Anode functional layer material for direct ammonia proton fuel cell and preparation method and application thereof

Abstract

The present invention first proposes an anode functional layer material to modify DA-PCFC, to achieve the simultaneous improvement of performance and durability. In this work, a kind of AFL material Pr 0.6 Sr 0.4 (Co 0.2 Fe 0.8 ) 0.85 Ru 0.15 O 3‑δ (PSCFR15) is developed, and then treated under high temperature reducing atmosphere to form embedded nano CoFeRu alloy modified composite material. The introduction of this composite material as AFL significantly improves the NH3 decomposition activity of the anode. Therefore, compared with non-AFL DA-PCFC operating with H2 and NH3 fuel, DA-PCFC with PSCFR15-AFL achieves excellent peak power density. In addition, the AFL also avoids the direct contact between the Ni-based ceramic anode and the high concentration NH3 fuel, inhibits the sintering of the Ni catalyst, and enhances the durability of the DA-PCFC.

Description

Technical Field

[0001] This invention belongs to the field of solid oxide fuel cell technology, and relates to an anode functional layer material, specifically a direct ammonia proton fuel cell anode functional layer material, its preparation method, and its application. Background Technology

[0002] Solid oxide fuel cells (SOFCs) are advanced energy conversion devices that have attracted widespread attention due to their high efficiency, low emissions, and fuel flexibility. Traditional oxygen-ion conducting SOFCs based on yttrium-stabilized zirconia as the electrolyte typically operate at high temperatures (above 800°C), leading to several technical challenges such as high cost and poor operational stability. Proton-conducting SOFCs (also known as proton ceramic fuel cells, PCFCs) can overcome these problems due to their lower operating temperatures (350-650°C), as the activation energy for proton conduction is much lower than that for oxygen ion conduction in oxide electrolytes. However, the most widely used fuels for PCFCs are hydrogen (H2) and hydrocarbons, both of which have limitations: H2 presents a high risk of hydrogen leakage, low bulk density and liquefaction temperature, and high storage / transportation costs; hydrocarbons cause severe coking and CO2 emissions on conventional nickel-based cermet anodes, significantly limiting the large-scale application of PCFCs.

[0003] Ammonia (NH3) is a very promising PCFC fuel, easier to detect leaks, store, and transport than H2 because it can be liquefied at room temperature and medium pressure. Furthermore, the carbon-free nature of NH3 can effectively address the serious coke deposition on nickel-based cermet anodes and CO2 emissions when operating with hydrocarbon fuels. Additionally, due to its low susceptibility to harmful NO... x For emission suppression, direct ammonia PCFC (DA-PCFC) is cleaner than direct ammonia oxygen ion conduction SOFC (DA-OSOFC). This is because the operation of PCFC differs from that of O-SOFC, where oxygen ions migrate from the cathode to the anode and react with NH3 to produce NO. x Therefore, the combination of NH3 fuel and PCFC is a promising clean energy system.

[0004] Despite its promising prospects, two main issues hinder the large-scale application of DA-PCFC. One issue is the insufficient activity of conventional Ni-based cermet anodes in PCFCs for the decomposition of NH3. When NH3 is used as fuel, it first decomposes into N2 and H2 under the catalysis of the anode. Typically, conventional Ni-based cermet anodes in PCFCs, including Ni-BaZr... 0.1 Ce 0.7 Y 0.2 O 3-δ (BZCY), Ni-BaZr 0.1Ce 0.7 Y 0.1 Yb 0.1 O 3-δ (BZCYYb). Nickel catalysts in nickel-based ceramic anodes prepared by mechanical mixing are typically large in size, leading to insufficient active sites and limiting catalytic activity for NH3 decomposition. Furthermore, another factor determining the activity of NH3 decomposition is the nitrogen adsorption enthalpy of the catalyst, as NH3 decomposition is related to both NH3 adsorption and N2 desorption. Optimal nitrogen adsorption enthalpy is crucial for achieving high NH3 decomposition activity. However, metallic Ni exhibits an unfavorable nitrogen adsorption enthalpy, resulting in lower NH3 decomposition activity for Ni compared to some other metal catalysts, such as Fe, Co, and Ru. Another problem is the severe sintering of conventional Ni-based cermet anodes operating with NH3 fuel. One possible reason is that metallic nickel can chemically adsorb and dehydrogenate and rehydrogenate ammonia. This reaction may alter the wetting and diffusion of the metal crystallites onto the support, thus weakening the interaction bonds between Ni particles and the support surface, leading to severe sintering of the Ni catalyst. Severe sintering of the nickel catalyst can also lead to the migration and agglomeration of nickel particles in the anode, significantly reducing its mechanical strength and thermal compatibility with the electrolyte, resulting in severe performance degradation. Summary of the Invention

