shape, and the lower surface of the electrolyte substrate is connected with Al with a Pt heating electrode through an inorganic adhesive2O3And bonding the ceramic heating plate. The invention adopts pyrochlore type Ca to dope Gd2Zr2O7The solid electrolyte is combined with a ZnO sensitive electrode material with a rod-shaped structure to prepare the hybrid potential type HCHO sensor. The sensor follows a hybrid potential sensing mechanism, can be effectively used for detecting indoor pollutants, and has very important practical application value.

Description

Gd2Zr2O7Solid electrolyte type formaldehyde sensor and preparation method thereof
Technical Field
The invention belongs to the technical field of gas sensors, and particularly relates to Ca-doped Gd with rod-shaped ZnO as a sensitive electrode2Zr2O7A solid electrolyte type formaldehyde (HCHO) sensor and a preparation method thereof,can be used for detecting indoor air pollutants, in particular formaldehyde.
Background
In recent decades, with the improvement of living standard and health consciousness of people, the indoor air quality problem has increasingly become the focus of public attention. Among the numerous indoor harmful gases, formaldehyde (HCHO) is becoming the first killer to harm human health, and the use of various decorative materials in large quantities is becoming the main source of HCHO. HCHO causes irritation to the skin, mucous membranes and respiratory tract of the human body, and the risk of developing cancer in people who are exposed to high concentrations of HCHO for a long time is greatly increased. In addition, HCHO is an important industrial raw material, and is widely used in the fields of textile, wood processing and other industries, so that the chance of contacting people is increased. Therefore, the detection and prevention of HCHO has long been a problem to be addressed and urgently solved (Ministry of science and technology of the people's republic of China. poisoning prevention and emergency treatment [ M ]. xuzhou: China university Press, 2010: 34-36; Wei nationality, Yang courage, China's formaldehyde production status and technical progress [ J ]. China chemical trade, 2015,7(22): 127; Shaoxing market supervision and management bureau, world health organization International cancer research institute carcinogen List 1 type carcinogen List (120 in total) [ EB/OL ]. [2018.09.27]. http:// scjg.sx.gov.cn/art/2018/9/27/art _1484741_21554630. html). Compared with methods such as chromatography and fluorescence spectrophotometry, the development of a high-sensitivity HCHO gas sensor is necessary in both timeliness and economy. The sensors are diversified, and the hybrid potential type sensor based on the solid electrolyte and the oxide sensitive electrode has more excellent stability and selectivity compared with other types (semiconductor oxide and the like), so that the development of the HCHO sensor of the type has very important practical application value (N.Miura, T.Sato, A review of mixed-potential type zirconia-based sensors [ J ], Ionics,2014,20,901 and 925).
The sensitive mechanism of a mixed potential type HCHO sensor can be explained as follows: HCHO diffuses through the sensitive electrode layer to reach a gas/sensitive material/electrolyte three-phase reaction interface (TPB), part of gas is consumed in the diffusion process to generate gas phase reaction (1), and the gas reaching the TPB simultaneously generates electrochemical reduction reaction (2) and oxidation reaction (3) on the interface to form a local primary cell. When the reaction rates of (2) and (3) are equal, the reaction reaches the equilibrium, and a mixed potential is formed on the sensitive electrode, and the potential difference between the mixed potential and the reference electrode is used as a detection signal of the sensor. The magnitude of the detection signal depends on the rate of the electrochemical reactions (2) and (3), which is related to the reactive sites at the three-phase interface, the electrochemical and chemical catalytic activity of the sensitive electrode material, the microstructure of the electrode material (such as porosity, particle size, morphology, etc.) j.w. fergus, Sensing mechanism of non-equilibrium Solid-electrolyte-based sensors [ J ], J. Solid State actuators, 2011,15, 971-porous sensors 984, x.li, g.m. kale, influx of Sensing electrode and electrolyte on performance of porous mixed-porous sensors [ J ], sensors, atoms. actuators B. 2007,123, che254 261).
The reaction formula is as follows:
HCHO+O2＝CO2+H2O (1)
O2+4e-＝2O2- (2)
HCHO+2O2-＝CO2+H2O+4e- (3)
at present, a great deal of research is done on the development of solid electrolyte and sensitive electrode materials for the development of solid electrolyte type gas sensors, both domestically and abroad, but few solid electrolyte type gas sensors for HCHO detection have been reported until now. The variety of the solid electrolyte is widened, the matching with different oxide sensitive electrodes is realized, and the method is an effective strategy for developing the solid electrolyte type HCHO sensor.
