KR101680626B1 - protonic ceramic fuel cells and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a proton conductive oxide fuel cell and a method of manufacturing the same, and more particularly, to a proton conductive oxide fuel cell and a method for manufacturing the proton conductive oxide fuel cell. The proton conductive carbonaceous fuel cell is characterized in that a heterogeneous material having low cost, By introducing an intermediate layer containing an oxide and a metal catalyst, interfacial defects that may occur between the constituent layers are prevented, the long-term stability of the unit cell is secured, and the internal resistance is reduced to improve the performance of the fuel cell.

Description

TECHNICAL FIELD The present invention relates to a proton conductive oxide fuel cell and a proton conductive ceramic fuel cell,

The present invention relates to a proton conductive oxide fuel cell and a method of manufacturing the same, and more particularly, to a high output proton conductive oxide fuel cell including an anode support based on a heterogeneous material, an intermediate layer, and an electrolyte layer having a denser structure, ≪ / RTI >

A fuel cell is a cell that converts the chemical energy of a fuel into electrical energy. The fuel cell is divided into various types according to electrolytes. Among them, solid oxide fuel cells, which have the highest theoretical efficiency and can use various fuels, are attracting attention as next generation energy conversion systems, and oxygen ion conductors are mainly used as electrolyte materials. Recently, a proton conductive oxide fuel cell using a hydrogen-ion conductive oxide as an electrolyte, which improves the durability of a solid oxide fuel cell by lowering the operating temperature, is attracting attention.

Such a proton conductive oxide fuel cell is composed of a porous anode and an air electrode sandwiching an electrolyte membrane having a dense structure in which gas can not permeate. A fuel such as hydrogen is supplied to the fuel electrode, and is electrochemically oxidized to be separated into hydrogen ions (protons or protons) and electrons. The electrons flow to the external circuit and move to the cathode, and the protons pass through the electrolyte membrane and reach the cathode. The proton and the electrons thus supplied react with oxygen in the air electrode to generate water, and electric energy is generated using the potential difference between the air electrode and the fuel electrode.

In the proton conductive oxide fuel cell having such a multilayer structure, it is important to provide the mechanical strength of the whole unit cell and to maintain the shape of the unit cell. In the case of electrolyte, the electrode is used as a support because it can not obtain a high output when it is made thick to serve as a support because the resistance is larger than that of the electrode. In particular, since the anode has lower polarization resistance than the cathode, the anode is mainly used as a support to obtain sufficient mechanical strength and low polarization resistance. In order to reduce the difference in thermal expansion coefficient with the electrolyte and to improve the interfacial adhesion, There are many types of supports.

Generally, a proton conductive oxide fuel cell is manufactured by using a powder process and a sintering process. Typically, a proton conductive oxide fuel cell uses a yttria-doped barium zirconate (BZY) electrolyte and a nickel (Ni) Fuel cells are known, and the unit cell configuration is composed of Ni-BZY fuel electrode, BZY electrolyte, BZY and a catalyst composite air electrode.

The barium zirconate oxide used as the electrolyte material is relatively light and has a high ion conductivity at an operating temperature range of 600 to 400 ° C in a low temperature range based on low activation energy compared to an oxygen ion conductor by conducting hydrogen ions However, it requires a high sintering temperature of 1700 DEG C or higher and a long sintering time. Such a high sintering temperature causes a deterioration of physical properties due to volatilization of constituent materials such as barium Ba, There is a problem that the production of single cells is very difficult from the viewpoint of process, resulting in limitation of equipment and high cost of process (Patent Document 1).

In order to solve the above problem, when the oxide film material of the electrolyte membrane is replaced with BZY, yttria-doped barium cerate (BCY) oxide is used, the sintering temperature is low but it is chemically unstable. There is a problem that it can not be used for a long time because it is very vulnerable to H ₂ O generated as a result of the reaction of the fuel or the fuel cell.

