CN112952170A - Fuel cell/electrolytic cell porous metal support and additive manufacturing method thereof - Google Patents

Fuel cell/electrolytic cell porous metal support and additive manufacturing method thereof Download PDF

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CN112952170A
CN112952170A CN202110181899.1A CN202110181899A CN112952170A CN 112952170 A CN112952170 A CN 112952170A CN 202110181899 A CN202110181899 A CN 202110181899A CN 112952170 A CN112952170 A CN 112952170A
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metal support
porous metal
additive manufacturing
base layer
holes
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刘敏
刘太楷
宋琛
邓春明
董东东
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Institute of New Materials of Guangdong Academy of Sciences
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
    • H01M8/1226—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material characterised by the supporting layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y50/00—Data acquisition or data processing for additive manufacturing
    • B33Y50/02—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1231—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte with both reactants being gaseous or vaporised
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inert Electrodes (AREA)
  • Fuel Cell (AREA)

Abstract

The application discloses a porous metal support body of a fuel cell/an electrolytic cell and a material increase preparation method thereof, belonging to the field of fuel cells/electrolytic cells. The porous metal support includes: a flat base layer and a plurality of through holes integrally formed in the base layer. The through-holes have an equivalent pore diameter of not more than 200 μm, a depth of less than or equal to 1.5 times the thickness of the base layer, and are present in an amount such that the porosity of the base layer is from 5% to 80%. The porous metal support body is integrally formed by additive manufacturing. The molding process comprises the following steps: the method comprises the steps of obtaining a three-dimensional model of the porous metal support body, processing the model, planning a preparation path, preparing an additive manufacturing material, setting preparation parameters and preparing the porous support body. The porous metal support body adopts a through straight hole design and adopts an additive manufacturing technology to realize fine regulation and control of a mechanism in the porous metal support body, and compared with the traditional process, the implementation of the invention is beneficial to efficient electrode development and research and application of a high-performance battery/electrolytic cell.

Description

Fuel cell/electrolytic cell porous metal support and additive manufacturing method thereof
Technical Field
The application relates to the field of fuel cells/electrolytic cells, in particular to a porous metal support body of a fuel cell/electrolytic cell and an additive manufacturing method thereof.
Background
A solid oxide fuel cell/electrolyzer is a highly efficient energy conversion device that can convert the chemical energy of a fuel gas into electrical energy/electrical energy into chemical energy with high efficiency.
Solid oxide fuel cells/electrolyzers consist primarily of an anode, an electrolyte, and a cathode. Currently, there are thicker electrolyte supported solid oxide fuel cells/electrolyzers, thicker anode supported solid oxide fuel cells/electrolyzers, thicker cathode supported solid oxide fuel cells/electrolyzers, and metal supported solid oxide fuel cells/electrolyzers.
Disclosure of Invention
In order to solve the problem that the performance of a metal-supported solid oxide fuel cell/electrolytic cell is poor, the application provides a porous metal support body of the fuel cell/electrolytic cell and an additive manufacturing method thereof.
The application is realized as follows:
in a first aspect, examples of the present application provide a porous metal support for a solid oxide fuel cell/electrolyser as a support structure. The porous support comprises a base layer and a plurality of through straight holes arranged on the base layer. The base layer is flat and has a first surface and a second surface which are oppositely distributed in the thickness direction. All the through straight holes are integrally formed in the base layer and penetrate through the first surface and the second surface. All of the through-holes are present in an amount such that the porosity of the base layer is from 5% to 80%, each of said through-holes having an equivalent pore diameter of not more than 200 μm.
The equivalent aperture can be limited by selecting the maximum perimeter of the cross-sectional profile of the through straight hole. Because, when the equivalent pore diameter of the through-holes is too large, the thickness of the coating layer is increased to prepare a dense coating layer on the surface, and the increase of the thickness entails more impedance and efficiency loss. The calculation mode of the equivalent aperture is as follows:
(1) first, the cross-sectional area S of the straight hole is obtained, if the cross-sectional area S is a square hole, the cross-sectional area S is the product of the side length, and if the cross-sectional area S is a triangular hole, the cross-sectional area S is a half of the height.
(2) And then calculating the diameter of the equivalent circle by taking the obtained cross-sectional area of the through straight hole as the area of the equivalent circle, wherein the calculation formula is as follows:
Figure BDA0002941683170000021
the diameter D value obtained by the above formula is the diameter of the equivalent circle.
