A high temperature solid state gas sensor and uses thereof

Abstract

The application relates to the technical field of gas sensors, in particular to a high-temperature solid-state gas sensor and application thereof. The high-temperature solid-state gas sensor comprises an electrolyte layer and sensing electrode layers and reference electrode layers located on both sides of the electrolyte layer; wherein the electrolyte layer contains a cation-anion ion conductor oxide, and the cation-anion ion conductor oxide can conduct protons and oxygen ions. The high-temperature solid-state gas sensor provided by the application contains the cation-anion ion conductor oxide capable of conducting protons and oxygen ions in the electrolyte layer, can be used for simultaneously detecting hydrogen-containing gas, oxygen-containing gas and hydrocarbon gas, and has better applicability to the to-be-detected gas.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of gas sensor, in particular to a high-temperature solid-state gas sensor and its use. BACKGROUND

[0002] Gas detection technology plays a vital role in industrial production and logistics transportation. At present, the commonly used gas detection technologies mainly include gas chromatography / mass spectrometry (GC / MS), differential mobility spectrometry (DMS), ion mobility spectrometry (IMS) and selective ion flow tube mass spectrometry (SIFT-MS) and the like, but these technologies often require large equipment, which has the disadvantages of being difficult to move, high price, complex operation, needing pretreatment, long detection time and the like.

[0003] In recent years, with the rapid development of gas sensor technology, gas sensing technology has become one of the mainstream technologies for gas detection. Gas sensors can be used to monitor the progress of various combustion reactions and have been widely used in environmental protection, materials, chemical industry, energy, aerospace and other fields.

[0004] Semiconductor gas sensors mainly utilize the reaction or adsorption of gas molecules to be detected on the surface of semiconductor sensitive materials, so that electron transfer occurs between the gas molecules and the semiconductor sensitive materials, causing changes in the electrical properties of the semiconductor sensitive materials, such as resistance, and then sensing the composition and concentration of the gas to be detected. High-temperature solid-state gas sensors based on high-temperature solid oxide electrolyte have the advantages of high sensitivity, good selectivity, high precision, good stability and high reliability in harsh environments, and are more suitable for in-situ monitoring of pollution sources in continuous high-temperature and harsh environments, and are also suitable for human exhalation detection in the presence of a variety of gases with large humidity changes, and are also suitable for low-concentration toxic gas detection and the like.

[0005] However, the conventional high-temperature solid-state gas sensor can only detect a single type of gas, such as only detecting gas containing oxygen elements or only detecting gas containing hydrogen elements, and has poor applicability to the gas to be detected. SUMMARY

[0006] Therefore, the technical problem to be solved by the present application is to overcome the defects of the prior art high-temperature solid-state gas sensor, which can only detect a single type of gas and has poor applicability to the gas to be detected, so as to provide a high-temperature solid-state gas sensor and its use.

[0007] To this end, the present application provides a high-temperature solid-state gas sensor, which comprises an electrolyte layer and sensing electrode layers and reference electrode layers located on both sides of the electrolyte layer; wherein,

[0008] The electrolyte layer contains a bipolar ion conductor oxide, and the bipolar ion conductor oxide can conduct protons and oxygen ions.

[0009] Optionally, the ambipolar ion conductor oxide has a chemical formula of Ba x M z1 M’ z2 O y wherein 1≤x≤7, 0≤z1≤4, 0≤z2≤4, 3≤y≤20, M and M’ are each independently selected from at least one of Nb, Mo, Ta and W;

[0010] Optionally, the ambipolar ion conductor oxide includes at least one of Ba7Nb4MoO 20 , Ba3NbMoO 8.5 , Ba7Ta 3.7 Mo 1.3 O 20 , Ba3W 1.2 Nb 0.8 O 8.5 , Ba3WNbO 8.5 , Ba3TaNbO 8.5 and BaW4NbO 20 .

[0011] Optionally, the electrolyte layer includes a porous electrolyte layer and a dense electrolyte layer, the sensing electrode layer is located on one side of the porous electrolyte layer, and the reference electrode layer is located on one side of the dense electrolyte layer.

[0012] Optionally, the thickness of the porous electrolyte layer is 20-500 μm, and the thickness of the dense electrolyte layer is 100-1000 μm.

[0013] Optionally, the porosity of the porous electrolyte layer is 10-50%, and the density of the dense electrolyte layer is 90%-98%.

