An anode material for an ammonia fuel proton conductor solid oxide fuel cell

Abstract

This invention discloses an anode material for ammonia-fueled proton conductor solid oxide fuel cells. The chemical formula of the anode material is xCo / 100-xBZY+Ni-BZCYYb, where x represents the percentage content of Co, with the total molar amount of metal elements in Co / BZY being 100%, and 10≤x≤30. To address the problems of poor low-temperature ammonia decomposition activity in PCFCs under operating conditions, and the potential for Ni phase nitriding, morphological corrosion / porosity, and nickel phase agglomeration and coarsening after exposure to high concentrations of ammonia, leading to rapid performance degradation, a highly active Co / BZY catalyst layer is loaded onto the Ni-BZCYYb anode, significantly improving its activity and durability. This method is characterized by its simple process, low cost, and ease of operation. This invention has theoretical and practical significance for promoting the development of stable and durable anode materials for NH3-PCFCs.

Description

Technical Field

[0001] This invention belongs to the field of high-temperature fuel cell technology, specifically relating to an anode material for an ammonia fuel proton conductor solid oxide fuel cell. Background Technology

[0002] Solid oxide fuel cells (SOCs) are a promising technology capable of efficiently generating electricity from a variety of fuels, potentially alleviating the growing global energy demand. They are characterized by high energy conversion efficiency, low emissions, and good fuel flexibility. Hydrogen is an excellent carbon-free energy carrier and is considered the preferred fuel for fuel cells, but its storage and long-distance transportation remain significant challenges. Therefore, further research is needed to find alternative, sustainable, and clean fuels. Ammonia possesses unique physicochemical properties, such as a high hydrogen content (17.7 wt.%) and high energy density (4 kWh / kg⁻¹). -1 It does not cause carbon emissions, is low-cost, easily liquefiable under mild conditions (liquefiable at room temperature and moderate pressure), and is easy to transport and store, and has been considered one of the most promising hydrogen carriers for proton conductor oxide fuel cells (PCFCs).

[0003] The ammonia decomposition reaction is an endothermic process, and complete ammonia conversion can be achieved at 500℃. Therefore, compared to traditional oxygen-ion-based SOFCs (O-SOFCs), proton ceramic fuel cells (PCFCs) with relatively lower operating temperatures of 500-700℃, using ammonia directly as fuel, have greater application prospects. Firstly, water vapor is generated at the cathode in the PCFC, achieving high fuel utilization. Secondly, since there is no oxygen ion transport in the anode or electrolyte, potential NO emissions are avoided. x The formation of NH3. When ammonia is used as fuel to supply a PCFC, the conversion process of ammonia at the anode includes a thermocatalytic process and an electrocatalytic process, which can be described by the following steps: First, NH3 is adsorbed onto the anode surface. Under the catalysis of nickel, the adsorbed NH3 is thermally decomposed into H2 and N2. Then, H2 is converted into protons, and the protons are electrochemically oxidized to H2O.

[0004] However, traditional nickel-ceramic anodes exhibit poor catalytic activity for ammonia decomposition, and at high NH3 concentrations, nickel metal is prone to coarsening, leading to anode surface structure degradation and a rapid decline in battery performance. On the other hand, the poor proton conductivity of the electrolyte at lower temperatures results in high ohmic resistance in PCFCs, leading to poor battery output power. Furthermore, the inefficient charge transfer rate at the electrode-electrolyte interface is a significant challenge in developing efficient and durable ammonia-based proton-conducting solid oxide fuels. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the purpose of this invention is to provide a highly efficient and durable anode material for ammonia-fueled proton conductor solid oxide fuel cells; this invention develops a high-performance and excellent-durability PCFC using NH3 as fuel, which has the advantages of convenient and simple manufacturing and low cost. This is achieved through Ni-BaZr... 0.1 Ce 0.7 Y 0.1 Yb 0.1 Co-BZY (Co / BaZr) is added to the surface of the O3(Ni-BZCYYb) anode. 0.8 Y 0.2 O 3-δ The catalyst formed xCo / 100-xBZY (x = 10, 20, and 30) + Ni-BaZr, exhibiting high activity and excellent durability. 0.1 Ce 0.7 Y 0.1 Yb 0.1 O3 anode. Under typical PCFC operating conditions, it has xCo / 100-xBZY (x = 10, 20, and 30) + Ni-BaZr. 0.1 Ce 0.7 Y 0.1 Yb 0.1 The O3 anode battery, when using ammonia as fuel, achieves high power output and excellent durability.

[0006] The purpose of the present invention is achieved through the following technical solutions:

[0007] The first aspect of the present invention provides:

[0008] A solid oxide fuel cell anode material for ammonia fuel proton conductors, with the chemical formula:

[0009] xCo / 100-xBZY+Ni-BZCYYb, where x is the percentage content of Co, with the total molar amount of metal elements in Co / BZY being 100%, and 10≤x≤30.

[0010] In one implementation, x = 10, 20, or 30.

