A method for producing a porous anode support

Abstract

This invention relates to the field of solid oxide battery technology, specifically disclosing a method for preparing a porous anode support for solid oxide fuel cells, comprising the following steps: Step S10, introducing a dry mixture of Ni and YSZ powder into the powder supply chamber of a 3D printer, scanning it with a first energy and a first scanning speed, and then scanning it with a second energy and a second scanning speed to obtain a bottom layer structure; Step S20, scanning the bottom layer structure with a third energy and a third speed to obtain a porous anode support; wherein, the first scanning speed is greater than the second scanning speed, the first energy is less than the second energy, the third speed is not less than the first scanning speed, and the third energy is greater than the second energy. This invention, by layering and proportioning different energies and scanning speeds, produces a porous anode support with a simple process, low cost, and high operability.

Description

Technical Field

[0001] This invention relates to the field of solid oxide battery technology, and in particular to a method for preparing a porous anode support. Background Technology

[0002] Solid oxide fuel cells (SOFCs) are all-solid-state chemical power generation devices that can directly convert the chemical energy of fuel into electrical energy under medium- and high-temperature environments. Their power generation efficiency reaches 45%–60%, and their combined heat and power (CHP) efficiency is over 80%, making them one of the key technologies in the current new energy field. Traditional SOFC fabrication methods typically include casting, molding, screen printing, vacuum evaporation, and magnetron sputtering. Among these, casting, molding, and screen printing require lengthy debinding and high-temperature co-firing, resulting in long fabrication cycles and high costs. Furthermore, after high-temperature co-firing, it is difficult to obtain a porous anode structure with an ideal three-phase interface. Vacuum evaporation and magnetron sputtering methods have high requirements for equipment and materials. In addition, traditional fabrication processes are not only complex and have extremely long production cycles, leading to considerable overall costs, but these methods can only produce simple configurations, severely restricting the development of SOFC technology. Summary of the Invention

[0003] The main objective of this invention is to propose a method for preparing a porous anode support, aiming to overcome the disadvantages of difficult preparation and high manufacturing cost of porous anode supports.

[0004] To achieve the above objectives, the present invention proposes a method for preparing a porous anode support, the method comprising the following steps:

[0005] Step S10: The dried Ni and YSZ mixed powder is introduced into the powder supply chamber of the 3D printer, and scanned 3 to 5 times with the first laser to obtain the bottom layer structure. The energy of the first laser is the first energy, and the speed of the first laser is the first scanning speed.

[0006] Step S20: A porous anode support is formed by scanning the underlying structure with a second laser.

[0007] The first energy increases with the number of scans in the range of 12W to 20W, and the first scanning speed decreases with the number of scans in the range of 200mm / s to 334mm / s.

[0008] Optionally, the first energy is A, where 60W ≤ A ≤ 120W;

[0009] The first scanning speed is B, where 400mm / s≤A≤1400mm / s.

[0010] Optionally, the second laser includes a second energy and a second scanning speed, wherein the second energy is C, where 180W≤C≤200W, and the second scanning speed is D, where 1400mm / s≤D≤1800mm / s.

[0011] Optionally, in step S10, the scan is performed under a nitrogen atmosphere; and / or,

[0012] In step S20, the scan is performed under a nitrogen atmosphere.

[0013] Optionally, before step S10, the method further includes:

[0014] Step S110: Mix Ni powder and YSZ powder and dry at 80℃~100℃ for 2h~4h to obtain the dried Ni and YSZ mixed powder.

[0015] Optionally, the mass ratio of the Ni powder to the YSZ powder is (4:6 to 6:4).

[0016] Optionally, before step S110, the method further includes:

[0017] Step S109: Use 3D modeling software to create a 3D model, use slicing software to slice the model, and import the data into the 3D printer.

[0018] Optionally, in step S10, the substrate used in the 3D printer is a stainless steel substrate.

