Anode-supported solid oxide fuel cell and preparation method thereof

Abstract

The present invention discloses an anode-supported solid oxide fuel cell and a preparation method thereof, wherein the anode-supported solid oxide fuel cell comprises: an anode support, comprising an anode support layer, an anode functional layer and a sealing area; the anode support layer is a flat substrate, in which a plurality of gas transmission channels running through the upper and lower sides are arranged; the anode functional layer is arranged on the anode support layer, and is a concave-convex structure, and the protruding part of the concave-convex structure is suspended on the anode support layer; the sealing area is arranged at the end of the anode functional layer; the electrolyte layer is arranged on the anode functional layer, and the edge extends to the sealing area; the cathode layer is arranged on the electrolyte layer, and the cathode layer overlaps with the anode functional layer in position. The anode functional layer of the solid oxide fuel cell is designed as a hollow concave-convex structure, which can increase the active area of ​​the electrochemical reaction of the fuel gas, reduce the influence of activation polarization, and thus improve the electrical performance of the battery.

Description

Technical Field

[0001] The present invention relates to the field of solid oxide fuel cells, and in particular to an anode-supported solid oxide fuel cell and a preparation method thereof. Background Art

[0002] Solid oxide fuel cell configurations include anode-supported, electrolyte-supported and cathode-supported types; anode-supported solid oxide fuel cells are one of the most widely researched, developed and applied types. The electrochemical performance of solid oxide fuel cells is mainly affected by concentration polarization, ohmic polarization and activation polarization. Anode-supported solid oxide fuel cells use thicker anode layers to support electrolyte layers and cathode layers. The thickness of the electrolyte layer is thinner, and the ohmic polarization is significantly reduced, that is, the anode-supported cell is less affected by ohmic polarization; the anode layer of the anode-supported cell is composed of an anode support layer and an anode functional layer. The concentration polarization caused by the fuel gas transmission resistance in the anode support layer and the activation polarization caused by the electrochemical reaction at the three-phase interface in the anode functional layer are the main factors affecting the electrochemical performance of the anode-supported cell.

[0003] CN115064709A discloses a method for constructing an ordered electrode of a high-temperature solid oxide fuel cell / electrolyzer. The invention patent adopts laser irradiation technology to prepare a battery electrode with an ordered concave-convex structure on the surface. The design of the ordered concave-convex structure can effectively expand the interface length between the electrode and the reactant and improve the electrochemical performance of the battery. However, the ordered concave-convex structure of the electrode is a solid structure. The gas phase substance in the electrode is transmitted from the electrode surface to the reaction interface through the micropores made by the pore-forming agent. The micropores formed by the pore-forming agent are tortuous. The diffusion path of the gas phase substance in the electrode is long and the diffusion resistance is large, which is not conducive to the improvement of the electrochemical performance of the battery. Moreover, the laser irradiation technology can only be used for the design of the electrode surface structure, and the processing time is long. CN203871425U discloses a solid oxide fuel cell and a battery stack. The battery in the invention patent presents a solid concave-convex structure. The design of the concave-convex structure is conducive to increasing the effective reaction area of ​​the battery. However, the anode support layer also has the problem of a long diffusion path and a large diffusion resistance for the fuel gas to be transmitted to the reaction interface. In addition, CN218414668U discloses a solid oxide fuel cell structure and a battery stack. In this invention patent, the current collecting layer of the battery is provided with a protruding structure, and the protruding structure cooperates with the metal connecting plate to form a gas flow channel, thereby avoiding processing the gas flow channel on the metal plate, reducing the complexity of the production process, and reducing the processing cost. However, the design of the protruding structure in the current collecting layer does not play any role in improving the electrochemical performance of the battery. Summary of the invention

[0004] The purpose of the present invention is to overcome the shortcomings of the prior art and provide an anode-supported solid oxide fuel cell and a preparation method thereof. The anode functional layer of the solid oxide fuel cell is designed as a concave-convex ordered structure. This design structure can increase the active area of ​​the electrochemical reaction of the fuel gas and reduce the influence of activation polarization, thereby improving the electrical performance of the battery.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is:

[0006] The first aspect of the present invention provides an anode-supported solid oxide fuel cell, comprising the following structure:

[0007] An anode support, the anode support comprising an anode support layer, an anode functional layer and a sealing area; the anode support layer is a flat plate substrate, and a plurality of gas transmission channels running through the flat plate substrate are arranged in the flat plate substrate; the anode functional layer is arranged on the anode support layer and is a concave-convex structure, and the convex part of the concave-convex structure is suspended on the anode support layer; the sealing area is arranged at the end of the anode functional layer to facilitate sealing and assembly;

[0008] An electrolyte layer, wherein the electrolyte layer is disposed on the anode functional layer and an edge of the electrolyte layer extends to the sealing area;

[0009] The cathode layer is disposed on the electrolyte layer, and the cathode layer overlaps with the anode functional layer in position, and the edge of the cathode layer does not extend to the sealing area.