[0005] To address the aforementioned technical problems, the present invention aims to provide a functional layer material for the anode of a direct ammonia proton fuel cell, thereby overcoming the problem of Ni sintering that easily occurs in conventional Ni-based ceramic anodes during durability testing in a high-concentration NH3 atmosphere.

[0006] To achieve the aforementioned technical objectives, a direct ammonia proton fuel cell anode functional layer material is provided, which is obtained by calcining a precursor in a reducing atmosphere. The precursor has the general chemical formula ABO. 3-δ In the formula, δ represents the oxygen vacancy content, and the molecular formula of the precursor is Pr. 0.6 Sr 0.4 (Co 0.2 Fe 0.8 ) 1-x Ru x O 3-δ In the formula, 0 ≤ x ≤ 0.2.

[0007] Ideally, x is 0, 0.05, 0.1, 0.15, and 0.2.

[0008] Furthermore, x is 0.15.

[0009] Another object of the present invention is to provide a method for preparing the above-mentioned anode functional layer material of a direct ammonia proton fuel cell, comprising the following steps: (a) Press Pr 0.6Sr 0.4 (Co 0.2 Fe 0.8 ) 1-x Ru x O 3-δ Weigh out the corresponding masses of Pr(NO3)3•6H2O, Sr(NO3)2, Co(NO3)2•6H2O, Fe(NO3)3•9H2O and RuCl3•aH2O according to the stoichiometric ratio, add deionized water and stir to dissolve to obtain a mixed solution; add a complexing agent, then add ammonia dropwise until the pH of the solution is 7-8, and allow the water to evaporate under heating and stirring to obtain a gel-like substance; dry the gel-like substance; (b) The product of step (a) is calcined in air to obtain the precursor; (c) The precursor can be treated at high temperature in a reducing atmosphere.

[0010] Optimally, in step (a), the complexing agent is a mixture of ethylenediaminetetraacetic acid and citric acid monohydrate in a molar ratio of 1:2.

[0011] Ideally, in step (a), the molar ratio of total metal ions, ethylenediaminetetraacetic acid, citric acid monohydrate, and solute in the alkaline solution is 1:0.5-2.5:1-3:3-20.

[0012] Ideally, in step (a), the drying conditions are 140-180°C and baking for 5-10 hours.

[0013] Ideally, in step (b), the calcination is carried out at a temperature of 900~1100℃ for 5~12h with a heating rate of 2~5℃ / min.

[0014] Ideally, in step (c), the treatment is carried out in an H2-Ar atmosphere at a temperature of 750-850°C for 8-12 hours.

[0015] The purpose of this invention is to provide an application of the above-mentioned direct ammonia proton fuel cell anode functional layer material, which is used as the anode catalytic functional layer of PCFC.

[0016] This invention proposes for the first time an anode functional layer material to modify DA-PCFC, achieving improved performance and durability. The functional layer material, after high-temperature reduction, forms an embedded nano-CoFeRu alloy, effectively protecting the anode structure, improving catalytic performance, reducing the NH3 concentration in the anode, and inhibiting the sintering of Ni particles. When 15% Ru is doped at the B site and the material is reduced, a catalytic material with higher catalytic activity and better catalytic stability can be obtained. This invention also synthesizes Pr via a sol-gel method. 0.6 Sr 0.4 (Co 0.2Fe 0.8 ) 1-x Ru x O 3-δ (PSCFR) Anode functional layer material, in which all elements are uniformly distributed and the synthesis method is simple and efficient. Attached Figure Description