In addition, when the number of through holes is too small, the reaction gas in the fuel cell cannot efficiently and smoothly pass through the through holes. When the number of through-going straight holes is too large, it is difficult to prepare a dense coating on the surface thereof, resulting in failure of the battery/electrolytic cell or extremely low efficiency. In other words, a suitable porosity allows, on the one hand, a large passage of the reaction gases, a timely evacuation of the product gases, and, on the other hand, provides sufficient mechanical support for the functional coating made on its surface, thus increasing the service life of the cell/electrolyser.
The porous metal support is made of one or more of iron-based alloy, nickel-based alloy, cobalt-based alloy and chromium-based alloy. The contour shapes of the radial sections penetrating through the straight holes respectively and independently comprise a circle, a square, a diamond, an ellipse, a flat shape or a triangle; the contour shape of the through straight hole on the first surface is the same as or different from the contour shape of the through straight hole on the second surface; the circumferences of the through straight holes along the profile of the radial section are the same or gradually changed in the axial full-length range; the inner wall of the through straight hole is concave-convex or flat.
In a second aspect, examples of the present application provide a method of additive manufacturing of a fuel cell/electrolyser porous metal support, and the method of manufacturing comprises: determining the technical requirements to be met by the porous metal support body, designing the hole type, the pore size and the hole number of straight holes penetrating through the porous metal support body, and drawing a three-dimensional model; slicing the three-dimensional model to obtain two-dimensional cut-layer data, and planning and processing a preparation path according to the obtained two-dimensional cut-layer data to obtain preparation path data which can be executed by the additive manufacturing equipment; determining the type and state of the porous metal support material according to the technical requirements and preparation process requirements to be met by the porous metal support; and guiding the preparation path into additive manufacturing equipment, filling materials, setting preparation parameters, starting automatic preparation, and obtaining the porous metal support body with the through straight hole.
Wherein the additive manufacturing apparatus includes, but is not limited to, a laser 3D printing apparatus, an electron beam 3D printing apparatus. The preparation parameters include one or more of power, scan speed, scan angle, and scan interval of the additive manufacturing. The power range of additive manufacturing is 50-3000W, the scanning speed is 0.5-80 m/s, the scanning angle is 10-90 degrees, and the scanning interval is 20-300 microns.
In the implementation process, the porous substrate with the pore structure of the specific construction mode provided by the embodiment of the application has the advantages of proper porosity, proper pore type and short gas diffusion process, so that the diffusion resistance of the reaction gas is reduced, and the exchange efficiency of the reaction gas is improved.
Compared with the prior art, the scheme of the application example has the following advantages and beneficial effects:
(1) the design of the through straight hole is adopted, so that the diffusion process of the reaction gas is reduced under the condition of ensuring the permeation of the reaction gas, the gas diffusion resistance is reduced, and the open-circuit voltage of the battery/electrolytic cell and the utilization rate of the reaction gas are improved.
(2) The additive manufacturing process is adopted to realize the refined preparation of the porous metal support body with the through straight holes, the precise control of the aperture, the hole pattern and the porosity of the through straight holes is realized under the condition of ensuring the porosity, and meanwhile, the control of the surface state of the porous support body can be realized. Compared with the existing manufacturing processes such as powder metallurgy and the like, the method can realize the accurate control of the internal structure of the porous support body, and is beneficial to the development of an electrode with high-efficiency mass transfer effect and the research and application of a high-efficiency battery/electrolytic cell.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
FIG. 1 is a schematic structural view of a porous matrix in an example of the present application;
FIG. 2 is a schematic diagram of the structure of a solid oxide fuel cell/electrolyser in an example of the present application;
FIG. 3-1 shows a schematic flow diagram of reactant gas and product gas exhaust during operation of the solid oxide fuel cell/electrolyzer of FIG. 2;
FIG. 3-2 is an enlarged partial schematic view of the intake and exhaust in the gas flow direction of FIG. 3-1;
3-3 are schematic diagrams showing reactant and product flow within a porous support having non-through straight pores;
FIG. 4 is a surface topography of a square through straight-hole porous support prepared by additive manufacturing;
FIG. 5 is a micro-topography of a square through straight-hole porous support prepared by additive manufacturing;
FIG. 6 is a surface topography of a square through straight-hole porous support prepared by additive manufacturing when laser spots are lapped;
fig. 7 is a partial schematic structural view of straight through holes provided in a porous substrate in an example of the present application.