In order to solve the above problem, the sintering temperature is lowered by adding copper oxide, zinc oxide, or the like as a sintering aid to the BZY. However, the performance deterioration due to the sintering aid and the still high sintering temperature of 1500 DEG C or more are the limiting points. In another method, yttria doped barium cerate-zirconate (BCZY), which is a synthesis of BZY and BCY, has been developed. However, problems such as difficulty in synthesizing a single phase powder and high sintering temperature exist.

The problems of ozone formation and chemical instability of such proton conductive oxides continue to be a problem in forming a support mixed with a metal catalyst. The anode containing BZY, BCY, or BCZY requires a very high sintering temperature in order to obtain the desired structural strength and shape, and chemical stability is deteriorated to cause surface defects such as secondary phase, It is difficult to do.

Patent Document 1. Korean Patent Publication No. 10-2013-0022828

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above problems, and an object of the present invention is to provide a fuel cell comprising: a fuel electrode support based on a heterogeneous material which is not a proton conductor easy to manufacture; A proton conductive oxide-based fuel electrode intermediate layer, and a proton conductive oxide electrolyte layer, and to provide a high output proton conductive oxide fuel cell.

Another object of the present invention is to provide a method for manufacturing a cost-effective proton conductive oxide fuel cell that has a dense structure while lowering the sintering temperature of the proton conductive oxide by a thin film process and a sintering process.

In order to accomplish the above object, the present invention provides a fuel cell comprising: a fuel electrode support including a heterogeneous material-based porous composite; An intermediate layer located on the anode support and comprising a proton conductive oxide and a metal catalyst; An electrolyte layer formed on the intermediate layer, the electrolyte layer including a proton conductive oxide; And a cathode layer formed on the electrolyte layer. The present invention also provides a proton conductive oxide fuel cell comprising:

And a fuel electrode functional layer between the anode support and the intermediate layer.

Wherein the heterogeneous material-based porous composite comprises at least one selected from the group consisting of zirconia-based, ceria-based, lanthanum gallate-based and perovskite-based oxides, and any one selected from the group consisting of nickel, ruthenium, palladium, rhodium, Or more of the metal catalyst.

Wherein the heterogeneous material-based porous composite comprises at least one selected from the group consisting of zirconium oxide, cerium oxide and mixtures thereof, and at least one selected from the group consisting of nickel, ruthenium, palladium, rhodium and platinum And a metal catalyst.

Wherein the proton conductive oxide is selected from the group consisting of doped barium zirconate, doped barium cerate, and doped barium zirconate-cerate. .

Wherein the intermediate layer has a mixed volume ratio of the proton conductor oxide and the metal catalyst of 30 to 70: 30 to 70.

The anode functional layer may be formed of at least one selected from the group consisting of zirconium oxide, cerium oxide, lanthanum gallate, barium cerate, barium zirconate, barium zirconate- Barium zirconate-cerate, and a doped phase thereof, and at least one metal catalyst selected from the group consisting of nickel, ruthenium, palladium, rhodium and platinum.

According to another aspect of the present invention, there is provided a method of manufacturing a fuel cell, comprising: laminating an intermediate layer comprising a proton conductive oxide and a metal catalyst on an anode support comprising a heterogeneous material-based porous composite; II) post-heat-treating the intermediate layer; III) laminating an electrolyte layer containing a proton conductive oxide on the intermediate layer; And (IV) laminating a cathode layer on the electrolyte layer. The present invention also provides a method of manufacturing a proton conductive oxide fuel cell.

And heat treating the electrolyte layer between the step (III) and the step (IV).

(I), (III), and (IV) may be performed using a thin film process. The thin film process may be performed by physical vapor deposition (PVD), chemical vapor deposition (CVD) A chemical solution deposition (CSD) method, and spray pyrolysis.

The physical vapor deposition (PVD) may be pulsed laser deposition (PLD).

The anode support is manufactured using a powder process, and the powder process is a tape casting, a powder press operation, or a screen printing.