[0011] In one embodiment, the Co particles in the Co / BZY have a particle size of 10-80 nm.

[0012] In one embodiment, the thickness of the Co / BZY is 10-20 μm.

[0013] In one embodiment, Ni-BZCYYb consists of a functional layer and a support layer, the thickness of the functional layer being 10-30 μm and the thickness of the support layer being 700-900 μm; xCo / 100-xBZY is on the surface of the Ni-BZCYYb support layer.

[0014] In one embodiment, the Ni-BZCYYb anode comprises two layers: an anode functional layer (thickness ~20 μm) and an anode support layer (thickness ~800 μm). The anode functional layer has finer pores and a larger surface area, providing more three-phase boundaries for electrochemical reactions. The anode support layer has larger pores and continuous channels, providing a convenient path for gas transport.

[0015] In one embodiment, xCo / 100-xBZY is obtained by reducing xCo3O4 / 100-xBZY;

[0016] In one embodiment, the Ni-BZCYYb functional layer is obtained by reducing the NiO-BZCYYb functional layer; the mass ratio of BZCYYb to NiO in the NiO-BZCYYb functional layer is (1-3):(2-5);

[0017] In one embodiment, the Ni-BZCYYb support layer is obtained by reducing the NiO-BZCYYb support layer; the mass ratio of BZCYYb to NiO in the NiO-BZCYYb support layer is (10-20):(20-30);

[0018] In one embodiment, xCo3O4 / 100-xBZY is added to the surface of NiO-BZCYYb by screen printing.

[0019] In one embodiment, the preparation method of xCo3O4 / 100-xBZY is as follows:

[0020] Ba(NO3)2, Zr(NO3)4, Y(NO3)3 and Co(NO3)2·6H2O were added to a nitric acid aqueous solution according to the stoichiometric ratio, followed by the addition of citric acid. Then, ammonia was added to adjust the pH of the solution to 7-8. After stirring and mixing evenly, the solution was heated to dryness to obtain the precursor. Finally, the precursor was calcined at 1100-1200℃ for 6-8 hours to obtain xCo3O4 / 100-xBZY.

[0021] In one embodiment, the molar ratio of the total amount of metal ions to citric acid is 1:(2-3).

[0022] In one embodiment, the preparation of the Co / BZY catalyst includes the following steps:

[0023] Co3O4 / BaZr with different ratios was synthesized using the citrate method. 0.8 Y 0.2 O 3-δ(Co / BZY) catalyst powder. First, a certain amount of dilute nitric acid (about 10 ml) was added to about 200 ml of deionized water. Then, Ba(NO3)2, Zr(NO3)4, Y(NO3)3, and Co(NO3)2·6H2O were added sequentially to the nitric acid water (concentration about 3 wt%) according to the stoichiometric ratio of 0.01 mol Co / BZY. A certain amount of citric acid (CA) was added (the molar ratio of metal ions to CA was 1:2). Then, an appropriate amount of ammonia was added to adjust the pH of the solution to 7-8. After the solution was heated and stirred until fully mixed (about 6 hours), the solution was poured into a ceramic evaporating dish and heated further until it completely transformed into a gel. The gel was then further heated to obtain an ash-like precursor. Finally, Co3O4 / BaZr... 0.8 Y 0.2 O 3-δ Co3O4 / BaZr can be obtained by calcining the precursor powder at 1100℃ for 6 hours. 0.8 Y 0.2 O 3-δ Powder. Then synthesize powders with a ratio of 10Co3O4 / 90BaZr. 0.8 Y 0.2 O 3-δ 20Co3O4 / 80BaZr 0.8 Y 0.2 O 3-δ and 30Co3O4 / 70BaZr 0.8 Y 0.2 O 3-δ Catalyst powders of different proportions were obtained by reducing Co3O4 / BZY catalyst powders in H2 at 700℃ for 2 hours. Catalyst powders of different proportions (x = 10, 20 and 30) were obtained.

[0024] A second aspect of the invention provides:

[0025] An ammonia-fueled proton conductor solid oxide fuel cell includes a proton conductor electrolyte and an anode and a cathode located on both sides of the proton conductor electrolyte, wherein the anode is the aforementioned ammonia-fueled proton conductor solid oxide fuel cell anode material.

[0026] In one embodiment, the proton conductor electrolyte is BZCYYb, and the thickness of the proton conductor electrolyte is 5-10 μm; the cathode is PBSCF, and the thickness of the cathode is 10-20 μm.

[0027] In one embodiment, the fuel cell is xCo / 100-xBZY (x = 10, 20, and 30).

[0028] +Ni-BZCYYb|BZCYYb|PBSCF.

[0029] In one embodiment, the fuel cell refers to a proton conductor oxide fuel cell that uses ammonia as fuel.

[0030] In one embodiment, the anode material 20Co / 80BZY+Ni-BZCYYb is used to improve the anode's ammonia decomposition activity and long-term stability.

