Composite electrode material and preparation method thereof, anode electrode and fuel cell

Abstract

The invention provides a composite electrode material and a preparation method thereof, an anode electrode and a fuel cell, the composite electrode material comprises: an yttrium oxide-zirconium oxide carrier having a porous structure, the surface of the yttrium oxide-zirconium oxide carrier being divided into a pore inner surface and a pore outer surface, the yttrium oxide-zirconium oxide carrier being used as a structural skeleton of the composite electrode material; the cobalt sulfide coating layer is coated on the outer surface of the yttrium oxide-zirconium oxide carrier. The electrode material prepared by the method has better catalytic activity, the catalytic performance of the electrode material can be further improved, and the preparation method is simple to operate, mild in reaction condition and suitable for large-scale production.

Description

Technical Field

[0001] This application relates to the field of battery materials technology, and in particular to a composite electrode material and its preparation method, an anode electrode, and a fuel cell. Background Technology

[0002] One of the major challenges facing the commercialization of solid oxide fuel cells (SOFCs) is the continuous performance degradation under long-term operating conditions. This is primarily due to prolonged exposure to high temperatures, cooling, and redox cycles, which significantly alters the microstructure of the electrodes. The nickel anode undergoes volume fluctuations due to the reduction of NiO to Ni during the redox cycle, leading to a decrease in mechanical strength. Furthermore, agglomeration of oxide particles at the cathode and Ni particles at the anode reduces the catalytic surface area. Simultaneously, the aforementioned processes generate additional low-conductivity phases. Thermal stress caused by the mismatch in thermal expansion coefficients between different components (e.g., connector / anode, anode / electrolyte, electrolyte / cathode, cathode / connector) also degrades the cell's mechanical properties, thus affecting its electrochemical performance.

[0003] Therefore, the most common solution to address these issues is to modify the battery's electrode materials, using materials with perovskite structures, such as Ni-Ce, for the anode, electrolyte, and cathode. 0.8 Sm 0.2 O 2-δ (SDC), La 0.8 Sr 0.2 Ga 0.8 Mg 0.2 O 3-δ (LSGM), Sm 0.5 Sr 0.5 CoO 3-δ Batteries with a fully perovskite structure, such as those using SSC (Self-Containing Cells), benefit from the presence of perovskite materials. These materials have similar coefficients of thermal expansion and high electrical conductivity. However, perovskite materials are expensive; for example, Ga in LSGM electrolytes is relatively costly, hindering large-scale commercial use. Furthermore, perovskite materials readily react with other substances under certain conditions, generating new impurity phases that degrade overall electrochemical performance. For example, cathode materials such as La... x Sr 1-x (Cr) 1-y Fe y )O 3+δ(x>0.1, δ=0.1~0.5), with a conductivity as high as 100 S / cm at 800℃, but during long-term operation, it reacts with BaO and SrO in the sealing material to form BaCrO4 and SrCrO4 phases, leading to mechanical damage to the battery. Currently, the most widely used cathode material is La. x Sr 1-x Co y Fe 1-y O 3-δ LSCF reacts with YSZ to form a high-resistivity pyrochlore phase: La2Zr2O7; LSGM may also react with Ni to form non-conductive phases such as LaNiO3 and LaSrGa3O7, thereby reducing electrode performance. Furthermore, the fabrication process for batteries using perovskite materials as electrodes is still immature, and suitable materials and fabrication methods need to be found.

[0004] Chinese Patent Application No. CN 107376886 A discloses a method for initially loading a Ti-containing mixed solution onto coal-based activated carbon using capillary adsorption through the pores of the activated carbon. Further hydrothermal reaction involves in-situ hydrolysis and condensation of the Ti-containing mixed solution adsorbed on the activated carbon within the pores or surface of the activated carbon, generating TiO2 nanospheres. This yields a coal-based activated carbon-loaded TiO2 composite material, in which stable Ti-OC bonds are formed at the interface between the activated carbon and the TiO2 nanospheres, providing a stable connection through intermolecular forces and enhancing the photocatalytic activity of TiO2. The method employs an impregnation-hydrothermal approach to synthesize the coal-based activated carbon-loaded TiO2 composite material. The preparation process avoids high-temperature calcination and does not introduce organic or inorganic reagents during the hydrothermal reaction. Furthermore, the amount of TiO2 ultimately loaded onto the activated carbon is controlled by adjusting the impregnation time during the preparation of the Ti-containing mixed solution. However, the catalyst prepared by the above patent is a nanosphere particle, which still needs to be sintered at high temperature when applied to electrode materials, so that the carrier material is sintered and shaped. During the sintering process, especially during the hydrothermal reaction, the size and morphology of the obtained particles will change significantly, losing the unique morphology and size advantages of the product prepared by the hydrothermal method.