[0019] The method for preparing a porous anode support provided by this invention utilizes a novel material system combining the different material properties of metals and ceramics. Simultaneously, process parameters are controlled, with a first laser scanning 3 to 5 times. The energy of the first laser gradually increases with each scan, while the scanning speed gradually decreases. This setup prevents Ni and YSZ powders from separating due to density differences. Rapid scanning also reduces breakage and splashing of the YSZ powder. Utilizing the low melting point of Ni powder, it melts at lower energy levels, acting as a binder to effectively hold the YSZ powder in place. Increasing the scanning energy and decreasing the scanning speed allows for thorough sintering and melting of the YSZ powder, further enhancing the bonding strength and facilitating better printing and forming the underlying structure. Subsequent scanning with a second laser ensures rapid melting and sintering of the mixed Ni and YSZ powders, preventing them from shifting and maintaining their original powder accumulation. The higher scanning speed also ensures that the powder particles do not receive sufficient energy for complete sintering, resulting in a semi-sintered state. Ultimately, a porous structure with a well-distributed powder accumulation is obtained, forming a porous anode support. This method of layering and proportioning different energies and scanning speeds makes the fabrication process of porous anode supports simpler and more controllable. Attached Figure Description

[0020] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0021] Figure 1 This is a schematic flowchart of an embodiment of the porous anode support preparation method provided by the present invention;

[0022] Figure 2 A physical image of the Ni-YSZ anode porous support for a solid fuel cell printed according to Embodiment 1 of the present invention (one of them);

[0023] Figure 3 The image shown is a physical picture (second part) of the porous Ni-YSZ anode support for a solid fuel cell printed according to Embodiment 1 of the present invention.

[0024] Figure 4 Metallographic image of the cross-section of the Ni-YSZ anode porous support for a solid fuel cell printed in Embodiment 1 of the present invention;

[0025] Figure 5 This is a SEM image of the cross-section of the Ni-YSZ anode porous support for a solid fuel cell printed in Example 1 of the present invention.

[0026] The realization of the objective, functional features and advantages of the present invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0027] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them.

[0028] It should be noted that, unless specific conditions are specified in the embodiments, conventional conditions or conditions recommended by the manufacturer should be followed. Reagents or instruments whose manufacturers are not specified are all commercially available products. Furthermore, the meaning of "and / or" throughout the text includes three parallel solutions; for example, "A and / or B" includes solution A, solution B, or a solution that simultaneously satisfies A and B. In addition, the technical solutions of the various embodiments can be combined with each other, but this must be based on the ability of those skilled in the art to implement them. When the combination of technical solutions is contradictory or impossible to implement, such a combination should be considered non-existent and not within the scope of protection claimed by this invention. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without inventive effort are within the scope of protection of this invention.

[0029] Traditional manufacturing processes are not only complex and time-consuming, resulting in high overall costs, but they can also only produce simple configurations, severely hindering the development of solid oxide fuel cell technology. Selective laser melting (SLM) 3D printing technology and a "metal + ceramic" material system utilize the low melting point of metal as a binder for shaping. By controlling laser energy to achieve a "semi-sintered" powder deposition state, and combining "energy-incremental rapid scanning" and "high-energy rapid" technologies, porous anode supports are fabricated. This method offers advantages such as simple process, high operability, short preparation cycle, and the ability to effectively utilize the short process and flexible fabrication capabilities of 3D printing technology to create complex configurations.

[0030] In view of this, please refer to Figure 1 This invention proposes a method for preparing a porous anode support, comprising the following steps:

[0031] Step S10: The dry Ni and YSZ mixed powder is introduced into the powder supply chamber of the 3D printer and scanned 3 to 5 times with the first laser to obtain the bottom layer structure. The energy of the first laser is the first energy, and the speed of the first laser is the first scanning speed.

[0032] Before step S10, the method further includes:

[0033] Step S109: Use 3D modeling software to create a 3D model, use slicing software to slice it, and import the data into the 3D printer.

[0034] Specifically, the three-dimensional model is a 10×10×10mm cube, and is sliced ​​using the slicing software Autodesk-Netfabb. The data is then imported into a 3D printer, where the substrate of the 3D printer is a 316L stainless steel substrate, and the 3D printer is an SLM printer, model SP-1003D.

[0035] Step S110: Mix Ni powder and YSZ powder and dry at 80℃~100℃ for 2h~4h to obtain dry Ni and YSZ mixed powder.

[0036] It is worth noting that both Ni powder and YSZ powder are micron-sized powders. Ni powder is spherical or near-spherical with a diameter of 5–30 μm, while YSZ powder is spherical granulated powder with a diameter of 10–45 μm. The mass ratio of Ni powder to YSZ powder is (4:6 to 6:4). After mixing the Ni and YSZ powders, ball milling is performed. In this embodiment, mechanical ball milling is used, specifically dry ball milling. The ball mill is a GMS1-4 jar mill, the grinding media is 1.0 mm 99% zirconia beads, the material-to-ball ratio is 1:3, the ball milling speed is 200–400 RPM, and the ball milling time is 8–12 hours. The mixture is then dried at 80–100℃ for 2–4 hours to obtain a dry mixed powder of Ni and YSZ.

