A method for synthesizing an ammonia-resistant proton conductor material for a direct ammonia fuel cell

Abstract

The application provides a synthesis method of an ammonia-resistant proton conductor material of a direct ammonia fuel cell, comprising the following steps: step one: selecting a proton conductor material, according to the molar proportion of metal cations therein, weighing metal salts containing corresponding metal elements, and mixing the metal salts with a solvent to obtain a mixed solution; step two: heating and stirring the mixed solution under an ultrasonic environment, adjusting the pH value of the solution until the metal salts are fully dissolved to obtain a clear mixed precursor solution; step three: performing heat preservation treatment on the clear mixed precursor solution, generating a precursor droplet group through an aerosol generator, fully mixing the precursor droplet group with a carrier gas, and forming a precursor aerosol; and step four: introducing the precursor aerosol into an ammonia-containing flame field to react, so as to obtain a new ammonia-resistant proton conductor material. The synthesis method is one-step continuous, simple and effective, the process is precisely controllable, the product is strong in ammonia resistance and stable in quality, and the scale-up synthesis is easy to realize.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of ammonia-hydrogen fuel cells, and particularly relates to a synthesis method of an ammonia-resistant proton conductor material for a direct ammonia fuel cell. BACKGROUND

[0002] Under the background of the transformation of global energy structure to low carbon, hydrogen energy is concerned by the academic and industrial circles due to its advantages such as green and clean, rich resources and the like, and has become an important part of the energy layout of many developed countries. However, the problems such as difficult storage and transportation and poor safety of hydrogen restrict its economic, efficient and large-scale use. In comparison, ammonia, as a mature hydrogen storage carrier energy, also belongs to zero-carbon fuel, and its volumetric energy density is much higher than that of hydrogen, and the storage and transportation cost is lower, and the safety standard and related infrastructure are very perfect, which can inject new impetus for the development of clean energy. Among many ammonia energy conversion and utilization technologies, fuel cells are not limited by the Carnot cycle, and are one of the ideal routes to realize clean and efficient utilization. Among them, the direct ammonia intermediate-temperature solid oxide fuel cell (400-600℃) based on proton conduction not only has the advantages of compact device structure, high fuel utilization rate, good thermal stability and small thermal integration difficulty, but also can effectively avoid the NOx poisoning caused by ammonia side reactions, and is more suitable for the characteristics and needs of ammonia energy compared with low-temperature proton exchange membrane fuel cells and high-temperature oxygen ion-conducting solid oxide fuel cells.

[0003] As the cornerstone of realizing efficient proton conduction in direct ammonia intermediate-temperature solid oxide fuel cells, the chemical stability and proton conductivity of proton conductors are crucial. At present, the commonly used proton conductor materials are mainly represented by multi-element BaCexZryYzM1-x-y-zO3-δ (BCZYM-based) ABO3 perovskites composed of Ba, Zr, Ce, Y and other metal elements (M), such as the classic BaCe0.7Zr0.1Y0.1Yb0.1O3-δ, which exhibits excellent proton conductivity and chemical stability characteristics in traditional hydrogen or carbon-hydrogen fuel systems, and also has anti-coking and sulfur-resistant properties, and is expected to become a candidate material for the next generation of high-performance proton conductors. However, in the face of emerging ammonia energy, the existing particle synthesis technologies such as high-temperature solid-phase reaction sintering method, hydrothermal method, sol-gel method and co-precipitation method have insufficient ammonia corrosion resistance of the prepared BCZYM-based proton conductor materials, and the proton conductivity will gradually decrease after long-term exposure to ammonia fuel, which will affect the long-term efficient and stable operation of the direct ammonia fuel cell, and seriously hinder the large-scale commercial application. SUMMARY

[0004] To solve the above problems, the application provides a synthesis method of an ammonia-resistant proton conductor material for a direct ammonia fuel cell, so as to solve the problem of insufficient ammonia fuel resistance of the proton conductor material prepared by a traditional synthesis method and improve the proton conductivity of the prepared material.

