KR102600903B1 - Method for manufacturing metal supported solid oxide fuel cell using light sintering - Google Patents

Abstract

The present invention includes preparing a metal support, manufacturing an anode layer on the metal support using an optical sintering process, manufacturing an electrolyte layer on the anode layer, By providing a manufacturing method of a metal-supported solid oxide fuel cell (SOFC) that includes the step of manufacturing a cathode layer on an electrolyte layer, optical sintering is performed instead of the existing thermal sintering process, thereby eliminating the existing heat sintering process. It has the effect of solving the problem of oxidation of the metal support caused by the sintering process and the problem of performance degradation due to material diffusion.

Description

Manufacturing method of metal-supported solid oxide fuel cell using optical sintering {METHOD FOR MANUFACTURING METAL SUPPORTED SOLID OXIDE FUEL CELL USING LIGHT SINTERING}

The present invention relates to a method of manufacturing a solid oxide fuel cell, and more specifically, to a method of manufacturing a metal-supported solid oxide fuel cell including the step of forming an anode layer using an optical sintering process.

In the manufacturing process of the anode, electrolyte, and cathode, which are components of a metal-supported solid oxide fuel cell (SOFC), the conventional technology consists of a porous metal support. A method of stacking elements sequentially and thermally sintering the components using a sintering furnace was used, but the process time was delayed and production costs were high because the temperature required for sintering ceramic electrodes and electrolytes was high. There were increasing problems.

In addition, restrictions on high-temperature sintering occur due to the oxidation characteristics of the metal support at high temperature, and the performance of the metal support and oxidation electrode deteriorates due to material diffusion between the metal support and the oxidation electrode at high temperature, and the heat due to an increase in the difference in thermal expansion coefficient Various complex problems occurred, including the occurrence of thermal stress.

To solve this problem, conventionally, in the case of a non-vacuum process, a diffusion prevention layer is applied between the metal support and the anode, and the reduction is performed to prevent oxidation of the metal support. Although the method of sintering in an atmosphere is applied, it has the limitation that productivity is greatly reduced due to the additional increase in the manufacturing process and equipment. On the other hand, a method of manufacturing a metal support-type solid oxide fuel cell using a vacuum deposition process such as sputtering or pulse laser deposition, rather than a non-vacuum method to avoid such high temperature sintering, is also being introduced. These methods also require heat treatment after manufacturing in order for the ceramic electrode and electrolyte to exhibit appropriate performance, and oxidation of the gold support is a problem during this process.

The present invention replaces the method of high-temperature heat treatment for a long time in a conventional electric furnace in manufacturing a metal-supported solid oxide fuel cell including a porous metal support, an anode, an electrolyte, and an air electrode, and uses a light sintering method in which irradiation is performed for a short period of time. The aim is to provide a manufacturing method for a metal-supported solid oxide fuel cell.

In order to achieve the problem to be solved, a method for manufacturing a metal-supported solid oxide fuel cell (SOFC) is provided.

A method of manufacturing a metal-supported solid oxide fuel cell (SOFC) according to an embodiment of the present invention includes preparing a metal support, forming a cathode precursor layer on the metal support, and a photo-sintering process on the cathode precursor layer. It includes manufacturing an anode layer using, manufacturing an electrolyte layer on the anode layer, and manufacturing a cathode layer on the electrolyte layer. do.

The optical sintering process may use white light emitted from any one selected from the group consisting of a xenon flash lamp, neon (Ne) flash lamp, and krypton (Kr) flash lamp.

The photosintering process may be performed 1 to 100 times per cycle.

In one cycle of the photosintering process, the light irradiation time is 0.01 to 50 ms, the pulse gap is 0.01 to 5000 ms, the pulse number is 1 to 100, and the metal The support temperature may be 0 to 600° C. and the light irradiation intensity may be 100 to 180 J/cm ² .

The cathode precursor layer is any one selected from Group A consisting of NiO and LST (Lanthanum strontium titanate) and Group B consisting of YSZ (Yttria stabilized zirconia), GDC (Gadolinia doped ceria), and LSGM (Lanthanum strontium gallate magnesite). It can include either one.