[0005] In summary, given the problems of complex preparation processes or poor catalytic activity in existing electrode materials, there is an urgent need to provide a method for preparing electrode materials to improve these issues. Summary of the Invention

[0006] The main objective of this invention is to provide a composite electrode material and its preparation method, an anode electrode, and a fuel cell, in order to solve the problems of complex preparation processes or poor catalytic activity in the electrode materials of the prior art.

[0007] To achieve the above objectives, according to one aspect of the present invention, a composite electrode material is provided, comprising: a yttrium oxide-zirconia support having a porous structure, wherein the surface of the yttrium oxide-zirconia support is divided into an inner surface and an outer surface, which serves as the structural framework of the composite electrode material; and a cobalt sulfide coating layer coating the outer surface of the yttrium oxide-zirconia support.

[0008] Furthermore, in the composite electrode material, the weight ratio of yttrium oxide-zirconia support to cobalt sulfide coating is (1-100):1; preferably (1-5):1.

[0009] Furthermore, the yttrium oxide-zirconia support has a porous structure with a porosity of 10–30% and a pore size of 10–50 μm.

[0010] Furthermore, the thickness of the cobalt sulfide coating is 1–5 μm.

[0011] To achieve the above objectives, according to one aspect of the present invention, a method for preparing a composite electrode material is provided, the method comprising: providing a yttrium oxide-zirconia support; and coating the outer surface of the yttrium oxide-zirconia support with cobalt sulfide to obtain the composite electrode material.

[0012] Further, the preparation method includes: step S1, mixing yttrium oxide-zirconia powder and a pore-forming agent and then sintering to obtain a yttrium oxide-zirconia support; step S2, dispersing cobalt salt, thiocyanate compound and urea in deionized water, adding yttrium oxide-zirconia support to completely immerse it, and performing hydrothermal reaction and heat treatment in sequence, repeating the hydrothermal reaction and heat treatment to coat cobalt sulfide on the outer surface of the yttrium oxide-zirconia support to obtain a composite electrode material.

[0013] Further, in step S2, the cobalt salt is selected from one or more of cobalt nitrate, cobalt acetate, or cobalt chloride.

[0014] Furthermore, in step S2, the hydrothermal reaction is carried out in a hydrothermal reactor at a temperature of 160–220°C for a reaction time of 0.5–24 h.

[0015] Furthermore, in step S2, the heat treatment is carried out in an inert atmosphere, wherein the inert gas in the inert atmosphere is selected from one or more of nitrogen, helium or argon.

[0016] Furthermore, the sintering temperature is 1200–1500℃, and the time is 0.5–5h.

[0017] Further, in step S2, the thio compound is selected from one or more of thioacetamide, thiourea, or sodium thiosulfate.

[0018] Furthermore, in step S2, the hydrothermal reaction and heat treatment are repeated 1 to 10 times to coat cobalt sulfide on the outer surface of the yttrium oxide-zirconia support.

[0019] Further, in step S2, the weight ratio of cobalt salt, thiochemical compound and urea is (0.5-2):(0.5-2):1 by weight percentage.

[0020] Further, in step S1, the pore-forming agent is selected from one or more of starch, graphite, or polymethyl methacrylate.

[0021] Furthermore, the heat treatment temperature is 300–700℃, and the sintering time is 0.5–5h.

[0022] Furthermore, in step S1, the pore-forming agent is starch.

[0023] Furthermore, in the yttrium oxide-zirconia powder, the weight content of yttrium oxide is 8%, and the molar content of zirconia is 92%.

[0024] According to another aspect of the present invention, an anode electrode is provided, which comprises the above-described composite electrode material, or a composite electrode material obtained by the preparation method of the above-described composite electrode material.

[0025] Furthermore, the anode electrode is obtained by drying a composite electrode material.

[0026] According to another aspect of the present invention, a fuel cell is provided, including an anode electrode, which is the aforementioned anode electrode.