[0005] The application solves the technical problem by adopting the technical scheme of a synthesis method of an ammonia-resistant proton conductor material for a direct ammonia fuel cell, which comprises the following steps: Step 1: selecting a proton conductor material, according to the molar ratio of metal cations in the selected proton conductor material, weighing metal salts containing corresponding metal elements, and mixing the weighed metal salts with an energetic solvent to obtain a mixed solution; Step 2: heating and stirring the mixed solution in an ultrasonic environment, adding ammonia water to the stirred mixed solution to adjust the pH value of the solution until the metal salts are fully dissolved, so as to obtain a clear mixed precursor solution in which metal elements are stably dispersed; Step 3: heat-treating the clear mixed precursor solution, generating a precursor droplet group by an aerosol generator, fully mixing the precursor droplet group with a carrier gas, and forming a precursor aerosol; and Step 4: introducing the precursor aerosol into an ammonia-containing flame field for reaction to obtain a new ammonia-resistant proton conductor material suitable for a direct ammonia fuel cell.

[0006] Further, in Step 1, the metal cations in the selected proton conductor material are barium ions, zirconium ions, cerium ions and yttrium ions, the metal salts are diethylhexanoate, nitrate, chloride, isopropyl alcohol salt, acetate or oxalate, and the energetic solvent is one or a combination of deionized water, ethanol, propanol, isopropyl alcohol, acetic acid, propionic acid, diethylhexanoic acid and N,N-dimethylformamide.

[0007] Further, the heat value of the energetic solvent is greater than 1000 kJ / mol.

[0008] Further, in Step 2, the frequency of the ultrasonic environment is 20-40 kHz, the temperature of the heating and stirring is 40-80℃, and the rotation speed of the heating and stirring is 200-800 rpm.

[0009] Further, in Step 2, the pH value of the solution after adding ammonia water is 5.2-7.2, and the molar concentration of the metal cations in the obtained clear mixed precursor solution in which metal elements are stably dispersed is 0.1-0.6 mol / L.

[0010] Further, in Step 3, the clear mixed precursor solution is heat-treated at a temperature of 40-80℃.

[0011] Further, in Step 3, the size of the precursor droplets obtained by the aerosol generator is less than 1 μm, and the carrier gas mixed with the precursor droplet group is air or a mixture of nitrogen and oxygen.

[0012] Further, in step four, the temperature of the ammonia-containing flame field is 1400-2400 DEG C; the fuel component of the ammonia-containing flame field is a mixed gas composed of hydrogen, methane and ammonia; the proportion of ammonia in the ammonia-containing flame field is 0-100 vol%; the oxidant component of the ammonia-containing flame field is oxygen; and the atmosphere of the ammonia-containing flame field is a reducing atmosphere or an oxidizing atmosphere.

[0013] Further, in step four, the precursor aerosol is introduced into the ammonia-containing flame field along the central direction of the ammonia-containing flame field for reaction, and the ammonia in the ammonia-containing flame field is distributed circumferentially in the ammonia-containing flame field.

[0014] Further, in step four, the obtained new ammonia-resistant proton conductor material suitable for direct ammonia fuel cells is in a particle structure, and the particle diameter of the new ammonia-resistant proton conductor material suitable for direct ammonia fuel cells is 10-60 nm.

[0015] The synthesis method of the ammonia-resistant proton conductor material for a direct ammonia fuel cell has a continuous process, is simple and effective, is precisely controllable, has stable product quality, and is easy to realize scale-up synthesis; the new ammonia-resistant proton conductor material obtained has high crystal purity, uniform mixing of metal elements at the atomic level, high sintering activity, and can significantly improve the ammonia corrosion resistance of the proton conductor after in-situ ammonia modification during the synthesis process; after sintering at a temperature of 1300 DEG C or higher for 5 hours, the new ammonia-resistant proton conductor material maintains a proton conductivity of not less than 0.01 S / cm after running for 100 hours in an ammonia-containing atmosphere at 600 DEG C. BRIEF DESCRIPTION OF DRAWINGS

[0016] In order to more clearly illustrate the specific embodiments of the present application, the following will briefly introduce the drawings needed in the specific embodiments. Obviously, the drawings described below are some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor.