[0017] Figure 1 It is Pr 0.6 Sr 0.4 (Co 0.2 Fe 0.8 ) 1-x Ru x O 3-δ XRD patterns of oxides (x=0, 0.05, 0.1, 0.15, 0.2) after calcination at 1000 °C in air for 5 h followed by natural cooling to room temperature; Figure 2 The XRD patterns of PSCFRx series oxides were obtained after being treated at 800℃ in a 10 vol.% H2-Ar atmosphere for 10 h and allowed to cool naturally to room temperature. Figure 3 These are SEM images of PSCF and PSCFR0.15 oxides before and after reduction; Figure 4 This is a hydrogen temperature program curve for PSCF and PSCFR0.15 oxides; Figure 5 The graph shows the catalytic activity test results of the reduced PSCFRx series oxides (r-PSCFRx) and Ni-BZCYYb|r-PSCFR0.15 for ammonia at 450-650℃. Figure 6 (a) IP and IV curves of a single cell without a catalytic functional layer using H2 as fuel; (b) IP and IV curves of a single cell without a catalytic functional layer using NH3 as fuel; (c) IP and IV curves of a single cell with an r-PSCFR0.15 catalytic functional layer using H2 as fuel; (d) IP and IV curves of a single cell with an r-PSCFR0.15 catalytic functional layer using NH3 as fuel. Figure 7 The electrochemical impedance spectroscopy spectra of PCFCs without catalytic functional layers (a) and (b) and those containing r-PSCFR0.15 catalytic functional layers (c) and (d) in H2 and NH3 fuels are shown. Figure 8 The stability of PCFCs without a catalytic functional layer (a) and those containing an r-PSCFR0.15 catalytic functional layer (b) under H2 and NH3 conditions; Figure 9These are SEM images of single cells after stability testing, showing the cells without a catalytic functional layer (a) and with an r-PSCFR0.15 catalytic functional layer (b). Detailed Implementation

[0018] The present invention relates to a functional layer material for the anode of a direct ammonia proton fuel cell, which is obtained by calcining a precursor in a reducing atmosphere. The precursor has the general chemical formula ABO. 3-δ In the formula, δ represents the oxygen vacancy content, and the molecular formula of the precursor is Pr. 0.6 Sr 0.4 (Co 0.2 Fe 0.8 ) 1-x Ru x O 3-δ In the formula, 0 ≤ x ≤ 0.2. x is preferably 0, 0.05, 0.1, 0.15, and 0.2, with 0.15 being the optimal value. After reduction treatment, it exhibits high catalytic activity and good catalytic stability. It forms a highly active catalytic functional layer on the anode surface of a direct ammonia proton ceramic fuel cell to protect the anode structure, improve catalytic performance, and reduce the NH3 concentration at the anode, ensuring that the morphology of the Ni particles remains unchanged. When 15% Ru is doped at the B site and the material is reduced, a catalytic material with even higher catalytic activity and better catalytic stability can be obtained.

[0019] The above-mentioned method for preparing the anode functional layer material of a direct ammonia proton fuel cell includes the following steps: (a) according to Pr 0.6 Sr 0.4 (Co 0.2 Fe 0.8 ) 1-x Ru x O 3-δ Weigh out the corresponding masses of Pr(NO3)3•6H2O, Sr(NO3)2, Co(NO3)2•6H2O, Fe(NO3)3•9H2O, and RuCl3•aH2O according to their stoichiometric ratios, add deionized water and stir to dissolve to obtain a mixed solution; add a complexing agent, then add ammonia dropwise until the solution pH is 7-8, and evaporate the water under heating and stirring to obtain a gel-like substance; dry the gel-like substance; (b) calcine the product of step (a) in air to obtain the precursor (product abbreviated as PSCFR); (c) treat the precursor at high temperature in a reducing atmosphere (product abbreviated as r-PSCFRx). Pr was synthesized by the sol-gel method. 0.6 Sr 0.4 (Co 0.2 Fe 0.8 ) 1-x Ru x O 3-δ(PSCFR) Anode functional layer material, in which all elements are uniformly distributed and the synthesis method is simple and efficient.

