Power collection network of solid oxide battery and preparation method of power collection network

Abstract

The invention relates to the technical field of solid oxide fuel cells and electrolytic cells, in particular to a power collection network of a solid oxide cell and a preparation method of the power collection network. The current collecting net is oxide AxB3-xO4 with a spinel structure, A and B are respectively selected from one or more of Fe, Co, Ni, Cu, Zn, Mn, Al, Ti, Cr, Ca, Mg, Ce, La, Pr and Gd, A and B are different elements, and x is more than or equal to 0.5 and less than or equal to 2.5; the thickness of the current collecting net ranges from 0.05 mm to 3 mm, and the porosity of the current collecting net ranges from 60% to 98%. The current collecting net provided by the invention has both elasticity and conductivity, can improve the current export efficiency and oxygen electrode mass transfer between the stack oxygen electrode and the bipolar plate, reduces the stack weight to adapt to a lightweight scene, and is low in preparation cost.

Description

Technical Field

[0001] This invention relates to the field of solid oxide fuel cells (SOFC) and electrolyzers (SOEC), and specifically to a current collector grid for a solid oxide battery and its preparation method. Background Technology

[0002] Solid oxide batteries (SOCs) include solid oxide fuel cells (SOFCs) and solid oxide electrolyzers (SOECs). The stack is the core of the SOC. Assembling a planar stack requires components including: hydrogen electrode connection plates, seals, hydrogen electrode current collectors, solar cells, oxygen electrode current collectors, seals, and cathode connection plates. Current is conducted between the electrodes and bipolar plates through physical contact; traditional designs typically use rigid metal contacts such as nickel mesh or hard alloy mesh / plates.

[0003] However, during SOC high-temperature operation (600~1000°C), repeated temperature rises and falls can easily lead to poor interfacial contact due to differences in the thermal expansion coefficients of different component materials, resulting in the following problems: 1) Increased contact resistance: Thermal deformation or oxidation reduces the contact area, increasing ohmic losses. 2) Accumulation of mechanical stress: Rigid contacts cannot compensate for microcracks caused by thermal cycling, accelerating component aging. 3) Uneven current distribution: Localized poor contact causes current density distortion, reducing battery efficiency. Among these, the current extraction resistance between the oxygen electrode and the bipolar plates directly affects the performance and stability of the battery stack. Existing improvement schemes (such as adding an anti-oxidation coating to the bipolar plates) can partially alleviate the problems, but they are difficult to balance high-temperature oxidation resistance, elastic recovery capability, and low contact resistance. Therefore, a new power extraction structure is urgently needed to optimize interface performance. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a solid oxide battery current collector grid and its preparation method.

[0005] In a first aspect, the present invention provides a current collector for a solid oxide battery, wherein the current collector is a spinel-structured oxide A. x B 3-x O4, A, and B are each selected from one or more of Fe, Co, Ni, Cu, Zn, Mn, Al, Ti, Cr, Ca, Mg, Ce, La, Pr, and Gd, and A and B are different elements, with 0.5 ≤ x ≤ 2.5; the thickness of the current collector is 0.05~3 mm, and the porosity of the current collector is 60%~98%. The current collector provided by this invention has both elasticity and conductivity, which can improve the current conduction efficiency between the oxygen electrode and the bipolar plate of the fuel cell stack and the mass transfer of the oxygen electrode, reduce the weight of the fuel cell stack to adapt to lightweight scenarios, and has low manufacturing cost.

[0006] Preferably, the thickness of the current collector is 0.1~3mm, more preferably 0.5~1.5mm. This better adapts to the oxygen electrode structure, enhances the contact stability with the electrode, and improves current conduction efficiency.

[0007] Preferably, the porosity of the current collector is 65%~90%, more preferably 70%~85%. This further optimizes the mass transfer effect of the oxygen electrode, while taking into account structural strength and lightweight design, making it more suitable for the actual operation requirements of the fuel cell stack.