The electrolyte layer is a group consisting of scandia stabilized zirconia (ScSZ), Yttria stabilized zirconia (YSZ), Samaria doped ceria (SDC), Gadolinia doped ceria (GDC), Lanthanum strontium gallate magnesite (LSGM), and Erbium stabilized bismuth oxide (ESB). It may contain at least one or more substances selected from.

The air cathode layer may be any one selected from the group consisting of a lanthanum oxide-based perovskite material, a double perovskite structure-based material, and a nickelate-based material.

The electrolyte layer and the cathode layer may be manufactured through a heat treatment process, an optical sintering process, or a combination process thereof.

The heat sintering process can be performed at 1000 to 1400 °C for 2 to 5 hours.

A metal-supported solid oxide fuel cell (SOFC) according to another embodiment of the present invention may be manufactured using the above manufacturing method.

The metal-supported solid oxide fuel cell (SOFC) may be characterized in that diffusion of chromium (Cr) or iron (Fe) of the metal support in the metal-supported solid oxide fuel cell into the anode layer is suppressed.

According to an embodiment of the present invention, by performing optical sintering instead of the existing thermal sintering process, there is an effect of solving the problem of oxidation of the metal support and performance degradation due to material diffusion caused by the existing thermal sintering process.

In addition, material diffusion between the metal support and the anode can be suppressed, which not only solves the problem of thermal expansion and performance degradation, but also simplifies the equipment installation since it does not require a reducing atmosphere such as hydrogen gas. .

In addition, sintering proceeds for a short time under atmospheric conditions, which has the effect of reducing process time and maximizing productivity.

Figure 1 shows a process diagram of a method for manufacturing a metal-supported solid oxide fuel cell according to an embodiment of the present invention.
Figure 2 shows a detailed process diagram of the manufacturing method of a metal-supported solid oxide fuel cell in one embodiment of the present invention.
Figure 3 shows a scanning electron microscope (SEM) image of a sample prepared according to an embodiment of the present invention.
Figure 4 shows the results of EDX mapping of a sample prepared according to an embodiment of the present invention.
Figure 5 shows the results of EDX line profile of a sample prepared according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings and the contents described in the accompanying drawings, but the present invention is not limited or limited by the embodiments.

The terminology used herein is for describing embodiments and is not intended to limit the invention. As used herein, singular forms also include plural forms, unless specifically stated otherwise in the context. As used herein, “comprises” and/or “comprising” refers to the presence of one or more other components, steps, operations and/or elements. or does not rule out addition.

As used herein, “embodiment,” “example,” “aspect,” “example,” etc. should be construed to mean that any aspect or design described is better or advantageous than other aspects or designs. It's not like that.

The terms used in the description below have been selected as general and universal in the related technical field, but there may be different terms depending on technological developments and/or changes, customs, technicians' preferences, etc. Accordingly, the terms used in the description below should not be understood as limiting the technical idea, but should be understood as illustrative terms for describing embodiments.

In addition, in certain cases, there are terms arbitrarily selected by the applicant, and in this case, the detailed meaning will be described in the relevant description. Therefore, the terms used in the description below should be understood based on the meaning of the term and the overall content of the specification, not just the name of the term.

Meanwhile, terms such as first and second may be used to describe various components, but the components are not limited by the terms. Terms are used only to distinguish one component from another.

Additionally, a part of an act, layer, area, component request, etc., is said to be "on" or "on" another part, not only when it is directly on top of the other part, but also when there are other acts, layers, areas, or components in between. Also includes cases where etc. are included.

Unless otherwise defined, all terms (including technical and scientific terms) used in this specification may be used with meanings that can be commonly understood by those skilled in the art to which the present invention pertains. Additionally, terms defined in commonly used dictionaries are not to be interpreted ideally or excessively unless clearly specifically defined.

Meanwhile, in describing the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description will be omitted. In addition, the terminology used in this specification is a term used to appropriately express the embodiments of the present invention, and may vary depending on the intention of the user or operator or the customs of the field to which the present invention belongs. Therefore, definitions of these terms should be made based on the content throughout this specification.

Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings.

The present invention relates to a method of manufacturing a metal support type solid oxide fuel cell (SOFC) including a structure in which a metal support, an anode layer, an electrolyte layer, and a cathode layer are sequentially stacked.