Disclosure of Invention
The invention aims to provide Ca-doped Gd taking rod-shaped ZnO as a sensitive electrode2Zr2O7A solid electrolyte type HCHO sensor and a method for manufacturing the same. The sensor obtained by the invention has high sensitivity, and also has good selectivity and stability.
The HCHO sensor is based on a pyrochlore structureIs a new solid electrolyte-Ca doped Gd2Zr2O7A novel HCHO sensor constructed by using rod-shaped ZnO with high electrochemical catalytic performance as a sensitive electrode, Ca-doped Gd2Zr2O7The solid electrolyte acts as an ion conducting layer.
The Ca-doped Gd of the invention takes rod-shaped ZnO as a sensitive electrode2Zr2O7The solid electrolyte type HCHO sensor has a structure shown in FIG. 1, and comprises Al with Pt heating electrode2O3Ceramic heating plate, Ca-doped Gd2Zr2O7The electrolyte substrate, the reference electrode and the sensitive electrode; the reference electrode and the sensitive electrode are respectively prepared at two ends of the upper surface of the electrolyte substrate in a strip shape, and the lower surface of the electrolyte substrate is connected with Al with a Pt heating electrode through an inorganic adhesive2O3And bonding the ceramic heating plate. The method takes rod-shaped ZnO as a sensitive electrode, and utilizes a small amount of Ca to dope an electrolyte to obtain Gd2-xCaxZr2O7(x is 0.02-0.1), and the purpose of improving the sensitivity is achieved by selecting the optimal doping ratio.
The Ca-doped Gd of the invention takes rod-shaped ZnO as a sensitive electrode2Zr2O7The preparation method of the solid electrolyte type HCHO sensor comprises the following steps:
A. preparation of electrolyte substrate:
gd (NO) is added according to the stoichiometric ratio3)3·6H2O、Ca(NO3)2·2H2O and ZrOCl2·8H2Dissolving O in 40mL of deionized water, uniformly stirring to ensure that the sum of all cation concentrations is 0.25mol/L, adding 25mmol of urea serving as a precipitator into the solution, fully stirring for 20-40 min, and transferring the solution into a polytetrafluoroethylene reaction kettle to react for 20-30 h at 160-190 ℃ to obtain white precipitate; collecting the precipitate, alternately cleaning and centrifuging by using deionized water and ethanol, pre-sintering the dried precipitate at 500-700 ℃ to remove organic impurities, tabletting under the pressure of 280-300 MPa, and sintering at 1400-1600 ℃ for 3-5 h to obtain pyrochlore Gd2-xCaxZr2O7(x is 0.02 to 0.1) a solid electrolyte, and then cutting the electrolyte into a substrate having a certain length, width and thickness;
B. preparing a sensitive electrode material:
0.2g of ZnCl2·2H2O and 2g Na2CO3Dissolving the ZnO-containing ZnO-sensitive electrode material in 40mL of deionized water to form a uniform solution, placing the uniform solution in a polytetrafluoroethylene reaction kettle, reacting for 10-15 h at 100-120 ℃ to obtain a white precipitate, alternately centrifuging and washing a reaction product by deionized water and ethanol, drying to obtain a prepolymer precipitate, heating to 700-900 ℃ at a heating rate of 1.5-3.0 ℃/min, and sintering for 3-5 h to obtain a rod-shaped ZnO-sensitive electrode material;
C. manufacturing a sensor:
(1) manufacturing a Pt reference electrode: gd obtained in step A2-xCaxZr2O7(x is 0.02-0.1) manufacturing a Pt reference electrode with the thickness of 10-20 microns by using Pt slurry at one end of the upper surface of the solid electrolyte substrate, folding one Pt wire, adhering the Pt wire to the middle position of the reference electrode to be used as an electrode lead, folding the other Pt wire, adhering the other end of the Pt wire to the upper surface of the electrolyte substrate by using the Pt slurry to be used as a sensitive electrode lead; then baking the electrolyte substrate for 20-40 min at 90-120 ℃, sintering for 20-40 min at 900-1100 ℃, removing the organic solvent in the Pt slurry, ensuring the good contact between the reference electrode and the sensitive electrode lead and the electrolyte substrate, and finally cooling to room temperature;
(2) manufacturing a ZnO sensitive electrode: b, mixing the ZnO sensitive electrode material obtained in the step B with deionized water to form slurry, wherein the mass concentration of the slurry is 2-20%; preparing a sensitive electrode with the thickness of 0.2-0.3 mm at the reference electrode lead at the other end of the upper surface of the electrolyte substrate which is symmetrical to the reference electrode by using ZnO slurry;
(3) gd prepared with the reference electrode and the sensitive electrode2-xCaxZr2O7(x is 0.02-0.1) sintering the electrolyte substrate at 700-900 ℃ for 1.5-3.0 h to ensure that the sensitive electrode and the sensitive electrode are in close contact with the electrolyte substrate, wherein the temperature rise rate during sintering is 1.5-3.0 ℃/min;
(4) preparation ofInorganic binder: measuring 2-4 mL of water glass (Na)2SiO3·9H2O) and 0.7 to 1.0g of Al2O3Mixing and uniformly stirring the powder to obtain the required inorganic adhesive;
(5) al with "M" -type Pt heating electrode on the lower surface and surface of electrolyte substrate using inorganic binder2O3The ceramic heating plates are bonded together;
in which Al with "M" type Pt heating electrode2O3The ceramic heating plate is made of Al2O3The ceramic heating plate was screen printed with Pt.