[0017] Figure 1 The synthesis method of the ammonia-resistant proton conductor material for a direct ammonia fuel cell has a continuous process, is simple and effective, is precisely controllable, has stable product quality, and is easy to realize scale-up synthesis; the new ammonia-resistant proton conductor material obtained has high crystal purity, uniform mixing of metal elements at the atomic level, high sintering activity, and can significantly improve the ammonia corrosion resistance of the proton conductor after in-situ ammonia modification during the synthesis process; after sintering at a temperature of 1300 DEG C or higher for 5 hours, the new ammonia-resistant proton conductor material maintains a proton conductivity of not less than 0.01 S / cm after running for 100 hours in an ammonia-containing atmosphere at 600 DEG C. DETAILED DESCRIPTION

[0018] In order to more clearly illustrate the specific embodiments of the present application, the following will briefly introduce the drawings needed in the specific embodiments. Obviously, the drawings described below are some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor.

[0019] The term "embodiment" is mentioned herein means that the specific features, structures, or characteristics described in connection with the embodiment can be included in at least one embodiment of the present application. The term "embodiment" appearing in various places in the specification does not necessarily refer to the same embodiment, nor does it particularly limit the independence or association between other embodiments. In principle, in the present application, as long as there is no technical contradiction or conflict, each technical feature mentioned in each embodiment can be combined in any way to form a corresponding implementable technical solution.

[0020] Unless otherwise defined, the meanings of the technical terms used herein are the same as those commonly understood by those skilled in the art to which the present application belongs; the use of related terms herein is only for the purpose of describing specific embodiments, and is not intended to limit the present application.

[0021] Hereinafter, the embodiments of the present application are specifically disclosed with appropriate reference to the accompanying drawings. However, there will be cases where unnecessary detailed description is omitted. For example, there are cases where detailed description of matters well known to those skilled in the art, repeated description of substantially the same structure are omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate understanding by those skilled in the art. In addition, the accompanying drawings and the following description are provided to enable those skilled in the art to fully understand the present application, and are not intended to limit the subject matter recited in the claims.

[0022] The "range" disclosed in the present application is defined in the form of a lower limit and an upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundaries of a particular range. The range defined in this way can be inclusive or exclusive of the end values, and can be arbitrarily combined, i.e., any lower limit can be combined with any upper limit to form a range. For example, if the ranges 60-120 and 80-110 are listed for a particular parameter, it is understood that the ranges 60-110 and 80-120 are also contemplated. In addition, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In the present application, unless otherwise stated, the numerical range "a-b" represents a shorthand notation for any real combination of numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed herein, and "0-5" is only a shorthand notation for these numerical combinations. In addition, when a parameter is stated to be ≥2 integers, it is equivalent to disclose that the parameter is, for example, integer 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0023] Unless otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form new technical solutions.

[0024] All the technical features and optional technical features of the present application can be combined with each other to form new technical solutions, if not specifically stated.

[0025] All the steps of the present application can be performed in sequence or randomly, preferably in sequence, if not specifically stated. For example, the method comprises steps (a) and (b), which means that the method can comprise steps (a) and (b) performed in sequence, or steps (b) and (a) performed in sequence. For example, the method can further comprise step (c), which means that step (c) can be added to the method in any sequence, for example, the method can comprise steps (a), (b) and (c), or steps (a), (c) and (b), or steps (c), (a) and (b), etc.

