CN112751044B - Anode material for solid oxide fuel cell and preparation method thereof - Google Patents

Abstract

The invention provides an anode material of a solid oxide fuel cell and a preparation method thereof. The fuel gas first undergoes a reforming reaction inside the solid oxide fuel cell, and then diffuses to the anode for electrochemical reaction. The anode material uses a nickel-based material as the matrix, and the matrix is compounded with the additive material, and along the flow direction of the fuel gas, the additive is added. The content of the material is gradually reduced, and the catalytic reforming activity of the additive material to the fuel gas is less than that of nickel. The internal reforming reaction rate of the solid oxide fuel cell using the anode material is evenly distributed, which is beneficial to improve the stability and life of the cell.

Description

Anode material for solid oxide fuel cell and preparation method thereof

technical field

The invention relates to the technical field of solid oxide fuel cells, in particular to an anode material of a solid oxide fuel cell and a preparation method thereof.

Background technique

Since the development of industrialization, the global energy consumption has shown a rising trend. Environmental pollution and global climate change have attracted widespread attention. Governments around the world have focused on finding new clean energy and developing clean and efficient solutions for existing energy. support, and fuel cells stand out among many solutions because of their clean and efficient advantages.

Solid Oxide Fuel Cell (SOFC) is a clean and efficient all-solid-state energy conversion device that can directly convert chemical energy into electrical energy through electrochemical reactions. ℃), it shows a wide range of adaptability to various fuels such as methane, ammonia, alcohols, etc., and becomes the third generation of fuel cell power generation technology after phosphoric acid fuel cells and molten carbonate fuel cells.

The electrode materials of SOFC can be divided into anode materials and cathode materials. The anode material is generally required to have strong electrocatalytic ability, high ionic conductivity and electronic conductivity, and form a good thermal stress match with the adjacent functional layers. At the same time, the electrode material should have sufficient porosity to ensure the transport of reactive gases and provide enough three-phase interfaces. The anode materials mainly include nickel-based materials, copper-based materials, perovskite-type materials, etc. Among them, nickel-based materials include NiO/GDC, NiO/SDC, NiO/SSZ, NiO/YSZ, etc.; copper-based materials include CuO ₂ /CeO ₂ /SDC, CuO ₂ /CeO/YSZ, CuO ₂ /YSZ, Cu/YZT, etc. ; Perovskite materials include La _1-x Sr _x CrO ₃ , La _1-x Sr _x Cr _{1-y My} O ₃ , LST, LAC, etc. In addition, some noble metal materials can also be used as anode materials for SOFC, such as Pt and Ru.

Nickel-based materials are the most commonly used anode materials in SOFCs today. For example, NiO and the corresponding electrolyte materials GDC, SDC, SSZ, YSZ and other composite materials are used as the anode of SOFC, and after reduction, Ni/GDC, Ni/SDC, Ni/SSZ, Ni/YSZ composite porous electrodes are formed respectively. It not only meets the mass transfer requirements of the anode, but also increases the number of three-phase line regions (i.e., the intersection of the three regions of Ni-electrolyte material-pores) and matches its thermal expansion coefficient with the corresponding electrolyte. In addition, the presence of electrolyte materials It has a certain inhibitory effect on the agglomeration of Ni particles at high temperature. However, nickel-based materials also have certain limitations, such as being prone to sulfur poisoning and easily forming carbon deposits. Especially in the study of _CO2 electrolysis, when there are few reducing components in the fuel, Ni is easily oxidized to NiO , NiOH, Ni(OH) ₂ , etc. Compared with nickel-based materials, other materials such as metals or alloys are less prone to carbon deposition when used as anode materials for SOFCs, but their reactivity is low, which reduces the overall performance of the battery.

The fuel gas that can be directly used by the solid oxide fuel cell is mainly hydrogen, carbon monoxide and other gases with reducing properties. When the solid oxide fuel cell uses hydrogen as the fuel, the reaction mechanism is:

Anode: 2H ₂ +2O ^2- -4e ^- =2H ₂ O

Cathode: O ₂ +4e ^- =2O ^2-

Overall reaction: 2H ₂ +O ₂ =2H ₂ O

However, the energy storage density of hydrogen is low, which makes it difficult to store and transport it on a large scale. In addition, when hydrogen is introduced into the anode, excess air needs to be introduced into the cathode to dissipate heat to prevent damage to the interior of the battery due to heat accumulation.