[0031] In one implementation, the configuration is xCo / 100-xBZY (x = 10, 20, and 30).

[0032] A proton conductor solid oxide fuel cell with structure including proton conductor electrolyte BZCYYb, and xCo / 100-xBZY (x = 10, 20 and 30)+Ni-BZCYYb anode and PBSCF cathode located on both sides of the proton conductor electrolyte.

[0033] In one embodiment, the xCo / 100-xBZY (x = 10, 20, and 30) + Ni-BZCYYb anode refers to Ni-BaZr with a Co-BZY catalyst layer attached. 0.1 Ce 0.7 Y 0.1 Yb 0.1 O3(Ni-BZCYYb) anode.

[0034] In one embodiment, the proton conductor electrolyte is made of BZCYYb, with the chemical formula BaZr. 0.1 Ce 0.7 Y 0.1 Yb 0.1 O3.

[0035] In one embodiment, the proton conductor cathode is a PBSCF cathode, wherein the chemical formula of PBSCF is PrBa. 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5+δ , where δ represents the oxygen vacancy content.

[0036] A third aspect of the invention provides:

[0037] The above-described method for preparing a proton conductor solid oxide fuel cell with xCo / 100-xBZY (x = 10, 20, and 30) + Ni-BZCYYb|BZCYYb|PBSCF anode support involves first preparing a NiO-BZCYYb anode-supported half-cell (including a BZCYYb electrolyte layer, a NiO-BZCYYb anode support layer, and a NiO-BZCYYb anode functional layer) through co-casting and co-sintering. Then, a PBSCF cathode slurry is screen-printed onto the electrolyte surface of the half-cell, followed by calcination at 950°C for 2 hours in a high-temperature muffle furnace to obtain the desired NiO-BZCYYb|BZCYYb|PBSC single cell. Then, xCo3O4 / 100-xBZY (x = 10, 20 and 30) catalyst layers were added to the surface of NiO-BZCYYb anode by screen printing to obtain xCo3O4 / 100-xBZY (x = 10, 20 and 30) + NiO-BZCYYb|BZCYYb|PBSCF single cells. After reduction treatment, xCo / 100-xBZY (x = 10, 20 and 30) + Ni-BZCYYb|BZCYYb|PBSCF single cells were obtained.

[0038] In one embodiment, the co-casting and co-sintering method for the NiO-BZCYYb anode-supported half-cell is as follows: First, the electrolyte slurry, anode functional layer slurry, and anode support slurry are sequentially cast onto a polymer film, and then dried in air for 12 hours. After drying, the film is hammered into approximately 100 small pieces using a 15cm diameter mold. These pieces are then placed in a high-temperature muffle furnace and calcined at 600°C for 2 hours (this process is called degreasing). During degreasing, a slow heating rate is used to remove organic components from the pieces. Finally, the degreased pieces are placed in a high-temperature muffle furnace and calcined at 1450°C for 5 hours to obtain the desired Ni-BZCYYb anode-supported half-cell.

[0039] In one embodiment, the PBSCF cathode slurry is prepared as follows: 1g of PBSCF cathode powder, 0.004g of PVb, and 0.076g of terpineol are weighed and ground in a mortar for 1-3 hours to obtain the desired cathode slurry.

[0040] In one embodiment, the effective area of ​​the PBSCF cathode screen printing is 0.2826 cm². 2 .

[0041] A fourth aspect of the present invention provides:

[0042] The above-mentioned method for preparing PBSCF cathode powder is based on the sol-gel method.

[0043] In one embodiment, the sol-gel method includes the following steps:

[0044] Pr(NO3) was added in sequence according to stoichiometry. 3, Ba(NO3)2, Sr(NO3)2, Co(NO3)2·6H2O, and Fe(NO3)3·9H2O were dissolved in deionized water and heated and stirred until homogeneous. Glycine and citric acid monohydrate were added, and the water was evaporated under heating and stirring to obtain a gel-like substance. The gel-like substance was placed in an oven to dry, and the cathode material precursor was obtained. The precursor was then placed in a muffle furnace for calcination to obtain the desired battery cathode material.

[0045] In one embodiment, the total molar ratio of glycine and citric acid to Pr, Ba, Sr, Co, Co, and Fe is 0.75:0.75:1.

[0046] In one embodiment, the drying process is performed at 250°C for 2 hours.

[0047] In one embodiment, the calcination parameters are calcination at 900°C for 2 hours.

[0048] A fifth aspect of the present invention provides:

[0049] The above-mentioned method for preparing BZCYYb powder is a solid-phase method.

[0050] In one embodiment, the solid-state method includes the following steps: high-purity barium carbonate, zirconium oxide, cerium oxide, ytterbium oxide, and yttrium oxide powders are dissolved together in ethanol at a stoichiometric ratio and ball-milled for 24 hours to achieve uniform mixing. The mixed solution is then dried in an oven to obtain a dry powder. The dry powder is then pressed into tablets and calcined in a muffle furnace at 1100°C for 12 hours. The calcined powder is then added to ethanol and ball-milled again at high energy for 4 hours. After drying, the powder is pressed into tablets and then calcined again in a muffle furnace at 1100°C for 12 hours to obtain a pure perovskite phase. The obtained powder is then ball-milled in ethanol at high energy for 4 hours to obtain the desired BZCYYb powder.