Icon: 100-a porous matrix; 101-a base layer; 102-straight through holes; 200-solid oxide fuel cell/electrolyser; 201-a functional layer; 2011-cathode/anode; 2012-electrolyte; 2013-anode/cathode.
Detailed Description
At present, the metal support of the metal-supported solid oxide fuel cell is generally prepared by powder metallurgy technology, so as to obtain the metal support with a pore structure. Alternatively, in some techniques, the hole structure is made by laser drilling. Or, a porous structure is manufactured by hot-pressing sintering, and then the metal material is manufactured in the porous structure by a dipping method, a spraying wet method and the like. In addition, there are other fabrication processes.
However, in practice, the inventors have found that the current metal support fabrication process suffers from a number of drawbacks, even some of which significantly limit the performance of solid oxide fuel cells/electrolyzers.
For example, the porosity and pore structure of powder metallurgically produced metal supports cannot be easily controlled with precision. For example, the porosity of powder metallurgy cannot be predetermined and the structure of the pores is disordered, see fig. 3-3.
For example, laser drilling can only be applied to metal supports with small thickness, and the number, shape and size of holes are limited, which cannot be optimized and adjusted. When the thickness of the metal support is too large, the laser drilling accuracy and speed are greatly reduced. For example, when a metal substrate with a thickness of 2 mm is subjected to laser drilling, the drilled hole has a tapered cross section and a minimum hole diameter of 0.1 mm. If a porous region with a porosity of 50% is to be prepared over an area of 10cm x 15cm, thousands of holes are required, which is extremely time consuming and cannot meet the application requirements.
In general, the inventor realizes that the metal support prepared by the current process has the problem of irregular pore structure, so that the diffusion path of fuel gas in the metal support after entering is long, the diffusion direction is disordered, and the product gas after reaction is slowly discharged under the influence of the diffusion path, thereby limiting the performance of the solid oxide fuel cell/electrolytic cell.
In view of the above-described recognition, the inventors propose a porous matrix having an improved structure. The porous matrix may independently serve as a metal support in direct contact with a functional layer of the battery, such as an anode or cathode.
The metal-supported solid oxide fuel cell/electrolytic cell adopts a porous metal support, and an anode layer or a cathode layer, an electrolyte layer and the cathode layer or the anode layer are sequentially prepared on the porous metal support, so that a cell structure of metal support + anode (or cathode)/electrolyte/cathode (or anode) is formed. The metal-supported solid oxide fuel cell/electrolyzer has the advantages of obviously better cold-heat cycle performance and longer service life compared with other types of solid oxide fuel cells.
Since the metal support is directly contacted with the electrode functional layer, the metal support is required to be contacted tightly without gaps, and the metal support is required to allow gas to enter and discharge product gas, so that the metal support is required to have certain pores. Further, in order to improve the performance of the solid oxide fuel cell/electrolytic cell, it is required that the gas diffusion path inside the porous metal support is as short as possible, i.e., the reaction gas and the product gas can be introduced and discharged in a short time, see fig. 3-1 and fig. 3-2. While avoiding chaotic gas diffusion inside the porous metal support, see fig. 3-3. Therefore, the internal structure of the porous metal support is required to be a through hole and a straight hole or to be approximated to a straight hole.
In addition, since the operating temperature of the solid oxide fuel cell/electrolytic cell is generally 700 ℃ or higher, the metal support used is required to have characteristics such as good high-temperature stability, matching with the thermal expansion coefficient of the cell material, electrochemical stability, and good conductivity at high temperature.
Generally, the porous matrix in the present application has a porous structure of regular shape, thereby facilitating normal and orderly diffusion of the fuel gas, reducing the diffusion path, and facilitating transport of the fuel gas and the product gas. In the example, a regularly shaped porous structure is proposed as "through straight pores". Wherein, if the depth of the hole is less than the thickness of the support body, the hole is a non-through hole; straight holes mean that, in a cross section perpendicular to the thickness direction of the porous substrate holes, the edge line of the pattern of the holes in the cross section is substantially linear. Exemplarily, see fig. 7.
The porous substrate 100 includes a base layer 101 having a flat plate shape. The base layer 101 has a first surface and a second surface which are oppositely distributed in the thickness direction, and the base layer 101 further has a plurality of through straight holes 102 which are integrally formed in the base layer 101 and penetrate through the first surface and the second surface. The structure of the porous matrix 100 in the example is shown in fig. 1.
