WO2014119929A1

WO2014119929A1 - Method for fabricating cell for fuel battery

Info

Publication number: WO2014119929A1
Application number: PCT/KR2014/000857
Authority: WO
Inventors: 권오웅
Original assignee: 지브이퓨얼셀 주식회사
Priority date: 2013-01-29
Filing date: 2014-01-29
Publication date: 2014-08-07

Abstract

The present invention relates to a method for fabricating a cell for a fuel battery. The method according to the present invention includes the steps of: forming a first porous electrode layer; forming a first electrolyte layer on the first electrode layer; planarizing the surface obtained by removing the upper end of the first electrolyte layer; forming a filler layer on the planarized surface of the first electrolyte layer so as to fill the pin holes existing in the first electrolyte layer; removing the filler layer; forming a second electrolyte layer on the first electrolyte layer from which the filler layer has been removed; and forming a second electrode layer on the second electrolyte layer. According to the present invention, the surface obtained by removing the upper end part of the first electrolyte layer having pin holes is planarized, applied with a filler layer of a high density so as to fill the pin holes, and then applied with the second electrolyte layer, so that the electrolyte layer is improved so as to prevent problems such as short circuit or leakage.

Description

Fuel Cell Manufacturing Method

The present invention relates to a method for manufacturing a stack for a fuel cell, and more particularly, to a method for manufacturing a fuel cell for improving an electrolyte layer in which pinholes are generated in a solid oxide fuel cell.

Solid Oxide Fuel Cells (SOFCs) operate at the highest temperatures (700–1000 ° C) of fuel cells, using solid oxides with oxygen or hydrogen ion conductivity as electrolytes.

In particular, solid oxide fuel cells have a simpler structure than other fuel cells because all components are solid, there is no problem of electrolyte loss, replenishment and corrosion, no precious metal catalyst, and fuel supply through direct internal reforming. This is easy. In addition, it has the advantage that thermal combined cycle power generation using waste heat is possible because the high-temperature gas is discharged.

A typical solid oxide fuel cell is composed of a dense electrolyte layer of oxygen ion conductivity and a porous cathode and anode positioned on both sides thereof. The operating principle is that oxygen permeates through the porous cathode and reaches the electrolyte surface. Oxygen ions generated by the oxygen reduction reaction move to the fuel electrode through the dense electrolyte and react with hydrogen supplied to the porous anode to generate water. At this time, since electrons are generated at the anode and electrons are consumed at the cathode, electricity flows when the two electrodes are connected to each other. On the other hand, the solid oxide fuel cell generates electricity in one cell, but the amount of electricity is very small to be used in real life, so the cells are stacked and used as a large amount of electrical energy. The collection of several cells is called a stack.

The technology related to such a solid oxide fuel cell has been proposed in Patent Registration No. 0717130 and Patent Publication No. 2012-0075242.

Hereinafter, a solid oxide fuel cell disclosed in Korean Patent No. 0817130 and Japanese Patent Laid-Open No. 2012-0075242 will be briefly described.

Figure 1 is a photograph showing a cross-sectional view of a single cell of the anode-supported solid oxide fuel cell according to the prior art 1. Referring to FIG. 1, a unit cell includes a porous anode support, a cathode functional layer, an electrolyte layer, and a composite air electrode layer, and the composite air electrode layer is composed of a cathode functional layer, an air electrode, and a current collector layer.

2 is a cross-sectional view of an example of a metal support-type solid oxide fuel cell according to the related art 2. Referring to FIG. 2, the metal support-type metal oxide fuel cell of the related art 2 includes a metal support 101; A first electrode 103 formed on one surface of the metal support 101; An electrolyte 107 formed on one surface of the first electrode 103 and a second electrode 109 formed on one surface of the electrolyte 107 are formed in a stacked stack to supply and discharge fuel or air. It includes a manifold 110, the first electrode 103 and the second electrode 109 is composed of different electrodes of the air electrode or fuel electrode.