[0037] Specifically, in step S10, the first energy is A, where 60W ≤ A ≤ 120W, and the first scanning speed is B, where 400mm / s ≤ B ≤ 1400mm / s. This configuration, using the first energy and the first scanning speed, employs a low-energy, high-speed scan to prevent the Ni and YSZ powders from separating due to density differences in the dried Ni and YSZ mixed powder. The high-speed scan also reduces YSZ powder breakage and splashing. Furthermore, utilizing the low melting point of Ni powder, it melts even at low energy, fusing with the stainless steel substrate and acting as a binder to effectively fix the YSZ powder. The use of progressively increasing energy and progressively decreasing scanning speed aims to melt and sinter the YSZ powder, bonding it to the substrate and improving adhesion. The slow scanning speed ensures the YSZ powder is fully sintered.

[0038] It is worth noting that step S10 is performed entirely under a nitrogen atmosphere. The resulting bottom layer structure has three, four, and five layers, formed by successive scanning with the first laser. To make the bottom layer structure more stable, each layer is scanned three to five times with the corresponding first energy and first speed.

[0039] Step S20: A porous anode support is formed by scanning the underlying structure with a second laser.

[0040] The second laser includes a second energy and a second scanning speed, wherein the second energy is C, where 180W ≤ C ≤ 200W, and the second scanning speed is D, where 1400mm / s ≤ D ≤ 1800mm / s. Step S20 is performed entirely under a nitrogen atmosphere. The high-energy, rapid scanning allows the mixed Ni and YSZ powders to melt and sinter quickly, preventing them from moving and maintaining their original powder accumulation state. Simultaneously, the rapid scanning ensures that the mixed Ni and YSZ powder particles do not receive sufficient energy for complete sintering, resulting in a semi-sintered state. Ultimately, a porous structure with a distributed accumulation state is obtained, forming a porous anode support.

[0041] In the technical solution provided by this invention, a metal with a low melting point is used as a binder for molding. By controlling the process parameters, a porous structure is first obtained using low energy and high scanning speed. Then, the energy is gradually increased and the scanning speed is decreased to allow the powder to melt and sinter rapidly. Finally, high energy and high scanning speed are used to ensure that the molten particles do not have enough time to diffuse, migrate, bond, sinter, and grow into a dense structure, thereby obtaining a porous anode support. This method of layering and proportioning with different energies and scanning speeds makes the fabrication process of the porous anode support simpler and more controllable.

[0042] The technical solution of the present invention will be further described in detail below with reference to specific embodiments and accompanying drawings. It should be understood that the following embodiments are only used to explain the present invention and are not intended to limit the present invention.

[0043] Example 1

[0044] (1) Ni powder with a mass ratio of 5μm to 30μm and YSZ powder with a mass ratio of 1:1 were mixed and then dry ball milled. The ball mill was a GMS1-4 jar mill, the grinding media was zirconia beads with a diameter of 1.0mm and a purity of 99, the material-to-ball ratio was 1:3, the ball milling speed was 300 RPM, and the ball milling time was 10h.

[0045] (2) After ball milling, the mixed powder of Ni and YSZ was dried at 90°C for 3 hours to obtain dried mixed powder of Ni and YSZ.

[0046] (3) A three-dimensional model was created using three-dimensional modeling software. The model was a 10×10×10mm cube. The slicing software Autodesk-Netfabb was used for slicing. The data was then imported into the 3D printer. The substrate of the 3D printer was a 316L stainless steel substrate.

[0047] (4) The dry Ni and YSZ mixed powder is introduced into the powder supply chamber of the 3D printer and the three-layer structure is scanned with the first laser. The scanning gap is 0.04mm and each layer is scanned 4 times. The starting energy of the first energy is 60W and the ending energy is 120W, which increases with the number of scans in increments of 20W. The starting speed of the first scanning speed is 400mm / s and the ending speed is 1400mm / s, which decreases with the number of scans in increments of 334mm / s.

[0048] (5) Scan the subsequent powder layer structure on the bottom layer structure at 190W and 1600mm / s, with a scanning gap of 0.02mm and a thickness of 30μm for each layer. Scan each layer once to obtain a porous anode support.