Therefore, replacing hydrogen with ammonia or hydrocarbons into the battery for discharge can not only effectively solve the problems of large-scale storage and transportation, but also reduce the dependence on excess air and better thermally manage the battery. However, ammonia or hydrocarbons cannot be directly used in fuel cells to generate electricity. They must be converted into hydrogen and carbon monoxide through catalytic reforming reactions in the electrodes at high temperatures, and then diffused to the active anode for electrochemical reactions. The fuel cell is called a solid oxide fuel cell with internal reforming characteristics.

Solid oxide fuel cells with internal reforming characteristics often suffer from thermal effects or carbon deposition problems. For example, ammonia gas is used as the fuel gas to pass into the interior of the cell. When the anode material of the solid oxide fuel cell is a nickel-based material, nickel has good catalytic activity. The ammonia gas will first decompose under the catalysis of nickel to generate hydrogen and nitrogen, and then The generated hydrogen will diffuse to the three-phase wire interface to provide the electrochemical reaction needs. Ammonia decomposition is an endothermic reaction that can be used for battery cooling. However, as an excellent ammonia decomposition catalyst, nickel has high catalytic activity at high temperature, so that ammonia gas quickly decomposes after entering the interior of the battery, absorbing a lot of heat, causing the temperature of the area near the fuel inlet end of the battery to be too low. It is precisely because of this unbalanced exothermic and endothermic phenomenon that compared with the direct use of hydrogen fuel, the temperature gradient inside the battery is greatly increased, and the thermal stress caused by the excessive temperature gradient will affect the durability of the battery.

Several previous studies have pointed out that the low temperature region of the inlet can be alleviated by changing the boundary conditions of the battery inlet, such as the battery inlet flow rate, inlet gas composition and temperature, but this phenomenon cannot be completely eliminated by changing the boundary conditions of the inlet, and the inlet Boundary conditions also provide only limited support for human intervention in the physical fields inside the battery. By changing the catalytic activity of the nickel catalyst, the distribution of the ammonia decomposition rate in the battery can be effectively controlled, thereby controlling the temperature field and affecting the battery stress. In addition, during the ammonia decomposition process, the nickel surface in the nickel-based material will be nitrided, so a large amount of nickel nitride is generated at the fuel inlet, resulting in uneven spatial attenuation of battery performance and affecting long-term operation stability.

Hydrocarbons are used as the fuel gas to pass into the cell. When the anode material of the solid oxide fuel cell is a nickel-based material, the rapid reformation of the fuel gas on the nickel surface will bring about carbon deposition problems, especially in the vicinity of the fuel inlet. It will cause uneven carbon deposition inside the battery and affect the battery life.

Therefore, it is of great significance to realize the uniformity of the distribution of the reforming reaction rate inside the battery to improve the stability and life of the battery.

SUMMARY OF THE INVENTION

In view of the above-mentioned technical situation, the present invention aims to provide an anode material for a solid oxide fuel cell with internal reforming characteristics. The internal reforming reaction rate of the solid oxide fuel cell using the anode material is uniformly distributed, which is beneficial to improve the battery's performance. Stability and longevity.

In order to achieve the above technical purpose, the inventors adopted nickel-based materials as anode materials of solid oxide fuel cells. The material is compounded with the additive material, and the catalytic activity of the additive material is lower than that of nickel, which can inhibit the catalytic activity of nickel, and the content of the additive material is controlled to gradually decrease along the fuel flow direction, that is, the content of the additive material in the anode area near the fuel inlet is the most, thus It can effectively inhibit the catalytic activity of nickel and reduce the catalytic decomposition rate in the fuel inlet area, and along the fuel flow direction, the content of the additive material gradually decreases, the inhibition effect on the catalytic activity of nickel gradually decreases, and the influence on the catalytic decomposition rate It is also gradually reduced to achieve homogenization of the catalytic reforming reaction from the fuel inlet to the fuel outlet.

That is, the technical scheme of the present invention is: an anode material of a solid oxide fuel cell, the fuel gas first undergoes a reforming reaction inside the solid oxide fuel cell, and then an electrochemical reaction is carried out, and is characterized in that: the anode material is made of The nickel-based material is used as a matrix, and the matrix is compounded with the additive material, and the content of the additive material gradually decreases along the flow direction of the fuel gas; the catalytic reforming activity of the additive material on the fuel gas is lower than that of nickel.

Preferably, the fuel gas is ammonia gas and/or hydrocarbon gas.

The additive materials are not limited, including single metals, alloys, oxides, and the like. The metal material includes one or more of Cu, Fe, Pt, Ru and the like.