[0027] The electrode material prepared using the technical solution of this invention has good catalytic activity and further improved catalytic performance. Moreover, the preparation method is simple to operate and the reaction conditions are mild, making it suitable for large-scale production. Attached Figure Description

[0028] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments consistent with this application and, together with the description, serve to explain the principles of this application. In the drawings:

[0029] Figure 1 A SEM image (magnification 5000x) of the cross-section of the electrode material prepared according to Example 1 of the present invention is shown.

[0030] Figure 2 A SEM image (magnification of 5000x) of the cross-section of the carrier prepared according to Embodiment 1 of the present invention is shown.

[0031] Figure 3 An elemental distribution diagram of the electrode material prepared according to Example 1 of the present invention is shown;

[0032] Figure 4 The electrochemical performance curves of the electrode material prepared according to Example 1 of the present invention under full-cell conditions are shown; and

[0033] Figure 5 The electrochemical performance curves of the electrode material prepared according to Comparative Example 1 of the present invention under full-cell conditions are shown. Detailed Implementation

[0034] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0035] As described in the background section of this invention, existing electrode materials suffer from complex preparation processes or poor catalytic activity. Therefore, this invention provides a composite electrode material comprising: a yttrium oxide-zirconia support having a porous structure, wherein the surface of the yttrium oxide-zirconia support is divided into an inner pore surface and an outer surface, serving as the structural framework of the composite electrode material; and a cobalt sulfide coating layer covering the outer surface of the yttrium oxide-zirconia support.

[0036] The composite electrode material provided by the present invention includes: a yttrium oxide-zirconia support as the structural framework of the composite electrode material, and a cobalt sulfide coating layer on its outer surface. The cobalt sulfide is uniformly distributed and has a uniform size on the outer surface of the yttrium oxide-zirconia support. In particular, the yttrium oxide-zirconia support has a porous structure, which increases the catalytic active sites, improves catalytic activity, and enhances catalytic performance.

[0037] In a preferred embodiment, in the composite electrode material, the weight ratio of yttrium oxide-zirconia support to cobalt sulfide coating is (1-100):1, more preferably (1-5):1, to further enhance the catalytic active sites of the material and improve its catalytic performance; more preferably, the yttrium oxide-zirconia support has a porous structure with a porosity of 10-30% and a pore size of 10-50 μm.

[0038] To further improve the catalytic activity of the composite electrode while saving preparation costs, the thickness of the cobalt sulfide coating layer is 1–5 μm, thereby further improving its catalytic performance.

[0039] Another aspect of the present invention provides a method for preparing a composite electrode material, the method comprising: providing a yttrium oxide-zirconia support; and coating the outer surface of the yttrium oxide-zirconia support with cobalt sulfide to obtain the composite electrode material.

[0040] Those skilled in the art can first take a yttrium oxide-zirconia support, and then coat the outer surface of the yttrium oxide-zirconia support with cobalt sulfide to obtain a composite electrode material. The electrode material prepared by this method has good catalytic performance, and the cobalt sulfide on the surface of the material is uniformly distributed, dimensionally stable, and has high catalytic activity.

[0041] In a preferred embodiment, the preparation method includes: step S1, mixing yttrium oxide-zirconia powder and a pore-forming agent and then sintering the mixture to obtain a yttrium oxide-zirconia support; step S2, dispersing cobalt salt, thiocyanate compound and urea in deionized water, then adding the yttrium oxide-zirconia support and completely immersing it, and performing hydrothermal reaction and heat treatment in sequence, repeating the hydrothermal reaction and heat treatment to coat the outer surface of the yttrium oxide-zirconia support with cobalt sulfide to obtain a composite electrode material.

[0042] Those skilled in the art first mix yttrium oxide-zirconia powder and a pore-forming agent, then sinter them to obtain a yttrium oxide-zirconia support. Next, cobalt salt, a thiocyanate compound, and urea are dispersed in deionized water, and then the yttrium oxide-zirconia support is added and completely submerged. Hydrothermal reaction and heat treatment are then performed sequentially, and this process is repeated to coat the outer surface of the yttrium oxide-zirconia support with cobalt sulfide, resulting in a composite electrode material. This preparation method is an impregnation-hydrothermal synthesis method, which grows the cobalt sulfide active component in situ on the outer surface of the yttrium oxide-zirconia support, thereby further increasing the active sites, making the structure of cobalt sulfide more stable, and improving catalytic performance. Moreover, compared with traditional preparation methods, this method is simple to operate, has mild reaction conditions, is suitable for large-scale production, and has a broad industrial application potential.