However, in the unit cell of the anode-supported solid oxide fuel cell according to the prior art 1 and the solid oxide fuel cell according to the prior art 2, the electrolyte material flows through the pores in the process of forming the electrolyte on the porous support to form pinholes or the like. In order to solve this problem, a separate method is required.

As a result, the thin film fuel cell 100 based on the conventional porous substrate shown in FIG. 3 in common with the prior arts 1 and 2 has an electrolyte thin film under the influence of the rough electrode (mainly anode) surface during fabrication. Defects such as pinholes may occur in the 120, and these defects may cause problems such as shorting or leakage, which may adversely affect cell performance.

An object of the present invention is to solve the problems of the prior art as described above, to remove the top portion of the first electrolyte layer in which the pinhole is formed to planarize the surface, to a highly dense packed layer It is to provide a fuel cell cell manufacturing method that can prevent problems such as short (short) or leakage (leakage) through the improvement of the electrolyte layer by stacking the second electrolyte layer after filling the pin hole.

According to a feature of the present invention for achieving the above object, the present invention comprises the steps of forming a porous first electrode layer; Forming a first electrolyte layer on the first electrode layer; Removing the top of the first electrolyte layer to planarize the removal surface; Forming a filling layer on the planarized surface of the first electrolyte layer to fill pin holes formed in the first electrolyte layer; Removing the packed layer; Forming a second electrolyte layer on the first electrolyte layer from which the filling layer is removed; And forming a second electrode layer on the second electrolyte layer.

In addition, in the present invention, the planarization of the first electrolyte layer and the formation of the packed layer may be performed in one step, or the planarization of the first electrolyte layer and the formation of the packed layer may be performed in several steps by dividing the entire height.

In addition, the second electrolyte layer in the present invention may be formed of the same material as the first electrolyte layer, or may be formed of a different material.

In addition, the second electrolyte layer in the present invention may be formed by the same process as the first electrolyte layer, or may be formed by a different process.

In addition, the filling layer in the filling layer forming step of the present invention may be formed in a highly dense structure.

In addition, the filling layer in the present invention may be formed of a non-conductive material including an electrolyte or aluminum oxide (Al ₂ O ₃ ).

According to the present invention, the upper surface of the first electrolyte layer in which the pinholes are formed is partially removed to planarize the surface, and the pinholes are filled with a highly dense packed layer, followed by stacking the second electrolyte layer. The improvement of the layer has an effect that can prevent problems such as short (short) or leakage (leakage).

1 is a cross-sectional view of a single cell of a cathode support solid oxide fuel cell according to the related art.

2 is a cross-sectional view showing an example of a metal support-type solid oxide fuel cell according to the prior art 2.

3 is a reference diagram showing a state in which a pin hole is formed in the electrolyte layer in the prior art.

4 is a block diagram of a fuel cell manufacturing method according to a first embodiment of the present invention.

5A to 5G are flowcharts of a fuel cell manufacturing method according to a first embodiment of the present invention.

300: fuel cell

310: first electrode layer

320: first electrolyte layer

330: packed bed

340: second electrolyte layer

350: second electrode layer

The terms or words used in the present specification and claims are meant to be consistent with the technical spirit of the present invention on the basis of the principle that the inventor can appropriately define the concept of the term in order to best explain his invention. It must be interpreted as and concepts.

Throughout the specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding other components unless otherwise stated.

Hereinafter, the configuration steps of the embodiment of the fuel cell manufacturing method according to the present invention with reference to the drawings will be described in detail.

4 is a block diagram showing a fuel cell manufacturing method according to a first embodiment of the present invention, Figure 5a to 5g is a flowchart showing a fuel cell manufacturing method according to a first embodiment of the present invention. .

