Sensitive material, preparation method thereof, application of sensitive material as sensitive material of ammonia gas sensor, and ammonia gas sensor

Abstract

The invention relates to the field of ammonia gas sensors, in particular to a sensitive material, a preparation method of the sensitive material, application of the sensitive material as an ammonia gas sensor sensitive material and an ammonia gas sensor. On one hand, the sensitive material provided by the invention is based on the characteristic of high temperature resistance of a CeCoO3 perovskite material; on the other hand, the catalytic activity is enhanced based on the combination of the redox cycle of Ce < 3 + > / Ce < 4 + > and the electron transfer ability of Ag, the cerium-based material has oxygen vacancy defects to provide abundant reaction sites for catalytic reaction, and cerium has better thermal stability; in addition, the electron transfer efficiency in the sensitive material is improved on the basis of replacing cerium in crystal lattices with part of silver. Tests show that a sensor made of the sensitive material provided by the invention can complete ammonia concentration detection work at about 650 DEG C, has high anti-interference ability to NO and NO2, and is suitable for being applied to a high-temperature ammonia sensor for detecting ammonia concentration in an automobile exhaust treatment system.

Description

Technical Field

[0001] This invention relates to the field of ammonia sensors, specifically to sensitive materials, their preparation methods, applications as sensitive materials in ammonia sensors, and ammonia sensors themselves. Background Technology

[0002] Sensors are widely used in aquaculture, ammonia leak monitoring in chemical plants, and vehicle exhaust emission testing. Exhaust emission testing is particularly necessary given the increasingly serious problem of pollution from gasoline-powered vehicles. Today, internal combustion engines have become one of the world's leading sources of pollution, emitting large amounts of toxic and harmful gases that cause significant damage to the natural environment, human health, and flora and fauna. To control pollution, countries around the world have enacted increasingly stringent vehicle emission standards.

[0003] The main pollutants in automobile exhaust are nitrogen oxides (NOx). X Currently, the main method used is selective catalytic reduction (SCR) of urea, which converts urea into ammonia, and then uses the ammonia to reduce nitrogen oxides, yielding clean nitrogen and water to eliminate pollutants. However, urea is prone to crystallization at low temperatures, making this technology unsuitable for regions with low temperatures. Furthermore, urea pyrolysis products often clog the carrier, affecting catalytic efficiency. Therefore, researchers have developed solid-state ammonia selective catalytic reduction (SSCR), which solidifies ammonia in strontium chloride and releases gaseous ammonia upon heating when needed. Regardless of the technology, both utilize the reaction between ammonia and nitrogen oxides, with the main reaction formulas being: NH3 + NO + 1 / 4O2 = N2 + 3 / 2H2O and NH3 + 1 / 2NO2 + 1 / 4O2 = 3 / 4N2 + 3 / 2H2O.

[0004] Ammonia is a toxic gas with a strong, pungent odor, posing a threat to human health, the environment, and industrial safety. Long-term exposure to low concentrations can cause respiratory illnesses or damage to liver and kidney function. Ammonia reacts with acidic gases to form ammonium sulfate and ammonium nitrate particles, which contribute to PM2.5 formation. After settling, these particles increase the nitrogen load on soil and water bodies, damaging ecosystems. Ammonium ions are also directly toxic to aquatic organisms. When controlling nitrogen oxide pollution, we cannot ignore the consequences of ammonia pollution. Therefore, installing ammonia sensors in vehicle exhaust treatment systems is essential. This prevents ammonia from escaping from the reaction system and causing environmental pollution, and also allows for more precise control of ammonia release, thus conserving resources.

[0005] As is well known, the main components of engine exhaust are NO (nitric oxide) and NO2 (nitric oxide). Therefore, when developing ammonia sensors, it is essential to monitor the effects of these two gases on the sensor's sensitivity and response signal. This is a pressing issue that needs to be addressed in the development of ammonia sensors. To solve this problem, researchers have proposed many methods. Some methods involve changing the reference electrode, attempting to solve the problem by utilizing potential shift, but this also significantly reduces the sensor's sensitivity to ammonia. Other methods are very effective in improving the performance of a single nitrogen oxide, such as NO2. Some methods only achieve good anti-interference effects at lower temperatures, such as below 500℃, which is still some distance from the target operating temperature of around 650℃. Summary of the Invention

[0006] In view of this, the technical problem to be solved by the present invention is to provide a sensitive material and its preparation method, as well as its application as a sensitive material for an ammonia sensor. The sensitive material provided by the present invention, as a sensitive material for an ammonia sensor, has high resistance to NO and NO2 interference and a high operating temperature.