[0014] Optionally, the sensing electrode layer contains a catalyst, and the catalyst includes at least one of LaAlO3, LaCoO3, LaNiO3, BaCoO3, La 0.8 Sr 0.2 CoO3and BaNiO3.

[0015] Optionally, the thickness of the sensing electrode layer is 10-50 μm.

[0016] Optionally, the reference electrode layer includes at least one of a platinum metal layer, a palladium metal layer, a silver metal layer, a gold metal layer and an iridium metal layer.

[0017] Optionally, the thickness of the reference electrode layer is 10-50 μm.

[0018] The application also provides the use of the high-temperature solid-state gas sensor in detecting a gas containing hydrogen elements and / or oxygen elements.

[0019] Optionally, the gas containing hydrogen elements and / or oxygen elements comprises at least one of O2, CO, CO2, H2, H2O, H2S, NH3, CH3OH and C2H5OH.

[0020] The application also provides the use of the high-temperature solid-state gas sensor in monitoring engine exhaust, wherein the engine comprises a space engine, a gas turbine and an automobile engine.

[0021] The application has the following advantages:

[0022] 1. The high-temperature solid-state gas sensor provided by the application contains a bipolar ion conductor oxide capable of conducting protons and oxygen ions in the electrolyte layer, and can be used to detect hydrogen element-containing gas, oxygen element-containing gas and hydrocarbon gas at the same time, and has good applicability to the gas to be detected.

[0023] 2. The high-temperature solid-state gas sensor provided by the application uses a bipolar ion conductor oxide having high ion conductivity, thermal stability and chemical stability in the range of 400-1000 DEG C, so that the high-temperature solid-state gas sensor can be applied to long-time high-temperature environment operation, and is especially suitable for the exhaust detection field of space engines, gas turbines and automobile engines.

[0024] 3. The high-temperature solid-state gas sensor provided by the application comprises a porous electrolyte layer and a dense electrolyte layer, the porous electrolyte layer has a porous structure, is beneficial to the rapid diffusion of the gas to be detected, can increase the three-phase interface area of the gas to be detected, the sensing electrode layer and the electrolyte layer, and is beneficial to improving the detection sensitivity and can be used for ppb-level or ppm-level gas detection.

[0025] 4. The high-temperature solid-state gas sensor provided by the application contains a catalyst in the sensing electrode layer, the selected catalyst has high selectivity and sensitivity to the gas containing hydrogen elements and / or oxygen elements, and the high-temperature solid-state gas sensor has high selectivity and sensitivity to the gas containing hydrogen elements and / or oxygen elements. BRIEF DESCRIPTION OF DRAWINGS

[0026] In order to more clearly illustrate the specific embodiments of the application or the technical solutions in the prior art, the following will briefly introduce the drawings needed to be used in the description of the specific embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the application, and those skilled in the art can also obtain other drawings according to these drawings without creative labor.

[0027] Figure 1 Fig. 1 shows a schematic diagram of a high-temperature solid-state gas sensor according to the present application;

[0028] Figure 2 Fig. 4 shows a linear curve of a high-temperature solid-state gas sensor prepared according to Example 1 of the present application for detecting NH3;

[0029] Figure 3 Fig. 5 shows a linear curve of a high-temperature solid-state gas sensor prepared according to Example 1 of the present application for detecting CO2;

[0030] Figure 4 Fig. 8 shows a linear curve of a high-temperature solid-state gas sensor prepared according to Example 2 of the present application for detecting H2S;

[0031] Figure 5 Fig. 9 shows a linear curve of a high-temperature solid-state gas sensor prepared according to Example 2 of the present application for detecting CO2;

[0032] Figure 6 Fig. 12 shows a linear curve of a high-temperature solid-state gas sensor prepared according to Example 3 of the present application for detecting H2;

[0033] Figure 7 Fig. 13 shows a linear curve of a high-temperature solid-state gas sensor prepared according to Example 3 of the present application for detecting CO2;

[0034] Figure 8 Fig. 16 shows a linear curve of a high-temperature solid-state gas sensor prepared according to Comparative Example 1 of the present application for detecting NH3;

[0035] Figure 9 Fig. 19 shows a linear curve of a high-temperature solid-state gas sensor prepared according to Comparative Example 2 of the present application for detecting CO2.