Figure 1 shows a process diagram of a manufacturing method for a metal-supported solid oxide fuel cell according to one form of the present invention, comprising steps of preparing a metal support (S100) and forming an anode layer on the metal support (S200). , forming an electrolyte layer on the anode layer (S300) and forming an air electrode layer on the electrolyte layer (S400).

The method of manufacturing a metal-supported solid oxide fuel cell according to one embodiment of the present invention further includes forming a cathode precursor layer between preparing a metal support and forming an anode layer, wherein the anode layer is formed. The step may be forming through optical sintering.

More specifically, referring to FIG. 2, the specific manufacturing method of the metal support type solid oxide fuel cell includes preparing a metal support (S110), forming a cathode precursor layer on the metal support (S210), and forming the cathode. It includes forming an anode layer on the precursor layer using a photosintering process (S310), forming an electrolyte layer on the anode layer (S410), and forming a cathode layer on the electrolyte layer (S510). It is done.

Referring to FIG. 2, the step of forming a cathode precursor layer is further included between preparing the metal support and manufacturing the anode layer.

The cathode precursor layer may be laminated by a non-vacuum process, a vacuum process, or a combination thereof.

The non-vacuum process may be screen printing, spin coating, dip coating, or spray coating, and more specifically, solutions, inks, and pastes ( It may be performed by screen printing, spin coating, dip coating, or spray coating.

The vacuum process may be physical vapor deposition (PVD), chemical vapor deposition (CVD), or a combination thereof. The physical vapor deposition may be sputtering or pulsed laser deposition (PLD). The chemical vapor deposition may be atomic layer deposition (ALD).

When laminating the cathode precursor layer by the non-vacuum process, the anode layer may be formed by performing optical sintering after heat treatment to prevent rapid evaporation of organic substances. More specifically, optical sintering may be performed after low-temperature heat treatment. You can. At this time, the heat treatment may be performed at 200 to 500 ° C. for 1 to 5 hours.

The optical sintering process may use white light emitted from a xenon flash lamp, neon (Ne), or krypton (Kr) flash lamp, and the white light is the sum of visible light in the wavelength range of about 300 nm to 800 nm. It can be. More specifically, it is desirable to use microwave white light (Intense Pulsed Light, IPL) emitted from a xenon flash lamp.

The xenon flash lamp is the most popular because it has the advantage of relatively high efficiency and high light intensity compared to other lamps.

The photosintering process may be performed 1 to 100 times based on one cycle, and the photosintering conditions for each cycle performed 1 to 100 times may be the same or different. .

In one cycle of the photosintering process, the light irradiation time is 0.01 to 50 ms, the pulse gap is 0.01 to 5000 ms, the pulse number is 1 to 100, and the substrate The temperature is 0 to 600 ℃, and the light irradiation intensity is 100 to 180 J/㎠. It may be energy, and the preferred light irradiation intensity may be 150 to 171 J/cm2.

If the light irradiation time range, the pulse interval range, the pulse number range, the substrate temperature range, and the light irradiation intensity range are not met, sintering for particle growth and crystallinity development is not properly achieved due to insufficient light energy, If this range is exceeded, physical defects such as film peeling and cracks may occur due to too strong light energy.

The optical sintering process can adjust the light irradiation time, pulse interval, pulse number, and number of cycles, which are one cycle conditions, within each range, and preferably has energy within the light irradiation intensity range. One cycle conditions such as light irradiation time, pulse interval, number of pulses, and number of cycles can be adjusted.

At this time, the voltage of the lamp used in the photosintering process may be 650 to 700V, and preferably, the voltage of the xenon flash lamp used in the photosintering process may be 650 to 700V.

At this time, the temperature of the substrate may be the temperature of the metal support.

In the method of manufacturing a metal-supported solid oxide fuel cell according to one form of the present invention, an optical sintering process such as white light is performed for a very short time (within 10 s), so the metal support generated in the sintering process using existing heat energy is used. It can solve the problem of diffusion of oxides of the (substrate) and materials (Ni, Fe, Cr, etc.) between the metal support and the anode, and also has the advantage of reducing process time and cost, making mass production possible.

The metal support may be a material made of a metal, an alloy, or a combination thereof. More specifically, it may be one or more materials selected from the group consisting of stainless steel, Fe-Cr alloy, and Ni-Fe alloy. .