And the post-heat treatment of the intermediate layer is performed at 1100 to 1300 ° C.

Wherein the intermediate layer has a mixed volume ratio of the proton conductor oxide and the metal catalyst of 30 to 70: 30 to 70.

The heat treatment of the electrolyte is performed at 1000 to 1300 ° C.

The proton conductive oxide fuel cell of the present invention is characterized in that a heterogeneous material which is inexpensive, easy to process, excellent in structural-chemical stability and electron conductivity is selected as a fuel electrode support material, and a proton conductive excellent in ionic conductivity and electron conductivity By introducing an intermediate layer containing an oxide and a metal catalyst, a sufficient mechanical strength and a stable fine structure can be secured, and the effect of reducing the process cost due to the lowering of the sintering temperature can be obtained.

In addition, the proton conductive oxide fuel cell of the present invention can produce a dense and thin electrolyte layer without defects at a low temperature using a thin film process and a sintering process, and overcomes the material limitations of conventional proton conductive oxide fuel cells And is effective for improving long-term stability and performance.

1 is a cross-sectional view of a proton conductive oxide fuel cell according to the present invention.
2 is a cross-sectional view of a proton conductive oxide fuel cell of the present invention according to another embodiment.
3 (a) is a cross-sectional view of a fuel electrode support of a conventional proton conductive oxide fuel cell, and FIG. 3 (b) is a cross-sectional view of a fuel electrode support in a proton conductive oxide fuel cell according to the present invention.
4 is a scanning electron microscope (SEM) photograph of a surface of an intermediate layer formed on an anode support in a unit cell manufactured from an embodiment of the present invention.
5 is a scanning electron microscope (SEM) photograph of a section of a single cell produced from an embodiment of the present invention.
6 is a graph of current density-voltage-power density obtained by measuring the open circuit voltage and performance of a single cell manufactured from an embodiment of the present invention.
7 is a scanning electron microscope (SEM) photograph of the surface of the intermediate layer formed on the anode support of the unit cell manufactured from the comparative example of the present invention.
8 is a graph of current density-voltage-power density obtained by measuring the open circuit voltage and performance of a unit cell manufactured from the comparative example of the present invention.

Hereinafter, the proton conductive oxide fuel cell according to the present invention will be described in more detail.

The term "heterogeneous material-based porous composite " as used herein means a material constituting an anode support, wherein the anode, the electrolyte, the cathode and the anode are based on the same proton conductor material, Porous composite < / RTI > based on the material.

1 is a cross-sectional view of a proton conductive oxide fuel cell according to the present invention.

Referring to FIG. 1, a proton conductive oxide fuel cell 100 according to an embodiment of the present invention includes an anode support 110 including a heterogeneous material-based porous composite; An intermediate layer (120) on the anode support (110) and including a proton conductive oxide and a metal catalyst; An electrolyte layer 130 formed on the intermediate layer 120 and including a proton conductive oxide; And a cathode layer 140 formed on the electrolyte layer 130.

Since the anode support 110 of the proton conductive oxide fuel cell 100 according to the embodiment of the present invention greatly affects the densification of the intermediate layer 120 and the electrolyte layer 130 and the generation of defects during the manufacturing process, The porous composite contained in the support 110 is not limited to the electronically conductive heterogeneous material capable of suppressing coarsening of the metal, having sufficient strength and chemical stability not to break in the high-temperature sintering process. For example, it may be at least one selected from the group consisting of doped zirconia, doped ceria and doped lanthanum gallate, more preferably yttria stabilized zirconia (YSZ), gadolinia or samaria-doped ceria (GDC , SDC), lanthanum gallate (LSGM) doped with strontium oxide and magnesium oxide, and at least one metal catalyst selected from the group consisting of nickel, ruthenium, palladium, rhodium and platinum can do.