[0008] Further optimization involves A being Mn, and B being selected from one or more of Fe, Co, Ni, Cu, Zn, Al, Ti, Cr, Ca, Mg, Ce, La, Pr, and Gd, where 1 ≤ x ≤ 2.5. Examples include 1.5, 1.8, 1.9, 2, 2.1, and 2.2. When B is two of the above elements, it can be one or two of Co, Ce, Cu, and Ti, such as Co and Ce (molar ratio 0.95:0.05), Cu and Ti (molar ratio 0.95:0.05), etc. This can form a more stable spinel structure, enhancing conductivity and stability under oxidizing atmospheres, and significantly improving current extraction efficiency.

[0009] Secondly, the present invention provides a method for preparing the current collector of the solid oxide battery, comprising: cutting a foam alloy mesh into the same shape as the oxygen electrode according to the area of ​​the oxygen electrode of the battery cell; subjecting the cut foam alloy mesh to high-temperature oxidation treatment, wherein the composition of the foam alloy mesh includes at least two of Fe, Co, Ni, Cu, Zn, Mn, Al, Ti, Cr, Ca, Mg, Ce, La, Pr, and Gd. The current collector preparation process of the present invention includes two processes: current collector alloy mesh cutting and alloy mesh oxidation sintering. By cutting a foam alloy mesh containing at least two target elements and oxidizing it at high temperature, the process is simple and easy to operate. Its application significantly reduces the preparation cost of the battery stack and can efficiently prepare current collectors with the target spinel structure.

[0010] Preferably, the high-temperature oxidation treatment is carried out at a temperature of 300~850℃, more preferably 700~850℃. This ensures that the foam alloy mesh is fully converted into a stable spinel structure oxide, improving the performance stability of the current collector mesh.

[0011] Further preferably, the high-temperature oxidation treatment time is 5-50 hours, more preferably 10-20 hours. This ensures that the alloy mesh is fully and uniformly oxidized, forming a structurally stable spinel current collector mesh and enhancing long-term operating performance.

[0012] More preferably, the atmosphere for the high-temperature oxidation treatment is air or oxygen.

[0013] Thirdly, the present invention provides a solid oxide battery, employing the current collector of the solid oxide battery described above or the current collector of the solid oxide battery obtained by the preparation method described above. The solid oxide battery employing the above-described current collector exhibits excellent current extraction efficiency, stability, and lightweight characteristics, thereby improving the overall performance of the battery.

[0014] Preferably, the current collector is used for the oxygen electrode of the solid oxide battery and is located on the oxygen electrode side of the cell. Using the current collector for the oxygen electrode in this solid oxide battery optimizes current conduction and gas mass transfer between the oxygen electrode and the bipolar plates, significantly improving the oxygen electrode performance and the overall operating efficiency of the battery.

[0015] The beneficial effects of this invention are at least as follows: The current collector of this invention is formed by oxidation of a lightweight foam alloy mesh, resulting in a stable current collector under an oxidizing atmosphere. It possesses both elasticity and conductivity, improving the current conduction efficiency between the oxygen electrode and the bipolar plates of the fuel cell stack. The current collector of this invention has a high porosity, reaching over 70%, which reduces the weight of the current collector mesh while improving mass transfer at the oxygen electrode, thus significantly reducing the weight of the fuel cell stack. This makes it particularly suitable for applications requiring lightweight fuel cell stacks. The current collector of this invention is obtained through the oxidation treatment of a lightweight foam alloy mesh. The lightweight foam alloy mesh is easy to cut and process. Furthermore, the oxidation treatment can be performed during the fuel cell stack heating process without additional processing steps, significantly reducing the manufacturing cost of the fuel cell stack. Detailed Implementation

[0016] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0017] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this invention.

[0018] Unless otherwise specified, specific techniques or conditions in this invention embodiment shall be performed in accordance with the techniques or conditions described in the literature in this field, or in accordance with the product instructions. Devices, instruments, reagents, etc., without specified manufacturers are all conventional products that can be purchased through legitimate channels. All experimental reagents and raw materials involved are commercially available products, and all reagents are analytical grade products. In this invention embodiment, the raw materials used were purchased from Sinopharm Chemical Reagent Co., Ltd.