[0043] To further prepare cobalt sulfide, a cobalt sulfide coating layer is applied to the surface of the yttrium oxide-zirconia support. Preferably, the cobalt salt is selected from one or more of cobalt nitrate, cobalt acetate, or cobalt chloride; the thio compound is selected from one or more of thioacetamide, thiourea, or sodium thiosulfate; more preferably, the weight ratio of cobalt salt, thio compound, and urea is (0.5-2):(0.5-2):1 by weight percentage.

[0044] In a preferred embodiment, the hydrothermal reaction is carried out in a hydrothermal reactor at a temperature of 160–220°C for a time of 0.5–24 h to ensure a complete hydrothermal reaction and promote the formation of cobalt sulfide. More preferably, the heat treatment is carried out in an inert atmosphere, wherein the inert gas in the inert atmosphere is selected from one or more of nitrogen, helium, or argon. The sintering temperature is 1200–1500°C for a time of 0.5–5 h.

[0045] In a preferred embodiment, in step S2, the hydrothermal reaction and heat treatment are repeated 1 to 10 times to coat cobalt sulfide on the outer surface of the yttrium oxide-zirconia support, thereby further improving the structural stability of the catalyst and enhancing its catalytic performance.

[0046] To further prepare the yttrium oxide-zirconia support, the pore-forming agent is preferably selected from one or more of starch, graphite or polymethyl methacrylate, more preferably starch; to further prepare pores in the yttrium oxide-zirconia support, thereby providing a basis for hydrothermal reaction and heat treatment, the heat treatment temperature is preferably 300-700°C and the sintering time is preferably 0.5-5h.

[0047] In a preferred embodiment, the yttrium oxide-zirconia powder contains 8% yttrium oxide by weight and 92% zirconia by weight to improve its mechanical strength as a carrier, enhance its structural stability, and improve its catalytic performance.

[0048] In another aspect, the present invention provides an anode electrode comprising the above-described composite electrode material, or a composite electrode material obtained by a method for preparing composite electrode materials.

[0049] In a preferred embodiment, the anode electrode is obtained by drying a composite electrode material, thereby enhancing the purity of the electrode and improving its electrochemical performance.

[0050] Another aspect of the present invention provides a fuel cell including an anode electrode, wherein the anode electrode is the aforementioned anode electrode.

[0051] The present application will be further described in detail below with reference to specific embodiments, which should not be construed as limiting the scope of protection claimed in the present application.

[0052] Example 1

[0053] YSZ (yttrium oxide-zirconia powder, wherein the molar content of yttrium oxide is 8% and the molar content of zirconia is 92%) was mixed evenly with a starch pore-forming agent at a temperature of 160℃ for 4 hours and a rotation speed of 1000 rpm. Then, it was sintered at 1400℃ for 2 hours. At this high temperature, the pore-forming agent reacted with air, leaving uniform pores to provide impregnation sites. The remaining YSZ (where the molar content of yttrium oxide is 8% and the molar content of zirconia is 92%) served as a carrier. Next, 5 mmol of Co(NO3)2, 20 mmol of thioacetamide, and 25 mmol of urea were dissolved in deionized water and poured into a hydrothermal reactor. The sintered carrier was then completely immersed in the solution, ensuring the liquid completely submerged the carrier. After sealing, it was placed in a hydrothermal reactor and reacted at 180℃ for 4 hours. After removal, it was heat-treated in N2 at 400℃ for 2 hours. This hydrothermal treatment and heat treatment process was repeated 10 times to obtain the composite electrode. In the composite electrode material, the weight ratio of yttrium oxide-zirconia support to cobalt sulfide coating is 2:1. The yttrium oxide-zirconia support has a porous structure with a porosity of 10-30% and a pore size of 20-50 μm. The thickness of the cobalt sulfide coating is 1-5 μm. Figure 3 This is the elemental distribution diagram of the composite electrode material. Figure 4 The current-voltage-power electrochemical performance test curves of this composite electrode material are shown.

[0054] Comparative Example 1

[0055] The only difference from Example 1 is that there is no hydrothermal reaction step. Figure 5 The current-voltage-power electrochemical performance test curves of this composite electrode material are shown.