[0049] Example 2

[0050] (1) Ni powder with a mass ratio of 5μm to 30μm and YSZ powder with a mass ratio of 10μm to 45μm were mixed at a mass ratio of 4:6 and then dry ball milling was carried out. The ball mill was a GMS1-4 jar mill, the grinding media was zirconia beads with a diameter of 1.0mm and a purity of 99, the material-to-ball ratio was 1:3, the ball milling speed was 200RPM, and the ball milling time was 8h.

[0051] (2) After ball milling, the mixed powder of Ni and YSZ is dried at 80℃~100℃ for 2h~4h to obtain dried mixed powder of Ni and YSZ.

[0052] (3) A three-dimensional model was created using three-dimensional modeling software. The model was a 10×10×10mm cube. The slicing software Autodesk-Netfabb was used for slicing. The data was then imported into the 3D printer. The substrate of the 3D printer was a 316L stainless steel substrate.

[0053] (4) The dry Ni and YSZ mixed powder is introduced into the powder supply chamber of the 3D printer and the first laser scans the four-layer structure with a scanning gap of 0.04mm. Each layer is scanned 4 times: the initial energy of the first energy is 60W and the final energy is 120W, which increases with the number of scans by 15W. The initial speed of the first scanning speed is 400mm / s and the final speed is 1400mm / s, which decreases with the number of scans by 250mm / s.

[0054] (5) Scan the subsequent powder layer structure on the bottom layer structure at 200W and 1800mm / s, with a scanning gap of 0.02mm and a thickness of 30μm for each layer. Scan each layer once to obtain a porous anode support.

[0055] Example 3

[0056] (1) Ni powder with a mass ratio of 5μm to 30μm and YSZ powder with a mass ratio of 10μm to 45μm were mixed at a mass ratio of 6:4 and then dry ball milling was carried out. The ball mill was a GMS1-4 jar mill, the grinding media was zirconia beads with a diameter of 1.0mm and a purity of 99, the material-to-ball ratio was 1:3, the ball milling speed was 400RPM, and the ball milling time was 12h.

[0057] (2) After ball milling, the mixed powder of Ni and YSZ was dried at 100°C for 4 hours to obtain dried mixed powder of Ni and YSZ.

[0058] (3) A three-dimensional model was created using three-dimensional modeling software. The model was a 10×10×10mm cube. The slicing software Autodesk-Netfabb was used for slicing. The data was then imported into the 3D printer. The substrate of the 3D printer was a 316L stainless steel substrate.

[0059] (4) The dry Ni and YSZ mixed powder is introduced into the powder supply chamber of the 3D printer and the five-layer structure is scanned with the first laser. The scanning gap is 0.04mm and each layer is scanned 5 times. The starting energy of the first energy is 60W and the ending energy is 120W, which increases with the number of scans in increments of 12W. The starting speed of the first scanning speed is 400mm / s and the ending speed is 1400mm / s, which decreases with the number of scans in increments of 200mm / s.

[0060] (5) Scan the subsequent powder layer structure on the bottom layer structure at 180W and 1400mm / s, with a scanning gap of 0.02mm and a thickness of 30μm for each layer. Scan each layer once to obtain a porous anode support.

[0061] Example 4

[0062] (1) Ni powder with a mass ratio of 5μm to 30μm and YSZ powder with a mass ratio of 1:1 are mixed and then dry ball milled. The ball mill is a GMS1-4 jar mill, the grinding media is zirconia beads with a diameter of 1.0mm and a purity of 99, the material-to-ball ratio is 1:3, the ball milling speed is 400RPM, and the ball milling time is 8h to 12h.

[0063] (2) After ball milling, the mixed powder of Ni and YSZ is dried at 80℃~100℃ for 4h to obtain dried mixed powder of Ni and YSZ.

[0064] (3) A three-dimensional model was created using three-dimensional modeling software. The model was a 10×10×10mm cube. The slicing software Autodesk-Netfabb was used for slicing. The data was then imported into the 3D printer. The substrate of the 3D printer was a 316L stainless steel substrate.

[0065] (4) The dry Ni and YSZ mixed powder is introduced into the powder supply chamber of the 3D printer and the three-layer structure is scanned with the first laser. The scanning gap is 0.04mm and each layer is scanned 4 times. The starting energy of the first energy is 60W and the ending energy is 120W, which increases with the number of scans in increments of 20W. The starting speed of the first scanning speed is 400mm / s and the ending speed is 1400mm / s, which decreases at a rate of 334mm / s.

[0066] (5) Scan the subsequent powder layer structure on the bottom layer structure at 180W and 1700mm / s, with a scanning gap of 0.02mm and a thickness of 30μm for each layer. Scan each layer once to obtain a porous anode support.