[0007] This invention provides sensitive materials, including:

[0008] CeCoO3 and Ag doped in the CeCoO3;

[0009] The molar ratio of Ag to Ce in the sensitive material is 1:(5-40).

[0010] Preferably, the molar ratio of Ag to Ce in the sensitive material is 1:(18-22).

[0011] The sensitive material provided by this invention belongs to the perovskite type. The perovskite material structure is ABO3, where the A-site is typically a rare earth / alkaline earth metal ion and the B-site is a transition metal ion. Because the element at the A-site can be partially substituted, it generates more defects and oxygen vacancies, giving perovskite materials a flexible and versatile structure that can be designed and modified to achieve different functions. The perovskite material structure of the sensitive material provided by this invention is CeCoO3. The CeCoO3 perovskite structure gives the sensitive material high-temperature resistance, enabling it to play a promoting role in flue gas combustion (≥600℃). Furthermore, to improve the material's catalytic performance for ammonia, the sensitive material provided by this invention also incorporates noble metal ions into the perovskite lattice. Specifically, Ag (silver) ions are introduced at the A-site of the perovskite structure to partially replace Ce (cerium), ultimately forming an Ag-doped CeCoO3 composite material.

[0012] This invention also provides a method for preparing a sensitive material, comprising the following steps:

[0013] S1) Under the action of a weak acid, the Ce source compound, the Co source compound, and the Ag source compound are heated to react; the molar ratio of Ce in the Ce source compound to Co in the Co source compound is (1-1.2):(1-1.2), and the molar ratio of Ag in the Ag source compound to Ce in the Ce source compound is 1:(5-40).

[0014] S2) The reaction product obtained in step S1) is calcined to obtain the sensitive material.

[0015] This invention first involves heating a Ce-derived compound, a Co-derived compound, and an Ag-derived compound in the presence of a weak acid. Specifically, the Ce-derived compound, Co-derived compound, Ag-derived compound, and weak acid are heated in a solvent. More specifically, the Ce-derived compound and Co-derived compound are dissolved in water, an Ag-derived compound is added and stirred, and then the weak acid is added while heating and stirring. The heating temperature of this invention is 70°C to 90°C, preferably 80°C; the heating time depends on the product morphology, and the heating reaction is stopped when a gel-like product is obtained. Specifically, the heating time is 2 to 3 hours.

[0016] The molar ratio of Ce in the Ce source compound to Co in the Co source compound of this invention is 1:(1-1.1), and the molar ratio of Ag in the Ag source compound to Ce in the Ce source compound is 1:(5-40). Preferably, the molar ratio of Ag in the Ag source compound to Ce in the Ce source compound is 1:(18-22). In this invention, if the amount of Ce in the Ce source compound is excessive compared to the amount of Co in the Co source compound, it will affect Ag insertion into the crystal lattice, causing all products to form CeCoO3, thus affecting the synthesis of the sensitive material of this invention.

[0017] The weak acid described in this invention refers to an acid that can only partially ionize in aqueous solution, specifically a weak acid with a pKa of 2 to 5, more specifically selected from at least one of citric acid, benzoic acid, gluconic acid, and pyruvic acid, preferably citric acid; the Ce source compound is selected from at least one of cerium nitrate, cerium sulfate, cerium acetate, and cerium phosphate, preferably cerium nitrate; the Co source compound is selected from at least one of cobalt nitrate, cobalt sulfate, cobalt acetate, and cobalt chloride, preferably cobalt nitrate; the Ag source compound is selected from at least one of silver nitrate and silver sulfate, preferably silver nitrate. In some embodiments of this invention, cerium nitrate and cobalt nitrate are dissolved in water, silver nitrate is added and stirred, and then citric acid is added while heating and stirring.