(6) Welding and packaging the bonded device to prepare the Ca-doped Gd with the rod-shaped ZnO as the sensitive electrode2Zr2O7Solid electrolyte type HCHO sensors.
The invention has the advantages that:
(1) a novel pyrochlore type Ca-doped Gd is developed2Zr2O7The solid electrolyte has good thermal stability and chemical stability, and the types of the solid electrolyte are widened.
(2) ZnO with a rod-like structure is prepared by a simple hydrothermal method to serve as a sensitive electrode material of the sensor, the preparation method is simple, and the mass industrial production is facilitated.
(3) The prepared ZnO sensitive electrode material has a rod-shaped structure, a loose and porous structure is formed by accumulation on the surface of an electrolyte, and the diffusion and migration of gas in the ZnO sensitive electrode material are facilitated, so that the gas quantity consumed by gas-phase reaction is reduced, and the sensitivity of the sensor is improved.
(4) A small amount of metal Ca is used for doping the solid electrolyte, so that the structure of the solid electrolyte is stabilized, and the sensitivity of the sensor is improved.
(5) The first use of pyrochlore type Ca doped Gd2Zr2O7The solid electrolyte and the ZnO sensitive electrode are matched, so that the solid electrolyte type gas sensor can effectively detect HCHO.
Drawings
FIG. 1: hair brushGd of Ming Dynasty2Zr2O7Schematic structural view of solid electrolyte type HCHO sensor.
The names of the parts are as follows: al (Al)2O3 Ceramic heating plate 1, Pt heating electrode 2, inorganic adhesive 3, Ca-doped Gd2Zr2O7The device comprises a solid electrolyte substrate 4, a Pt wire 5, a ZnO sensitive electrode 6 and a Pt reference electrode 7.
FIG. 2: the Ca-doped Gd prepared by the invention2Zr2O7XRD and raman spectra of the solid electrolyte.
As shown in FIG. 2, Gd is doped with Ca2Zr2O7The XRD (a) and Raman spectrogram (b) of the solid electrolyte can determine that the electrolyte material has a pyrochlore structure by observing and calibrating characteristic peaks, which shows that the electrolyte material prepared by the method is pyrochlore Gd2-xCaxZr2O7(x＝0.02～0.1)。
FIG. 3: the XRD pattern of the ZnO sensitive electrode material prepared by the invention.
As shown in FIG. 3, which is an XRD pattern of the ZnO sensitive electrode material, by comparing with a standard spectrogram, the spectrogram of the material prepared by the invention is consistent with that of the standard card JCPDS #36-1451, which shows that the sensitive electrode material prepared by the invention is pure ZnO.
FIG. 4: SEM images of different magnifications of the ZnO sensitive electrode material prepared by the invention.
As shown in fig. 4, the SEM image of the prepared ZnO sensitive electrode material shows that the prepared ZnO sensitive electrode material has a rod-like structure, and the surface of the ZnO sensitive electrode material is stacked to form a loose and porous structure, which is beneficial to the migration and diffusion of gas therein.