[0051] In one implementation, the tablet is compressed at a pressure of 10 MPa.

[0052] A sixth aspect of the present invention provides:

[0053] The above configuration is a current collection method for a proton conductor fuel cell with configurations of xCo / 100-xBZY (x = 10, 20 and 30) + Ni-BZCYYb|BZCYYb|PBSCF.

[0054] In one embodiment, the current collection method of the proton conductor fuel cell is as follows: current collection is performed by connecting the electrode surface to silver wires using silver paste (DAD-87, purchased from Shanghai Synthetic Resin Research Institute).

[0055] The present invention has the following beneficial effects:

[0056] The anode of this invention is formed by adding Co-BZY catalysts with different Co contents to the surface of the Ni-BZCYYb anode, thus forming Co-modified xCo / 100-xBZY (x = 10, 20, and 30) + Ni-BaZr. 0.1 Ce 0.7 Y 0.1 Yb 0.1 O3(Co / BZY+Ni-BZCYYb) anode.

[0057] The proton conductor solid oxide fuel cell configured as 20Co / 80BZY+Ni-BZCYYb|BZCYYb|PBSCF of this invention exhibits excellent electrochemical performance when ammonia is used as the fuel gas, with peak power densities of 1.609 W / cm³ at 700℃, 650℃, 600℃, and 550℃. -2 1.387W cm -2 0.974W cm -2 , and 0.626W cm -2 At a temperature of 550℃ and a current of 200mA cm -2 At a constant current density, 20Co / 80BZY+Ni fueled by ammonia

[0058] The -BZCYYb|BZCYYb|PBSCF battery exhibited excellent stability, with a degradation rate of only 0.047 V h per hour during 100 hours of long-term operation. -1 .

[0059] The 20Co / 80BZY+Ni-BZCYYb|BZCYYb|PBSCF proton conductor solid oxide fuel cell of the present invention also exhibits excellent electrochemical performance when hydrogen is used as the fuel gas. Attached Figure Description

[0060] Figure 1 This is a SEM image of the reduced 20Co / 80BZY catalyst according to the present invention;

[0061] Figure 2 SEM images (a) of the 20Co / 80BZY+Ni-BZCYYb anode of the present invention; SEM image (b) of the anode functional layer; and SEM images (c and d) of the anode support layer.

[0062] Figure 3 The images show: (a) TEM image of the 20Co / 80BZY catalyst of the present invention; (b) HRTEM image of the BZY phase in the 20Co / 80BZY catalyst; (c) HRTEM image of the Co phase in the 20Co / 80BZY catalyst; (d) FFT image of the HRTEM image of the BZY phase in the 20Co / 80BZY catalyst; and (e) FFT image of the HRTEM image of the Co phase in the 20Co / 80BZY catalyst.

[0063] Figure 4 The XRD comparison images are of Co3O4-BZY after reduction, and 20Co3O4 / 80BZY and NiO-BZCYYb powders after uniform reduction by mixing them in a 1:1 ratio according to the present invention.

[0064] Figure 5 The graphs showing the polarization resistance and ohmic resistance of the proton conductor solid oxide fuel cell configured with Ni-BZCYYb|BZCYYb|PBSCF and xCo / 100-xBZY (x = 10, 20 and 30) + Ni-BZCYYb|BZCYYb|PBSCF as a function of temperature when generating electricity with ammonia as the fuel gas, are shown in the present invention.

[0065] Figure 6 The diagram shows the IVP curves of the proton conductor solid oxide fuel cell configured as Ni-BZCYYb|BZCYYb|PBSCF, which is involved in this invention, when generating electricity using ammonia and hydrogen as fuel gases in the range of 550 to 700°C.

[0066] Figure 7 Impedance diagrams of the proton conductor solid oxide fuel cell configured as Ni-BZCYYb|BZCYYb|PBSCF, which is involved in this invention, were tested in the range of 550 to 700°C when generating electricity using ammonia and hydrogen as fuel gases.

[0067] Figure 8 The diagram shows the IVP curves of the proton conductor solid oxide fuel cell configured as 20Co / 80BZY+Ni-BZCYYb|BZCYYb|PBSCF, which is involved in this invention, when generating electricity using ammonia and hydrogen as fuel gases in the range of 550 to 700°C.

[0068] Figure 9 Impedance diagrams of the proton conductor solid oxide fuel cell configured as 20Co / 80BZY+Ni-BZCYYb|BZCYYb|PBSCF, which is involved in this invention, were tested in the range of 550 to 700°C when generating electricity using ammonia and hydrogen as fuel gases.