[0018] This invention involves heating a Ce-source compound, a Co-source compound, and an Ag-source compound to react them, then calcining the resulting reaction product to obtain a sensitive material. Specifically, the reaction product is dried and then calcined to obtain the sensitive material. The drying temperature is 100℃~120℃, preferably 110℃; the drying time is 10h~14h, preferably 12h. The calcination temperature is 500℃~900℃, preferably 500℃~600℃; the calcination time is 2h~4h, preferably 2.5h~3.5h. The heating and cooling rates during calcination are independently 2℃ / min~4℃ / min, preferably 3℃ / min.

[0019] This invention also provides the application of the sensitive material described in any of the above-described technical solutions, or the sensitive material obtained by the preparation method described in any of the above-described technical solutions, as a sensitive material for an ammonia sensor. When the sensitive material provided by this invention is used as a sensitive electrode in an ammonia sensor, it can not only operate at 650°C, but also effectively detect residual nitrogen oxides (NOx) in the exhaust gas. X It has good anti-interference ability and is very suitable for use as a high-temperature ammonia sensor to detect the concentration of ammonia in automotive exhaust gas treatment systems.

[0020] The present invention also provides an ammonia sensor, comprising:

[0021] Solid electrolyte, working electrode, and reference electrode;

[0022] The working electrode of this invention is obtained from the sensitive material described in any of the above-described technical solutions or the sensitive material prepared by the preparation method described in any of the above-described technical solutions. The solid electrolyte of this invention preferably comprises a dense layer and a porous layer. This design allows for sufficient contact and permeation between the sensitive material of the working electrode and the solid electrolyte layer, facilitating rapid oxygen transport and promoting the redox reaction of target molecules on the working electrode.

[0023] Preferably, the ammonia sensor provided by the present invention includes:

[0024] Yttrium oxide stabilized zirconia dense layer

[0025] A porous yttrium oxide layer loaded with sensitive material is disposed on the dense yttrium oxide stabilized zirconia layer.

[0026] The first Pt electrode is disposed on the yttrium-stabilized zirconia dense layer;

[0027] The second Pt electrode is disposed on the yttrium oxide-stabilized zirconia porous layer loaded with the sensitive material.

[0028] This invention provides a sensitive material, its preparation method, and its application as a sensitive material for ammonia sensors. This invention is the first to use CeCoO3-based perovskite materials for high-temperature ammonia detection in a sensor, and obtains a novel sensor working electrode sensitive material by doping the A-site of the perovskite material with the noble metal Ag, namely, an Ag-doped CeCoO3 composite material. The sensitive material provided by this invention is based on the high-temperature resistance of CeCoO3-based perovskite materials, and also on the Ce3... + / Ce 4+ The combination of redox cycles and Ag's electron transfer capabilities enhances catalytic activity. Specifically, the interconversion of the two valence states of cerium results in higher activity in catalytic reactions, enabling more effective participation in the adsorption and reaction of gas molecules. Furthermore, the presence of oxygen vacancy defects in cerium-based materials allows for reversible adsorption and release of oxygen, providing abundant reaction sites and thus improving detection efficiency. Additionally, cerium exhibits better thermal stability, maintaining a stable crystal structure at high temperatures. Moreover, silver, with its superior electrical conductivity compared to cerium, significantly improves electron transfer efficiency in the sensitive material when partially replacing cerium in the crystal lattice. Experiments show that the sensor made from the sensitive material provided by this invention can detect ammonia concentration at approximately 650°C and exhibits high anti-interference capability against NO and NO2 at 650°C, making it highly suitable for use as a high-temperature ammonia sensor in automotive exhaust treatment systems. Attached Figure Description

[0029] Figure 1 This is a scanning electron microscope image of the Ag-doped CeCoO3 composite material in Example 3 of the present invention;

[0030] Figure 2 The XRD pattern of the Ag-doped CeCoO3 composite material in Example 3 of this invention;

[0031] Figure 3 This is a schematic diagram of the structure of the sensor described in this invention. Detailed Implementation

[0032] This invention discloses a sensitive material, its preparation method, and its application as a sensitive material in an ammonia sensor. Those skilled in the art can refer to this document and appropriately modify the process parameters to achieve the desired result. It is particularly important to note that all similar substitutions and modifications are obvious to those skilled in the art and are considered to be included in this invention. The methods and applications of this invention have been described through preferred embodiments; those skilled in the art will clearly be able to modify or appropriately alter and combine the methods and applications described herein without departing from the content, spirit, and scope of this invention to realize and apply the technology of this invention.