[0056] Performance testing:

[0057] Take it 0.5 Sr 0.5 Co 0.8 Fe 0.2 O3 material was used as the cathode, and the electrode materials prepared in the above embodiments and comparative examples were used as the anode, with dense Zr as the electrolyte. 0.92 Y 0.8 O2(YSZ) is used as the cathode, which is a porous Ni-YSZ support layer, thus forming a full cell. The voltage and power density versus current density curves of the electrode materials prepared in the test examples and comparative examples at 650℃, 700℃, and 750℃ are shown.

[0058] The products prepared in the above embodiments and comparative examples were subjected to performance tests. The maximum power at the same temperature was tested, and the test results are shown in Table 1.

[0059] Table 1

[0060]

[0061] As can be seen from the above description, the embodiments of the present invention achieve the following technical effects:

[0062] Depend on Figure 1 and Figure 2 SEM images of the cross-sections of the electrode material and carrier prepared in Example 1 show that the carrier skeleton was very smooth before hydrothermal impregnation, and after the hydrothermal impregnation reaction, the surface of the carrier skeleton was uniformly covered with a layer of tiny electrode particles. Figure 3 The elemental distribution diagram of the electrode material prepared in Example 1 shows that the electrode material is the electrode material provided by the present invention.

[0063] Based on the test results of Example 1 and Comparative Example 1, and Figure 4 and Figure 5 The performance test curves show that the electrode material prepared using the method of this invention exhibits superior electrochemical performance. This preparation method is an impregnation-hydrothermal synthesis method, in which the cobalt sulfide active component is grown in situ on the outer surface of a yttrium oxide-zirconia support, thereby further increasing the active sites and making the structure of cobalt sulfide more stable and its catalytic performance better. Moreover, compared with traditional preparation methods, this method is simple to operate, has mild reaction conditions, is suitable for large-scale production, and has a broad industrial application potential.

[0064] While this specification contains numerous specific implementation details, these should not be construed as limiting the scope of any invention or the scope of the claims, but rather are primarily intended to describe features of specific embodiments of a particular invention. Certain features described in the various embodiments herein may also be implemented in combination in a single embodiment. Conversely, various features described in a single embodiment may also be implemented separately in various embodiments or in any suitable sub-combination. Furthermore, while features may function in certain combinations as described above and even initially claimed in this way, one or more features from a claimed combination may be removed from that combination in some cases, and a claimed combination may refer to a sub-combination or a variation thereof.

[0065] Similarly, although the operations are depicted in a specific order in the accompanying drawings, this should not be construed as requiring these operations to be performed in the specific order shown or sequentially, or requiring all illustrated operations to be performed to achieve the desired result. In some cases, multitasking and parallel processing may be advantageous. Furthermore, the separation of various system modules and components in the above embodiments should not be construed as requiring such separation in all embodiments, and it should be understood that the described program components and systems can generally be integrated together in a single software product or packaged into multiple software products.

[0066] Thus, specific embodiments of the subject matter have been described. Other embodiments are within the scope of the appended claims. In some cases, the actions recited in the claims may be performed in a different order and still achieve the desired result. Furthermore, the processes depicted in the drawings are not necessarily shown in a specific order or sequence to achieve the desired result. In some implementations, multitasking and parallel processing may be advantageous.

[0067] It should be noted that, in this document, relational terms such as "first" and "second" are used merely to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0068] The above description is merely a specific embodiment of this application, enabling those skilled in the art to understand or implement this application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of this application. Therefore, this application is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features claimed herein.

Claims

1. A composite electrode material, characterized by, The composite electrode material comprises: a yttria-zirconia carrier having a porous structure, and a surface of the yttria-zirconia carrier is divided into an inner pore surface and an outer surface, which serves as a structural framework of the composite electrode material; a cobalt sulfide coating layer coated on the outer surface of the yttria-zirconia carrier.

2. The composite electrode material of claim 1, wherein, In the composite electrode material, the weight ratio of the yttria-zirconia carrier to the cobalt sulfide coating layer is (1-100):1; and / or The weight ratio of the yttria-zirconia carrier to the cobalt sulfide coating layer is (1-5):

1.

3. The composite electrode material according to claim 1 or 2, characterized in that, The yttria-zirconia carrier has a porous structure, and the porosity thereof is 10-30%, and the pore size is 10-50 μm.

4. The composite electrode material of any one of claims 1 to 3, wherein, The thickness of the cobalt sulfide coating layer is 1-5 μm.