[0020] In step (a), the complexing agent is a mixture of ethylenediaminetetraacetic acid and citric acid monohydrate in a molar ratio of 1:2; the molar ratio of total metal ions, ethylenediaminetetraacetic acid, citric acid monohydrate, and solute in the alkaline solution is 1:0.5-2.5:1-3:3-20; the drying conditions are 140-180℃ for 5-10 hours. In step (b), the calcination is carried out at 900-1100℃ for 5-12 hours with a heating rate of 2-5℃ / min. In step (c), the treatment is carried out in an H2-Ar atmosphere at 750-850℃ for 8-12 hours. The above-mentioned direct ammonia proton fuel cell anode functional layer material is used as the anode catalytic functional layer of a PCFC.

[0021] The present invention will be further described in detail below with reference to specific embodiments, but the present invention is not limited to the following embodiments. The implementation conditions used in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not specified are conventional conditions in this industry. Example 1

[0022] This embodiment provides a method for reducing Pr, a direct ammonia proton fuel cell anode functional layer material. 0.6 Sr 0.4 (Co 0.2 Fe 0.8 ) 1-x Ru x O 3-δ The preparation method of (r-PSCFRx) is as follows: (1) According to Pr 0.6 Sr 0.4 (Co 0.2 Fe 0.8 ) 0.85 Ru 0.15 O 3-δWeigh out 13.0503 g of Pr(NO3)3•6H2O, 4.2326 g of Sr(NO3)2, 2.4738 g of Co(NO3)2•6H2O, 13.7360 g of Fe(NO3)3•9H2O, and 1.5557 g of RuCl3•aH2O in a clean beaker. Add an appropriate amount of deionized water (the amount of deionized water is not important, as long as it can dissolve the above metal salts, which will be dried later). Stir on an electric heating stirring table to dissolve and obtain a clear solution (i.e., a mixed solution). Weigh out 29.2240 g of ethylenediaminetetraacetic acid and 42.0280 g of citric acid monohydrate in a molar ratio of 1:1:2. 4 g of hydrated citric acid was dissolved in deionized water as a complexing agent; an appropriate amount of ammonia solution (90 ml, commercially available concentration of 25-28%) was added dropwise to bring the pH to between 7 and 8. Then, the mixture was stirred under magnetic stirring until the water was completely evaporated to obtain a gel-like substance. The gel-like substance was then placed in an oven and calcined at 180 °C for 5 hours to fully dry it. (b) The product from step (a) was placed in a high-temperature muffle furnace and calcined at 1000 °C for 5 h to obtain the precursor sample (denoted as PSCFR0.15). The heating curve is shown in [reference needed]. Figure 4 ; (c) Place the obtained PSCFR0.15 sample into a small boat, then place the small boat into a tube furnace and continuously pass 80 ml of 10 vol.% H2-Ar (i.e., the volume content of H2 in the mixed gas is 10%). Heat the tube furnace to 800℃ and keep it at 800℃ for 10 h. After the temperature in the tube furnace drops to room temperature, the reduced r-PSCFR0.15 sample can be obtained.

[0023] The amount of RuCl3•aH2O was also adjusted so that x was 0, 0.05, 0.1, and 0.2, respectively. The final samples were denoted as r-PSCF, r-PSCF0.05, r-PSCFR0.1, and r-PSCFR0.2. XRD and SEM images of the samples from each step are shown below. Figures 1 to 3 As shown.

[0024] Figure 1The XRD patterns of the PSCFRx (x = 0, 0.05, 0.1, 0.15, 0.2) series of powder oxides prepared in Example 1, after calcination at 1000 °C in air for 5 h and subsequent natural cooling to room temperature (i.e., the products of step (b)). The results show that the PSCF, PSCFR0.05, PSCFR0.1, PSCFR0.15, and PSCFR0.2 samples are all in a pure cubic perovskite phase, and no characteristic peaks of other impurities were found. This indicates that the doping of Ru cations does not change the crystal structure of the samples, but rather successfully integrates them into the cubic perovskite lattice.