However, the heterogeneous material-based porous composite may include an insulator having sufficient strength without causing a chemical reaction in the sintering process with the metal catalyst, and the metal catalyst may include an undoped zirconia or an undoped ceria- Materials, and the like. When the proton conductive anode support is used for the proton conductive anode support, it is possible to further reduce the cost due to the low raw material cost, and to suppress the secondary phase formation with the metal catalyst and barium in the high temperature sintering process.

The anode support 110 may have a single-layer structure or may have a multi-layer structure of two or more layers. In the case of a multi-layer structure, the pore size of each layer is different, It is possible to form the electrolyte layer 130 and improve the interlayer coupling degree as well as to improve the structural stability of the intermediate layer 120 and the electrolyte layer 130 when the fuel cell is driven.

The metal catalyst included in the anode support 110 and the intermediate layer 120 may be at least one selected from the group consisting of nickel, ruthenium, palladium, rhodium, and platinum.

The proton conductive oxide included in the intermediate layer 120 and the electrolyte layer 130 may be any one selected from the group consisting of doped barium zirconate, doped barium sulfate and doped barium zirconate- , More preferably yttrium doped barium zirconate (BZY), yttrium doped barium chelate (BCY), and yttrium doped barium zirconate-chelate (BCZY).

Particularly, when the anode support 110 includes YSZ and a nickel metal catalyst, and the diffusion layer 120 includes BZY and nickel, a defect between the anode support 110 and the intermediate layer 120 And not only does it form a tightly coupled relationship with each other, but also forms a close connection with the electrolyte layer 130, so that the open circuit voltage and output characteristics can be remarkably increased.

The intermediate layer 120 may be a porous microstructure, and the intermediate layer 120 may be a thin and thin thin film having a thickness of 2 to 4 μm.

The intermediate layer 120 may have a mixed volume ratio of the proton conductor oxide and the metal catalyst of 30 to 70:30 to 70. If the mixing ratio is out of the range of the mixing volume ratio, The proton conductive oxide fuel cell having the effect described in the present invention can not be realized due to the loss of electronic conductivity due to the shortage.

Since the fuel electrode support 110 includes a dissimilar material that is less expensive than the intermediate layer 120, and is easy to process and has excellent mechanical-chemical stability, it is sintered at a lower temperature than the anode support made of a proton conductive oxide and a metal catalyst, Defects are hardly generated, thereby preventing defects in the formation of the intermediate layer (120) or the electrolyte layer (130).

In addition, the anode support 110 may have a structure in which sufficient fuel electrode reaction points necessary for driving the fuel cell are secured in the intermediate layer 120 while the ion flow with the intermediate layer 120 is not continuous by using a dissimilar material, It has a continuous electron flow through the included metal catalyst, so that it does not deteriorate the performance of the fuel cell, but rather is closely and intimately connected to the intermediate layer 120 and the electrolyte layer 130, To increase the open circuit voltage and power density. A cross section of the fuel electrode support 110 is shown in FIG. 3B.

The proton conductive oxide fuel cell 100 of the present invention may further include a fuel electrode functional layer 111 between the fuel electrode support 110 and the intermediate layer 120. The structure of the proton conductive oxide fuel cell 100 is shown in FIG.

The anode function layer 111 includes a metal catalyst and an oxide and the oxide of the anode function layer 110 may be the same material as the anode and the intermediate layers 120 and 120, The metal catalyst of the fuel electrode functional layer 110 may be a material different from that of the fuel electrode support 110 and the intermediate layer 120 and may be a dissimilar material to the intermediate layer 120, In order to maintain the electrical connection between the fuel electrode support 110 and the intermediate layer 120, they must be the same.