According to these drawings, the fuel cell manufacturing method according to an embodiment of the present invention is a porous first electrode layer forming step (S200), the first electrolyte layer forming step (S210), the first electrolyte layer surface planarization step (S220), A filling layer forming step (S230), a filling layer removing step (S240), a second electrolyte layer forming step (S250), and a second electrode layer forming step (S260) are included.

The porous first electrode layer forming step (S200) is a step of forming the first electrode layer 310 to have a porous (porous). [See Fig. 5 (a)]

At this time, the first electrode layer forming step (S200) is made of a material such as platinum (platinum, Pt), palladium (Pd), nickel (Ni), ruthenium (Ru), etc., which is a high-performance catalyst, sputtering, pulsed laser deposition Anodes are deposited by chemical vapor deposition (CVD), such as physical vapor deposition (PVD), atomic layer deposition (ALD), etc. (Pulsed Laser Deposition, PLD). In this step, the first electrode layer 310, which is an electrode, is formed.

The first electrolyte layer forming step (S210) is a step of depositing and forming the first electrolyte layer 320 on the first electrode layer 310. At this time, in the first electrolyte layer forming step (S210), the first electrode layer 310 is formed to have a porosity, so that small pin-holes are formed under the influence of the uneven electrode surface. [See Fig. 5 (b)]

In addition, the first electrolyte layer 320 may include zirconium oxide (Zr _x O _y ), cerium oxide (Ce _x O _y ), lanthanum galate, barium cerate, and barium zirconate ( Choose from a wide range of ionic conductors, such as Barium Zirconate, bismuth-based oxides or Oxygen ion conducting materials such as various doping phases of these materials, or Proton conducting materials have. Here, the first electrolyte layer 320 may be applied with an electrolyte material such as Gd-doped CeO 2 (GDC) or Yttria-stabilized zirconia (YSZ), and may be sputtered or pulsed laser deposition (PLD). It is deposited by a method such as chemical vapor deposition (CVD) such as physical vapor deposition (PVD), atomic layer deposition (ALD).

The first electrolyte layer surface planarization step (S220) is a step of removing and planarizing an upper end of the first electrolyte layer 320 to finish the surface of the first electrolyte layer 320 with the second electrolyte layer 330. In this case, the first electrolyte layer surface planarization step (S220) may be performed by reactive ion etching (RIE). [See Fig. 5 (c)]

In the filling layer forming step S230, the filling layer 330 may be atomized to fill pin-holes formed in the first electrolyte layer 320 on the planarized surface of the first electrolyte layer 320. It is a step of depositing and forming by a method such as Chemical Vapor Deposition (CVD), such as Atomic Layer Deposition (ALD). [See Fig. 5 (d)]

In this case, the filling layer 330 in the filling layer forming step (S230) is formed to have a highly dense structure to fill a defect space such as a pin hole when forming.

That is, the filling layer 330 has a small fin in the first electrolyte layer 320 under the influence of the rough surface of the uneven first electrode layer 310 in the process of forming the first electrolyte layer 320. As holes are generated, a short circuit or leakage occurs in the fuel cell. To solve this problem, the inside of the pin hole is filled with the filling of the filling layer 330.

Meanwhile, the filling layer 330 may be formed of a non-conductive material such as aluminum oxide (Al ₂ O ₃ ) as well as an electrolyte.

Removing the filling layer (S240) is a step of removing the filling layer 330 through a process such as reactive ion etching (RIE), so that the filling of the filling layer 330 to fill only the pin hole. 1 This is a step of removing a portion in contact with the surface of the electrolyte layer 320. [See Fig. 5 (e)]

In the forming of the second electrolyte layer (S250), the first electrolyte layer is filled with the pinholes filled with the filling of the filling layer 330 while removing the upper end of the filling layer 330 in contact with the surface of the first electrolyte layer 320. A second electrolyte layer 340 having a dense structure is formed by depositing a thin film on the planarized surface of the 320. [See Fig. 5 (f)]

The second electrolyte layer 340 may include zirconium oxide (Zr _x O _y ), cerium oxide (Ce _x O _y ), lanthanum galate, barium cerate, and barium zirconate ( Choose from a wide range of ionic conductors, such as Barium Zirconate, bismuth-based oxides or Oxygen ion conducting materials such as various doping phases of these materials, or Proton conducting materials have. Here, an electrolyte material such as Gd-doped CeO 2 (GDC) or Yttria-stabilized zirconia (YSZ) may be applied to the second electrolyte layer 340. It is deposited by a method such as chemical vapor deposition (CVD) such as physical vapor deposition (PVD), atomic layer deposition (ALD).