As an implementation manner, the additive material is attached to the substrate, and along the flow direction of the fuel gas, the attached amount of the additive material gradually decreases. The matrix material is often a porous material, and preferably, the additive material is incorporated into the porous structure of the matrix material.

The structure of the solid oxide fuel cell is not limited, including a flat plate type, a tubular type and the like.

Considering the thermal stress caused by the uneven temperature distribution and the flatness of the cell, it is preferable to adopt a symmetrical double cathode structure, that is, the solid oxide fuel cell uses the anode layer as the support layer, and has an upper and lower distribution structure, specifically: the anode layer, The electrolyte layer and the cathode layer are stacked up and down along the thickness direction, the electrolyte layer includes a first electrolyte layer and a second electrolyte layer, the first electrolyte layer is located on the upper surface of the anode layer, the second electrolyte layer is located on the lower surface of the anode layer; the cathode layer includes a first electrolyte layer and a second electrolyte layer. A cathode layer and a second cathode layer, the first cathode layer is located on the upper surface of the first electrolyte layer, and the second cathode layer is located on the lower surface of the second electrolyte layer. At this time, the anode layer is provided with several hollow channels for fuel gas circulation, the hollow channels have two open ends, one open end is used for fuel gas to flow into the hollow channel, and the other open end is used for fuel gas to flow out of the hollow channel, Two open ends are provided on the sides of the anode layer.

The present invention also provides a method for preparing the anode material of the above solid oxide fuel cell, comprising the following steps:

(1) the additive material is dissolved in the solvent to obtain the additive material solution;

(2) contacting the additive material solution with the matrix, and along the flow direction of the fuel gas, the quality of the additive material solution in contact with the matrix gradually decreases; after the solvent is volatilized, calcining is performed to obtain a composite of the matrix and the additive material Material.

In the step (2), the method for contacting the added material solution with the matrix is not limited.

For example, the additive material solution is contacted with the substrate by methods such as drop coating, coating, printing, etc., and along the flow direction of the fuel gas, the mass of the additive material solution in contact with the substrate gradually decreases;

The additive material solution is poured into the tubular matrix structure, heated to volatilize the solvent, the liquid level of the additive material solution gradually drops until the solvent is completely volatilized, and then calcined; during this process, in the height direction of the tubular structure, different height positions The time of being impregnated by the solution is different, so the amount of the additive material attached to the inner wall of the tubular structure after calcination shows a changing trend, and it gradually increases from high to low.

When the solid oxide fuel cell has a symmetrical double-cathode structure, as an implementation method, the anode layer uses a nickel-based material as the matrix, and the additive material is attached to the wall of the hollow channel. Since the matrix material is a porous material, preferably, the additive material enters the matrix. in the porous structure of the material. In this structure, the present invention also provides a preparation method for preparing the anode, comprising the following steps:

(1) preparing a nickel-based material layer with a hollow channel;

(2) Seal the opening of one end of the hollow channel and keep the opening of the other end facing upward;

(3) injecting the additive material solution from the opening of the other end of the hollow channel, dissolving the additive material in a solvent to obtain the additive material solution, heating to volatilize the solvent, the liquid level of the additive material solution gradually decreasing until the solvent is completely volatilized, and then calcining ; In this process, in the height direction of the hollow channel, the time of being immersed by the solution at different heights is different, so the adhesion amount of the additive material formed on the inner wall of the channel after calcination changes, and gradually increases from high to low;

(4) Repeat step (3) several times.

The preparation method of the step (1) is not limited. As an implementation method, a nickel-based material is used as a raw material, a high-temperature volatile substance with a certain size is filled in it as a pore-forming agent, and sintering is performed after molding to volatilize the pore-forming agent to obtain a nickel-based material with a hollow channel. layer, and the hollow channel has open ends on the sides of the nickel-based material layer;

The material of the pore-forming agent is not limited, including carbon rods, carbon materials of other shapes such as graphite and carbon nanotubes.

The molding method is not limited, including hot pressing, casting and other methods.