5. A method of producing the composite electrode material according to any one of claims 1 to 4, characterized by, The preparation method comprises: providing a yttria-zirconia carrier; coating cobalt sulfide on the outer surface of the yttria-zirconia carrier to obtain the composite electrode material.

6. The method of claim 5, wherein the composite electrode material is prepared by a process comprising: The preparation method comprises: Step S1: mixing yttria-zirconia powder and a pore-forming agent, and then performing sintering treatment to obtain the yttria-zirconia carrier; Step S2: dispersing cobalt salt, a thio compound and urea in deionized water, then adding the yttria-zirconia carrier to completely immerse the yttria-zirconia carrier, and then sequentially performing hydrothermal reaction and heat treatment, and repeating the hydrothermal reaction and heat treatment to coat cobalt sulfide on the outer surface of the yttria-zirconia carrier to obtain the composite electrode material.

7. The method of claim 6, wherein the composite electrode material is prepared by a process comprising: In the step S2, the cobalt salt is selected from one or more of cobalt nitrate, cobalt acetate or cobalt chloride.

8. The method of claim 6, wherein the composite electrode material is prepared by a process comprising: In the step S2, the hydrothermal reaction is performed in a hydrothermal kettle, and the hydrothermal reaction temperature is 160-220°C, and the reaction time is 0.5-24 h.

9. The method of claim 6, wherein the composite electrode material is prepared by a process comprising: mixing a lithium metal oxide, a conductive agent, and a binder to form a mixture; and coating the mixture on a current collector to form the composite electrode material. In the step S2, the heat treatment is performed in an inert atmosphere, and the inert gas in the inert atmosphere is selected from one or more of nitrogen, helium or argon.

10. The method of claim 6, wherein the composite electrode material is prepared by a process comprising: mixing a lithium metal oxide, a conductive agent, and a binder to form a mixture; and coating the mixture on a current collector to form the composite electrode material. The sintering temperature is 1200-1500°C, and the time is 0.5-5 h.

11. The method of claim 6, wherein the composite electrode material is prepared by a process comprising: mixing a lithium metal oxide, a conductive agent, and a binder to form a mixture; and coating the mixture on a current collector to form the composite electrode material. In the step S2, the thio compound is selected from one or more of thioacetamide, thiourea or sodium thiosulfate.

12. The method of claim 6, wherein the composite electrode material is prepared by a process comprising: In the step S2, the operation number of repeating the hydrothermal reaction and heat treatment is 1-10 to coat cobalt sulfide on the outer surface of the yttria-zirconia carrier.

13. The method of claim 6, wherein the composite electrode material is prepared by a process comprising: mixing a lithium metal oxide, a conductive agent, and a binder to form a mixture; and coating the mixture on a current collector to form the composite electrode material. In the step S2, the weight ratio of the cobalt salt, the thio compound and the urea is (0.5-2):(0.5-2):1 in terms of weight percentage.

14. The method of claim 6, wherein the composite electrode material is prepared by a process comprising: In the step S1, the pore-forming agent is selected from one or more of starch, graphite or polymethyl methacrylate.

15. The method of claim 6, wherein the composite electrode material is prepared by a process comprising: mixing a lithium metal oxide, a conductive agent, and a binder to form a mixture; and coating the mixture on a current collector to form the composite electrode material. The heat treatment temperature is 300-700°C, and the sintering time is 0.5-5 h.

16. The method of claim 6, wherein the composite electrode material is prepared by a process comprising: In the step S1, the pore-forming agent is starch.

17. The method of claim 6, wherein the composite electrode material is prepared by a process comprising: mixing a lithium metal oxide, a conductive agent, and a binder to form a mixture; and coating the mixture on a current collector to form the composite electrode material. In the yttria-zirconia powder, the molar content of yttria is 8%, and the molar content of zirconia is 92%.

18. An anode electrode, characterized by, The anode electrode comprises the composite electrode material according to any one of claims 1-4, or the composite electrode material obtained by the preparation method of the composite electrode material according to any one of claims 5-17.

19. The anode electrode according to claim 18, characterized by The anode electrode is obtained by drying the composite electrode material.

20. A fuel cell comprising an anode electrode, characterised in that, The anode electrode is the anode electrode of claim 18 or 19. The anode electrode is the anode electrode of claim 18 or 19.

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