[0069] Figure 10The configuration involved in this invention is Ni-BZCYYb|BZCYYb|PBSCF and 20Co / 80BZY+Ni

[0070] The stability diagram of a single cell of a proton conductor solid oxide fuel cell (BZCYYb|BZCYYb|PBSCF) tested at 550°C when generating electricity using ammonia as fuel gas. Detailed Implementation

[0071] The present invention will be further described in detail below with reference to the embodiments and accompanying drawings, but the implementation of the present invention is not limited thereto.

[0072] The anode materials and proton conductor solid oxide fuel cells involved in this invention include, but are not limited to, the materials in the following embodiments, and the optimization methods and preparation methods involved include, but are not limited to, the methods in the following embodiments. Any modifications or equivalent substitutions to the technical solutions of this invention that do not depart from the spirit and scope of the invention should be covered within the protection scope of this invention.

[0073] Example 1

[0074] This embodiment provides a method for preparing xCo3O4 / 100-xBZY (x = 10, 20, and 30) as a precursor material for the anode catalyst layer of a proton conductor fuel cell. The specific steps are as follows:

[0075] (1) Weigh Ba(NO3)2, Zr(NO3)4, Y(NO3)3 and Co(NO3)2·6H2O according to the stoichiometric ratio of Co3O4 / BZY and add them sequentially to a nitric acid aqueous solution (concentration of about 3wt%). The total concentration of metal ions is 0.05M.

[0076] (2) Add a certain amount of citric acid (CA) (the molar ratio of metal ions to CA is 1:2).

[0077] (3) Add an appropriate amount of ammonia water to adjust the pH of the solution to 7-8.

[0078] (4) After the solution is thoroughly heated and mixed evenly at 180°C using a magnetic stirrer (approximately 6 hours), the solution is poured into a ceramic evaporating dish and heated at 250°C until it completely transforms into a gel. The gel is then heated further to obtain a gray precursor. Finally, the gray precursor powder is calcined at 1100°C for 6 hours to obtain the precursor material Co3O4 / BaZr. 0.8 Y 0.2 O 3-δ .

[0079] Example 2

[0080] This embodiment provides a method for preparing a proton conductor solid oxide fuel cell, namely xCo3O4 / 100-xBZY (x = 10, 20 and 30) + Ni-BZCYYb|BZCYYb|PBSCF. The specific steps are as follows:

[0081] (1) Preparation of BZCYYb(BaZr) 0.1 Ce 0.7 Y 0.1 Yb 0.1 O3) powder, processed using a solid-state method, as follows:

[0082] High-purity barium carbonate, zirconium oxide, cerium oxide, ytterbium oxide, and yttrium oxide powders were dissolved together in ethanol at stoichiometric ratios and ball-milled for 24 hours to obtain a homogeneous mixture. The solution was then dried in an oven at 70°C to obtain a dry powder. The dry powder was then pressed into tablets at 10 MPa and calcined in a muffle furnace at 1100°C for 12 hours. The calcined powder was then added to ethanol and ball-milled again at high energy for 4 hours. After drying, it was pressed into small discs using a die with a diameter of approximately 13 mm. The discs were then calcined in a muffle furnace at 1100°C for 12 hours to obtain a pure perovskite phase. The resulting powder was then ball-milled in ethanol at high energy for 4 hours to obtain the desired BZCYYb powder.

[0083] (2) Preparation of PBSCF (PrBa 0.5 Sr 0.5 Co 1.5 Fe 0.5 O 5+δ The cathode powder was prepared using the sol-gel method, as follows:

[0084] Pr(NO3)3, Ba(NO3)2, Sr(NO3)2, Co(NO3)2·6H2O, and Fe(NO3)3·9H2O were dissolved in deionized water according to stoichiometric ratio and heated and stirred until homogeneous. Glycine and citric acid monohydrate (the total molar ratio of glycine and citric acid to Pr, Ba, Sr, Co, Co, and Fe was 0.75:0.75:1) were added, and the water was evaporated under heating and stirring to obtain a gel-like substance. The gel-like substance was dried in an oven (treated at 250℃ for 2 hours) to obtain the cathode material precursor. The precursor was then calcined in a muffle furnace (calcined at 900℃ for 2 hours) to obtain the desired battery cathode PBSCF material.

[0085] (3) First, NiO-BZCYYb anode-supported half-cells (including BZCYYb electrolyte layer, NiO-BZCYYb anode support layer and NiO-BZCYYb anode functional layer) are prepared by co-casting and co-sintering, as follows:

[0086] Electrolyte BZCYYb slurry (5g BZCYYb mixed with 3g ethanol, 0.5g plasticizer and 1g PVB binder), anode functional layer slurry (2g BZCYYb, 3g NiO mixed with 3g ethanol, 0.5g plasticizer and 1g PVB binder), and anode support slurry (15g BZCYYb, 25g NiO mixed with 12g ethanol, 2.5g plasticizer and 5g PVB binder) were sequentially cast onto polymer films with thicknesses of approximately 8μm, 20μm, and 800μm, respectively. The films were then air-dried for 12 hours. After drying, approximately 100 small pieces were formed using a 15cm diameter mold. These pieces were then calcined in a high-temperature muffle furnace at 600℃ for 2 hours (this process is called degreasing). During degreasing, a slow heating rate (2℃ / h) was used to remove organic components from the pieces. Finally, the degreased sheet was placed in a high-temperature muffle furnace and calcined at 1450°C for 5 hours to obtain the desired NiO-BZCYYb anode-supported half-cell.