The present invention composites the nickel-based material and the additive material as the anode material of the solid oxide fuel cell, and has the following beneficial effects:

(1) The catalytic activity of the additive material for ammonia decomposition and hydrocarbon fuel reforming is low. The nickel-based material is compounded with the additive material. The additive material can effectively inhibit the reforming reaction by occupying the reactive sites or forming an alloy with nickel. occur;

(2) By adjusting the content of the additive material, different inhibition intensities can be formed at different positions inside the cell, thereby controlling the reaction rate distribution in the cell; the present invention controls the content of the additive material to gradually decrease along the flow direction of the fuel gas, The catalytic decomposition rate in the fuel inlet area can be reduced to the greatest extent, and the reduction rate of the catalytic decomposition rate is gradually reduced along the fuel flow direction, so as to realize the homogenization of the catalytic reforming reaction from the fuel inlet to the fuel outlet;

(3) The preparation method provided by the present invention is simple and feasible, and realizes the rapid modification of the catalytic activity of the solid oxide fuel cell anode material to the reforming reaction;

(4) As a preference, the method of pouring the additive material solution into the tubular structure matrix of the present invention can control the falling rate of the liquid level at different heights by controlling the evaporation temperature of the solvent, thereby controlling the time for the inner wall of the tubular structure to be immersed in the solution. Gradient distribution, this method is simple and easy to implement, and can obtain accurate gradient distribution.

Description of drawings

FIG. 1 is a schematic structural diagram of a solid oxide fuel cell with a symmetrical double cathode structure in an embodiment of the present invention.

FIG. 2 is an assembly view of the battery shown in FIG. 1 .

FIG. 3 is a schematic diagram of a calculation model and a schematic diagram of the inhibition intensity distribution for calculating the temperature field under different copper distributions using the numerical simulation method.

Figure 4 is a grid of numerical simulations used to calculate the temperature field under different copper distributions.

Figure 5 shows the internal temperature field distribution of the battery corresponding to different inlet suppression strengths under the condition of discharge using the numerical simulation method.

Figure 6 shows the internal temperature field distribution with the numerical simulation method and the inlet suppression strength is 0.

Figure 7 shows the internal temperature field distribution with an inlet suppression strength of 0.8 using a numerical simulation method.

Figure 8 shows the internal temperature field distribution with the numerical simulation method and the inlet suppression strength is 1.

FIG. 9 is a schematic diagram of the preparation of the anode layer of the battery.

FIG. 10 is a schematic diagram of the structure of the battery after assembly in step (5) of this embodiment.

Fig. 11 is the SEM and EDS test results of the position ① in Fig. 10 .

FIG. 12 is the SEM and EDS test results of the ② position in FIG. 10 .

FIG. 13 is the SEM and EDS test results of the position ③ in FIG. 10 .

Detailed ways

The present invention will be further described in detail below with reference to the embodiments and the accompanying drawings. It should be noted that the following embodiments are intended to facilitate the understanding of the present invention, but do not have any limiting effect on it.

1-4 are: anode layer 1 , first electrolyte layer 21 , second electrolyte layer 22 , first cathode layer 31 , second cathode layer 32 , first open end 41 , second open end 42 , the first anode cover plate 51, the second anode cover plate 52, the anode outer sealing layer 53, the first cathode cover plate 61, the second cathode cover plate 62, the first side surface 71 of the anode layer, the second side surface 72 of the anode layer , the first part of the cover plate 521 , the second part of the cover plate 522 , the syringe 8 , the packaging bolt 9 , the battery 10 , the hollow channel 11 , and the rubber gasket 12 .

In this embodiment, the solid oxide fuel cell adopts a symmetrical double-cathode structure, that is, the solid oxide fuel cell uses the anode layer 1 as the support layer, and is in an up-down distribution structure, specifically: the anode layer 1, the electrolyte layer and the cathode layer along the thickness The direction is stacked up and down, the electrolyte layer includes a first electrolyte layer 21 and a second electrolyte layer 22, the first electrolyte layer 21 is located on the upper surface of the anode layer 1, and the second electrolyte layer 22 is located on the lower surface of the anode layer 1; The cathode layer includes a first electrolyte layer 21 and a second electrolyte layer 22. The cathode layer 31 and the second cathode layer 32 , the first cathode layer 31 is located on the upper surface of the first electrolyte layer 21 , and the second cathode layer 32 is located on the lower surface of the second electrolyte layer 22 . The anode layer 1 is provided with several hollow channels for fuel gas circulation, and the hollow channel has two open ends, called the first open end 41 and the second open end 42 (in FIG. 1 , the second open end 42 is at the first opening The opposite side of the end 41, the second open end is not shown in FIG. 1), the first open end 41 is used for the fuel gas to flow into the hollow passage, which is arranged on the first side 71 of the anode layer, and the second open end 42 is used for the fuel gas. The outflow hollow passage is provided on the second side 72 of the anode layer.