[0026] The terms "comprise" and "contain" mentioned in the present application mean open or closed, if not specifically stated. For example, the terms "comprise" and "contain" can mean that other components not listed can also be included, or only the listed components can be included.

[0027] The terms "above" and "below" used in the present application include the number, for example, "one or more" means one or more, and "one or more of A and B" means "A", "B", or "A and B".

[0028] In the present application, the term "or" is inclusive, if not specifically stated. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, any one of the following conditions satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or A and B are both true (or exist).

[0029] As shown in the synthesis method of the ammonia-resistant proton conductor material of the direct ammonia fuel cell according to the present application, the method comprises the following steps: Figure 1

[0030] Step one: select a proton conductor material, according to the molar ratio of metal cations in the selected proton conductor material, weigh the metal salt containing the corresponding metal element, and mix the weighed metal salt with the solvent to obtain a mixed solution;

[0031] Step two: heat and stir the mixed solution under ultrasonic environment, add ammonia water to the stirred mixed solution to adjust the pH value of the solution, until the metal salt is fully dissolved, to obtain a clear mixed precursor solution with stable dispersion of metal elements;

[0032] ​Step three: incubating the clear mixed precursor solution and generating a group of precursor droplets by an aerosol generator, mixing the group of precursor droplets with a carrier gas and forming a precursor aerosol;

[0033] Step four: burning the precursor aerosol in an ammonia-containing flame field to obtain a novel ammonia-resistant proton conductor material suitable for a direct ammonia fuel cell.

[0034] The synthesis method of the ammonia-resistant proton conductor material of the direct ammonia fuel cell described in the present application has continuous process, simple and effective method, precise controllable process, stable product quality, and is easy to realize scale-up synthesis; and the obtained novel ammonia-resistant proton conductor material has high crystal purity, uniform atomic-level mixing of metal elements, high sintering activity, and can significantly improve the ammonia corrosion resistance of the proton conductor through in-situ ammonia modification during the synthesis process; after sintering at a temperature above 1300℃ for 5h, the proton conductivity of the novel ammonia-resistant proton conductor material remains not less than 0.01S / cm under the condition of operating at 600℃ in an ammonia-containing atmosphere.

[0035] In step one, the molar ratio of the metal salt containing the corresponding metal is equal to the molar ratio of Ba, Zr, Ce, Y and M in the selected BaCexZryYzM1-x-y-zO3-δ (BCZYM-based) proton conductor material; further, the metal salt containing the corresponding metal element is diethylhexanoate, nitrate, chloride, isopropyl alcohol salt, acetate or oxalate; the energetic solvent is a mixed solvent of one or more combinations of deionized water, ethanol, propanol, isopropanol, acetic acid, propionic acid, diethylhexanoic acid and N,N-dimethylformamide; preferably, the heat value of the energetic solvent is greater than 1000kJ / mol, so as to promote the high-temperature gas phase reaction of the precursor, and further make the generated proton conductor particles have more uniform morphology and particle size distribution.

[0036] In step two, the frequency of the ultrasonic environment is 20-40kHz; the temperature of the heating and stirring is 40-80℃, and the rotation speed of the heating and stirring is 200-800rpm; ammonia water is added to adjust the pH value of the solution, and the pH value of the adjusted solution is 5.2-7.2; the molar concentration of the metal cations in the obtained clear mixed precursor solution with stable dispersion of metal elements is 0.1-0.6mol / L.

[0037] In step three, the incubation temperature of the clear mixed precursor solution is 40-80℃; the size of the precursor droplets obtained by the aerosol generator is submicron (<1μm); the carrier gas mixed with the group of precursor droplets is air or a mixed gas of nitrogen and oxygen, and the solution is incubated to reduce the viscosity of the solution, which is beneficial to the aerosol generator to generate smaller precursor droplets.