FIG. 5: doping Gd based on different proportions of Ca2-xCaxZr2O7(x is 0.02 to 0.1) response-concentration log curve of solid electrolyte sensor to HCHO.
As shown in FIG. 5, Gd is a solid electrolyte with different Ca doping ratios2-xCaxZr2O7(x is 0.02 to 0.1) response value of the sensor (i.e., the sensor response value is obtainedResponse signal V of sensor in HCHO atmosphere with different concentrations obtained by Rigo testerHCHOAnd a response signal V in airairDifference av) versus the logarithm of HCHO concentration. As can be seen from the graph, the response values of the four different sensors are all in a better linear relationship with the logarithm of the HCHO concentration, with the slope being defined as the sensitivity, and the sensitivities of comparative examples 1, 2, 3 and example 1 are-25, -15, -5 and-30 mV/decade, respectively. As a result, it was found that Gd was used at a Ca doping ratio of 0.021.98Ca0.02Zr2O7Sensors made with electrolyte substrates and rod-like ZnO as the sensing electrode have the highest sensitivity to HCHO.
FIG. 6: gd taking rod-shaped ZnO as sensitive electrode1.98Ca0.02Zr2O7Schematic of the selectivity of solid electrolyte type HCHO sensors.
As shown in FIG. 6, Gd is used1.98Ca0.02Zr2O7The selectivity of the sensor made of the electrolyte substrate and the rod-shaped ZnO as the sensitive electrode is improved. It can be seen that the devices exhibit the greatest sensitivity to HCHO and lower response to other interfering gases at different operating temperatures. Thus, the device has good selectivity under different working temperatures.
Detailed Description
Comparative example 1:
preparing ZnO sensitive electrode material by hydrothermal method in Gd without Ca doping2Zr2O7The HCHO sensor is manufactured on the solid electrolyte substrate, and the gas-sensitive performance of the sensor is tested, and the specific process is as follows:
1. preparation of Gd2Zr2O7Solid electrolyte substrate: adding 10mmol Gd (NO)3)3·6H2O and 10mmol of ZrOCl2·8H2Dissolving O in 40mL of deionized water, stirring to form a uniform solution, adding 25mmol of urea serving as a precipitator into the solution, stirring for 30min, transferring the solution into a 100mL polytetrafluoroethylene reaction kettle after the solution is completely and uniformly mixed, and reacting for 24h at 180 ℃. The precipitate obtained by the reaction is treated by deionized waterAnd drying after alternately centrifuging and cleaning with ethanol, pre-sintering for 4 hours at 600 ℃ to fully dry and remove impurities in the electrolyte, forming a wafer with the diameter of 13mm and the thickness of 1mm on a pre-sintered sample under the pressure of 280MPa, then sintering for 4 hours at 1500 ℃ to obtain an electrolyte plate, and finally cutting the obtained electrolyte plate into electrolyte substrates with the diameter of 2mm multiplied by 0.3mm for manufacturing the sensor.
2. Manufacturing a Pt reference electrode: gd obtained in 12Zr2O7One side of the upper surface of the solid electrolyte substrate is provided with a layer of Pt reference electrode with the size of 0.5mm multiplied by 2mm and the thickness of 15 mu m by using Pt slurry, meanwhile, a Pt wire is folded and then adhered to the middle position of the reference electrode to lead out an electrode lead, and another Pt wire is folded and then also adhered to the other end of the electrolyte substrate by using the Pt slurry to be used as a spare reference electrode lead; and then baking the electrolyte substrate at 110 ℃ for 30min, sintering the electrolyte substrate at 1000 ℃ for 30min, removing the organic solvent in the Pt slurry, ensuring good contact between the reference electrode and the electrolyte substrate, and finally cooling to room temperature.
3. Manufacturing a ZnO sensitive electrode: firstly, preparing ZnO sensitive electrode material by a hydrothermal method. 0.2g of ZnCl2·2H2O and 2g Na2CO3Dissolving the ZnO precursor solution in 40mL of deionized water to form a uniform solution, placing the uniform solution in a 100mL polytetrafluoroethylene reaction kettle to react for 12h at 110 ℃ to obtain white precipitate, alternately and centrifugally washing a reaction product by using the deionized water and ethanol, drying to obtain prepolymer precipitate, heating to 800 ℃ at a heating rate of 2 ℃/min, and sintering for 4h to obtain the ZnO sensitive electrode material with a rod-shaped structure.