Wherein each through straight hole equivalent pore diameter is not more than 200 microns. Wherein "radial cross-section" is a plane perpendicular to the first surface (or perpendicular to the second surface). The number of the through holes 102 is limited to 5% to 80% of the porosity of the base layer, with an equivalent pore size of not more than 200 μm. Further, in some examples, the circumference of each through hole 102 along the profile of a cross section perpendicular to the radial direction is 15 to 720 micrometers, and the porosity of the base layer is 10 to 65%. By controlling the equivalent pore diameter, porosity and number of the through-straight pores within a proper range, when preparing the electrode coating and the electrolyte coating thereon, a denser electrolyte coating can be obtained without making the electrode coating too thick.
The through holes 102 may be arranged in a manner that the axial direction is parallel to the thickness direction of the base layer, or may be arranged in a manner that the axial direction intersects the thickness direction of the base layer. When the axial directions of the plurality of through-holes 102 intersect with the thickness direction of the base layer, the length of the through-holes 102 in the axial direction is greater than the thickness of the base layer and equal to or less than 1.5 times, for example, 1.1 times, 1.2 times, 1.3 times, 1.4 times, and the like. If the depth of the through-holes is more than 1.5 times the thickness of the support, the inclination angle of the through-holes is too large, resulting in an increase in the diffusion of the reaction gas in the porous matrix, and accordingly, the gas resistance is also large, and the discharge of the product gas is also made more difficult.
Further, the shape of the through hole 102 may be optional according to different requirements, for example, the contour shape of the radial cross section of the through hole 102 is a circle, a square, a diamond, an ellipse, a flat hole or a triangular hole. A first definition: the contour shape of the radial cross section of each through-hole 102 independently includes a circular, square, diamond, oval, flat or triangular hole.
The through hole 102 may be a cylindrical-like hole in which the inner diameter is constant. However, in other examples, the through hole 102 may have a gradual change in the circumferential length (or inner diameter) along the radial cross-sectional profile over the entire axial length, such as a frustum-shaped through hole 102 (the cross-section in the thickness direction of the substrate is trapezoidal). The inner wall of the through hole 102 may be contoured (e.g., have dimples or protrusions) or flat.
In addition, the above description discusses the arrangement, shape, size, etc. of a single through straight hole 102. It should be noted that in the porous matrix, there are a plurality of through-holes 102, and therefore, the above-described characteristics of different through-holes 102 may be the same or different. For example, a part of the through holes 102 is arranged in the thickness direction of the base layer (the axial direction is parallel to the thickness direction), and the remaining part of the through holes 102 is arranged obliquely in the thickness direction of the base layer (the axial direction intersects the thickness direction).
The base layer is made of metal material and can be one or more of iron-based alloy, nickel-based alloy, cobalt-based alloy and chromium-based alloy.
Based on the porous matrix 100 shown in fig. 1, a solid oxide fuel cell/electrolyser 200 can also be provided, the structure of which is shown in fig. 2. The solid oxide fuel cell/electrolyser 200 comprises a porous substrate 100 and a functional layer 201. Wherein functional layer 201 includes a cathode/anode 2011, an electrolyte 2012, and an anode/cathode 2013. Where the anode/cathode 2013 is in contact with the porous matrix 100.
Based on the porous matrix 100 shown in fig. 1, a solid oxide fuel cell/electrolyser 200 can also be provided, the structure of which is shown in fig. 2. The solid oxide fuel cell/electrolyser 200 comprises a porous substrate 100 and a functional layer 201. Wherein the battery functional layer 201 includes a cathode/anode 2011, an electrolyte 2012, and an anode/cathode 2013. Where the anode/cathode 2013 is in contact with the porous matrix 100.
Since the reactions occurring when the cell and the electrolytic cell are operated are inverse to each other, the structure can be applied to both a fuel cell and an electrolytic cell. When used as a solid oxide fuel cell and an electrolytic cell, the cathode and anode of the two can be reversed with respect to each other. I.e. the anode structure in a fuel cell, and the cathode in an electrolytic cell.
Fig. 3-1 is a schematic flow diagram of the reactant gas inlet (solid arrows) and the product gas outlet (dashed arrows) when the solid oxide fuel cell/electrolyzer 200 is in operation. In particular, the gas flow direction within anode/cathode 2013 is as shown in fig. 3-2. Wherein, the solid line arrows indicate the reaction gas input from the through holes 102 of the porous substrate 100 to the functional layer 201; the dotted arrows indicate the product gas exhaust gas output from the functional layer 201 to the through-holes 102 of the porous substrate 100.