On the other hand, the second electrolyte layer forming step (S250) is to finish the upper surface of the first electrolyte layer 320 with the second electrolyte layer 330.

In addition, the first electrolyte layer surface planarization step S220 and the filling layer forming step S230 may be performed at a time by a height corresponding to the removal height of the first electrolyte layer 320 and the formation height of the filling layer 330. In addition, the total height corresponding to the removal height of the first electrolyte layer 320 and the formation height of the filling layer 330 may be divided into a plurality of steps by the divided heights, and the steps may be sequentially performed.

In addition, when the first electrolyte layer forming step S210 and the second electrolyte layer forming step S250 are performed, the electrolyte materials forming the first electrolyte layer 320 and the second electrolyte layer 340 are the same material. It may be formed of or made of different materials.

Further, when the first electrolyte layer forming step S210 and the second electrolyte layer forming step S250 are performed, the process of forming the first electrolyte layer 320 and the second electrolyte layer 340 is the same. It may be carried out in a process or in a different process.

For example, the first electrolyte layer 320 and the second electrolyte layer 340 are the same material (for example, YSZ), but may be an application using a different material (for example, GDC), the first electrolyte layer in the deposition process The chemical vapor deposition method 320 may include chemical vapor deposition (CVD) such as physical vapor deposition (PVD), atomic layer deposition (ALD), and the like, such as sputtering and pulsed laser deposition (PLD). Chemical Vapor Deposition) and the second electrolyte layer 340 may be performed by a chemical vapor deposition (CVD) process, such as atomic layer deposition (ALD). Can be.

The second electrode layer forming step S260 is a step of forming the second electrode layer 350 on the second electrolyte layer 340. (See Fig. 5 (g))

At this time, the second electrode layer forming step (S260) is made of a high performance catalyst such as platinum (platinum, Pt), palladium (Pd), nickel (Ni), ruthenium (Ru), sputtering, pulsed laser deposition method Cathode is deposited by a method such as chemical vapor deposition (CVD) such as physical vapor deposition (PVD), atomic layer deposition (ALD), etc. (Pulsed Laser Deposition, PLD), etc. In this step, the second electrode layer 350 is formed as an electrode.

The fuel cell 300 manufactured by the fuel cell manufacturing method of the present invention includes a first electrode layer 310, a first electrolyte layer 320, a second electrolyte layer 340, and a second electrode layer 350. do.

Here, the first and second electrolyte layers 320 and 340 provide a passage for the movement of ions between the electrodes but block the movement of electrons and separate fuel and oxygen, and are formed by the catalyst. The 310 and the second electrode layer 350 serve to provide a large surface area for the electrochemical reaction to occur and to provide a movement path for electrons generated at this time.

The first electrode layer 310 is an anode electrode and is made of a material such as platinum (platinum, Pt), palladium (Pd), nickel (Ni), ruthenium (Ru), etc., which is a high-performance catalyst, and is formed by sputtering and pulse laser deposition ( Physical vapor deposition (PVD) such as Pulsed Laser Deposition (PLD), etc., is deposited by chemical vapor deposition (CVD) such as Atomic Layer Deposition (ALD). .

On the other hand, the first electrode layer 310 is formed to have a porous (porous) for gas infiltration and expansion of the reaction area.