[0033] In a specific embodiment of the present invention, the target product, Ag-doped CeCoO3 composite material, is prepared according to the following steps: Ce(NO3)3·6H2O and Co(NO3)2·6H2O are dissolved in deionized water at a metal ratio of 1:1 and stirred thoroughly. Then, a certain proportion of AgNO3 is added to the above solution, and stirring is continued for 5 minutes. Then, citric acid is added to the solution at a ratio of 1:1 to all metal ions, and the mixture is heated to 80°C while stirring until a gel-like product is obtained. Heating is then stopped. The obtained product is dried at 110°C for 12 hours, and then placed in a muffle furnace and heated to 500°C–900°C at a heating and cooling rate of 3°C / min. The maximum temperature is maintained for 2–4 hours to obtain the target product, Ag-doped CeCoO3 composite material.

[0034] There are no particular restrictions on the source of any raw materials used in this invention; they can be purchased from the market or prepared using conventional methods known to those skilled in the art.

[0035] The purity of all raw materials used in this invention is not particularly limited. However, this invention preferably uses materials of analytical grade, metal nanoparticle composite materials, or materials with conventional purity requirements in the field of sensor sensitive materials.

[0036] All raw materials of this invention are conventional in the field, and each brand name and abbreviation is clear and distinct in its relevant application. Those skilled in the art can purchase them from the market or prepare them by conventional methods based on the brand name, abbreviation and corresponding application.

[0037] The present invention will be further described below with reference to the embodiments:

[0038] Example 1

[0039] Ce(NO3)3·6H2O and Co(NO3)2·6H2O were dissolved in deionized water at a metal ratio of 1:1 and stirred thoroughly. AgNO3 was then added to the solution at a silver:cerium ratio of 1:5, and stirring continued for 5 minutes. Citric acid was then added to the solution at a ratio of 1:1 to all metal ions, and the mixture was heated to 80°C while stirring until a gel-like product was obtained. Heating was then stopped. The product was dried at 110°C for 12 hours, then placed in a muffle furnace and heated to 500°C at a heating and cooling rate of 3°C / min, maintaining the maximum temperature for 3 hours to obtain the target product.

[0040] Example 2

[0041] Ce(NO3)3·6H2O and Co(NO3)2·6H2O were dissolved in deionized water at a metal ratio of 1:1 and stirred thoroughly. AgNO3 was then added to the solution at a silver:cerium ratio of 1:10, and stirring continued for 5 minutes. Citric acid was then added to the solution at a ratio of 1:1 to all metal ions, and the mixture was heated to 80°C while stirring until a gel-like product was obtained. Heating was then stopped. The product was dried at 110°C for 12 hours, then placed in a muffle furnace and heated to 500°C at a heating and cooling rate of 3°C / min, maintaining the maximum temperature for 3 hours to obtain the target product.

[0042] Example 3

[0043] Ce(NO3)3·6H2O and Co(NO3)2·6H2O were dissolved in deionized water at a metal ratio of 1:1 and stirred thoroughly. AgNO3 was then added to the solution at a silver:cerium ratio of 1:20, and stirring continued for 5 minutes. Citric acid was then added to the solution at a ratio of 1:1 to all metal ions, and the mixture was heated to 80°C while stirring until a gel-like product was obtained. Heating was then stopped. The product was dried at 110°C for 12 hours, then placed in a muffle furnace and heated to 500°C at a heating and cooling rate of 3°C / min, maintaining the maximum temperature for 3 hours to obtain the target product.

[0044] Example 4

[0045] Ce(NO3)3·6H2O and Co(NO3)2·6H2O were dissolved in deionized water at a metal ratio of 1:1 and stirred thoroughly. AgNO3 was then added to the solution at a silver:cerium ratio of 1:40, and stirring continued for 5 minutes. Citric acid was then added to the solution at a ratio of 1:1 to all metal ions, and the mixture was heated to 80°C while stirring until a gel-like product was obtained. Heating was then stopped. The product was dried at 110°C for 12 hours, then placed in a muffle furnace and heated to 500°C at a heating and cooling rate of 3°C / min, maintaining the maximum temperature for 3 hours to obtain the target product.