And (3) preparing 5mg of ZnO powder into slurry by using 100mg of deionized water, and coating a layer of sensitive electrode with the size of 0.5mm multiplied by 2mm and the thickness of 0.25mm on the reference electrode lead at the other end of the upper surface of the electrolyte substrate which is symmetrical to the reference electrode in the step (2) with the ZnO slurry.
And heating the manufactured electrolyte substrate with the reference electrode and the sensitive electrode to 800 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 2 hours, and then cooling to room temperature.
3. A ceramic heating plate having a heating electrode is bonded. Using an inorganic binder (Al)2O3Water glassGlass Na2SiO3·9H2O, about 5: 1 preparation) the lower surface (side not coated with electrode) of the electrolyte substrate was brought into contact with Al with Pt heater electrode of the same size2O3Bonding with a ceramic heating plate (2 mm in length, 2mm in width and 0.2mm in thickness);
4. and welding and packaging the device. Welding the device on a hexagonal tube seat, sleeving a protective cover on the hexagonal tube seat, and manufacturing the Ca-doped Gd with the rod-shaped ZnO as the sensitive electrode2Zr2O7Solid electrolyte type HCHO sensors.
Comparative example 2:
preparing ZnO sensitive electrode material by hydrothermal method at Gd1.95Ca0.05Zr2O7And manufacturing an HCHO sensor on the solid electrolyte substrate, and testing the gas-sensitive performance of the sensor. The manufacturing method comprises the following steps:
the same procedure as in comparative example 1 was followed, using 9.75mmol of Gd (NO)3)3·6H2O、0.25mmol Ca(NO3)2·2H2O and 10mmol of ZrOCl2·8H2Preparation of Gd from O1.95Ca0.05Zr2O7A solid electrolyte. The remaining steps are referred to comparative example 1.
Comparative example 3:
preparing ZnO sensitive electrode material by hydrothermal method at Gd1.9Ca0.1Zr2O7And manufacturing an HCHO sensor on the solid electrolyte substrate, and testing the gas-sensitive performance of the sensor. The manufacturing method comprises the following steps:
the same procedure as in comparative example 1 was followed, using 9.5mmol of Gd (NO)3)3·6H2O、0.5mmol Ca(NO3)2·2H2O and 10mmol of ZrOCl2·8H2Preparation of Gd from O1.9Ca0.1Zr2O7A solid electrolyte. The remaining steps are referred to comparative example 1.
Example 1:
preparing ZnO sensitive electrode material by hydrothermal method at Gd1.98Ca0.02Zr2O7And manufacturing an HCHO sensor on the solid electrolyte substrate, and testing the gas-sensitive performance of the sensor. The manufacturing method comprises the following steps:
using 9.9mmol Gd (NO)3)3·6H2O、0.1mmol Ca(NO3)2·2H2O and 10mmol of ZrOCl2·8H2Preparation of Gd from O1.98Ca0.02Zr2O7A solid electrolyte. Device fabrication the remaining steps refer to comparative example 1.
The sensors were connected to a Rigol signal tester, and voltage signal tests were carried out by placing the sensors in an atmosphere of air, 1ppm HCHO, 2ppm HCHO, 5ppm HCHO, 10ppm HCHO, 20ppm HCHO, 50ppm HCHO, and 100ppm HCHO, respectively.
Table 1 shows the respective Gd concentrations of ZnO as the sensitive electrode2Zr2O7、Gd1.98Ca0.02Zr2O7、 Gd1.95Ca0.05Zr2O7And Gd1.9Ca0.1Zr2O7The difference value of the electromotive force of the HCHO sensor manufactured on the solid electrolyte substrate in HCHO atmosphere with different concentrations and the electromotive force in air changes along with the change value of the HCHO concentration. As can be seen from the table, based on Gd1.98Ca0.02Zr2O7The sensor made of the solid electrolyte has good response characteristics to HCHO, has the highest response value to HCHO at various concentrations, and has the highest sensitivity to 1-100ppm HCHO. Therefore, the doping of a small amount of Ca is beneficial to improving the performance of the solid electrolyte, so that the sensing performance of the sensor is improved.