The anode functional layer 111 is preferably selected from the group consisting of zirconium oxide, cerium oxide, lanthanum gallate, barium cerate, barium zirconate, barium zirconate-serrate and their doped phases as the oxide (SDC), gadolinia-doped ceria (GDC), yttria-stabilized zirconia (YSZ), and the like. Scandia-stabilized zirconia (ScSZ), strontium manganese-doped lanthanum gallate (LSGM), yttria-doped barium zirconate (BZY), yttria doped lanthanum gallate The yttria-doped barium cerate (BCY) and the yttria-doped barium zirconate-cerate (BCZ) Y). ≪ / RTI >

The metal catalyst of the anode functional layer 111 may be at least one metal catalyst selected from the group consisting of nickel, ruthenium, palladium, rhodium and platinum.

The proton conductive oxide fuel cell 100 further includes the anode function layer 111 to prevent structural defects of the intermediate layer 120 and the electrolyte 130 by reducing the surface defects of the anode function layer 111, The porous structure in which the size of the pores is increased in the support body 110 is enabled to improve the performance of the fuel cell by lowering the polarization resistance of the proton conductive oxide fuel cell. In addition, it plays a role of securing the structural stability of the proton conductive oxide fuel cell by sequentially reducing the size of the pores from the anode support 110 having a gap of several hundred micrometers to the intermediate layer 120 having a nanometer-sized pore .

When the anode function layer 111 includes a proton conductor which is the same or similar to the intermediate layer 120, it is possible to prevent interfacial defects by increasing the material conformability and to prevent the active region of the anode- 111) to improve the performance of the fuel cell by lowering the polarization resistance of the proton conductive oxide fuel cell.

In order to obtain high performance at a low temperature, the electrolyte layer 130 is preferably a dense structure having a thickness of 2 μm or less and no defects. In order to form the electrolyte layer 130 having such a structure, It is advantageous to use the thin film process described above while using the substrate 120 as a support.

The air electrode 140 may be formed of at least one material selected from the group consisting of platinum Pt, silver Ag, lanthanum-strontium manganese oxide LSM, lanthanum-strontium iron oxide LSF, lanthanum-strontium cobalt iron oxide LSCF, A single phase of lanthanum oxide-based perovskite such as oxide (LSC), samarium-strontium cobalt oxide (SSC), or a mixture of hydrogen ion conductive oxides such as BZY, BCY and BZCY It may be more than one. However, the present invention is not limited thereto.

Another aspect of the present invention is directed to a method of making a proton conductive oxide fuel cell comprising the steps of:

I) laminating an intermediate layer on an anode support comprising a heterogeneous material-based porous composite,

II) post-heat-treating the intermediate layer,

III) laminating an electrolyte layer on the intermediate layer and

IV) laminating a cathode layer on the electrolyte layer.

More specifically, to describe the manufacturing method, first, the fuel electrode support including the porous composite is manufactured using a powder process, wherein the powder process may be tape casting, powder press operation, or screen printing.

In addition, since the fuel electrode support greatly affects the densification of the intermediate layer and the electrolyte layer or the generation of defects during the manufacturing process, the porous composite included in the fuel electrode support has sufficient strength and chemical stability not to be broken in the high temperature sintering process, (GDC, SDC) doped with zirconia, gadolinia, or samaria-doped ceria (YSZ) or the like such as yttria stabilized zirconia (YSZ) or the like may be used as the electron conduction heterogeneous material capable of suppressing metal coarsening Doped ceria, doped lanthanum gallate such as lanthanum gallate (LSGM) doped with strontium oxide and magnesium oxide, and at least one selected from the group consisting of nickel, ruthenium, palladium, rhodium and platinum. And may include one or more metal catalysts.

Particularly, in the case where the fuel electrode support includes YSZ and a nickel metal catalyst, and the EVA layer includes a combination of BZY and nickel, there is no defect between the anode support and the intermediate layer, But also the electrolyte layer, the open circuit voltage and the output characteristic can be remarkably increased.

Next, physical vapor deposition (PVD), chemical vapor deposition (CVD), chemical solution deposition (CSD), and spraying (chemical vapor deposition) are sequentially performed on the anode support to form an intermediate layer by a thin film process. And pyrolysis (spray pyrolysis).