The cathode precursor layer is one selected from Group A consisting of nickel oxide (NiO) and Lanthanum strontium titanate (LST), and Group B consisting of Yttria stabilized zirconia (YSZ), Gadolinia doped ceria (GDC), and Lanthanum strontium gallate magnesite (LSGM). It may include one selected from .

That is, the material group included in the cathode precursor layer may be one from the group consisting of NiO + YSZ, NiO + GDC, NiO + LSGM, LST + YSZ, LST + GDC, and LST + LSGM.

The electrolyte layer forming step further includes forming an electrolyte precursor layer before forming the electrolyte layer.

The electrolyte precursor layer may be laminated by a non-vacuum process, a vacuum process, or a combination thereof.

The non-vacuum process may be screen printing, spin coating, dip coating, or spray coating, and more specifically, solutions, inks, and pastes ( It may be performed by screen printing, spin coating, dip coating, or spray coating.

The vacuum process may be physical vapor deposition (PVD), chemical vapor deposition (CVD), or a combination thereof. The physical vapor deposition may be sputtering or pulsed laser deposition (PLD). The chemical vapor deposition may be atomic layer deposition (ALD).

When laminating an electrolyte precursor layer by the non-vacuum process, the anode layer may be formed by performing optical sintering after heat treatment to prevent rapid evaporation of organic substances. More specifically, optical sintering may be performed after low-temperature heat treatment. You can. At this time, the heat treatment may be performed at 200 to 500 ° C. for 1 to 5 hours.

The electrolyte layer may be formed of the electrolyte precursor layer through a heat sintering process, a light sintering process, or a mixture of these processes, and if necessary, heat sintering and light sintering to increase light sintering efficiency or lower the heat sintering temperature. It can be applied in combination on a net basis, or light sintering and heat sintering can be applied sequentially.

When forming the electrolyte layer, the thermal sintering process and the optical sintering process are applied in combination in order to lower the thermal sintering temperature, or when the optical sintering process and the thermal sintering process are applied sequentially, the thermal sintering process is optical sintering. Pre-heat treatment to remove organic substances before the process can be performed at 200 to 500 ° C. for 1 to 5 hours.

However, when forming the electrolyte layer, the heat sintering process alone, which is not applied in combination or sequentially with the light sintering process as described above, can be sintered at 1300 to 1400°C for 5 hours.

The optical sintering process used when forming the electrolyte layer can be manufactured using the optical sintering process conditions applied when forming the anode layer.

The electrolyte layer is a group consisting of scandia stabilized zirconia (ScSZ), Yttria stabilized zirconia (YSZ), Samaria doped ceria (SDC), Gadolinia doped ceria (GDC), Lanthanum strontium gallate magnesite (LSGM), and Erbium stabilized bismuth oxide (ESB). It may contain one or more substances selected from.

The air cathode layer forming step further includes forming an air cathode precursor layer before forming the air cathode layer.

The cathode precursor layer may be laminated by a non-vacuum process, a vacuum process, or a combination thereof.

The non-vacuum process may be screen printing, spin coating, dip coating, or spray coating, and more specifically, solutions, inks, and pastes ( It may be performed by screen printing, spin coating, dip coating, or spray coating.

The vacuum process may be physical vapor deposition (PVD), chemical vapor deposition (CVD), or a combination thereof. The physical vapor deposition may be sputtering or pulsed laser deposition (PLD). The chemical vapor deposition may be atomic layer deposition (ALD).

When laminating the cathode precursor layer by the non-vacuum process, the anode layer may be formed by performing optical sintering after heat treatment to prevent rapid evaporation of organic substances. More specifically, optical sintering may be performed after low-temperature heat treatment. You can. At this time, the heat treatment may be performed at 200 to 500 ° C. for 1 to 5 hours.

The air cathode layer may be formed by using the air cathode precursor layer through a heat sintering process, a light sintering process, or a combination process thereof, and, if necessary, heat sintering and light sintering to increase the light sintering efficiency or lower the heat sintering temperature. It can be applied in combination on a net basis, or light sintering and heat sintering can be applied sequentially.

When forming the air electrode layer, thermal sintering and optical sintering are applied in combination to lower the thermal sintering temperature, or when optical sintering and thermal sintering are applied sequentially, the thermal sintering is performed to remove organic substances before optical sintering. Pre-heat treatment may be performed at 200 to 500° C. for 1 to 5 hours.