In order to make it easier for the skilled person to carry out the present application, a method for making a porous metal support that can be used as a support in a solid oxide fuel cell/electrolyser is also presented in the examples.
The manufacturing method comprises the following steps.
Step S101: and acquiring a three-dimensional model of the porous metal support.
Determining and designing the hole pattern, the pore size and the hole number of straight holes penetrating through the porous metal support body according to the technical requirements which need to be met by the porous metal support body, and drawing a three-dimensional model;
wherein the porous metal support comprises a plurality of through straight holes and a flat plate-shaped base layer. The base layer is provided with a first surface and a second surface which are oppositely distributed in the thickness direction, and all the through straight holes are integrally formed in the base layer and penetrate through the first surface and the second surface. The plurality of through-holes are present in an amount such that the porosity of the base layer is from 5% to 80%.
Step S102: model processing and preparation path planning.
And slicing the three-dimensional model to obtain two-dimensional cut-layer data, and planning and processing a preparation path according to the obtained two-dimensional cut-layer data to obtain preparation path data which can be executed by the additive manufacturing equipment.
Step S103: preparing an additive manufacturing material
Determining the type and state of the porous metal support material according to the technical requirements and preparation process requirements to be met by the porous metal support;
additive manufacturing is typically performed using powder materials. The selected material may be one or more of iron-based alloy, nickel-based alloy, cobalt-based alloy, and chromium-based alloy. And the manufacturing material may be a granular aggregate, i.e., powder, or a slurry or paste material, corresponding to additive manufacturing. The specific shape of the particles may be, for example, spherical, elliptical or oblate, or even irregular.
Step S104: setting preparation parameters and preparing porous support
Guiding the preparation path in the step S102 into additive manufacturing equipment, filling the manufacturing material in the step S103, setting preparation parameters, starting automatic preparation, and obtaining the porous metal support body with the through straight hole;
the porous matrix with different construction modes can be selected to carry out structure control on the porous matrix according to preparation parameters. The preset parameter may be, for example, one or more of power, scanning speed, scanning angle, and scanning interval of additive manufacturing. Wherein the power may affect the hole dimensional accuracy, surface flatness; the scanning speed influences the hole precision, the preparation efficiency and the defect number; scanning angle control pass; the scan interval controls the aperture size.
In some examples, the predetermined parameter may be a power range of additive manufacturing of 50-300W, a scanning speed of 500-2000 mm/s, and a scanning angle defined by an included angle between scanning paths of two adjacent two-dimensional slices of 30-90 °, wherein the scanning interval is 20-260 μm. In other examples, the preparation parameters can also be that the power range of additive manufacturing is 500-3000W, the scanning speed is 5-80 m/s, the scanning angle is 30-90 degrees with the included angle between the scanning paths of two adjacent two-dimensional slices, and the scanning interval is 100-300 microns.
The present application is described in further detail with reference to examples below.
Example 1
Establishing a three-dimensional model (the structure is shown in figure 1) with a square through straight-hole porous structure through computer drawing, carrying out slicing conversion on the three-dimensional model to obtain two-dimensional slice data, carrying out preparation path planning and generation on the basis of the two-dimensional slice data to obtain preparation path data, introducing the preparation path data into metal 3D printing equipment, and loading 430 stainless steel powder into a printing chamber. The laser power was set at 90 watts, the scan speed was 1000 mm/sec, the scan angle was 90 °, and the scan interval was 150 μm. Subsequently, automatic printing was performed to obtain a porous structure as shown in fig. 4.
Example 2
A three-dimensional model with a square through-hole cellular structure (structure shown in FIG. 1) was created by computer graphics. And slicing and converting the three-dimensional model to obtain two-dimensional slice data, planning and generating a preparation path on the basis of the two-dimensional slice data to obtain preparation path data, introducing the preparation path data into metal 3D printing equipment, and loading 304 stainless steel powder into a printing chamber. The laser power was set at 70 watts, the scan speed was 900 mm/sec, the scan angle was 90 °, the scan interval was 200 μm, and automatic printing was performed to obtain the porous structure shown in fig. 5.