[0036] Reference numerals:

[0037] 1 dense electrolyte layer; 2 porous electrolyte layer;

[0038] 3 sensing electrode layer; 4 reference electrode layer;

[0039] 5 housing. DETAILED DESCRIPTION

[0040] The following examples are provided to better enable those skilled in the art to further understand the application, and are not intended to limit the scope of the application or the protection afforded. Any product derived from the application or from the combination of the application with other prior art features, which is the same as or similar to the application, falls within the scope of the present application.

[0041] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0042] Figure 1 A schematic diagram illustrating the structure of a high-temperature solid-state gas sensor according to the present invention is shown. Figure 1 As shown, the high-temperature solid gas sensor of the present invention includes an electrolyte layer and a sensing electrode layer 3 and a reference electrode layer 4 located on both sides of the electrolyte layer. The electrolyte layer includes a porous electrolyte layer 2 and a dense electrolyte layer 1. The sensing electrode layer 3 is located on one side of the porous electrolyte layer 2, and the reference electrode layer 4 is located on one side of the dense electrolyte layer 1. The electrolyte layer, the sensing electrode layer 3, and the reference electrode layer 4 are disposed within a housing 5.

[0043] The gas to be tested enters the detection gas chamber and undergoes a redox reaction with the catalyst on the sensing electrode layer 3 at the three-phase interface formed by the porous electrolyte layer 2 and the sensing electrode layer 3, decomposing into protons or oxygen ions and other ions. The generated protons or oxygen ions then move through the dense electrolyte layer 1 towards the air chamber with lower hydrogen and oxygen partial pressures, thereby generating a chemical potential difference between the two chambers. Using the hydrogen or oxygen partial pressure on the reference electrode 4 side as a reference value, when the hydrogen or oxygen partial pressures between the sensing electrode 3 and the reference electrode 4 are different, the chemical potential difference between the two chambers can be used as the sensing signal of the high-temperature solid-state gas sensor.

[0044] For a high-temperature solid gas sensor based on anode and cathode dual-ion conductors, two electrochemical reactions occur simultaneously on the sensing electrode, forming a local cell. When the rates of the two electrochemical reactions reach dynamic equilibrium, that is, when the magnitudes of the anodic current and the cathode current are equal and the directions are opposite, the potential generated is the hybrid potential. The magnitude of the hybrid potential is related to the kinetics of the reaction.

[0045] Example 1

[0046] A high-temperature solid-state gas sensor was prepared using the following method:

[0047] (1) Using solid-phase or sol-gel methods, Ba7Nb4MoO4 was prepared from Ba(NO3)2, NbO(NO3)3 and (NH4)2MoO4 as raw materials to produce Ba7Nb4MoO4. 20 Powder, and take 1g of Ba7Nb4MoO 20 The powder was placed in a stainless steel circular mold with a diameter of 15 mm and pressed at a pressure of 100 MPa for 1 minute to obtain a blank with a thickness of 1 mm. The blank was then calcined at 1500℃ for 5 hours to obtain a dense electrolyte layer with a density of 95%.

[0048] (2) Take 1 g of Ba7Nb4MoO 20 powder, mix with 0.2 g of pore-forming agent (polyvinyl butyral ester, PVB), and add a mixture of glycerol, ethanol and ethylene glycol in a volume ratio of 1:2:1 as solvent to the mixed powder, ball mill for 15 minutes, prepare a slurry with a solid content of 30%, and use a spray coating method to spray the slurry on one side of the dense electrolyte layer, with a spray thickness of 20 μm, then fire the sprayed material at 1200°C for 2 hours, so that the sprayed slurry forms a porous electrolyte layer with a porosity of 20% on one side of the dense electrolyte layer, thereby obtaining an electrolyte layer;

[0049] (3) Using a sol-gel method, prepare LaAlO3 catalyst powder with lanthanum nitrate and aluminum nitrate as raw materials, and take 1 g of LaAlO3 catalyst powder, mix with 0.5 g of pore-forming agent (polyvinyl butyral ester, PVB), add a mixture of glycerol, ethanol and ethylene glycol in a volume ratio of 1:2:1 as solvent to the mixed powder, ball mill for 15 minutes, prepare a slurry with a solid content of 30%, and use a spray coating method to spray the slurry on one side of the porous electrolyte layer of the electrolyte layer, with a spray diameter of 10 mm and a thickness of 20 μm, then fire the sprayed material at 1000°C for 1 hour, so that the sprayed slurry forms a sensing electrode layer on one side of the porous electrolyte layer of the electrolyte layer, then use a platinum wire with one end welded to the electrode;

[0050] (4) Use platinum paste as raw material to apply a reference electrode layer with a diameter of 10 mm and a thickness of 20 μm on one side of the dense electrolyte layer of the electrolyte layer, and fire at 1000°C for 1 hour, then use a platinum wire with one end welded to the electrode;

[0051] (5) Mount the assembly obtained in step (4) on the corresponding electrode of the ceramic tube holder to obtain a high-temperature solid-state gas sensor.