[0087] (4) The preparation method of PBSCF cathode paste is as follows: Weigh 1g of PBSCF cathode powder, 0.004g of PVb and 0.076g of terpineol and grind them in a mortar for 1-3 hours to obtain the required cathode paste.

[0088] The PBSCF cathode paste was screen-printed onto the electrolyte surface of the half-cell (effective area 0.2826 cm²). 2 The material (approximately 10 μm thick) was then placed in a high-temperature muffle furnace and calcined at 950 °C for 2 h to obtain the desired NiO-BZCYYb|BZCYYb|PBSCF single cell.

[0089] (5) Then, the xCo3O4 / 100-xBZY (x = 10, 20, and 30) catalyst precursor material was added to the NiO-BZCYYb anode surface of the above single cell (thickness approximately 10 μm) by screen printing. Specifically, 1 g of xCo3O4 / 100-xBZY (x = 10, 20, and 30) catalyst precursor material powder, 0.004 g of PVb, and 0.076 g of terpineol were weighed and ground in a mortar for 1-3 hours to obtain the desired catalyst slurry; thus, xCo3O4 / 100-xBZY (x = 10, 20, and 30) was obtained.

[0090] +NiO-BZCYYb|BZCYYb|PBSCF single cell.

[0091] Example 3

[0092] This embodiment provides a method for testing the electrochemical performance of a proton conductor solid oxide fuel cell, specifically including the following steps: xCo3O4 / 100-xBZY (x = 10, 20, and 30) + NiO-BZCYYb|BZCYYb|PBSCF

[0093] (1) Before the electrochemical test, the electrode surface was connected to the silver mesh section using silver paste (DAD-87, purchased from Shanghai Synthetic Resin Research Institute) for current collection.

[0094] (2) The battery is sealed with a ceramic sealant.

[0095] (3) Heat the single cell to 700°C in air.

[0096] (4) Purge the tube with nitrogen gas for 5 minutes (flow rate of 20 ml / min) to purge the air from the tube.

[0097] (5) After the air inside the tube is purged, nitrogen is cut into humidified H2 (~3% H2O) (flow rate of 30ml / min) for reducing the anode, while the cathode is exposed to ambient air.

[0098] (6) After introducing H2 into the anode for about 20 minutes (flow rate of 20 ml / min), a stable OCV can be observed in the battery.

[0099] (7) Then the hydrogen gas at the anode was cut into NH3 (flow rate of 20 ml / min), and the open circuit voltage (OCV), current-voltage (IV) and impedance spectrum characteristics of the battery under ammonia atmosphere were tested using an electrochemical workstation (AMETEKPARSTAT MC). The test temperature was 550℃ to 700℃.

[0100] Characterization results

[0101] 1. Electron microscopy characterization

[0102] Figure 1 The image shows the powder morphology of the synthesized 20Co3O4 / 80BZY catalyst after reduction in H2. It can be seen that the Co phase with particle shape is distributed in the gaps of the BZY phase.

[0103] Electron microscopy images of the Ni-BZCYYb anode layers of the 20Co / 80BZY+Ni-BZCYYb|BZCYYb|PBSCF proton conductor solid oxide fuel cell obtained after reduction are presented in the following figures. Figure 2 It can be seen that the anode of the PCFC, Ni-BZCYYb, is composed of two layers. Figure 2a) in the diagram: Anode functional layer (AFL, ~20 μm) and anode support layer (ASL, ~800 μm). The anode functional layer has finer pores and a larger surface area (mainly due to NiO reduction), providing more three-phase boundaries for electrochemical reactions, such as... Figure 2 In contrast, the anode support layer has larger porosity and continuous channels (mainly due to the removal of pore formations), providing a convenient path for gas transport, such as... Figure 2 c and Figure 2 d in the text.

[0104] Figure 3 Transmission electron microscopy (TEM) images and energy dispersive spectroscopy (EDS) elemental spectra of the 20Co / 80BZY catalyst obtained after reduction were obtained to analyze the elemental distribution and composition of the catalyst. Figure 3 a and high-resolution TEM ( Figure 3 Results b) indicate that the catalyst consists of two phases: a Co phase and a BZY phase. Ba, Zr, Y, and O elements are uniformly distributed within the BZY phase. Co phase particles with a size of approximately 10-80 nm are distributed in the interstices of the BZY phase. Figure 3 As shown in b and d, the interplanar spacing is approximately 0.297 nm, corresponding to the (110) plane of BZY (PDF#70-3667). Figure 3 As shown in c and e, the interplanar spacing is approximately 0.192 nm, corresponding to the (101) plane of Co (PDF#89-4307). This indicates that the 20Co / 80BZY catalyst after hydrogen treatment consists of two phases: Co and BZY.