[0038] In step four, the temperature of the ammonia-containing flame field is 1400-2400℃; the fuel component of the ammonia-containing flame field is a mixed gas composed of hydrogen, methane and ammonia, wherein the proportion of ammonia is 0-100vol%; the oxidant component of the ammonia-containing flame field is oxygen; the atmosphere of the ammonia-containing flame field is a reducing atmosphere or an oxidizing atmosphere; more specifically, the precursor aerosol is axially introduced into the temperature and component adjustable ammonia-containing flame field along the central direction of the ammonia-containing flame field, wherein the ammonia is distributed circumferentially in the flame field; by axially introducing the precursor aerosol along the central direction into the temperature and component adjustable ammonia-containing flame field, firstly, the temperature and component field experienced by the precursor droplets during reaction is more uniform, and the uniformity of the particle structure characteristics is also better; secondly, the modification of ammonia on the particle ammonia corrosion resistance is more sufficient, and the ammonia resistance can be significantly enhanced.

[0039] The precursor aerosol is ignited in the ammonia-containing flame field with circumferential distribution of ammonia to form a central aerosol flame, and after high-temperature evaporation, reaction nucleation, condensation growth and ammonia modification, a new ammonia-resistant proton conductor material suitable for direct ammonia fuel cells is obtained;

[0040] More specifically, the new ammonia-resistant proton conductor material suitable for direct ammonia fuel cells is a particle structure, and the particle diameter of the new ammonia-resistant proton conductor material suitable for direct ammonia fuel cells is 10-60nm.

[0041] The synthesis method of the ammonia-resistant proton conductor material suitable for ammonia fuel cells is further described below in combination with examples.

[0042] Example 1

[0043] A synthesis method of an ammonia-resistant proton conductor material for a direct ammonia fuel cell, comprising the following steps:

[0044] Step one: select a proton conductor material containing Ba, Ce, Zr, Y, Yb cations, according to the molar ratio of Ba, Ce, Zr, Y, Yb in the selected proton conductor material, respectively take 21.19g of barium diethylhexanoate, 19.94g of cerium diethylhexanoate, 1.89g of cerium diethylhexanoate, 2.59g of yttrium diethylhexanoate and 1.17g of ytterbium isopropyl alcohol, add to the mixed solvent of ethanol, isopropyl alcohol and diethylhexanoic acid with a volume ratio of 8:1:1, to obtain a mixed solution, and the total concentration of metal ions in the solution is 0.1mol / L;

[0045] Step two: heat and stir the mixed solution under the condition of 80℃ and 40kHz ultrasonic environment, the stirring rotor rotates at a speed of 800rpm, add ammonia water to the stirred mixed solution to adjust the pH value of the solution to 6.2, until the metal salt is fully dissolved, and a clear mixed precursor solution with stable dispersion of metal elements is obtained after full dissolution.

[0046] Step three: the clear mixed precursor solution is placed in 80℃ and the average particle size of the precursor droplet group generated by the aerosol generator is 0.2-0.5μm, the precursor droplet group is mixed with oxygen carrier gas and forms a precursor aerosol;

[0047] Step four: the precursor aerosol is reacted from the central axis into a circumferential high-temperature ammonia-containing flame field of 1800℃, which is generated by the combustion of hydrogen and ammonia mixed fuel and oxygen, the proportion of ammonia in the fuel is 30%, the overall atmosphere is a micro-reducing atmosphere, and a new type of ammonia-resistant proton conductor material suitable for direct ammonia fuel cells is obtained, and the prepared new type of ammonia-resistant proton conductor material suitable for direct ammonia fuel cells is granular and the average particle diameter is 15nm.