[0052] Experimental Example 1

[0053] (1) Connect the high-temperature solid-state gas sensor prepared in Example 1 to a solartron electrochemical workstation, and place the high-temperature solid-state gas sensor in pure air, 10 ppm NH3, 20 ppm NH3, 50 ppm NH3, 100 ppm NH3, 200 ppm NH3 and 500 ppm NH3 atmospheres respectively, and test the voltage signal to obtain the difference in electromotive force (ΔEMF) of the high-temperature solid-state gas sensor in each NH3 atmosphere and in pure air, and draw a linear curve of the difference in electromotive force (ΔEMF) versus NH3 concentration, as shown in Figure 2 .

[0054] From Figure 2It can be seen that within the NH3 concentration range of 10–500 ppm, the difference in electromotive force (ΔEMF) is linearly related to the NH3 concentration.

[0055] (2) The high-temperature solid-state gas sensor prepared in Example 1 was connected to a Solartron electrochemical workstation. The sensor was placed in atmospheres of pure air, 10 ppm CO2, 20 ppm CO2, 50 ppm CO2, 100 ppm CO2, 200 ppm CO2, and 500 ppm CO2, respectively, and voltage signals were measured to obtain the difference in electromotive force (ΔEMF) between the high-temperature solid-state gas sensor in each CO2 atmosphere and in pure air. A linear curve of this electromotive force difference (ΔEMF) versus CO2 concentration was plotted, as shown below. Figure 3 As shown.

[0056] Depend on Figure 3 It can be seen that within the CO2 concentration range of 10 to 500 ppm, the difference in electromotive force (ΔEMF) is linearly related to the CO2 concentration.

[0057] Example 2

[0058] A high-temperature solid-state gas sensor was prepared using the following method:

[0059] (1) Using solid-phase or sol-gel methods, Ba3NbMoO4 was prepared from Ba(NO3)2, NbO(NO3)3 and (NH4)2MoO4 as raw materials to produce Ba3NbMoO4. 8.5 Powder, and take 1g of Ba3NbMoO 8.5 The powder was placed in a stainless steel circular mold with a diameter of 15 mm and pressed at a pressure of 100 MPa for 1 minute to obtain a blank with a thickness of 1 mm. The blank was then calcined at 1450℃ for 5 hours to obtain a dense electrolyte layer with a density of 95%.

[0060] (2) Take 1g of Ba3NbMoO 8.5 The powder was mixed with 0.05g of pore-forming agent (polyvinyl butyral, PVB), and a mixture of glycerol, ethanol and ethylene glycol in a volume ratio of 1:2:1 was added to the mixed powder as a solvent. The mixture was ball-milled for 15 minutes to obtain a slurry with a solid content of 30%. The obtained slurry was then sprayed onto one side of the above-mentioned dense electrolyte layer using a spraying method, with a spraying thickness of 20μm. The sprayed material was then calcined at 1200℃ for 2 hours to form a porous electrolyte layer with a porosity of 30% on one side of the above-mentioned dense electrolyte layer, thereby obtaining the electrolyte layer.

[0061] (3) Using sol-gel method, LaCoO3 catalyst powder is prepared with lanthanum nitrate and cobalt nitrate as raw materials, 1 g of LaCoO3 catalyst powder is mixed with 0.3 g of pore-forming agent (polyvinyl butyral ester, PVB), a mixture of glycerol, ethanol and ethylene glycol with a volume ratio of 1:2:1 is added to the mixed powder as solvent, ball milling for 15 minutes to obtain a slurry with a solid content of 30%, and the obtained slurry is sprayed on the porous electrolyte layer side of the above-mentioned electrolyte layer using spray coating method, the spraying diameter is 10 mm and the thickness is 20 μm, then the sprayed material is calcined at 1000°C for 1 hour, so that the sprayed slurry forms a sensing electrode layer on the porous electrolyte layer side of the above-mentioned electrolyte layer, and then a platinum wire is welded on the electrode with one end;