[0019] Example 1 This embodiment provides a current collector and a solid oxide electrolytic cell stack including the current collector. The current collector is a spinel-structured oxide, Mn₂CoO₄, with a thickness of 1.5 mm and a porosity of 70%. The solid oxide electrolytic cell stack includes 10 battery cells, each with an external dimension of 100 mm * 100 mm. The battery is a hydrogen electrode support structure, and the cathode dimension is 90 mm * 90 mm. The stack assembly, from bottom to top, consists of a lower end plate, a lower insulating plate, a hydrogen electrode current collector end plate, a hydrogen electrode current collector, a seal, battery cells, a seal, an oxygen electrode foam Mn-Co alloy mesh, an oxygen electrode connecting plate, nine repeating units, a seal, an oxygen electrode foam Mn-Co alloy mesh, a seal, an oxygen electrode current collector end plate, an upper insulating plate, and an upper end plate. The repeating units, from bottom to top, are: a hydrogen electrode connecting plate, a hydrogen electrode current collector, a seal, battery cells, a seal, an oxygen electrode foam Mn-Co alloy mesh, and an oxygen electrode connecting plate. The Mn-Co alloy mesh has a Mn to Co molar ratio of 2:1, a thickness of 1.5 mm, and a porosity of 70%. After the fuel cell stack is assembled, it is placed in the test bench and the test bench is started. The hydrogen electrode is fed with N2 at a rate of 0.5 L / min, and the oxygen electrode is fed with air at a rate of 0.5 L / min. The fuel cell stack is heated to 800 °C at a rate of 3 °C / min, and then held at 800 °C for 5 hours. After holding at 800 °C, the oxygen electrode foam Mn-Co alloy mesh transforms into an oxygen electrode current collector mesh with a chemical composition of Mn2CoO4, a thickness of 1.5 mm, and a porosity of 70%.

[0020] The fuel cell stack was then tested. The hydrogen electrode was tested with 5 L / min H2O and 5 L / min H2, while the oxygen electrode was tested with 2 L / min air. The fuel cell stack was at 13V, with an initial current of 30.08A. After 100 hours of testing, the current increased to 32.55A.

[0021] Example 2 This embodiment provides a current collector and a solid oxide electrolytic cell stack including the current collector. The current collector is a spinel-structured oxide, Mn₂CoO₄, with a thickness of 1.5 mm and a porosity of 70%. The solid oxide electrolytic cell stack includes 10 battery cells, each with an external dimension of 100 mm * 100 mm. The battery is a hydrogen electrode support structure, and the cathode dimension is 90 mm * 90 mm. The stack assembly, from bottom to top, consists of a lower end plate, a lower insulating plate, a hydrogen electrode current collector end plate, a hydrogen electrode current collector, a seal, battery cells, a seal, an oxygen electrode foam Mn-Co alloy mesh, an oxygen electrode connecting plate, nine repeating units, a seal, an oxygen electrode foam Mn-Co alloy mesh, a seal, an oxygen electrode current collector end plate, an upper insulating plate, and an upper end plate. The repeating units, from bottom to top, are: a hydrogen electrode connecting plate, a hydrogen electrode current collector, a seal, battery cells, a seal, an oxygen electrode foam Mn-Co alloy mesh, and an oxygen electrode connecting plate. The Mn-Co alloy mesh has a Mn to Co molar ratio of 2:1, a thickness of 1.5 mm, and a porosity of 70%. After the fuel cell stack is assembled, it is placed in the test bench and the test bench is started. The hydrogen electrode is fed with N2 at a rate of 0.5 L / min, and the oxygen electrode is fed with oxygen at a rate of 0.5 L / min. The fuel cell stack is heated to 800 °C at a rate of 3 °C / min, and then held at 800 °C for 5 hours. After holding at 800 °C, the Mn-Co alloy mesh foam of the oxygen electrode transforms into an oxygen electrode current collector with a chemical composition of Mn2CoO4, a thickness of 1.5 mm, and a porosity of 70%.

[0022] The fuel cell stack was then tested. The hydrogen electrode was tested with 5 L / min H2O and 5 L / min H2, while the oxygen electrode was tested with 2 L / min air. The fuel cell stack was at 13V, with an initial current of 30.78A. After 100 hours of testing, the current increased to 32.95A.