Example 3
A three-dimensional model with a circular through-hole cellular structure (structure shown in FIG. 1) was created by computer graphics. And slicing and converting the three-dimensional model to obtain two-dimensional slice data, planning and generating a preparation path on the basis of the two-dimensional slice data to obtain preparation path data, introducing the preparation path data into metal 3D printing equipment, and filling Inconel625 alloy raw powder into a printing chamber. The circular porous structure as shown in fig. 6 was obtained by performing automatic printing with a laser power of 100 w, a scanning speed of 1300 mm/sec and a scanning interval of 200 μm.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (10)

1. A fuel cell/electrolyser porous metal support for solid oxide fuel cells/electrolysers as support structure, characterized in that it comprises:
a flat plate-like base layer having a first surface and a second surface which are arranged to face each other in a thickness direction;
the through straight holes are integrally formed in the base layer and penetrate through the first surface and the second surface;
each through straight hole has an equivalent pore diameter of not more than 200 microns;
the plurality of through-holes are present in an amount such that the porosity of the base layer is from 5% to 80%.
2. The fuel cell/electrolyzer porous metal support of claim 1, characterized in that each of the through-straight pore equivalent pore sizes is from 10 to 180 microns and the porosity of the base layer is from 10 to 65%.
3. The fuel cell/electrolyzer porous metal support according to claim 1 or 2, characterized in that the axial direction of some or all of the plurality of through-straight holes is parallel to the thickness direction of the base layer;
or the axial direction of part or all of the plurality of through straight holes is crossed with the thickness direction of the base layer, and the length of the through straight holes which are crossed with the thickness direction of the base layer along the axial direction is greater than the thickness of the base layer and is less than or equal to 1.5 times of the thickness of the base layer.
4. The fuel cell/electrolyser porous metal support of claim 1, characterized in that said porous metal support has one or more of the following definitions:
a first definition: the outline shape of the radial section of each through straight hole independently comprises a circle, a square, a diamond, an ellipse, a flat or a triangle;
the second definition: the contour shape of the through straight hole on the first surface is the same as or different from the contour shape of the through straight hole on the second surface;
the third limitation is that: the circumferences of the through straight holes along the profile of the radial section are the same or gradually changed within the axial full-length range;
the fourth limitation is that: the inner wall of the through straight hole is concave-convex or flat.
5. The fuel cell/electrolyzer porous metal support of claim 1 or 4, characterized in that the base layer is made of one or more of iron-based alloy, nickel-based alloy, cobalt-based alloy, chromium-based alloy.
6. A method for additive manufacturing of a porous metal support, the method comprising:
determining the technical requirements to be met by the porous metal support body, designing the hole type, the pore size and the hole number of straight holes penetrating through the porous metal support body, and drawing a three-dimensional model;
slicing the three-dimensional model to obtain two-dimensional cut-layer data, and planning and processing a preparation path according to the obtained two-dimensional cut-layer data to obtain preparation path data which can be executed by the additive manufacturing equipment;
determining the type and state of the porous metal support material according to the technical requirements and preparation process requirements of the porous metal support body;
and guiding the preparation path into additive manufacturing equipment, filling the material, setting preparation parameters, starting automatic preparation, and obtaining the porous metal support body with the through straight holes.
7. The additive manufacturing method of a porous metal support according to claim 6, wherein the manufacturing apparatus comprises a laser 3D printing apparatus, an electron beam 3D printing apparatus.
8. The method of additive manufacturing of a porous metal support according to claim 7, wherein structural control of the porous metal support is performed according to preset parameters, the preset parameters comprising one or more of power, scan speed, scan angle and scan interval of additive manufacturing.
9. The additive manufacturing method of a porous metal support according to claim 8, wherein the adjustment and manufacturing of the porous metal support structure with through holes are realized through the scanning angle and the scanning interval, and the adjustment and manufacturing method includes the internal pore size, the pore type, the porosity and the spatial distribution of the through holes of the porous metal support.
10. The additive manufacturing method of a porous metal support according to claim 8, wherein the power range of additive manufacturing is 50-3000W, the scanning speed is 0.5-80 m/s, the scanning angle is 10-90 degrees, and the scanning interval is 20-300 microns;
optionally, the power range of additive manufacturing is 50-300W, the scanning speed is 500-2000 mm/s, the scanning angle is 30-90 degrees, and the scanning interval is 20-260 microns;
optionally, the power range of additive manufacturing is 500-3000W, the scanning speed is 5-80 m/s, the scanning angle is 30-90 degrees, and the scanning interval is 100-300 microns.
CN202110181899.1A 2021-02-09 2021-02-09 Fuel cell/electrolytic cell porous metal support and additive manufacturing method thereof Pending CN112952170A (en)

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