[0048] Example 2

[0049] A synthesis method of an ammonia-resistant proton conductor material for a direct ammonia fuel cell, comprising the following steps:

[0050] Step one: select a proton conductor material containing Ba, Ce, Zr, Y, Yb cations, according to the molar ratio of Ba, Ce, Zr, Y, Yb in the selected proton conductor material, respectively, 63.56g of barium diethylhexanoate, 59.82g of cerium diethylhexanoate, 5.66g of cerium diethylhexanoate, 7.78g of yttrium diethylhexanoate and 3.50g of ytterbium isopropyl alcohol are added into a mixed solvent of ethanol, isopropyl alcohol and diethylhexanoic acid with a volume ratio of 7:1:1, to obtain a mixed solution, and the total concentration of metal ions in the solution is 0.3mol / L;

[0051] Step two: the mixed solution is heated and stirred under the condition of 60℃ and 30kHz ultrasonic environment, the stirring rotor rotates at a speed of 600rpm, ammonia water is added to the stirred mixed solution to adjust the pH value of the solution to 6.8, until the metal salt is fully dissolved, and a clear mixed precursor solution with stable dispersion of metal elements is obtained after full dissolution;

[0052] Step three: the clear mixed precursor solution is placed in 60℃ and the average particle size of the precursor droplet group generated by the aerosol generator is 0.3-0.6μm, the precursor droplet group is mixed with oxygen carrier gas and forms a precursor aerosol;

[0053] Step four: the precursor aerosol is reacted from the central axis into a circumferential high-temperature ammonia-containing flame field of about 1600℃, wherein the ammonia-containing flame field is generated by combustion of hydrogen and ammonia mixed fuel and oxygen, the proportion of ammonia in the fuel is 35%, the overall atmosphere is a slightly reducing atmosphere, and a new type of ammonia-resistant proton conductor material suitable for a direct ammonia fuel cell is obtained. The new type of ammonia-resistant proton conductor material suitable for the direct ammonia fuel cell prepared is in a granular form and the average particle diameter is 23 nm.

[0054] Example 3

[0055] A synthesis method of an ammonia-resistant proton conductor material for a direct ammonia fuel cell, comprising the following steps:

[0056] Step one: a proton conductor material containing Ba, Ce, Zr, Y and Yb ions is selected, according to the molar ratio of Ba, Ce, Zr, Y and Yb in the selected proton conductor material, 105.93g of barium diethylhexanoate, 99.70g of cerium diethylhexanoate, 9.44g of cerium diethylhexanoate, 12.96g of yttrium diethylhexanoate and 5.83g of ytterbium isopropoxide are respectively weighed and added into a mixed solvent of ethanol, isopropyl alcohol and diethylhexanoic acid in a volume ratio of 9:1:1 to obtain a mixed solution, and the total concentration of metal ions in the solution is 0.5mol / L;

[0057] Step two: the mixed solution is heated and stirred in a 40℃ 20kHz ultrasonic environment, the stirring rotor rotates at a speed of 400rpm, ammonia water is added to the stirred mixed solution to adjust the pH value of the solution to 7.0, until the metal salt is fully dissolved, and a clear mixed precursor solution with stable dispersion of metal elements is obtained after full dissolution;

[0058] Step three: the clear mixed precursor solution is placed in a 40℃ incubator, and a precursor droplet group with an average particle size of 0.5-0.8μm is generated by an aerosol generator, the precursor droplet group is mixed with oxygen carrier gas to form a precursor aerosol;

[0059] Step four: the precursor aerosol is reacted from the central axis into a circumferential high-temperature ammonia-containing flame field of about 1400℃, wherein the ammonia-containing flame field is generated by combustion of hydrogen and ammonia mixed fuel and oxygen, the proportion of ammonia in the fuel is 50%, the overall atmosphere is a slightly reducing atmosphere, and a new type of ammonia-resistant proton conductor material suitable for a direct ammonia fuel cell is obtained. The new type of ammonia-resistant proton conductor material suitable for the direct ammonia fuel cell prepared is in a granular form and the particle diameter is 36nm.