[0023] Example 3 This embodiment provides a current collector and a solid oxide electrolytic cell stack including the current collector. The current collector is a spinel-structured oxide, Mn₂CoO₄, with a thickness of 0.3 mm and a porosity of 70%. The solid oxide electrolytic cell stack includes 10 battery cells, each with an external dimension of 100 mm * 100 mm. The battery is a hydrogen electrode support structure, and the cathode size is 90 mm * 90 mm. The stack assembly, from bottom to top, consists of a lower end plate, a lower insulating plate, a hydrogen electrode current collector end plate, a hydrogen electrode current collector, a seal, battery cells, a seal, an oxygen electrode foam Mn-Co alloy mesh, an oxygen electrode connecting plate, nine repeating units, a seal, an oxygen electrode foam Mn-Co alloy mesh, a seal, an oxygen electrode current collector end plate, an upper insulating plate, and an upper end plate. The repeating units, from bottom to top, are: a hydrogen electrode connecting plate, a hydrogen electrode current collector, a seal, battery cells, a seal, an oxygen electrode foam Mn-Co alloy mesh, and an oxygen electrode connecting plate. The Mn-Co alloy mesh has a Mn to Co molar ratio of 2:1, a thickness of 0.3 mm, and a porosity of 70%. After the fuel cell stack is assembled, it is placed in the test bench and the test bench is started. The hydrogen electrode is fed with N2 at a rate of 0.5 L / min, and the oxygen electrode is fed with air at a rate of 0.5 L / min. The fuel cell stack is heated to 800 °C at a rate of 3 °C / min, and then held at 800 °C for 5 hours. After holding at 800 °C, the oxygen electrode foam Mn-Co alloy mesh transforms into an oxygen electrode foam current collector with a chemical composition of Mn2CoO4, a thickness of 0.3 mm, and a porosity of 70%.

[0024] The fuel cell stack was then tested. The hydrogen electrode was tested with 5 L / min H2O and 5 L / min H2, while the oxygen electrode was tested with 2 L / min air. The fuel cell stack was at 13V, with an initial current of 19.07A. After 100 hours of testing, the current increased to 20.13A.

[0025] Example 4 This embodiment provides a current collector and a solid oxide electrolytic cell stack including the current collector. The current collector is a spinel-structured oxide Mn2Co. 0.95 Ce 0.05The solid oxide electrolyzer contains O4, with a thickness of 1.5 mm and a porosity of 70%. It comprises 10 cells, each 100 mm x 100 mm in size, with a hydrogen electrode support structure and a cathode size of 90 mm x 90 mm. The stack assembly, from bottom to top, consists of a lower end plate, a lower insulating plate, a hydrogen electrode current collector plate, a hydrogen electrode current collector mesh, a seal, cells, a seal, an oxygen electrode foam Mn-Cu-Ce alloy mesh, an oxygen electrode connecting plate, nine repeating units, a seal, an oxygen electrode foam Mn-Co-Ce alloy mesh, a seal, an oxygen electrode current collector plate, an upper insulating plate, and an upper end plate. The repeating units, from bottom to top, are: a hydrogen electrode connecting plate, a hydrogen electrode current collector mesh, a seal, cells, a seal, an oxygen electrode foam Mn-Co-Ce alloy mesh, and an oxygen electrode connecting plate. The Mn-Co-Ce alloy mesh has a molar ratio of Mn, Co, and Ce of 2:0.95:0.05, a thickness of 1.5 mm, and a porosity of 70%. After the fuel cell stack was assembled, it was placed in the test bench and the test bench was started. The hydrogen electrode was supplied with N2 at a rate of 0.5 L / min, and the oxygen electrode with air at a rate of 0.5 L / min. The stack was heated to 800 °C at a rate of 3 °C / min and then held at 800 °C for 5 hours. After this holding period, the oxygen electrode foam Mn-Co-Ce alloy mesh transformed into an oxygen electrode foam current collector with a chemical composition of Mn2Co. 0.95 Ce 0.05 O4, with a thickness of 1.5 mm and a porosity of 70%.

[0026] The fuel cell stack was then tested. The hydrogen electrode was tested with 5 L / min H2O and 5 L / min H2, while the oxygen electrode was tested with 2 L / min air. The fuel cell stack was at 13V, with an initial current of 35.48A. After 100 hours of testing, the current increased to 43.26A.