The first electrolyte layer 320 is formed on the first electrode layer 310, and includes zirconium oxide (Zr _x O _y ), cerium oxide (Ce _x O _y ), lanthanum galate, and barium cerate. Ion conductors such as oxygen ion conducting materials, such as Cerate, Barium Zirconate, bismuth-based oxides or various doping phases of these materials, or Proton conducting materials You can choose from a wide range of categories. Here, an electrolyte material such as Gd-doped CeO 2 (GDC) or Yttria-stabilized zirconia (YSZ) may be applied to the first electrolyte layer 320.

Here, the first electrolyte layer 320 is formed such that the first electrode layer 310 has a porosity, and small pin-holes are formed therein under the influence of the uneven surface of the first electrode layer 310. .

Meanwhile, the pinhole formed in the first electrolyte layer 320 is filled with the filling layer 330.

The second electrolyte layer 340 is formed to have a dense structure on the first electrolyte layer 320 having a flat surface, so that the pin holes of the first electrolyte layer 320 are filled with the filling material of the filling layer 330. While filling, the upper surface of the first electrolyte layer 320 is closed to prevent cracks.

Meanwhile, the second electrolyte layer 340 may be formed of the same material or different materials from the first electrolyte layer 320 and the electrolyte material. For example, although the first electrolyte layer 320 and the second electrolyte layer 340 are the same material (for example, YSZ), an application using another material (for example, GDC) is possible.

The second electrode layer 350 is a cathode electrode formed on the second electrolyte layer 340, and is made of a high performance catalyst such as platinum (platinum, Pt), palladium (Pd), nickel (Ni), ruthenium (Ru), or the like. Chemical vapor deposition (CVD: Chemical Vapor) such as physical vapor deposition (PVD), atomic layer deposition (ALD), etc., such as sputtering, pulsed laser deposition (PLD), etc. It is formed by vapor deposition by a method such as Deposition).

As described above, the present invention has been described by way of limited embodiments and drawings, but the present invention is not limited to the above embodiments, and those skilled in the art to which the present invention pertains various modifications and variations from such descriptions. This is possible.

Therefore, the scope of the present invention should not be limited to the described embodiments, but should be defined not only by the claims below but also by the equivalents of the claims.

The present invention relates to a fuel cell manufacturing method, the present invention comprises the steps of forming a porous first electrode layer; Forming a first electrolyte layer on the first electrode layer; Removing the top of the first electrolyte layer to planarize the removal surface; Forming a filling layer on the planarized surface of the first electrolyte layer to fill pin holes formed in the first electrolyte layer; Removing the packed layer; Forming a second electrolyte layer on the first electrolyte layer from which the filling layer is removed; And forming a second electrode layer on the second electrolyte layer.

Claims

Forming a porous first electrode layer;

Forming a first electrolyte layer on the first electrode layer;

Removing the top of the first electrolyte layer to planarize the removal surface;

Forming a filling layer on the planarized surface of the first electrolyte layer to fill pin holes formed in the first electrolyte layer;

Removing the packed layer;

Forming a second electrolyte layer on the first electrolyte layer from which the filling layer is removed; And

And forming a second electrode layer on the second electrolyte layer.
The method of claim 1,

The planarization of the first electrolyte layer and the formation of the filling layer is carried out in one step, or the planarization of the first electrolyte layer and the formation of the filling layer is proceeded in several steps by dividing the entire height sequentially.
The method according to claim 1 or 2,

The second electrolyte layer is formed of the same material as the first electrolyte layer, or a fuel cell cell manufacturing method is formed of a different material.
The method according to claim 1 or 2,

The second electrolyte layer is formed in the same process as the first electrolyte layer, or a method for manufacturing a cell for a fuel cell is formed by a different process.
The method of claim 1,

The method of claim 1, wherein the filling layer in the filling layer forming step is formed in a highly dense structure.
The method of claim 5,

The filling layer is a fuel cell cell manufacturing method formed of a non-conductive material containing an electrolyte or aluminum oxide (Al 2 O 3 ).