As shown in FIG. 2 , encapsulating the battery includes using the first anode cover plate 51 to encapsulate the first side surface 71 of the anode layer, using the second anode cover plate 52 to encapsulate the second side surface 72 of the anode layer, and using the second anode cover plate 52 to encapsulate the second side surface 72 of the anode layer. The encapsulation of the first cathode layer by the first cathode cap plate 61 and the encapsulation of the second cathode layer by the second cathode cap plate 62 .

In this embodiment, the anode layer is made of Ni/YSZ composite porous material, referred to as Ni/YSZ for short, and Cu is attached to the inner wall of the middle channel to form a Cu-Ni/YSZ composite electrode, the fuel gas is ammonia gas, and along the fuel gas In the flow direction, the Cu content gradually decreased.

First, the numerical simulation method is used to calculate the temperature field under different copper distributions. The calculation is based on the finite element method, using a fully coupled numerical model, the calculation process and literature: Wang Y,Gu Y,Zhang H,Yang J,Wang J,Guan W,et al.Efficient and durable ammonia power generation by symmetricflat-tube solid The consistency of oxide fuel cells.Applied Energy.2020; 270. can ensure the accuracy and reliability of the calculation. The geometric model used in the calculation and the distribution of suppression intensity are shown in Figure 3, and the finite element mesh is shown in Figure 4. Using the same geometric model as the actual cell size, the solution region is simplified according to the symmetry of the cell structure and operating conditions. The solved geometric region includes the first anode cover plate, the second anode cover plate, the fuel flow field and the solid region of the battery itself. . The electrochemical discharge process is not included, which means that the content of the simulation is the internal ammonia decomposition process of the battery in the OCV state.

As can be seen from Figure 3 above, the suppression intensity of linear change is adopted, that is, the inhibition of ammonia decomposition catalysis at the fuel inlet is the strongest, and the fuel outlet is not suppressed, and a linear transition is adopted in the middle. By adjusting the inhibition at the fuel inlet The intensity values can represent different internal copper distributions, simulating temperature distributions under different suppression conditions. Among them, R ₀ represents the uninhibited decomposition reaction rate, and a ₀ represents the inhibition strength. The larger the inhibition strength is, the smaller the value of a ₀ is.

The simulation results are shown in Figures 5, 6, 7, and 8. From the simulation results, it can be seen that:

(1) When the fuel inlet is not restrained, as shown in Figure 6, in the original temperature field, there is a low temperature area near the fuel inlet;

(2) As the suppression intensity at the fuel inlet gradually increases, the minimum temperature gradually increases, and the temperature field gradually becomes regionally uniform; when the suppression intensity is 0.8, the minimum temperature reaches the highest, as shown in Figure 7, the maximum temperature difference at this time Compared with the original battery, it is 47% smaller, and the ammonia conversion rate is only slightly reduced;

(3) As the suppression intensity continues to increase, the low temperature region even begins to gradually move towards the anode outlet of the cell, as shown in Figure 8, that is, the suppression at the fuel inlet is too strong;

From the box plot shown in Figure 5, it can be seen that there are a large number of abnormal temperature points caused by ammonia decomposition and endotherm in the original temperature field. The temperature field within the battery becomes more uniform.

The preparation method of this anode layer is as follows:

(1) The anode battery support is prepared by dry pressing or extrusion molding, and then the full battery is fabricated by a multi-step screen printing and sintering process.

Using Ni/YSZ as a raw material, filling carbon rods in it as a pore-forming agent, press molding, and then sintering to volatilize the pore-forming agent to obtain an anode layer with a hollow channel, and the two open ends of the hollow channel are provided with on the side of the anode layer.

(2) Using the anode layer as a support layer, a multi-step screen printing and sintering process was used to prepare a full cell.

(3) As shown in FIG. 9 , the first anode cover plate 51 is used to seal the first side surface 71 of the anode layer, the first anode cover plate 52 is used to seal the second side surface 72 of the anode layer, and the battery outer sealing layer 53 is The YSZ thin layer seals the outside of the anode support. A layer of rubber gasket 12 is arranged in the first anode cover plate 51 , when the first anode cover plate 51 pressurizes and seals the first side 71 of the anode layer, the rubber gasket 12 will closely adhere to the first port 41 of the hollow channel , so that the first port 41 of the hollow channel is sealed;

The second anode cover plate 52 is composed of a first part 521 of the cover plate and a second part 522 of the cover plate. The first part of the cover plate 521 is used to seal the periphery of the second side surface 72 of the anode layer, and the second part of the cover plate 522 is used to seal the anode The remainder of the second side 72 of the layer. First, the first part 521 of the cover plate is used to seal around the contour of the second side surface 72 of the anode layer, so that the second open end 42 of the hollow channel 11 is not sealed and is in an open state.