[0062] (4) Using platinum paste as raw material, a reference electrode layer with a diameter of 10 mm and a thickness of 20 μm is applied on the dense electrolyte layer side of the above-mentioned electrolyte layer, and is calcined at 1000°C for 1 hour, and then a platinum wire is welded on the electrode with one end;

[0063] (5) The assembly obtained in step (4) is mounted on the corresponding electrode of the ceramic tube holder to obtain a high-temperature solid-state gas sensor.

[0064] Experimental Example 2

[0065] (1) The high-temperature solid-state gas sensor prepared in Example 2 is connected to a solartron electrochemical workstation, and the high-temperature solid-state gas sensor is placed in a pure air, 10 ppm H2S, 20 ppm H2S, 50 ppm H2S, 100 ppm H2S, 200 ppm H2S and 500 ppm H2S atmosphere respectively, and the voltage signal test is carried out to obtain the difference in electromotive force (ΔEMF) of the high-temperature solid-state gas sensor in each H2S atmosphere and in pure air, and a linear curve of the difference in electromotive force (ΔEMF) and H2S concentration is drawn, as shown in Figure 4 .

[0066] As can be seen from Figure 4 , in the range of H2S concentration of 10-500 ppm, the difference in electromotive force (ΔEMF) and H2S concentration is linearly related.

[0067] (2) The high-temperature solid-state gas sensor prepared in Example 2 was connected to a solartron electrochemical workstation, and the high-temperature solid-state gas sensor was placed in an atmosphere of pure air, 10 ppm CO2, 20 ppm CO2, 50 ppm CO2, 100 ppm CO2, 200 ppm CO2 and 500 ppm CO2 respectively, and a voltage signal test was performed to obtain the difference in electromotive force (ΔEMF) of the high-temperature solid-state gas sensor in each CO2 atmosphere and in pure air, and a linear curve of the difference in electromotive force (ΔEMF) versus CO2 concentration was plotted, as shown in Figure 5 .

[0068] From Figure 5 it can be seen that the difference in electromotive force (ΔEMF) is linearly related to the CO2 concentration in the range of 10-500 ppm.

[0069] Example 3

[0070] The high-temperature solid-state gas sensor was prepared as follows:

[0071] (1) Ba7Ta 3.7 Mo 1.3 O 20 powder was prepared by a solid phase method or a sol-gel method using BaO, Ta2O5 and MoO3 as raw materials, 1 g of the Ba7Ta 3.7 Mo 1.3 O 20 powder was placed in a stainless steel circular mold with a diameter of 15 mm, and a pressure of 100 MPa was maintained for 1 minute to press a green body with a thickness of 1 mm, and then the obtained green body was calcined at 1400°C for 10 hours to obtain a dense electrolyte layer with a density of 95%;

[0072] (2) 1 g of Ba7Ta 3.7 Mo 1.3 O 20 powder was mixed with 0.02 g of a pore-forming agent (starch), and a mixture of glycerol, ethanol and isopropyl alcohol with a volume ratio of 1:2:1 was added to the mixed powder as a solvent, and ball milling was performed for 15 minutes to obtain a slurry with a solid content of 30%, and the obtained slurry was sprayed on one side of the dense electrolyte layer using a spraying method, and the spraying thickness was 20 μm, and then the sprayed material was calcined at 1000°C for 2 hours to form a porous electrolyte layer with a porosity of 30% on one side of the dense electrolyte layer, thereby obtaining an electrolyte layer;

[0073] (3) Using sol-gel method, LaNiO3 catalyst powder is prepared with lanthanum nitrate and nickel nitrate as raw materials, 1 g of LaNiO3 catalyst powder is mixed with 0.2 g of pore-forming agent (starch), a mixture of glycerol, ethanol and isopropyl alcohol with a volume ratio of 1:2:1 is added to the mixed powder as solvent, ball milling for 15 minutes, a slurry with a solid content of 30% is prepared, and the obtained slurry is sprayed on the porous electrolyte layer side of the above-mentioned electrolyte layer using spray coating method, the spraying diameter is 10 mm and the thickness is 20 μm, then the sprayed material is calcined at 1000°C for 1 hour, so that the sprayed slurry forms a sensing electrode layer on the porous electrolyte layer side of the above-mentioned electrolyte layer, then a platinum wire is welded on the electrode with one end;

[0074] (4) Using platinum paste as raw material, a reference electrode layer with a diameter of 10 mm and a thickness of 20 μm is coated on the dense electrolyte layer side of the above-mentioned electrolyte layer, and is calcined at 1000°C for 1 hour, then a platinum wire is welded on the electrode with one end;

[0075] (5) The assembly obtained in step (4) is mounted on the corresponding electrode of the ceramic tube seat to obtain a high-temperature solid-state gas sensor.