[0046] Example 5

[0047] Ce(NO3)3·6H2O and Co(NO3)2·6H2O were dissolved in deionized water at a metal ratio of 1:1 and stirred thoroughly. AgNO3 was then added to the solution at a silver:cerium ratio of 1:20, and stirring continued for 5 minutes. Citric acid was then added to the solution at a ratio of 1:1 to all metal ions, and the mixture was heated to 80°C while stirring until a gel-like product was obtained. Heating was then stopped. The product was dried at 110°C for 12 hours, then placed in a muffle furnace and heated to 700°C at a heating and cooling rate of 3°C / min, maintaining the maximum temperature for 3 hours to obtain the target product.

[0048] Example 6

[0049] Ce(NO3)3·6H2O and Co(NO3)2·6H2O were dissolved in deionized water at a metal ratio of 1:1 and stirred thoroughly. AgNO3 was then added to the solution at a silver:cerium ratio of 1:20, and stirring continued for 5 minutes. Citric acid was then added to the solution at a ratio of 1:1 to all metal ions, and the mixture was heated to 80°C while stirring until a gel-like product was obtained. Heating was then stopped. The product was dried at 110°C for 12 hours, then placed in a muffle furnace and heated to 900°C at a heating and cooling rate of 3°C / min, maintaining the maximum temperature for 3 hours to obtain the target product.

[0050] Example 7

[0051] Ce(NO3)3·6H2O and Co(NO3)2·6H2O were dissolved in deionized water at a metal ratio of 1:1 and stirred thoroughly. AgNO3 was then added to the solution at a silver:cerium ratio of 1:20, and stirring continued for 5 minutes. Citric acid was then added to the solution at a ratio of 1:1 to all metal ions, and the mixture was heated to 80°C while stirring until a gel-like product was obtained. Heating was then stopped. The product was dried at 110°C for 12 hours, then placed in a muffle furnace and heated to 500°C at a heating and cooling rate of 3°C / min, maintaining the maximum temperature for 2 hours to obtain the target product.

[0052] Example 8

[0053] Ce(NO3)3·6H2O and Co(NO3)2·6H2O were dissolved in deionized water at a metal ratio of 1:1 and stirred thoroughly. AgNO3 was then added to the solution at a silver:cerium ratio of 1:20, and stirring continued for 5 minutes. Citric acid was then added to the solution at a ratio of 1:1 to all metal ions, and the mixture was heated to 80°C while stirring until a gel-like product was obtained. Heating was then stopped. The product was dried at 110°C for 12 hours, then placed in a muffle furnace and heated to 500°C at a heating and cooling rate of 3°C / min, maintaining the maximum temperature for 4 hours to obtain the target product.

[0054] The target product obtained in Example 3 above was imaged using a scanning electron microscope, and the results are as follows: Figure 1 As shown, Figure 1 This is a scanning electron microscope (SEM) image of the Ag-doped CeCoO3 composite material in Example 3 of this invention. Figure 2As can be seen, the material of this invention has a porous morphology, composed of countless interwoven and crisscrossing channels of various sizes, with very thin pore walls. This structure maximizes the contact area between the gas and the sensitive material, which is highly beneficial for the rapid reaction of the gas in the sensitive material. Therefore, the material of this invention exhibits excellent catalytic performance for ammonia. The amount of silver in this invention is a crucial variable. When the silver content is excessive, as in Example 1, silver not only exists in the crystal lattice but also has some silver nanoparticles on the surface of the material. This does not increase the catalytic performance but instead affects the reaction of ammonia on the material surface. Temperature is another important variable. As the calcination temperature increases, the porous structure of the material gradually disappears, forming a more regular crystal structure. The contact area decreases, significantly reducing the adsorption of ammonia by the material, and the gas cannot circulate within the material, affecting the sensor's performance.

[0055] The target product obtained in Example 3 above was subjected to XRD testing, and the results are as follows: Figure 2 As shown, Figure 2 This is the XRD pattern of the Ag-doped CeCoO3 composite material in Example 3 of the present invention. Figure 2 As can be seen, the material of this invention has the basic structure of perovskite material, with no silver nanoparticles on the surface. Silver has been doped into the lattice of the material. This doping method improves the microstructure of perovskite material, increases the specific surface area of ​​the material, and greatly improves the detection performance of the material of this invention for ammonia, thereby relatively reducing the influence of nitrogen oxides on the sensor.