However, when forming the air gap layer, the heat sintering process alone, which is not applied in combination or sequentially with the optical sintering process as described above, can be sintered at 1000 to 1100°C for 2 hours.

The optical sintering process used when forming the air electrode layer can be manufactured using the optical sintering process conditions applied when forming the anode layer.

The air cathode layer may be a lanthanum oxide-based perovskite material, a double perovskite structure-based material, or a nickelate-based material. The lanthanum oxide-based perovskite material includes lanthanum-strontium manganese oxide (LSM), lanthanum-strontium cobalt oxide (LSC), lanthanum-strontium iron oxide (LSF), lanthanum-strontium cobalt iron oxide (LSCF), and samarium-strontium iron oxide (LSCF). It may be one or more types selected from the group consisting of strontium cobalt oxide (SSC). The double perovskite structure-based material may be PBNO (PrBaNi ₂ O _5+δ ) or PBCO (PrBaCO ₂ O _5+δ ). The nickelate-based material may be lanthanum nickelate (LNO) or PNO (Pr ₂ NiO _4+δ ).

According to another embodiment of the present invention, a metal-supported solid oxide fuel cell (SOFC) is provided, which is manufactured by the above manufacturing method.

The metal-supported solid oxide fuel cell (SOFC) suppresses the diffusion of oxides of the metal support (substrate) and substances such as Ni, Fe, Cr, etc. between the metal support and the anode generated in the sintering process using existing heat energy. It is characterized as a metal-supported solid oxide fuel cell (SOFC), which is a metal-supported solid oxide fuel cell (SOFC) in which substances contained in the metal support do not diffuse into the anode layer. (SOFC).

Hereinafter, the present invention will be described in more detail through examples. These examples are for illustrating the present invention in more detail, and the scope of the present invention is not limited by these examples.

Preparation example 1.

Metal support preparation process and coating of cathode precursor layer

A stainless steel substrate (metal support) is manufactured using commercial stainless steel powder (~325 mesh, Type 430-L (Alfa aesar)).

에서 4시간 소결한다. Put 1g of stainless steel powder into a 12 mm After 1050

Sinter for 4 hours.

Before proceeding with the sintering, the process of maintaining a low vacuum of -100 kPa for 5 minutes using a vacuum pump and filling the mixed gas with 5% H ₂ and 95% Ar to normal pressure is repeated three times to remove and reduce the air inside the sintering furnace. Create an atmosphere. In addition, while sintering is in progress, a mixed gas of 5% H ₂ and 95% Ar is supplied at a constant flow rate of 100 sccm (standard cubic centimeter per minute). The metal support substrate manufactured using stainless steel has a size of 12 mm x 12 mm x 1 mm.

A NiO-YSZ cathode precursor layer is formed on the metal support substrate.

The NiO-YSZ cathode precursor layer uses commercial NiO-YSZ paste. The commercial NiO-YSZ paste composition ratio is NiO:8YSZ = 57:43, BET = 8.73m2/g, PSD(d50) = 0.43um NiO-YSZ paste (Kceracell) is used, and coated through screen printing method. , After coating with NiO-YSZ paste, dry at 100°C for 1 hour.

Example 1.

Fuel layer formation process

The metal support coated with the NiO-YSZ cathode precursor layer through Preparation Example 1 is sintered using white light emitted from a xenon flash lamp.

The voltage of the xenon flash lamp is 700V, irradiation time is 10ms, rest time is 500ms, and sintering is performed by irradiating white light in one cycle under the conditions of 6 pulse. The sintering is performed only for one cycle.

At this time, the light energy has a total energy of 171J/cm2. When irradiated with light, an Al ₂ O ₃ plate with a thickness of 5 mm is placed at the bottom of the metal support to increase heat capacity and prevent rapid heat transfer to the lower substrate. Additionally, during photosintering, the temperature of the metal support coated with the cathode precursor layer is maintained at 460°C using a heater. The fuel layer formed after sintering has a thickness of 15 to 30 μm.

Example 2.