[0076] Experimental Example 3

[0077] (1) The high-temperature solid-state gas sensor prepared in Example 3 is connected to an olartron electrochemical workstation, and the high-temperature solid-state gas sensor is placed in pure air, 10 ppm H2, 20 ppm H2, 50 ppm H2, 100 ppm H2, 200 ppm H2 and 500 ppm H2 atmospheres respectively, and voltage signal test is carried out to obtain the difference in electromotive force (ΔEMF) of the high-temperature solid-state gas sensor in each H2 atmosphere and in pure air, and a linear curve of the difference in electromotive force (ΔEMF) and H2 concentration is drawn, as shown in Figure 6 .

[0078] As can be seen from Figure 6 , in the range of H2 concentration of 10-500 ppm, the difference in electromotive force (ΔEMF) and H2 concentration are linearly related.

[0079] (2) The high-temperature solid-state gas sensor prepared in Example 3 was connected to a solartron electrochemical workstation, and the high-temperature solid-state gas sensor was placed in an atmosphere of pure air, 10 ppm CO2, 20 ppm CO2, 50 ppm CO2, 100 ppm CO2, 200 ppm CO2, and 500 ppm CO2, respectively, and a test of the voltage signal was performed to obtain the difference in electromotive force (ΔEMF) of the high-temperature solid-state gas sensor in each CO2 atmosphere and in pure air, and a linear curve of the difference in electromotive force (ΔEMF) versus the CO2 concentration was plotted, as shown in Figure 7 .

[0080] As can be seen from Figure 7 , the difference in electromotive force (ΔEMF) is linearly related to the CO2 concentration in the range of 10-500 ppm.

[0081] Comparative Example 1

[0082] A high-temperature solid-state gas sensor was prepared according to the method of Example 1, except that an equal amount of the proton conductor BaZr 0.8 Y 0.2 O3 was used to replace the double-ion conductor Ba7Nb4MoO 20 in Example 1.

[0083] Experimental Example 4

[0084] (1) The high-temperature solid-state gas sensor prepared in Comparative Example 1 was connected to a solartron electrochemical workstation, and the high-temperature solid-state gas sensor was placed in an atmosphere of pure air, 10 ppm NH3, 20 ppm NH3, 50 ppm NH3, 100 ppm NH3, 200 ppm NH3, 500 ppm NH3, and 1000 ppm NH3, respectively, and a test of the voltage signal was performed to obtain the difference in electromotive force (ΔEMF) of the high-temperature solid-state gas sensor in each NH3 atmosphere and in pure air, and a linear curve of the difference in electromotive force (ΔEMF) versus the NH3 concentration was plotted, as shown in Figure 8 .

[0085] As can be seen from Figure 8 , the difference in electromotive force (ΔEMF) is linearly related to the NH3 concentration in the range of 10-1000 ppm.

[0086] (2) The high-temperature solid-state gas sensor prepared in Comparative Example 1 was connected to a solartron electrochemical workstation, and the high-temperature solid-state gas sensor was placed in a pure air atmosphere, a 10 ppm CO2 atmosphere, a 20 ppm CO2 atmosphere, a 50 ppm CO2 atmosphere, a 100 ppm CO2 atmosphere, a 200 ppm CO2 atmosphere, and a 500 ppm CO2 atmosphere, respectively, to test the voltage signal. It was found that, in the range of 10-500 ppm of CO2 concentration, the above difference in electromotive force (ΔEMF) did not change significantly with the change in CO2 concentration.

[0087] Comparative Example 2

[0088] The high-temperature solid-state gas sensor was prepared according to the method of Example 1, except that an equal amount of oxygen ion conductor YSZ (yttria-stabilized zirconia) was used to replace the dual-ion conductor Ba7Nb4MoO18 in Example 1. 20 .