[0025] Figure 2 The samples were treated at 800 °C in a 10 vol.% H2-Ar atmosphere for 10 h, yielding reduced r-PSCF, r-PSCFR0.05, r-PSCFR0.1, r-PSCFR0.15, and r-PSCFR0.2. The primary cubic phase transformation of PSCFRx was tetragonal (Pr, Sr)FeO4 (space group: I4 / mmm) and cubic Sr(Co, Fe)O. 3-δ (Space group: Pm-3m) phase, accompanied by in-situ exsolution of Pr2O3 and CoFeRu alloy.

[0026] Figure 3 SEM images of PSCF and PSCFR0.15 oxides before and after reduction are presented. The PSCFR0.15 sample exhibits a sintered particle structure, primarily due to the addition of Ru. After reduction, the originally clearly defined particles of the PSCFR0.15 sample agglomerated into a single unit, a result of phase transformation. Numerous nanoparticles, composed of zero-valent Co, Fe, and Ru, were observed on the surface of the reduced sample on the perovskite substrate.

[0027] Figure 4 This is a characterization of H2 temperature-programmed reduction (H2-TPR) of PSCF and PSCFR0.15. For example... Figure 4 As shown, PSCF at approximately 309, 361, and 844 °C corresponds to partial Co. 3+ To Co 2+ , part of Fe 4+ / 3+ To Fe 2+ and Co 2+ / Fe 2+ To Co 0 / Fe 0The reduction process was observed. Significant changes were observed after replacing 15 mol% of the B site in PSCF to produce PSCFR0.15. The H2 consumption peak disappeared in the 300-400℃ temperature range, while a new peak appeared in the 200-250℃ range. The disappearance of the peak (300-400℃) can be attributed to the reduction of Co / Fe cations after Ru substitution, thereby inhibiting Co reduction. 3+ / Fe 4+ / 3+ To Co 2+ / Fe 2+ Partial restoration. Furthermore, the emergence of new peaks can be attributed to Ru... n+ Reduce to Ru 0 The peak temperature around 800℃ can be attributed to Fe. 2+ / Co 2+ Reduced to Fe respectively 0 / Co 0 As previously reported in the literature, H2-TPR results indicate that during the formation of the CoFeRu nanoalloy, Ru first exsolves, followed by the exsolution of Co and Fe, which then assemble with Ru to form an alloy catalyst. Example 2

[0028] This embodiment provides a method for fabricating a Ni-BZCYYb anode-supported single cell, with the following specific steps: (a) Take 1g of cathode powder BCFZYN (MZ Liang et al, Adv. Mater. 2022, 34,2106379.), 10mL of isopropanol, 2mL of ethylene glycol and 0.7mL of glycerol and pour them into a high-energy ball mill. After ball milling at 400 r / min for 30 min, transfer the slurry to a culture bottle with a dropper to obtain the required cathode slurry. (b) The prepared NiO-BZCYYb dry-pressed solar cell (MZ Liang et al, Adv. Mater.2022, 34, 2106379.) was placed on a heating table and preheated at 150 °C. The prepared cathode slurry was uniformly sprayed onto the electrolyte surface of the dry-pressed cell using a spray gun under the push of inert gas. After the liquid evaporated completely, the sprayed cell was placed in a high-temperature muffle furnace and calcined at 900 °C for 2 h to obtain the required single cell, which was used to test the battery performance in the temperature range of 450~650 °C. Example 3

[0029] This embodiment provides a method for preparing a single cell using an anode-supported r-PSCFR0.15 catalyst and a Ni-BZCYYb anode. The specific steps are as follows: (a) Weigh 1g of r-PSCFR0.15 powder prepared in Example 1, 10ml of isopropanol, 2ml of ethylene glycol and 0.8ml of glycerol and pour them into the culture bottle. Place the culture bottle in a CNC ultrasonic cleaner and sonicate for 30 minutes.

[0030] (b) The single cell prepared in Example 2 was placed anode-up on a heating table and preheated at 150 °C. The prepared slurry was uniformly sprayed onto the anode surface using a spray gun under inert gas propulsion. After the liquid had completely evaporated, the desired anode load r-PSCFR0.15 single cell was finally obtained. This was used for testing battery performance in the temperature range of 450~600 °C.