Electrolyte layer formation process (manufactured by non-vacuum process)

The metal support on which the fuel layer was formed in Example 1 was coated twice using a screen printing method using 8 mol% YSZ commercial paste (K-ceracell), and dried at 100° C. for 1 hour. Thereafter, heat sintering is performed at a temperature of approximately 1300 to 1400° C. for 5 hours. At this time, during heat sintering, a reducing atmosphere is created and sintered, similar to the production of the stainless steel substrate in Preparation Example 1. The manufactured electrolyte membrane has a thickness of approximately 8 to 10 μm.

Example 3.

Electrolyte layer formation process (manufactured by vacuum process)

₉₀ W (composition ratio: 90 W ( Deposit for 10 hours at a power of 0.4 A) and a process pressure of 5 mTorr. The manufactured electrolyte membrane has a thickness of approximately 1 to 2 μm.

Example 4.

Air layer formation process

On the metal support on which the electrolyte layer was formed according to Example 2 or Example 3, a commercial paste of La-Sr-Co-Fe oxide (LSCF) was applied (composition ratio: La:Sr:Co:Fe:O=0.6:0.4:0.2: 0.8:3), coated twice using a screen printing method, and dried at 100°C for 1 hour.

Afterwards, it is heat sintered at a temperature of approximately 1050°C for 2 hours. At this time, during heat sintering, a reducing atmosphere is created and sintered, similar to the production of the stainless steel substrate in Preparation Example 1. The manufactured air cathode membrane has a thickness of approximately 20 to 30 um.

Comparative Example 1.

Through Preparation Example 1, the metal support (stainless steel substrate) coated with the NiO-YSZ cathode precursor layer was sintered at 1200°C for 4 hours. When sintering is performed, a reducing atmosphere is created and sintered, similar to the production of the stainless steel substrate in Preparation Example 1. Before proceeding with sintering, the process of maintaining a low vacuum of -100 kPa for 5 minutes using a vacuum pump and filling the mixed gas with 5% _{H2 and} 95% Ar up to normal pressure was repeated three times to remove air inside the sintering furnace and create a reducing atmosphere. Create.

In addition, while sintering is in progress, a mixed gas of 5% H ₂ and 95% Ar is supplied at a constant flow rate of 100 sccm. The formed fuel layer has a thickness of 15 to 30 μm.

Characteristic evaluation 1.

The surface of the anode layer on the metal support prepared according to Preparation Example 1, Example 1, and Comparative Example 1 was photographed with a scanning electron microscope (SEM) to determine grain growth for each particle and the resulting connectivity. ) Check the increase.

The scanning electron microscopy results are shown in FIG. 3, specifically, the image of Preparation Example 1 before sintering is in FIG. 3(a), the image of Example 1 after light sintering is in FIG. 3(b), and the image of Preparation Example 1 before sintering is in FIG. 3(b). The image of Comparative Example 1 is shown in FIG. 3(c).

Referring to FIGS. 3(a) to 3(c), FIG. 3(a) is an image of Preparation Example 1 before sintering, showing insufficient particle growth, and FIG. 3(a) is an image of Example 1 after photosintering. b) and Figure 3(c), which is an image of heat-sintered Comparative Example 1, showed improved grain growth and connectivity after sintering.

Characteristic evaluation 2.

The cross section of the anode layer on the metal support prepared according to Example 1 and Comparative Example 1 was subjected to Energy Dispersive X-Ray Analysis (EDX mapping).

The energy dispersive X-ray analysis results are shown in Figures 4 and 5.

Specifically, FIG. 4 shows the EDX mapping result of Example 1 light-sintered in FIG. 4(b), and the EDX mapping result of Comparative Example 1 heat-sintered is shown in FIG. 4(a).

Specifically, Figure 5 shows the EDX mapping result of light-sintered Example 1 as a result of the EDX line profile in Figure 5(b), and the EDX mapping result of heat-sintered Comparative Example 1 is shown in Figure 5(a). .

Referring to FIG. 4(a), in the case of heat sintered Comparative Example 1, Cr, It can be confirmed that Fe is detected. This is the cause of deterioration of material properties and performance.

Referring to Figure 4(b), it can be seen that in the case of photosintered Example 1, sintering occurred without diffusion of Cr and Fe. Previously, through the image of FIG. 3, the degree of grain growth and increase in connectivity from the initial particle state before sintering in the microstructure was similar to that of existing thermal sintering, confirming a sufficient degree of sintering through optical sintering, and thus the implementation of the present invention. It was confirmed that the manufacturing method in the example can achieve sufficient sintering while suppressing Ni-Cr, Fe diffusion, which is a technical difficulty in the existing process.