By forming the fuel electrode intermediate layer using the thin film process, a fuel electrode containing a proton conductive oxide such as BZY, which requires a high-temperature sintering process at 1700 ° C or higher, can be formed at a temperature of 1400 ° C or lower, It prevents deterioration of performance and secures a fine-grained structure and a dense surface, thereby remarkably improving battery performance such as long-term stability, open circuit voltage and power density. Further, an intermediate layer having a thin and dense structure was obtained using a thin film process.

In the preparation of the intermediate layer, when the powder process is used, the proton conductive oxide and the metal catalyst are mixed and screen-printed or tape-casted on the anode support to be laminated and sintered. Since a high temperature is required for sintering, Chemical reactions can take place and barium escapes. Further, since the sintering shrinkage characteristics are different, problems such as defects, cracks and densification are caused. Therefore, in the case of using the fuel electrode support including the heterogeneous material-based porous composite, if the powder process is used to form the intermediate layer, it has a dense and tight connection structure between the respective layers as in the present invention, The proton conductive oxide fuel cell having excellent cell performance can not be realized.

In addition, if the powder process is used, the pore size can not be effectively controlled, and a desired pore structure can not be obtained. Therefore, an optimal reaction area can not be obtained, and high battery performance can not be obtained at a low temperature.

Thereafter, coagulation of the metal catalyst is suppressed in the intermediate layer, and post heat treatment is performed to induce grain growth. At this time, the post-heat treatment is performed within a temperature range of 1100 to 1300 ° C. If the temperature is less than 1100 ° C., the metal catalyst may aggregate, the strength of the intermediate layer may not be sufficiently secured, If the temperature exceeds 1300 DEG C, the sintering temperature of the fuel electrode support becomes higher than the sintering temperature of the fuel electrode support, and the microstructure suitable for the fuel electrode support is not realized. This causes additional processing cost and time. .

The anode functional layer may further include a step of laminating the anode functional layer before the intermediate layer is laminated on the anode support. The anode functional layer may be formed by a process such as screen printing, tape casting, spin coating and spray coating, By forming it on the support, it is possible to obtain a pore-graded microstructure from the anode support or the intermediate layer by adjusting it to have a desired pore structure. More specifically, such a structure plays a role of securing the structural stability of the fuel cell by sequentially reducing the size of the pores from the anode support having the pores of several hundreds of micrometers to the middle layer having the pores having the nanometer size.

The anode function layer reduces surface defects of the proton conductive oxide fuel cell to prevent structural defects of the intermediate layer and the electrolyte and enables the porous structure to increase the size of the pores in the anode support, thereby improving the performance of the fuel cell.

The anode functional layer includes a metal catalyst and an oxide, and the oxide preferably includes at least one of zirconium oxide, cerium oxide, lanthanum gallate, barium cerate, barium zirconate, barium zirconate- And more preferably selected from the group consisting of samaria-doped ceria (SDC), gadolinia-doped ceria (GDC), yttria-stabilized zirconia zirconia, YSZ, scandia-stabilized zirconia (ScSZ), strontium manganese-doped lanthanum gallate (LSGM), yttria-doped barium zirconate (BZY) , Yttria-doped barium cerate (BCY), yttria-doped barium zirconate-dop ed barium zirconate-cerate, BCZY), and the metal catalyst may be any one or more of metal catalysts selected from the group consisting of nickel, ruthenium, palladium, rhodium and platinum.

Finally, an electrolyte layer and a cathode layer are sequentially laminated on the intermediate layer. At this time, a thin film process similar to the step of laminating the intermediate layer is performed to laminate electrolyte layers having a small thickness, and then a porous cathode layer is formed.

The intermediate layer may have a mixing volume ratio of the proton conductive oxide and the metal catalyst of 30 to 70:30 to 70. If the mixing ratio is out of the range, the proton conductive oxide fuel cell having the effect of the present invention is not realized.