[0010] Preferably, the channel penetrating the anode support layer is a straight hole channel or a nearly straight hole channel; the cross-sectional profile shape of the gas transmission channel penetrating the anode support layer at any position is one or more of circular, elliptical or polygonal.

[0011] Further preferably, the penetrating gas transmission channels in the anode support layer make the porosity of the anode support layer 10%-65%.

[0012] Preferably, the longitudinal cross-sectional profile of the protruding portion of the anode functional layer is in one or more of a polygonal shape and an arc shape; and the supporting surface of the concave portion of the anode functional layer on the anode supporting layer is a planar structure.

[0013] Preferably, the protruding portion of the anode functional layer is connected to a channel running through the flat substrate, and the planar structure of the recessed portion of the anode functional layer on the anode supporting layer is completely supported by the solid portion of the flat substrate or connected to the channel running through the flat substrate.

[0014] Further preferably, a single protruding portion of the anode functional layer is connected to a single or multiple penetrating channels in the flat plate type substrate, and when the planar structure of the concave portion of the anode functional layer on the anode supporting layer is connected to the penetrating channels in the flat plate type substrate, the single concave portion covers the single or multiple penetrating channels in the flat plate type substrate.

[0015] Preferably, the anode support layer, the anode functional layer and the sealing area are integrally formed by additive manufacturing.

[0016] Preferably, the thickness of the anode support layer is 500-1000 μm, the thickness of the anode functional layer is 20-80 μm, the thickness of the electrolyte layer is 20-80 μm, and the thickness of the cathode layer is 20-80 μm.

[0017] The second aspect of the present invention provides a method for preparing the anode-supported solid oxide fuel cell, comprising the following steps:

[0018] An additive manufacturing method is used to prepare an anode support through one-piece molding; an electrolyte layer and a cathode layer are prepared layer by layer on the surface of the anode functional layer by thermal spraying, chemical vapor deposition, plasma spraying or additive manufacturing methods; the electrolyte layer covers the anode functional layer and the edge extends to the sealing area.

[0019] Preferably, the additive manufacturing method of the anode support includes one of stereolithography technology (SLA), digital light processing technology (DLP), fused deposition modeling technology (FDM), direct writing technology (DIW), and selective laser sintering technology (SLS).

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] The solid oxide fuel cell anode functional layer prepared by the present invention is designed as a hollow concave-convex structure, which is connected to the straight hole structure in the anode support layer. On the one hand, the fuel gas can be quickly transmitted from the surface of the support layer to the three-phase interface of the electrochemical reaction by convection. The gas transmission resistance is small and the gas diffusion path is short, which can significantly reduce the influence of concentration polarization. On the other hand, the convex structure is beneficial to increase the length of the three-phase reaction interface, increase the active area of ​​the electrochemical reaction, and significantly reduce the influence of activation polarization. That is, the simultaneous reduction of activation polarization and concentration polarization is beneficial to greatly improve the electrical performance of the battery.

[0022] The present invention adopts additive manufacturing technology to prepare an anode-supported solid oxide fuel cell. The anode functional layer is designed as a hollow concave-convex structure. The shape, area and thickness of this structure can be finely controlled to achieve the optimal state of the electrochemical performance of the battery and the mechanical strength of the structure, thereby obtaining a battery with excellent comprehensive performance.

[0023] The present invention adopts additive manufacturing technology to directly prepare an anode-supported solid oxide fuel cell with a complex structure by integrally forming materials. This not only simplifies the preparation process and shortens the preparation cycle, but also has a high degree of automation in the preparation process, making it easy to promote and apply large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 A three-dimensional model diagram of the solid oxide fuel cell of Example 1;

[0025] Figure 2 is a schematic diagram of the longitudinal cross-sectional structure of the solid oxide fuel cell of Example 1;

[0026] Figure 3 A three-dimensional model diagram of a solid oxide fuel cell of Example 2;

[0027] Figure 4 is a schematic diagram of the longitudinal cross-sectional structure of the solid oxide fuel cell of Example 2;