[0031] NH3 decomposition catalytic activity test Figure 5 The catalytic activity of r-PSCF, r-PSCF0.05, r-PSCFR0.1, r-PSCFR0.15, r-PSCFR0.2 samples and Ni-BZCYYb anode for ammonia was tested at 450 to 650 °C. The NH3 conversion rates of r-PSCFR0.15 at 650, 600, 550, 500, and 450 °C were 99%, 97%, 79%, 41%, and 20%, respectively, significantly higher than other PSCF catalysts with different Ru substitution levels. This indicates that 15 mol% Ru substitution at the B site is the optimal doping content in PSCF. Furthermore, the NH3 conversion rate of the r-PSCFR0.15|Ni-BZCYYb bilayer catalyst (r-PSCFR0.15 bottom layer, Ni-BZCYYb top layer) was investigated to simulate the actual operating conditions of DA-PCFC. The NH3 conversion rate of the r-PSCFR0.15|Ni-BZCYYb bilayer catalyst was significantly higher than that of the Ni-BZCYYb monolayer anode, confirming the promoting effect of the r-PSCFR0.15 catalytic functional layer on the NH3 decomposition activity of the anode, which is beneficial to improving the utilization rate of NH3 fuel.

[0032] Single-cell performance test Figure 6 (a) IP and IV curves of a single cell without a catalytic functional layer using H2 as fuel; (b) IP and IV curves of a single cell without a catalytic functional layer using NH3 as fuel; (c) IP and IV curves of a single cell with an r-PSCFR0.15 catalytic functional layer using H2 as fuel; (d) IP and IV curves of a single cell with an r-PSCFR0.15 catalytic functional layer using NH3 as fuel. When using H2 as fuel, the PCFC containing r-PSCFR0.15 achieves a peak power density (PPD) as high as 1180 mW cm⁻¹ at 650 °C. -2It is far superior to PCFC without a catalytic functional layer (900mW cm⁻¹ at 650℃). -2 When NH3 is used as fuel, the PCFC containing r-PSCFR0.15 has a PPD of 630 mW / cm³ at 650 °C. -2 PCFCs without a catalytic functional layer only have 460 mW / cm² at 650 °C. -2 The power density. Regardless of whether H2 or NH3 is used as fuel, PCFCs with r-PSCFR0.15 exhibit higher power output than PCFCs without a catalytic functional layer.

[0033] Figure 7 These are the electrochemical impedance spectroscopy (EIS) spectra of (a) and (b) PCFCs without a catalytic functional layer and (c) and (d) PCFCs with an r-PSCFR0.15 catalytic functional layer operating in H2 and NH3 fuels. EIS analysis showed that the PCFC with the r-PSCFR0.15 catalytic functional layer exhibited similar ohmic impedance and significantly lower electrode impedance compared to the PCFC without the catalytic functional layer. Considering that both cells used the same cathode, the lower electrode impedance of the PCFC with the r-PSCFR0.15 catalytic functional layer is attributed to the enhanced H2 fuel oxidation activity and NH3 decomposition activity promoted by the r-PSCFR15 functional layer.

[0034] Single-cell stability test Figure 8 The stability of (a) PCFCs without a catalytic functional layer and (b) PCFCs with an r-PSCFR0.15 catalytic functional layer in H2 and NH3. Constant current density (200 mA cm⁻¹) in NH3 fuel. -2 During operation, the operating voltage of the PCFC containing the r-PSCFR0.15 catalytic functional layer gradually increased within the range of 0-290 hours. This phenomenon is attributed to the slow exsolution of the CoFeRu alloy from the r-PSCFR0.15, leading to a gradual enhancement of NH3 catalytic activity. After 290 hours, the operating voltage of the cell slowly decreased, which may be attributed to the gradual sintering and aggregation of the CoFeRu alloy catalyst in the catalytic functional layer and the Ni catalyst at the anode. The average decay rate of the cell in NH3 fuel was 0.0002 V h. -1 However, for PCFCs without a catalytic functional layer, the operating voltage of the battery decreases significantly and rapidly under the same current density and fuel conditions, with an average decay rate of 0.0011 Vh. -1 This rapid decay is likely due to the direct contact between the anode and the high concentration of NH3 in the absence of a catalytic functional layer, leading to rapid sintering and aggregation of the Ni catalyst.