The method of manufacturing a proton conductive oxide fuel cell according to the present invention may further include the step of laminating an electrolyte layer on the intermediate layer and then heat treating the electrolyte layer. And the heat treatment temperature is preferably 1000 to 1300 ° C. If the heat treatment temperature is less than 1000 ° C, no further improvement in the phase and structure formed during thin film deposition can be expected. If the temperature exceeds 1300 ° C, problems such as the heat treatment conditions of the intermediate layer occur, Have critical implications.

Hereinafter, the present invention will be described in more detail with reference to Examples.

However, the following examples are provided for illustrative purposes only, and the scope of the present invention is not limited thereto.

Example .

NiO and YSZ powders were mixed (NiO: 8YSZ = 56: 44 wt%), and the NiO-YSZ slurry having the same composition and small powder size was coated on the top of the NiO-YSZ slurry by screen printing. Sintered to prepare a porous anode support having a two-stage pore-gradient structure. An NiO-BZY intermediate layer was deposited on the anode support by pulsed laser deposition, a physical vapor deposition method. More specifically, the NiO-BZY target was deposited to a thickness of about 2 to 4 micrometers on the anode support by pulsed laser deposition (PLD) at an oxygen process pressure of 50 mTorr while the temperature of the fuel electrode support was fixed at 700 ° C . Subsequently, the intermediate layer of NiO-BZY deposited on the NiO-YSZ anode support was post-heat treated at 1200 ° C for 1 hour. 4 is a SEM photograph of the surface of the NiO-BZY intermediate layer formed on the NiO-YSZ support in the unit cell manufactured from Example 1 of the present invention. According to this, it can be confirmed that the NiO-BZY is continuously and uniformly deposited without any defect according to the surface shape of the anode support.

The post heat treatment is to prevent the Ni metal from aggregating during the reduction process of the metal catalyst before the fuel cell is driven and to grow the particle size of the NiO-BZY in the intermediate layer. Then, an electrolyte layer of BZY was deposited on the intermediate layer of NiO-BZY at an oxygen process pressure of 50 mTorr and a deposition temperature of 700 ° C, followed by post-heat treatment at 1200 ° C for 3 hours. The lanthanum strontium cobalt oxide (LSC) cathode layer was deposited on the electrolyte at room temperature and oxygen pressure of 100 mTorr by pulsed laser deposition (PLD), and then post-heat treated at 650 ° C for 1 hour to obtain a proton conductive oxide fuel cell A unit cell was fabricated.

Comparative Example .

The anode support was NiO-BZY, and the anode support was formed into a two-stage pore-sloping structure with different porosity by tape casting and then sintered at 1400 ° C for 10 hours. An intermediate layer, an electrolyte, and an air electrode were formed on the anode support by a pulse laser deposition method in the same manner as in the above examples, thereby preparing a unit cell of a proton conductive oxide fuel cell.

5 is a SEM photograph of a section taken after driving a unit cell manufactured according to an embodiment of the present invention.

According to this, no defects such as cracking and separation were observed at the interface between constituent layers even after the single cell produced in the above example was driven. That is, each of the layers included in the unit cell manufactured in the Example was initially uniformly and continuously produced, meaning that there were no interface defects between the respective layers, and that no defect was observed even after the operation, Structure.

As a result, it can be seen that the unit cell manufactured from the above example has excellent structural stability.

FIG. 6 is a graph of current-voltage-output (IVP) measured to check the open-circuit voltage and performance of a single cell manufactured from the embodiment according to the operating temperature. The single cell manufactured from the example has an operating temperature of 600 캜 and a maximum output of 40 mW / cm ² And the maximum power was observed at 10 mW / cm ² at 450 ° C.

7 is a SEM photograph of a surface of a NiO-BZY intermediate layer formed on a NiO-BZY support in a unit cell manufactured from a comparative example of the present invention. According to this, the NiO fine particles generated in the NiO-BZY support sintering process cause defects on the surface of the NiO-BZY intermediate layer and make it difficult to form the electrolyte membrane densely. This is due to the insufficient performance of the electrolyte membrane during the operation of the fuel cell, resulting in unstable performance.