[0105] 2. XRD characterization

[0106] Figure 4 XRD patterns of 1:1 mixtures of xCo / 100-xBZY (x = 10, 20, and 30) and 20Co / 80BZY+Ni-BZCYYb anodes after reduction are shown. The results indicate that the catalyst consists of two phases, Co and BZY. Figure 4 As shown in Figure a, the peaks at 31.4° and 65.4° are characteristic peaks of Co (PDF#73-1701), and the Co peak intensity increases with increasing Co content. After reducing the synthesized xCo3O4 / 1-xBZY (x=10, 20, and 30) catalyst powders in different proportions in H2 at 700℃ for 2 h, the Co3O4 phase was reduced to the Co phase. After uniformly mixing 20Co3O4 / 80BZY and NiO-BZCYYb powders in a 1:1 ratio and reducing them in H2 at 700℃ for 2 h, the XRD pattern is shown in Figure a. Figure 4As shown in lines a and b (red lines), characteristic peaks of Ni, BaZrO3, and Co were detected, indicating that under the test conditions, the catalyst layer material and the anode did not undergo phase reaction and had good chemical compatibility.

[0107] 3. Output power characterization

[0108] Figure 5 Electrochemical impedance spectroscopy (EIS) of a symmetrical anode battery system. xCo3O4 / 100-xBZY (x = 10, 20, and 30) powder was mechanically mixed with organic additives (α-terpineol and ethyl cellulose) and ground into a Co3O4 / BZY catalyst slurry using a mortar and pestle. The slurry was then applied to both sides of the BZCYYb electrolyte sheet (anode active area 0.2826 cm²). 2 First, apply NiO-BZCYYb slurry (preparation method as above), then screen print Co3O4 / BZY catalyst layer slurry onto both sides of the BZCYYb electrolyte sheet (anode active area is 0.2826 cm²). 2 The symmetrical cell was then reduced in a test furnace at 700°C for 2 hours under a hydrogen atmosphere to form a porous anode catalyst layer. The atmosphere was then switched to ammonia for AC impedance testing.

[0109] For the blank Ni-BZCYYb anode, at 550, 600, 650 and 700 °C, its R p The values ​​were 51.55, 17.87, 5.67, and 2.28 Ωcm, respectively. 2 (See Figure 5 (a) The performance is significantly higher than that of Ni / BZCYYb anodes with added xCo / 100-xBZY (x = 10, 20, and 30) catalyst layers (see a). Figure 5 (b, c, and d in the original text). With the increase of Co content in the xCo / 100-xBZY ratio (x = 10, 20, and 30), the symmetric cell R... p First decrease, then increase; anodes with added 20Co / 80BZY catalyst layer at 550, 600, 650, and 700 °C, R p The values ​​were 3.82, 1.82, 1.01, and 0.65 Ωcm, respectively. 2 Its R p The values ​​were smaller than those of the blank anode at every temperature, indicating that the addition of the 20Co / 80BZY catalyst layer can accelerate the electrochemical reaction of the anode and improve the electrochemical performance of the Ni / BZCYYb anode under NH3 conditions.

[0110] Figure 6 It is Ni-BZCYYb(BaZr) 0.1 Ce 0.7 Y 0.1 Yb 0.1A single cell (Ni-BZCYYb|BZCYYb|PBSCF) prepared using O3 as the anode was subjected to IVP testing in the temperature range of 550–700 °C. The test results show that the maximum output power of Ni-BZCYYb|BZCYYb|PBSCF, using ammonia as fuel, reached 0.493, 0.773, 1.095, and 1.452 Wcm at 550, 600, 650, and 700 °C, respectively. -2 At 700℃, using hydrogen as fuel, the maximum output power reaches 1.80 W / cm². -2 .

[0111] Figure 7 To adopt Ni-BZCYYb(BaZr) 0.1 Ce 0.7 Y 0.1 Yb 0.1 Electrochemical impedance spectroscopy of a single cell (Ni-BZCYYb|BZCYYb|PBSCF) with O3 as the anode. Polarization resistance (R) is also shown when NH3 is used as fuel. p The values ​​at 700, 650, 600, and 550℃ are 0.065, 0.119, 0.277, and 0.618 Ωcm, respectively. 2 At 700°C, using hydrogen as fuel, R p It is 0.81Ωcm 2 .