[0035] Figure 9These are SEM images of single-cell stability tests after (a) the presence of the r-PSCFR0.15 catalytic functional layer and (b) the presence of the r-PSCFR0.15 catalytic functional layer. After NH3 treatment, the size of Ni particles on the anode with the r-PSCFR0.15 catalytic functional layer is significantly smaller than that on the anode without the catalytic functional layer. This means that the addition of the r-PSCFR0.15 catalytic functional layer effectively prevents direct contact between high-concentration NH3 and the Ni-BZCYYb anode, greatly inhibiting the sintering and aggregation of the Ni catalyst. This is also the reason why the PCFC containing the catalytic layer exhibits excellent stability during NH3 fuel operation.

[0036] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of the claims of this invention and their equivalents, this invention also intends to include these modifications and variations.

Claims

1. A functional layer material for the anode of a direct ammonia proton fuel cell, obtained by treating a precursor in an H2-Ar atmosphere at 750-850°C for 8-12 hours, wherein the precursor has the general chemical formula ABO. 3-δ In the formula, δ represents the oxygen vacancy content, characterized by: The precursor has the molecular formula Pr 0.6 Sr 0.4 (Co 0.2 Fe 0.8 ) 1-x Ru x O 3-δ In the formula, x is 0.15, which is synthesized through the following steps: (a) Press Pr 0.6 Sr 0.4 (Co 0.2 Fe 0.8 ) 1-x Ru x O 3-δ Weigh out the corresponding masses of Pr(NO3)3•6H2O, Sr(NO3)2, Co(NO3)2•6H2O, Fe(NO3)3•9H2O and RuCl3•aH2O according to the stoichiometric ratio, add deionized water and stir to dissolve to obtain a mixed solution; add a complexing agent, then add ammonia dropwise until the pH of the solution is 7-8, and allow the water to evaporate under heating and stirring to obtain a gel-like substance; dry the gel-like substance; (b) The product of step (a) is calcined in air to obtain the precursor.

2. A method for preparing an anode functional layer material for a direct ammonia proton fuel cell, characterized in that, Includes the following steps: (a) Press Pr 0.6 Sr 0.4 (Co 0.2 Fe 0.8 ) 1-x Ru x O 3-δ Weigh out the corresponding masses of Pr(NO3)3•6H2O, Sr(NO3)2, Co(NO3)2•6H2O, Fe(NO3)3•9H2O and RuCl3•aH2O according to the stoichiometric ratio, add deionized water and stir to dissolve to obtain a mixed solution; add a complexing agent, then add ammonia dropwise until the pH of the solution is 7-8, and allow the water to evaporate under heating and stirring to obtain a gel-like substance; dry the gel-like substance; (b) The product of step (a) is calcined in air to obtain the precursor; (c) The precursor is treated in an H2-Ar atmosphere at a temperature of 750-850°C for 8-12 hours.

3. The method for preparing the anode functional layer material of a direct ammonia proton fuel cell according to claim 2, characterized in that: In step (a), the complexing agent is a mixture of ethylenediaminetetraacetic acid and citric acid monohydrate in a molar ratio of 1:

2.

4. The method for preparing the anode functional layer material of a direct ammonia proton fuel cell according to claim 2, characterized in that: In step (a), the molar ratio of total metal ions, ethylenediaminetetraacetic acid, citric acid monohydrate and solute in alkaline solution is 1:0.5-2.5:1-3:3-20.

5. The method for preparing the anode functional layer material of a direct ammonia proton fuel cell according to claim 2, characterized in that: In step (a), the drying conditions are 140-180℃ and baking for 5-10 hours.

6. The method for preparing the anode functional layer material of a direct ammonia proton fuel cell according to claim 2, characterized in that: In step (b), the calcination is carried out at a temperature of 900~1100℃ for 5~12h with a heating rate of 2~5℃ / min.

7. The application of the anode functional layer material of the direct ammonia proton fuel cell according to claim 1, characterized in that: It is used in the anodic catalytic functional layer of PCFC.

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