[0067] Example 5

[0068] (1) Ni powder with a mass ratio of 5μm to 30μm and YSZ powder with a mass ratio of 1:1 were mixed and then dry ball milled. The ball mill was a GMS1-4 jar mill, the grinding media was zirconia beads with a diameter of 1.0mm and a purity of 99, the material-to-ball ratio was 1:3, the ball milling speed was 300RPM, and the ball milling time was 12h.

[0069] (2) After ball milling, the mixed powder of Ni and YSZ is dried at 80℃~100℃ for 4h to obtain dried mixed powder of Ni and YSZ.

[0070] (3) A three-dimensional model was created using three-dimensional modeling software. The model was a 10×10×10mm cube. The slicing software Autodesk-Netfabb was used for slicing. The data was then imported into the 3D printer. The substrate of the 3D printer was a 316L stainless steel substrate.

[0071] (4) The dry Ni and YSZ mixed powder is introduced into the powder supply chamber of the 3D printer and the five-layer structure is scanned with the first laser. The scanning gap is 0.04mm and each layer is scanned 4 times. The starting energy of the first energy is 60W and the ending energy is 120W, which increases with the number of scans in increments of 12W. The starting speed of the first scanning speed is 400mm / s and the ending speed is 1400mm / s, which decreases with the number of scans in increments of 200mm / s.

[0072] (5) Scan the subsequent powder layer structure on the bottom layer structure at 190W and 1600mm / s, with a scanning gap of 0.02mm and a thickness of 30μm for each layer. Scan each layer once to obtain a porous anode support.

[0073] Results Analysis

[0074] Please see Figure 2 and Figure 3 As shown in the figure, a porous Ni-YSZ cermet sample was successfully printed using SLM 3D printing technology. The printed sample is a complete block structure without obvious cracks or deformation. The printed sample has good forming effect, good surface quality, and compact structure, which demonstrates the effectiveness of the Ni-YSZ cermet printed by the porous anode support preparation method provided by this invention.

[0075] Please see Figure 4 and Figure 5 , Figure 4 Metallographic image of a cross-section of a Ni-YSZ porous anode support for a solid fuel cell printed by SLM. Figure 5 This is a SEM image of a cross-section of a Ni-YSZ porous anode support for a solid fuel cell, printed using SLM. The image clearly shows that the internal structure of the Ni-YSZ cermet is a uniformly distributed porous structure, consisting of a small number of larger pores and a large number of micropores. The largest macropores are approximately 200–400 μm, while the micropores are at the sub-micron level, meeting the basic requirements for porous structures in solid fuel cell anode supports.

[0076] The above are merely preferred embodiments of the present invention and do not limit the patent scope of the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the patent protection scope of the present invention.

Claims

1. A method for preparing a porous anode support for a solid oxide fuel cell, characterized in that, Includes the following steps: Step S10: Mix Ni powder and YSZ powder and dry at 80℃~100℃ for 2h~4h to obtain the dried Ni and YSZ mixed powder. Introduce the dried Ni and YSZ mixed powder into the powder supply chamber of the 3D printer and scan it 3~5 times with the first laser to obtain the bottom layer structure. The energy of the first laser is the first energy, and the speed of the first laser is the first scanning speed. The mass ratio of Ni powder to YSZ powder is (4∶6~6∶4). Step S20: A porous anode support is formed by scanning the underlying structure with a second laser. Wherein, the first energy increases with the number of scans in the range of 12W to 20W, and the first scanning speed decreases with the number of scans in the range of 200mm / s to 334mm / s; the first energy is A, where 60W≤A≤120W; the first scanning speed is B, where 400mm / s≤B≤1400mm / s. The second laser includes a second energy and a second scanning speed, wherein the second energy is C, where 180W≤C≤200W, and the second scanning speed is D, where 1400mm / s≤D≤1800mm / s; The substrate used in the 3D printer is a stainless steel substrate.

2. The method for preparing a porous anode support for a solid oxide fuel cell as described in claim 1, characterized in that, In step S10, the scan is performed under a nitrogen atmosphere; and / or, In step S20, the scan is performed under a nitrogen atmosphere.

3. The method for preparing a porous anode support for a solid oxide fuel cell as described in claim 1, characterized in that, Before step S10, the method further includes: Step S109: Use 3D modeling software to create a 3D model, use slicing software to slice the model, and then import the data into the 3D printer.

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