[0112] Figure 8 It is 20Co / 80BZY+Ni-BZCYYb(BaZr) 0.1 Ce 0.7 Y 0.1 Yb 0.1 A single cell (20Co / 80BZY+Ni-BZCYYb|BZCYYb|PBSCF) prepared using O3 as the anode underwent IVP testing within the temperature range of 550–700 °C. The test results show that the maximum output power of 20Co / 80BZY+Ni-BZCYYb|BZCYYb|PBSCF at 550, 600, 650, and 700 °C, using ammonia as fuel, reached 0.626, 0.974, 1.387, and 1.609 Wcm⁻¹, respectively. -2 At 700℃, using hydrogen as fuel, the maximum output power reaches 2.147 W / cm². -2 .

[0113] Figure 9 For 20Co / 80BZY+Ni-BZCYYb(BaZr) 0.1 Ce 0.7 Y 0.1 Yb 0.1Electrochemical impedance spectroscopy (EIS) of a single cell (20Co / 80BZY+Ni-BZCYYb|BZCYYb|PBSCF) with O3 as the anode. Ri of the single cell with an anode having a 20Co / 80BZY catalyst layer when using NH3 as fuel. p The values ​​decreased to 0.037, 0.086, 0.200, and 0.463 Ωcm at 700, 650, 600, and 550 °C, respectively. 2 At 700°C, using hydrogen as fuel, R p It is 0.027 Ωcm 2 The results indicate that the 20Co / 80BZY catalyst layer can accelerate the anodic reaction and reduce polarization resistance, thereby improving battery performance.

[0114] 4. Single-cell stability characterization

[0115] Figure 10 A single cell (20Co / 80BZY+Ni-BZCYYb) was prepared using 20Co / 80BZY+Ni as the anode.

[0116] -BZCYYb|BZCYYb|PBSCF), single-cell stability plot tested at 550℃, the plot shows the stability of the single cell under 200A cm⁻¹. -2 Under load current, after 100 hours, there was no significant voltage drop (0.047V / h), while the voltage of the Ni-BZCYYb|BZCYYb|PBSCF cell dropped significantly (0.169V / h). This shows that 20Co / 80BZY+Ni-BZCYYb as the anode material maintains excellent stability in an ammonia atmosphere, ensuring its commercialization.

Claims

1. An anode material for an ammonia-fueled proton conductor solid oxide fuel cell, characterized in that, The chemical formula is xCo / 100-xBZY+Ni-BZCYYb, where BZCYYb is an oxide of barium, zirconium, cerium, ytterbium, and yttrium; wherein, based on the total molar amount of metal elements in Co / BZY being 100%, x is the percentage content of Co, and 10≤x≤30; xCo / 100-xBZY is obtained by reducing xCo3O4 / 100-xBZY. Ni-BZCYYb consists of a functional layer and a support layer. The thickness of the functional layer is 10-30 µm, and the thickness of the support layer is 700-900 µm. xCo / 100-xBZY is on the surface of the Ni-BZCYYb support layer. The Ni-BZCYYb functional layer is obtained by reducing the NiO-BZCYYb functional layer; the mass ratio of BZCYYb to NiO in the NiO-BZCYYb functional layer is (1~3):(2~5); The Ni-BZCYYb support layer is obtained by reducing the NiO-BZCYYb support layer; the mass ratio of BZCYYb to NiO in the NiO-BZCYYb support layer is (10~20):(20~30); xCo3O4 / 100-xBZY was added to the surface of NiO-BZCYYb by screen printing. The preparation method of xCo3O4 / 100-xBZY is as follows: Ba(NO3)2, Zr(NO3)4, Y(NO3)3 and Co(NO3)2•6H2O were added to a nitric acid aqueous solution according to the stoichiometric ratio, followed by the addition of citric acid. Then, ammonia was added to adjust the pH of the solution to 7-8. After stirring and mixing evenly, the solution was heated to dryness to obtain the precursor. Finally, the precursor was calcined at 1100-1200 ℃ for 6-8 h to obtain xCo3O4 / 100-xBZY.

2. The anode material for ammonia fuel proton conductor solid oxide fuel cells according to claim 1, characterized in that, x = 10, 20, or 30.

3. The anode material for ammonia fuel proton conductor solid oxide fuel cells according to claim 1, characterized in that, The Co particles in Co / BZY have a particle size of 10-80 nm; the thickness of Co / BZY is 10-20 μm.

4. The anode material for an ammonia-fueled proton conductor solid oxide fuel cell according to claim 1, characterized in that, In the preparation method of xCo3O4 / 100-xBZY, the molar ratio of the total amount of metal ions to citric acid is 1:(2-3).

5. A proton conductor solid oxide fuel cell fueled with ammonia, characterized in that, It includes a proton conductor electrolyte and an anode and a cathode located on both sides of the proton conductor electrolyte, wherein the anode is the anode material of the ammonia fuel proton conductor solid oxide fuel cell as described in any one of claims 1-4.

6. The ammonia-fueled proton conductor solid oxide fuel cell according to claim 5, characterized in that, The proton conductor electrolyte is BZCYYb, with a thickness of 5-10 μm; the cathode is PBSCF, with a thickness of 10-20 μm.

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