[0028] Figure 5 A three-dimensional model diagram of a solid oxide fuel cell of Example 3;

[0029] Figure 6 is a schematic diagram of the longitudinal cross-sectional structure of the solid oxide fuel cell of Example 3;

[0030] Markings in the drawings: 100 - anode support; 101 - anode support layer; 1011 - penetrating channel; 102 - anode functional layer; 1021 - protruding portion; 1022 - recessed portion; 103 - sealing area; 200 - electrolyte layer; 300 - cathode layer. DETAILED DESCRIPTION

[0031] The specific embodiments of the present invention are further described below. It should be noted that the description of these embodiments is used to help understand the present invention, but does not constitute a limitation of the present invention. In addition, the technical features involved in each embodiment of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0032] The experimental methods in the following examples are conventional methods unless otherwise specified, and the experimental materials used in the following examples are commercially available unless otherwise specified.

[0033] Example 1

[0034] like Figure 1-2As shown, an anode-supported solid oxide fuel cell comprises: an anode support 100, an electrolyte layer 200 and a cathode layer 300; the anode support 100 comprises an anode support layer 101, an anode functional layer 102 and a sealing area 103; the anode functional layer 102 is arranged on the anode support layer 101, and the sealing area 103 is arranged at the end of the anode functional layer 102; the electrolyte layer 200 is arranged on the anode functional layer 102; and the cathode layer 300 is arranged on the electrolyte layer 200. The anode support layer 101 is a flat plate substrate, and a gas transmission channel 1011 is arranged in the flat plate substrate, which runs through the upper and lower parts; the through channel 1011 is a straight hole channel, and the cross-sectional profile shape of the straight hole channel at any position in the flat plate substrate is the same, and all are regular pentagons. The anode functional layer 102 is a concave-convex ordered structure, which is composed of a protruding portion 1021 and a concave portion 1022; the protruding portion 1021 is suspended on the anode support layer 101, and the concave portion 1022 is supported on the anode support layer 101; the longitudinal section profile of the protruding portion 1021 is a trapezoid, and the supporting surface of the concave portion 1022 on the anode support layer 101 is a plane structure; a single protruding portion 1021 is connected to a single through channel 1011 in the flat substrate, and a single concave portion 1022 on the anode support layer 101 is connected to a single through channel 1011 in the flat substrate. The electrolyte layer 200 covers the anode functional layer 102 and its edge extends to the sealing area 103; the area of ​​the cathode layer 300 is smaller than that of the electrolyte layer 200, and the cathode layer 300 overlaps with the anode functional layer 102 in position.

[0035] The method for preparing the above-mentioned anode-supported solid oxide fuel cell comprises:

[0036] (1) Selecting NiO-8YSZ as the anode support 100 material, selecting 8YSZ as the electrolyte layer 200 material, and selecting LSC as the cathode layer 300 material, thereby determining the preparation materials of the solid oxide fuel cell;

[0037] (2) The structure of the anode support 100 is designed using 3D software. The cross section is designed to be circular with a diameter of 60 mm. The thickness of the anode support layer 101 is designed to be 650 μm. The thickness of the anode functional layer 102 is designed to be 45 μm. A sealing area 103 is designed at the end of the anode functional layer 102. The thickness of the sealing area 103 is 2 mm.

[0038] (3) forming the anode support 100 using digital light processing (DLP) technology according to the design structure, wherein the forming process mainly includes preparing anode slurry, setting printing parameters and forming a three-dimensional structure;

[0039] (4) The green blank prepared by digital light processing (DLP) technology is first cleaned and dried, and then degreased and sintered to obtain an anode support 100 with a dense structure and good mechanical strength;

[0040] (5) The electrolyte layer 200 and the cathode layer 300 are deposited layer by layer on the anode support 100 using chemical vapor deposition technology; the electrolyte layer 200 covers the anode functional layer 102 and its edge extends to the sealing area 103, which is conducive to achieving the sealing of the battery.