[0089] Experimental Example 5

[0090] (1) The high-temperature solid-state gas sensor prepared in Comparative Example 2 was connected to a solartron electrochemical workstation, and the high-temperature solid-state gas sensor was placed in a pure air atmosphere, a 10 ppm NH3 atmosphere, a 20 ppm NH3 atmosphere, a 50 ppm NH3 atmosphere, a 100 ppm NH3 atmosphere, a 200 ppm NH3 atmosphere, and a 500 ppm NH3 atmosphere, respectively, to test the voltage signal. It was found that, in the range of 10-500 ppm of NH3 concentration, the above difference in electromotive force (ΔEMF) did not change significantly with the change in NH3 concentration.

[0091] (2) The high-temperature solid-state gas sensor prepared in Comparative Example 2 was connected to a solartron electrochemical workstation, and the high-temperature solid-state gas sensor was placed in a pure air atmosphere, a 10 ppm CO2 atmosphere, a 20 ppm CO2 atmosphere, a 50 ppm CO2 atmosphere, a 100 ppm CO2 atmosphere, a 200 ppm CO2 atmosphere, and a 500 ppm CO2 atmosphere, respectively, to test the voltage signal. The difference in electromotive force (ΔEMF) of the high-temperature solid-state gas sensor in each CO2 atmosphere and in pure air was obtained, and a linear curve of the difference in electromotive force (ΔEMF) versus CO2 concentration was plotted, as shown in Figure 9 .

[0092] As can be seen from Figure 9 , in the range of 10-500 ppm of CO2 concentration, the above difference in electromotive force (ΔEMF) has a linear relationship with the CO2 concentration.

[0093] Obviously, the above embodiments are merely example for clearly illustrating but not limitation to the embodiments. Based on the above description, other different forms of changes or variations can be made by those skilled in the art. Here, all the embodiments need not and can not be enumerated. The obvious changes or variations derived from the above description are still within the protection scope of the present application.

Claims

1. A high-temperature solid-state gas sensor, characterized in that, The high-temperature solid-state gas sensor includes an electrolyte layer and sensing electrode layers and a reference electrode layer located on both sides of the electrolyte layer; wherein, The electrolyte layer contains anionic and aionic dual-ion conductor oxide, which is capable of conducting protons and oxygen ions. The anionic and ionic dual-ion conductor oxide includes Ba7Nb4MoO. 20 Ba3NbMoO 8.5 Ba7Ta 3.7 Mo 1.3 O 20 Ba3W 1.2 Nb 0.8 O 8.5 、Ba3WNbO 8.5 、Ba3TaNbO 8.5 and BaW4NbO 20 At least one of them; The sensing electrode layer contains a catalyst, including LaAlO3, LaCoO3, LaNiO3, BaCoO3, and La. 0.8 Sr 0.2 At least one of CoO3 and BaNiO3; The electrolyte layer includes a porous electrolyte layer and a dense electrolyte layer. The sensing electrode layer is located on one side of the porous electrolyte layer, and the reference electrode layer is located on one side of the dense electrolyte layer. The porosity of the porous electrolyte layer is 10-50%, and the density of the dense electrolyte layer is 90%-98%.

2. The high-temperature solid-state gas sensor according to claim 1, characterized in that, The thickness of the porous electrolyte layer is 20–500 μm, and the thickness of the dense electrolyte layer is 100–1000 μm.

3. The high-temperature solid-state gas sensor according to claim 1, characterized in that, The thickness of the sensing electrode layer is 10–50 μm.

4. The high-temperature solid-state gas sensor according to any one of claims 1 to 3, characterized in that, The reference electrode layer includes at least one of a platinum metal layer, a palladium metal layer, a silver metal layer, a gold metal layer, and an iridium metal layer; The thickness of the reference electrode layer is 10–50 μm.

5. Use of the high-temperature solid gas sensor according to any one of claims 1 to 4 in detecting gases containing hydrogen and / or oxygen.

6. The use according to claim 5, characterized in that, The gas containing hydrogen and / or oxygen includes at least one of O2, CO, CO2, H2, H2O, H2S, NH3, CH3OH, and C2H5OH.

7. The use of the high-temperature solid gas sensor according to any one of claims 1 to 4 in engine exhaust gas monitoring, wherein the engine includes aerospace engines, gas turbines and automobile engines.

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