[0027] Example 5 This embodiment provides a current collector and a solid oxide electrolytic cell stack including the current collector. The current collector is a spinel-structured oxide, Mn₂CoO₄, with a thickness of 1.5 mm and a porosity of 70%. The solid oxide electrolytic cell stack includes 10 battery cells, each with an external dimension of 100 mm * 100 mm. The battery is a hydrogen electrode support structure, and the cathode dimension is 90 mm * 90 mm. The stack assembly, from bottom to top, consists of a lower end plate, a lower insulating plate, a hydrogen electrode current collector end plate, a hydrogen electrode current collector, a seal, battery cells, a seal, an oxygen electrode foam Mn-Co alloy mesh, an oxygen electrode connecting plate, nine repeating units, a seal, an oxygen electrode foam Mn-Co alloy mesh, a seal, an oxygen electrode current collector end plate, an upper insulating plate, and an upper end plate. The repeating units, from bottom to top, are: a hydrogen electrode connecting plate, a hydrogen electrode current collector, a seal, battery cells, a seal, an oxygen electrode foam Mn-Co alloy mesh, and an oxygen electrode connecting plate. The Mn-Co alloy mesh has a Mn to Co molar ratio of 2:1, a thickness of 1.5 mm, and a porosity of 70%. After the fuel cell stack is assembled, it is placed in the test bench and the test bench is started. The hydrogen electrode is supplied with N2 at a rate of 0.5 L / min, and the oxygen electrode with air at a rate of 0.5 L / min. The stack is heated to 400 °C at a rate of 3 °C / min, then held at 400 °C for 5 hours, and then heated to 800 °C at a rate of 3 °C / min. After holding at 400 °C, the oxygen electrode foam Mn-Co alloy mesh transforms into an oxygen electrode foam current collector, with a chemical composition of Mn₂CoO₄, a thickness of 1.5 mm, and a porosity of 70%.

[0028] The fuel cell stack was then tested. The hydrogen electrode was tested with 5 L / min H2O and 5 L / min H2, while the oxygen electrode was tested with 2 L / min air. The fuel cell stack was at 13V, with an initial current of 27.18A. After 100 hours of testing, the current increased to 31.05A.

[0029] Example 6 This embodiment provides a current collector and a solid oxide electrolytic cell stack including the current collector. The current collector is a spinel-structured oxide Mn2Cu. 0.95 Ti 0.05The O4 electrode has a thickness of 1.5 mm and a porosity of 65%. The solid oxide electrolyzer stack comprises 10 cells, each with dimensions of 100 mm x 100 mm. The cell features a hydrogen electrode support structure, and the cathode measures 90 mm x 90 mm. The stack assembly, from bottom to top, consists of a lower end plate, a lower insulating plate, a hydrogen electrode current collector plate, a hydrogen electrode current collector mesh, a seal, cells, a seal, an oxygen electrode foam Mn-Cu-Ti alloy mesh, an oxygen electrode connecting plate, nine repeating units, a seal, an oxygen electrode foam Mn-Cu-Ti alloy mesh, a seal, an oxygen electrode current collector plate, an upper insulating plate, and an upper end plate. The repeating units, from bottom to top, are: a hydrogen electrode connecting plate, a hydrogen electrode current collector mesh, a seal, cells, a seal, an oxygen electrode foam Mn-Cu-Ti alloy mesh, and an oxygen electrode connecting plate. The Mn-Cu-Ti alloy mesh has a molar ratio of Mn, Cu, and Ti of 2:0.95:0.05, a thickness of 1.5 mm, and a porosity of 65%. After the fuel cell stack was assembled, it was placed in the test bench and the test bench was started. The hydrogen electrode was supplied with N2 at a rate of 0.5 L / min, and the oxygen electrode with air at a rate of 0.5 L / min. The stack was heated to 800 °C at a rate of 3 °C / min and then held at 800 °C for 2 hours. After this holding period, the oxygen electrode foam Mn-Cu-Ti alloy mesh transformed into an oxygen electrode foam current collector with a chemical composition of Mn₂Cu. 0.95 Ti 0.05 O4, with a thickness of 1.5 mm and a porosity of 65%.