Referring to FIG. 5(a), in the case of Comparative Example 1 where heat sintering is performed, when sintering a Ni-YSZ cathode, in the existing heat sintering process, Ni from the Ni-YSZ cathode diffuses into the substrate and iron (Fe) and chromium (Cr) of the substrate ), etc. can be confirmed to be diffused to the cathode. Diffusion of these elements becomes a problem that reduces performance.

Referring to FIG. 5(b), in the case of Example 1 where light sintering was performed, it can be seen that Fe and Cr of stainless steel diffused into the Ni-YSZ layer in the existing heat sintering process, but did not diffuse during the IPL process.

Meanwhile, the embodiments of the present invention disclosed in the specification and drawings are merely provided as specific examples to aid understanding, and are not intended to limit the scope of the present invention. It is obvious to those skilled in the art that in addition to the embodiments disclosed herein, other modifications based on the technical idea of the present invention can be implemented.

Claims (11)

Preparing a metal support;
forming a cathode precursor layer on the metal support;
manufacturing an anode layer on the cathode precursor layer using a photo-sintering process;
Manufacturing an electrolyte layer on the anode layer; and
Comprising the step of manufacturing a cathode layer on the electrolyte layer,
Placing a substrate at the bottom of the metal support prevents rapid heat transfer to the metal support in the optical sintering process,
A method of manufacturing a metal-supported solid oxide fuel cell (SOFC), characterized in that the light irradiation intensity of the light sintering process is 100 to 180 J/cm ² .
According to clause 1,
The optical sintering process is a metal-supported solid oxide fuel characterized in that it uses white light irradiated from any one selected from the group consisting of a xenon flash lamp, neon (Ne) flash lamp, and krypton (Kr) flash lamp. Manufacturing method of battery (SOFC).
According to clause 1,
A method of manufacturing a metal-supported solid oxide fuel cell (SOFC), characterized in that the optical sintering process is performed 1 to 100 times based on one cycle.
According to clause 3,
One cycle of the photosintering process is,
A metal characterized in that the light irradiation time is 0.01 to 50 ms, the pulse gap is 0.01 to 5000 ms, the pulse number is 1 to 100, and the metal support temperature is 0 to 600 ° C. Manufacturing method of supported solid oxide fuel cell (SOFC).
According to clause 1,
The cathode precursor layer is any one selected from Group A consisting of NiO and LST (Lanthanum strontium titanate) and Group B consisting of YSZ (Yttria stabilized zirconia), GDC (Gadolinia doped ceria), and LSGM (Lanthanum strontium gallate magnesite). A method of manufacturing a metal-supported solid oxide fuel cell (SOFC), comprising any one of the following.
According to clause 1,
The electrolyte layer is a group consisting of scandia stabilized zirconia (ScSZ), Yttria stabilized zirconia (YSZ), Samaria doped ceria (SDC), Gadolinia doped ceria (GDC), Lanthanum strontium gallate magnesite (LSGM), and Erbium stabilized bismuth oxide (ESB). A method of manufacturing a metal-supported solid oxide fuel cell (SOFC), comprising at least one material selected from.
According to claim 1,
The air cathode layer is a metal-supported solid oxide, characterized in that one selected from the group consisting of a lanthanum oxide-based perovskite material, a double perovskite structure-based material, and a nickelate-based material. Manufacturing method of fuel cell.
According to paragraph 1,
A method of manufacturing a metal-supported solid oxide fuel cell (SOFC), wherein the electrolyte layer and the cathode layer are formed through a thermal sintering process, an optical sintering process, or a combination process thereof.
According to clause 8,
A method of manufacturing a metal-supported solid oxide fuel cell (SOFC), characterized in that the heat sintering process is performed at 1000 to 1400 ° C. for 2 to 5 hours.
A metal-supported solid oxide fuel cell, characterized in that manufactured by the manufacturing method of any one of claims 1 to 9.
According to clause 10,
The metal-supported solid oxide fuel cell is a metal-supported solid oxide fuel cell, characterized in that chromium (Cr) or iron (Fe) of the metal support in the metal-supported solid oxide fuel cell is suppressed from diffusion into the anode layer. battery.