Table 1: variation of Δ V with HCHO concentration for sensors based on different doping ratios
Figure GDA0003070507310000071

Claims (2)

1. Ca-doped Gd taking rod-shaped ZnO as sensitive electrode2Zr2O7A solid electrolyte HCHO sensor characterized by: from bottom to top, in turn from Al with Pt heating electrode2O3Ceramic heating plate, Ca-doped Gd2Zr2O7The reference electrode is arranged on the electrolyte substrate; the reference electrode and the ZnO sensitive electrode are respectively prepared at two ends of the upper surface of the electrolyte substrate in a strip shape, and the lower surface of the electrolyte substrate is connected with Al with a Pt heating electrode through an inorganic adhesive2O3Bonding the ceramic heating plates;
the electrolyte substrate is prepared by a method comprising,
gd (NO) is added according to the stoichiometric ratio3)3·6H2O、Ca(NO3)2·2H2O and ZrOCl2·8H2Dissolving O in 40mL of deionized water, uniformly stirring, adding 25mmol of urea serving as a precipitator into the solution, fully stirring for 20-40 min, transferring the solution into a polytetrafluoroethylene reaction kettle, and reacting for 20-30 h at 160-190 ℃ to obtain white precipitate, wherein the concentration of the sum of all cations is 0.25 mol/L; collecting the precipitate, alternately cleaning and centrifuging by using deionized water and ethanol, pre-sintering the dried precipitate at 500-700 ℃ to remove organic impurities, pressing the precipitate into sheets, and sintering the sheets at 1400-1600 ℃ for 3-5 hours to obtain pyrochlore Gd2-xCaxZr2O7A solid electrolyte, wherein x is 0.02 to 0.1; then cutting the substrate into a substrate with certain length, width and thickness;
the ZnO sensitive electrode material is prepared by the following method,
0.2g of ZnCl2·2H2O and 2g Na2CO3Dissolving the ZnO sensitive electrode material in 40mL of deionized water to form a uniform solution, placing the uniform solution in a polytetrafluoroethylene reaction kettle to react for 10-15 h at 100-120 ℃ to obtain white precipitate, alternately centrifuging and washing a reaction product by using deionized water and ethanol, drying to obtain prepolymer precipitate, heating to 700-900 ℃ at a heating rate of 1.5-3.0 ℃/min, and sintering for 3-5 h to obtain the ZnO sensitive electrode material with a rod-shaped structure.
2. The Ca-doped Gd of claim 1 with rod-like ZnO as sensitive electrode2Zr2O7The preparation method of the solid electrolyte type HCHO sensor comprises the following steps:
(1) manufacturing a Pt reference electrode: at Gd2-xCaxZr2O7Manufacturing a Pt reference electrode with the thickness of 10-20 microns at one end of the upper surface of the solid electrolyte substrate by using Pt slurry, folding a Pt wire and then adhering the Pt wire to the middle position of the reference electrode to be used as an electrode lead, and folding another Pt wire and then adhering the other end of the Pt slurry to the upper surface of the electrolyte substrate to be used as a sensitive electrode lead; then baking the electrolyte substrate for 20-40 min at 90-120 ℃, sintering for 20-40 min at 900-1100 ℃, removing the organic solvent in the Pt slurry, ensuring the good contact between the reference electrode and the sensitive electrode lead and the electrolyte substrate, and finally cooling to room temperature;
(2) manufacturing a ZnO sensitive electrode: mixing the ZnO sensitive electrode material into slurry with deionized water, wherein the mass concentration is 2-20%; preparing a sensitive electrode with the thickness of 0.2-0.3 mm at the reference electrode lead at the other end of the upper surface of the electrolyte substrate which is symmetrical to the reference electrode by using ZnO slurry;
(3) preparing Gd with the reference electrode and the sensitive electrode in the step (2)2-xCaxZr2O7Sintering the electrolyte substrate for 1.5-3.0 h at 700-900 ℃ to ensure that the sensitive electrode and the sensitive electrode are in close contact with the electrolyte substrate, wherein the temperature rise rate during sintering is 1.5-3.0 ℃/min;
(4) preparing an inorganic adhesive: measuring 2-4 mL of sodium silicate Na2SiO3·9H2O and 0.7-1.0 g Al2O3Mixing and uniformly stirring the powder to obtain the required inorganic adhesive;
(5) al with Pt heating electrode on the lower surface and surface of electrolyte substrate by using inorganic adhesive2O3The ceramic heating plates are bonded together;
(6) welding and packaging the bonded device to obtain the Ca-doped Gd with the rod-shaped ZnO as the sensitive electrode2Zr2O7Solid electrolyte type HCHO sensors.
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