[0030] The fuel cell stack was then tested. The hydrogen electrode was tested with 5 L / min H2O and 5 L / min H2, while the oxygen electrode was tested with 2 L / min air. The fuel cell stack was at 13V, with an initial current of 34.15A. After 100 hours of testing, the current increased to 38.73A.

[0031] Comparative Example 1 A solid oxide electrolyzer stack including a foam current collector. The stack comprises 10 solar cells, each with dimensions of 100mm x 100mm. The cells have a hydrogen electrode support structure, and the cathode dimensions are 90mm x 90mm. The stack assembly, from bottom to top, consists of a lower end plate, a lower insulating plate, a hydrogen electrode current collector plate, a hydrogen electrode current collector, a seal, solar cells, a seal, an oxygen electrode Ag mesh, an oxygen electrode connecting plate, nine repeating units, a seal, an oxygen electrode Ag mesh, a seal, an oxygen electrode current collector, an upper insulating plate, and an upper end plate. The repeating units, from bottom to top, are: a hydrogen electrode connecting plate, a hydrogen electrode current collector, a seal, solar cells, a seal, an oxygen electrode Ag mesh, and an oxygen electrode connecting plate. The Ag mesh has a thickness of 0.3mm, a porosity of 30%, and a unit price of [missing information]. After the stack assembly is completed, it is placed in a test bench, and the test bench is started. The hydrogen electrode is fed with N2 at a rate of 0.5 L / min, and the oxygen electrode is fed with air at a rate of 0.5 L / min. The fuel cell stack is heated to 800 °C at a rate of 3 °C / min.

[0032] The fuel cell stack was then tested. The hydrogen electrode was tested with 5 L / min H2O and 5 L / min H2, while the oxygen electrode was tested with 2 L / min air. The fuel cell stack was at 13V, with an initial current of 29.47A. After 100 hours of testing, the current increased to 28.22A.

[0033] Comparative Example 2 A solid oxide electrolyzer stack including a current collector network. The stack comprises 10 solar cells, each with dimensions of 100mm x 100mm. The cells have a hydrogen electrode support structure, and the cathode dimensions are 90mm x 90mm. The stack assembly, from bottom to top, consists of a lower end plate, a lower insulating plate, a hydrogen electrode current collector end plate, a hydrogen electrode current collector network, a seal, solar cells, a seal, an oxygen electrode foam Co mesh, an oxygen electrode connecting plate, nine repeating units, a seal, an oxygen electrode foam Co mesh, a seal, an oxygen electrode current collector end plate, an upper insulating plate, and an upper end plate. The repeating units, from bottom to top, are: a hydrogen electrode connecting plate, a hydrogen electrode current collector network, a seal, solar cells, a seal, an oxygen electrode foam Co mesh, and an oxygen electrode connecting plate. The foam Co mesh has a thickness of 1.5mm and a porosity of 70%. After the stack assembly is completed, it is placed in a test bench, and the test bench is activated. The hydrogen electrode is fed with N2 at a rate of 0.5 L / min, and the oxygen electrode is fed with air at a rate of 0.5 L / min. The stack is heated to 800 °C at a rate of 3 °C / min and then held at 800 °C for 5 hours. After holding, the foam Co mesh of the oxygen electrode is transformed into a current collector with the chemical composition Co3O4.

[0034] The fuel cell stack was then tested. The hydrogen electrode was tested with 5 L / min H2O and 5 L / min H2, while the oxygen electrode was tested with 2 L / min air. The fuel cell stack was at 13V, with an initial current of 26.47A. After 100 hours of testing, the current increased to 28.98A.