[0060] The three kinds of granular and different particle diameter new ammonia proton conductor materials for direct ammonia fuel cell prepared by the above examples 1-3 were calcined at 1400℃ for 5 hours, and then respectively operated at 600℃ for 100 hours in the atmosphere containing ammonia, and the proton conductivities were respectively:

[0061] Proton conductivity (S / cm) Example 1 0.015 Example 2 0.013 Example 3 0.011

[0062] It should be noted that the present application is not limited to the above-described embodiments. The above-described embodiments are merely examples, and embodiments having substantially the same configuration as the technical idea and exerting the same effects within the scope of the technical solution of the present application are all included in the technical scope of the present application. Furthermore, within the scope of the gist of the present application, various modifications that can be thought of by those skilled in the art, other modes constructed by combining part of the configuration elements of the embodiments are also included in the scope of the present application.

Claims

1. A method of synthesis of an ammonia-resistant proton conductor material for a direct ammonia fuel cell, characterized by, The method comprises the following steps: Step 1: selecting a proton conductor material, according to the molar ratio of metal cations in the selected proton conductor material, weighing metal salts containing corresponding metal elements, and mixing the weighed metal salts with an energetic solvent to obtain a mixed solution; Step 2: heating and stirring the mixed solution under an ultrasonic environment, adding ammonia water to the stirred mixed solution to adjust the pH value of the solution until the metal salts are fully dissolved to obtain a clear mixed precursor solution in which metal elements are stably dispersed; Step 3: heat-treating the clear mixed precursor solution, and generating a precursor droplet group through an aerosol generator, fully mixing the precursor droplet group with a carrier gas, and forming a precursor aerosol; Step 4: introducing the precursor aerosol into an ammonia-containing flame field for reaction to obtain an ammonia-resistant proton conductor material for a direct ammonia fuel cell; The heat value of the energetic solvent is greater than 1000 kJ / mol. In step 4, the temperature of the ammonia-containing flame field is 1400-2400℃; the fuel component of the ammonia-containing flame field is a mixed gas composed of hydrogen, methane and ammonia; the proportion of ammonia in the fuel is 30-50 vol%; and the oxidizing agent component of the ammonia-containing flame field is oxygen.

2. The method of claim 1, wherein the method is characterized by: In step 1, the metal cations in the selected proton conductor material are barium ions, zirconium ions, cerium ions and yttrium ions, the metal salts are diethylhexanoate, nitrate, chloride, isopropyl alcoholate, acetate or oxalate, and the energetic solvent is one or a combination of ethanol, propanol, isopropyl alcohol, propionic acid, diethylhexanoic acid and N,N-dimethylformamide.

3. The method of claim 1, wherein the method is characterized by: In step 2, the frequency of the ultrasonic environment is 20-40 kHz; the temperature of the heating and stirring is 40-80℃, and the rotation speed of the heating and stirring is 200-800 rpm.

4. The method of claim 3, wherein the method further comprises: adding a second metal oxide to the first metal oxide to form a second metal oxide layer on the first metal oxide layer. In step 2, the pH value of the solution after adding ammonia water for adjustment is 5.2-7.2, and the molar concentration of the metal cations in the obtained clear mixed precursor solution in which metal elements are stably dispersed is 0.1-0.6 mol / L.

5. The method of claim 1, wherein the method is characterized by: In step 3, the clear mixed precursor solution is heat-treated at a temperature of 40-80℃.

6. The method of claim 1, wherein the method is characterized by: In step 3, the size of the droplets of the precursor droplet group obtained through the aerosol generator is less than 1 μm; and the carrier gas mixed with the precursor droplet group is air or a mixed gas of nitrogen and oxygen.

7. The method of claim 1, wherein the method is characterized by: In step 4, the precursor aerosol is introduced into the ammonia-containing flame field along the central direction of the ammonia-containing flame field for reaction, and the ammonia in the ammonia-containing flame field is distributed circumferentially in the interior of the ammonia-containing flame field.

8. The method of claim 1, wherein the method is characterized by: In step 4, the ammonia-resistant proton conductor material is in a granular structure, and the particle diameter is 10-60 nm.

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