(4) The battery is erected, the second open end 42 of the hollow channel is directed upward, and a copper nitrate ethanol solution with a concentration of 1M is injected into the hollow channel from the second open end 42 of the hollow channel using a syringe, until the hollow channel is completely filled Then stand the battery in a constant temperature oven. After the solution is completely evaporated to dryness, the first anode cover plate 51 and the first part 521 of the cover plate are removed, and the copper nitrate crystals remaining on the surface of the battery are cleaned up, and then the battery is placed in the electric furnace. , and calcined at 300°C for two hours. After the copper nitrate was completely decomposed into copper oxide, the battery was taken out.

(5) Repeat steps (3) and (4) 4-5 times.

(6) The first side surface 71 of the anode layer is sealed with the first anode cover plate 51 , the second side surface 72 of the anode layer is sealed with the second anode cover plate 52 , and the first cathode is sealed with the first cathode cover plate 61 The encapsulation of the layers and the encapsulation of the second cathode layer by the second cathode cover plate 62, the resulting structure is shown in FIG. 10 .

SEM and EDS tests were carried out on the battery prepared above. The SEM and EDS test results of the ①, ②, and ③ positions marked in Figure 10 are shown in Figures 11, 12, and 13. It shows that inside the battery, copper is mainly distributed in the hollow space. The inner wall of the channel, and from the first port 41 to the second port 42 of the hollow channel, the copper content gradually decreases, that is, the use of the above method can effectively fabricate a gradient electrode with a gradually changing copper content, because with the solvent evaporation process. During the process, the liquid level in the hollow channel gradually decreases, and the inner wall part of the hollow channel closer to the bottom is in the immersion state for a longer time, which is equivalent to controlling the immersion time of different height parts inside the battery, thereby forming different copper loadings.

By controlling the evaporation temperature, the falling rate of the liquid level in different parts can be effectively controlled, and then the immersion time can be controlled to form a precisely distributed copper gradient.

The above embodiments describe the technical solutions of the present invention in detail. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the present invention. Anything done within the scope of the principles of the present invention Any modifications, additions or substitutions in similar manners, etc., shall be included within the protection scope of the present invention.

Claims (4)

1. the preparation method of the anode material of a kind of solid oxide fuel cell, fuel gas at first in the solid oxide fuel cell internal reformation reaction occurs, then carries out electrochemical reaction, it is characterized in that: The solid oxide fuel cell uses the anode layer as a support layer and is in an up-down distribution structure, specifically: the anode layer, the electrolyte layer and the cathode layer are stacked up and down along the thickness direction, the electrolyte layer includes a first electrolyte layer and a second electrolyte layer, An electrolyte layer is located on the upper surface of the anode layer, and the second electrolyte layer is located on the lower surface of the anode layer; the cathode layer includes a first cathode layer and a second cathode layer, the first cathode layer is located on the upper surface of the first electrolyte layer, and the second cathode layer a layer on the lower surface of the second electrolyte layer; The anode layer is provided with a number of hollow channels for fuel gas circulation, the hollow channel has two open ends, one open end is used for fuel gas to flow into the hollow channel, the other open end is used for fuel gas to flow out of the hollow channel, and the two open ends arranged on the side of the anode layer; Add material into the porous structure of the hollow channel walls; The anode material uses a nickel-based material as a matrix, and the matrix is compounded with an additive material, the additive material is attached to the substrate material, and the content of the additive material gradually decreases along the flow direction of the fuel gas; The catalytic reforming activity of the fuel gas is less than that of nickel; the steps are as follows: (1) Preparation of a nickel-based material layer with hollow channels; (2) Seal the opening of one end of the hollow channel and keep the opening of the other end facing upward; (3) injecting the additive material solution from the opening of the other end of the hollow channel, dissolving the additive material in the solvent to obtain the additive material solution, heating to volatilize the solvent, the liquid level of the additive material solution gradually decreasing until the solvent is completely volatilized, and then calcining ; (4) Repeat step (3) several times. 2. The preparation method according to claim 1, wherein the fuel gas is ammonia gas and/or hydrocarbon gas. 3. The preparation method of claim 1, wherein the additive material comprises one or more of a single metal, an alloy, and an oxide. 4. The preparation method of claim 3, wherein the additive material is one or more of Cu, Fe, Pt, and Ru.

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