[0035] Comparative Example 3 A solid oxide electrolyzer stack including a current collector network. The stack comprises 10 solar cells, each with dimensions of 100mm x 100mm. The cells have a hydrogen electrode support structure, and the cathode dimensions are 90mm x 90mm. The stack assembly, from bottom to top, consists of a lower end plate, a lower insulating plate, a hydrogen electrode current collector end plate, a hydrogen electrode current collector network, a seal, solar cells, a seal, an oxygen electrode foam Mn-Co alloy mesh, an oxygen electrode connecting plate, nine repeating units, a seal, an oxygen electrode foam Mn-Co alloy mesh, a seal, an oxygen electrode current collector end plate, an upper insulating plate, and an upper end plate. The repeating units, from bottom to top, are: a hydrogen electrode connecting plate, a hydrogen electrode current collector network, a seal, solar cells, a seal, an oxygen electrode foam Mn-Co alloy mesh, and an oxygen electrode connecting plate. The Mn-Co alloy mesh has a Mn to Co molar ratio of 2:1, a thickness of 1.5mm, and a porosity of 70%. After the stack assembly is completed, it is placed in a test bench, and the test bench is activated. The hydrogen electrode is fed with N2 at a rate of 0.5 L / min, and the oxygen electrode is fed with air at a rate of 0.5 L / min. The stack is heated to 300 °C at a rate of 3 °C / min and then held at 300 °C for 5 hours. After holding, the foam Mn-Co alloy of the oxygen electrode is transformed into the oxygen electrode current collector, with a chemical composition of Mn2CoO4 and Mn-Co alloy. Due to the low oxidation temperature and short oxidation time, the surface of the foam Mn-Co alloy is oxidized to Mn2CoO4, while the interior remains Mn-Co alloy.

[0036] The stack was then tested. The hydrogen electrode was tested with 5 L / min H₂O and 5 L / min H₂, while the oxygen electrode was tested with 2 L / min air. At 13V, the initial current was 28.98 A, and after 100 hours of testing, the current increased to 25.34 A. A comparison of Example 1 with Comparative Examples 1 and 2 shows that the solid oxide electrolytic cell stack loaded with the spinel structure current collector of this invention exhibits significantly improved performance, demonstrating excellent electrochemical performance and long-term operational stability. The comparison between Example 1 and Comparative Example 3 demonstrates the importance of thorough high-temperature oxidation treatment for obtaining a high-performance current collector. Examples 1-6 of this invention use spinel structure oxides with specific compositions and high porosity, formed by in-situ high-temperature oxidation of a foam alloy mesh, as the current collector, effectively improving current extraction efficiency, gas mass transfer efficiency, and long-term operational stability, all achieving excellent electrolytic performance.

[0037] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A current collector for a solid oxide cell, characterized by, The current collector is an oxide A of spinel structure x B 3-x O4, A and B are each selected from one or more of Fe, Co, Ni, Cu, Zn, Mn, Al, Ti, Cr, Ca, Mg, Ce, La, Pr, Gd, and A and B are different elements, 0.5≤x≤2.5; the thickness of the current collector is 0.05-3 mm, and the porosity of the current collector is 60%-98%.

2. The current collector of a solid oxide cell according to claim 1, characterized in that The thickness of the current collecting web is 0.1-3 mm, preferably 0.5-1.5 mm.

3. The current collector of a solid oxide cell according to claim 1 or 2, characterized in that The porosity of the current collecting web is 65%-90%, preferably 70%-85%.

4. The current collector of a solid oxide cell according to any one of claims 1 to 3, characterized in that A is Mn, B is selected from one or more of Fe, Co, Ni, Cu, Zn, Al, Ti, Cr, Ca, Mg, Ce, La, Pr, Gd, and 1≤x≤2.

5.

5. The method of producing a current collector for a solid oxide cell according to any one of claims 1 to 4, characterized in that, The method comprises: According to the oxygen electrode area of the battery piece, the foam alloy web is cut into the same shape as the oxygen electrode; the cut foam alloy web is subjected to high-temperature oxidation treatment, and the composition of the foam alloy web comprises at least two of Fe, Co, Ni, Cu, Zn, Mn, Al, Ti, Cr, Ca, Mg, Ce, La, Pr, and Gd.

6. The production method according to claim 5, characterized by, The temperature of the high-temperature oxidation treatment is 300-850°C, preferably 700-850°C.

7. The production method according to claim 5 or 6, characterized by, The time of the high-temperature oxidation treatment is 5-50 hours, preferably 10-20 hours.

8. The method of any one of claims 5-7, wherein, The atmosphere of the high-temperature oxidation treatment is air or oxygen.

9. A solid oxide cell, characterized by The current collecting web of the solid oxide battery according to any one of claims 1-4 or the current collecting web of the solid oxide battery prepared by the method according to any one of claims 5-8.

10. The solid oxide cell of claim 9, wherein, The current collecting web is used for the oxygen electrode of the solid oxide battery.