[0041] Example 2

[0042] like Figure 3-4 As shown, an anode-supported solid oxide fuel cell comprises: an anode support 100, an electrolyte layer 200 and a cathode layer 300; the anode support 100 comprises an anode support layer 101, an anode functional layer 102 and a sealing area 103; the anode functional layer 102 is arranged on the anode support layer 101, and the sealing area 103 is arranged at the end of the anode functional layer 102; the electrolyte layer 200 is arranged on the anode functional layer 102; and the cathode layer 300 is arranged on the electrolyte layer 200. The anode support layer 101 is a flat plate substrate, and a gas transmission channel 1011 is arranged in the flat plate substrate, which runs through the upper and lower parts; the through channel 1011 is a straight hole channel, and the cross-sectional profile shape of the straight hole channel at any position in the flat plate substrate is the same, and is a square. The anode functional layer 102 is a concave-convex ordered structure, which is composed of a protruding portion 1021 and a concave portion 1022; the protruding portion 1021 is suspended on the anode support layer 101, and the concave portion 1022 is supported on the anode support layer 101; the longitudinal section profile of the protruding portion 1021 is semicircular, and the supporting surface of the concave portion 1022 on the anode support layer 101 is a planar structure; a single protruding portion 1021 is connected to a single through channel 1011 in the flat substrate, and the planar structure of a single concave portion 1022 on the anode support layer 101 is completely supported on the solid part of the flat substrate. The electrolyte layer 200 covers the anode functional layer 102 and the edge extends to the sealing area 103; the area of ​​the cathode layer 300 is smaller than that of the electrolyte layer 200, and the cathode layer 300 overlaps with the anode functional layer 102 in position.

[0043] The method for preparing the above-mentioned anode-supported solid oxide fuel cell comprises:

[0044] (1) Selecting NiO-8YSZ as the anode support 100 material, selecting 8YSZ as the electrolyte layer 200 material, and selecting LSCF as the cathode layer 300 material, thereby determining the preparation materials of the solid oxide fuel cell;

[0045] (2) The structure of the anode support 100 is designed using 3D software. The cross section is designed to be circular with a diameter of 60 mm. The thickness of the anode support layer 101 is designed to be 750 μm. The thickness of the anode functional layer 102 is designed to be 60 μm. A sealing area 103 is designed at the end of the anode functional layer 102. The thickness of the sealing area 103 is 3 mm.

[0046] (3) forming the anode support 100 using digital light processing (DLP) technology according to the design structure, wherein the forming process mainly includes preparing anode slurry, setting printing parameters and forming a three-dimensional structure;

[0047] (4) The green blank prepared by digital light processing (DLP) technology is first cleaned and dried, and then degreased and sintered to obtain an anode support 100 with a dense structure and good mechanical strength;

[0048] (5) The electrolyte layer 200 and the cathode layer 300 are deposited layer by layer on the anode support 100 by ion spraying technology; the electrolyte layer 200 covers the anode functional layer 102 and its edge extends to the sealing area 103, which is conducive to achieving the sealing of the battery.

[0049] Example 3

[0050] like Figure 5-6As shown, an anode-supported solid oxide fuel cell comprises: an anode support 100, an electrolyte layer 200 and a cathode layer 300; the anode support 100 comprises an anode support layer 101, an anode functional layer 102 and a sealing area 103; the anode functional layer 102 is arranged on the anode support layer 101, and the sealing area 103 is arranged at the end of the anode functional layer 102; the electrolyte layer 200 is arranged on the anode functional layer 102; and the cathode layer 300 is arranged on the electrolyte layer 200. The anode support layer 101 is a flat plate substrate, and a gas transmission channel 1011 is arranged in the flat plate substrate, which runs through the upper and lower parts; the through channel 1011 is a straight hole channel, and the cross-sectional profile shape of the straight hole channel at any position in the flat plate substrate is the same, and is a circle. The anode functional layer 102 is a concave-convex ordered structure, which is composed of a protruding portion 1021 and a concave portion 1022; the protruding portion 1021 is suspended on the anode support layer 101, and the concave portion 1022 is supported on the anode support layer 101; the longitudinal section profile of the protruding portion 1021 is a triangle, and the supporting surface of the concave portion 1022 on the anode support layer 101 is a plane structure; a single protruding portion 1021 is connected to a single through channel 1011 in the flat substrate, and the plane structure of a single concave portion 1022 on the anode support layer 101 is completely supported on the solid part of the flat substrate. The electrolyte layer 200 covers the anode functional layer 102 and the edge extends to the sealing area 103; the area of ​​the cathode layer 300 is smaller than that of the electrolyte layer 200, and the cathode layer 300 overlaps with the anode functional layer 102 in position.

[0051] The method for preparing the above-mentioned anode-supported solid oxide fuel cell comprises:

[0052] (1) NiO-8YSZ is selected as the material of the anode support 100, ScSZ is selected as the material of the electrolyte layer 200, and LSCF is selected as the material of the cathode layer 300, thereby determining the preparation materials of the solid oxide fuel cell;

[0053] (2) The structure of the anode support 100 is designed using 3D software. The cross section is designed to be circular with a diameter of 60 mm. The thickness of the anode support layer 101 is designed to be 950 μm. The thickness of the anode functional layer 102 is designed to be 75 μm. A sealing area 103 is designed at the end of the anode functional layer 102. The thickness of the sealing area 103 is 5 mm.