[0056] Sensors were assembled using the sensitive materials prepared in the above embodiments. The solid electrolyte of the assembled sensors included a dense yttrium-stabilized zirconia layer and a porous layer disposed on the dense yttrium-stabilized zirconia layer. The sensitive material described in this invention was loaded on the porous yttrium-stabilized zirconia layer, and Pt was attached as a reference electrode to both the dense yttrium-stabilized zirconia layer and the porous yttrium-stabilized zirconia layer. Figure 3 As shown, Figure 3 This is a schematic diagram of the sensor described in this invention. At an operating temperature of 650℃, the effects of introducing 300ppm NO and NO2 into 300ppm ammonia gas on the ammonia sensor signal were tested. The percentage decrease in ammonia signal was compared; the smaller the signal decrease, the stronger the anti-interference capability of the sensor assembled with this sensitive material as the working electrode. Specifically, as shown in Table 1, Table 1 compares the anti-nitrogen oxide interference capabilities of sensors assembled with sensitive materials obtained under different preparation conditions when detecting ammonia.

[0057] Table 1

[0058]

[0059] Therefore, the sensor of this invention can detect ammonia concentration at around 650°C, which is faster than existing technologies based on La2Ag. x NiO 4+δ The ammonia sensor based on the sensitive material has a test temperature closer to the actual operating temperature, which also matches the target operating temperature of this invention. Based on the operating temperature, this invention also investigated the anti-interference capability of the ammonia sensor based on Ag-doped CeCoO3 composite material against NO and NO2 at 650℃. With 300ppm of ammonia and 300ppm of NO and NO2 introduced respectively, under optimal conditions, the detection signal decreased by 5.3% and 15.8% respectively. According to existing literature, the detection signal based on La2Ag... x NiO 4+δ When the ammonia sensor with sensitive material detected NO and NO2, the signal decreased by 7.6% and 17.8% respectively, indicating that the Ag-doped CeCoO3 composite material of the present invention has improved anti-interference ability.

[0060] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A sensitive material, characterized in that, Comprises: CeCoO3 and Ag doped in the CeCoO3; The molar ratio of Ag and Ce in the sensitive material is 1:(5-40).

2. The sensitive material according to claim 1, characterized in that, The molar ratio of Ag and Ce in the sensitive material is 1:(18-22).

3. A method for the preparation of a sensitive material, characterized in that, Comprises the following steps: S1) heating reaction of a Ce source compound, a Co source compound and an Ag source compound under the action of a weak acid; the molar ratio of Ce in the Ce source compound and Co in the Co source compound is 1:(1-1.1), and the molar ratio of Ag in the Ag source compound and Ce in the Ce source compound is 1:(5-40); S2) calcining the reaction product obtained in step S1) to obtain a sensitive material.

4. The production method according to claim 3, characterized by, In step S1), the molar ratio of Ag in the Ag source compound and Ce in the Ce source compound is 1:(18-22).

5. The preparation method according to claim 3, characterized in that, In step S1), the weak acid is at least one selected from citric acid, benzoic acid, gluconic acid and pyruvic acid; The Ce source compound is at least one selected from cerium nitrate, cerium sulfate, cerium acetate and cerium phosphate; The Co source compound is at least one selected from cobalt nitrate, cobalt sulfate, cobalt acetate and cobalt chloride; The Ag source compound is at least one selected from silver nitrate and silver sulfate.

6. The preparation method according to claim 3, characterized in that, In step S1), the temperature of the heating reaction is 70-90℃; The time of the heating reaction is 2-3h.

7. The preparation method according to claim 3, characterized in that, In step S2), the temperature of the calcining is 500-900℃, and the time of the calcining is 2-4h.

8. The production method according to claim 7, characterized by, The temperature of the calcining is 500-600℃, and the time of the calcining is 2.5-3.5h.

9. Use of the sensitive material of claim 1 or 2 or the sensitive material obtained by the preparation method of any one of claims 3-8 as a sensitive material of an ammonia gas sensor.

10. Ammonia sensor, characterized in that It comprises: A solid-state electrolyte, a working electrode and a reference electrode; The working electrode is obtained from the sensitive material of claim 1 or 2 or the sensitive material obtained by the preparation method of any one of claims 3-8.

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