8 is a graph of current-voltage-output (IVP) measured to check the open-circuit voltage and performance of the single cell produced from Comparative Example 1 according to the operating temperature. Embodiment was significantly lower performance is measured as compared to the example, specifically, the maximum output was observed by 5 mW / cm ² at the operating temperature is 600 ℃ and the maximum output of ^{13 mW / cm 2, 500 ℃} . It was confirmed that the open circuit voltage, which is an indicator of the stability of the single cell, is also low and the stability is low. As is apparent from the surface microstructure of the NiO-BZY substrate shown in FIG. 7, the NiO fine particles on the surface of the substrate generated during the sintering of the support serve as defects, causing interfacial defects between the intermediate layer and the dense It is unstable and shows low performance because it interferes with the electrolyte film formation.

Claims (15)

A porous anode support comprising Ni-YSZ;
An intermediate layer positioned on the anode support and comprising any one selected from the group consisting of Ni-BZY, Ni-BCY, and Ni-BCZY;
An electrolyte layer formed on the intermediate layer and including any one selected from the group consisting of BZY, BCY, and BCZY; And
And a cathode layer formed on the electrolyte layer,
The fuel electrode support has a multilayer structure of two or more layers,
Each of the layers of the anode support is characterized in that pore sizes are different from each other,
Wherein the electrolyte layer is fabricated through a thin film process. The method according to claim 1,
Further comprising an anode functional layer between the anode support and the intermediate layer. delete delete delete The method according to claim 1,
Wherein the intermediate layer has a mixed volume ratio of the proton conductor oxide and the metal catalyst in a range of 30 to 70: 30 to 70. The proton conductive oxide fuel cell according to claim 1, 3. The method of claim 2,
Wherein the anode functional layer is at least one selected from the group consisting of zirconium oxide, cerium oxide, lanthanum gallate, barium sulfate, barium zirconate, barium zirconate- Wherein the catalyst comprises at least one metal catalyst selected from the group consisting of palladium, rhodium, and platinum. (I) laminating an intermediate layer comprising any one selected from the group consisting of Ni-BZY, Ni-BCY and Ni-BCZY on a porous anode support comprising Ni-YSZ;
II) post-heat-treating the intermediate layer;
III) laminating an electrolyte layer containing any one selected from the group consisting of BZY, BCY and BCZY on the intermediate layer; And
And laminating a cathode layer on the electrolyte layer. ≪ RTI ID = 0.0 > 11. < / RTI > 9. The method of claim 8,
Further comprising the step of heat treating the electrolyte layer between the step (III) and the step (IV). 9. The method of claim 8,
The steps (I), (III), and (IV) above are characterized in that they are prepared using a thin film process,
The thin film process may be performed by any one selected from the group consisting of physical vapor deposition (PVD), chemical vapor deposition (CVD), chemical solution deposition (CSD), and spray pyrolysis Wherein the proton conductive oxide fuel cell is a single cell. 9. The method of claim 8,
Characterized in that the anode support is manufactured using a powder process,
Wherein the powder process is a tape casting process, a powder press process, or a screen printing process. 11. The method of claim 10,
Wherein the physical vapor deposition (PVD) is Pulsed-Laser Deposition (PLD). 2. The method of claim 1, wherein the physical vapor deposition (PVD) is pulsed laser deposition (PLD). 9. The method of claim 8,
Wherein the post-heat treatment is performed at a temperature of 1100 ° C to 1300 ° C. 9. The method of claim 8,
Wherein the intermediate layer has a mixing volume ratio of the proton conductive oxide and the metal catalyst in a range of 30 to 70:30 to 70. The proton conductive oxide fuel cell of claim 1, 10. The method of claim 9,
Wherein the heat treatment is performed at a temperature of 1000 ° C to 1300 ° C.

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