[0054] (3) forming the anode support 100 using digital light processing (DLP) technology according to the design structure, wherein the forming process mainly includes preparing anode slurry, setting printing parameters and forming a three-dimensional structure;

[0055] (4) The green blank prepared by digital light processing (DLP) technology is first cleaned and dried, and then degreased and sintered to obtain an anode support 100 with a dense structure and good mechanical strength;

[0056] (5) The electrolyte layer 200 and the cathode layer 300 are deposited layer by layer on the anode support 100 by thermal spraying technology; the electrolyte layer 200 covers the anode functional layer 102 and its edge extends to the sealing area 103, which is conducive to achieving the sealing of the battery.

[0057] The embodiments of the present invention are described in detail above, but the present invention is not limited to the described embodiments. For those skilled in the art, various changes, modifications, substitutions and variations of these embodiments are made without departing from the principles and spirit of the present invention, and still fall within the protection scope of the present invention.

Claims

1. An anode-supported solid oxide fuel cell, characterized in that: Includes the following structures: An anode support, the anode support comprising an anode support layer, an anode functional layer and a sealing area; the anode support layer is a flat plate substrate, and a plurality of gas transmission channels running through the flat plate substrate are arranged in the flat plate substrate; the anode functional layer is arranged on the anode support layer and is a concave-convex structure, and the convex part of the concave-convex structure is suspended on the anode support layer; the sealing area is arranged at the end of the anode functional layer; the convex part of the anode functional layer is connected with the channel running through the flat plate substrate, and the plane structure of the concave part of the anode functional layer on the anode support layer is completely supported by the entity part of the flat plate substrate or connected with the channel running through the flat plate substrate; An electrolyte layer, wherein the electrolyte layer is disposed on the anode functional layer and an edge of the electrolyte layer extends to the sealing area; The cathode layer is disposed on the electrolyte layer, and the cathode layer overlaps with the anode functional layer in position, and the edge of the cathode layer does not extend to the sealing area.

2. The anode-supported solid oxide fuel cell according to claim 1, characterized in that: The cross-sectional profile of the penetrating gas transmission channel in the anode support layer at any position is one or more of circular, elliptical or polygonal.

3. The anode-supported solid oxide fuel cell according to claim 2, characterized in that: The penetrating gas transmission channels in the anode support layer make the porosity of the anode support layer 10%-65%.

4. The anode-supported solid oxide fuel cell according to claim 1, characterized in that: The longitudinal section profile of the protruding portion of the anode functional layer is in one or more of a polygonal shape and an arc shape; the supporting surface of the concave portion of the anode functional layer on the anode supporting layer is a planar structure.

5. The anode-supported solid oxide fuel cell according to claim 1, characterized in that: A single protruding portion of the anode functional layer is connected to a single or multiple penetrating channels in the flat substrate. When the planar structure of the concave portion of the anode functional layer on the anode support layer is connected to the penetrating channels in the flat substrate, the single concave portion covers the single or multiple penetrating channels in the flat substrate.

6. The anode-supported solid oxide fuel cell according to claim 1, characterized in that: The anode support layer, the anode functional layer and the sealing area are integrally formed by additive manufacturing.

7. The anode-supported solid oxide fuel cell according to claim 1, characterized in that: The thickness of the anode support layer is 500-1000 μm, the thickness of the anode functional layer is 20-80 μm, the thickness of the electrolyte layer is 20-80 μm, and the thickness of the cathode layer is 20-80 μm.

8. A method for preparing an anode-supported solid oxide fuel cell according to any one of claims 1 to 7, characterized in that: The following steps are involved: An additive manufacturing method is used to prepare an anode support through one-piece molding; an electrolyte layer and a cathode layer are prepared layer by layer on the surface of the anode functional layer by thermal spraying, chemical vapor deposition, plasma spraying or additive manufacturing methods; the electrolyte layer covers the anode functional layer and the edge extends to the sealing area.

9. The method for preparing an anode-supported solid oxide fuel cell according to claim 8, characterized in that: The additive manufacturing method of the anode support includes one of stereolithography technology, digital light processing technology, molten deposition technology, direct writing printing technology, and laser selective sintering technology.

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