KR101153359B1 - Unit cell for fuel cell and manufacturing method thereof - Google Patents

Abstract

A hydrogen-activated layer sheet, an anode functional layer sheet, and an electrolyte membrane sheet by using a tape casting method so as to increase the electric power density by increasing the rate of oxidation of hydrogen, ii) A step of forming a stack by sequentially laminating a support sheet, a hydrogen-activating layer sheet, an anode functional layer sheet, and an electrolyte membrane sheet, iii) pressing the stack to produce a green body, iv) Forming a negative electrode support, a hydrogen activation layer, a negative electrode functional layer, and an electrolyte membrane on the electrolyte membrane; and v) forming a positive electrode on the electrolyte membrane.

Description

TECHNICAL FIELD [0001] The present invention relates to a unit cell for a fuel cell and a method of manufacturing the unit cell.

The present invention relates to a fuel cell. More particularly, the present invention relates to a unit cell of a fuel cell capable of increasing the rate of hydrogen oxidation and a method of manufacturing the same.

A fuel cell, for example, a solid oxide fuel cell (SOFC), has a structure in which a plurality of electricity generating units each comprising a unit cell and a separator plate are stacked. The unit cell includes an electrolyte membrane, an anode (air electrode) located on one surface of the electrolyte membrane, and a cathode (anode electrode) located on the other surface of the electrolyte membrane.

When oxygen is supplied to the anode and hydrogen is supplied to the cathode, oxygen ions generated by the reduction reaction of oxygen at the anode move to the cathode through the electrolyte membrane, and then water reacts with hydrogen supplied to the cathode. At this time, the electrons generated in the cathode are transferred to the anode and consumed, and electrons flow to the external circuit, and the unit cell generates electric energy by using the electron flow.

In the unit cell of the solid oxide fuel cell, the electrolyte membrane should be dense and not permeable to gas, and should not have electron conductivity, but high oxygen ion conductivity. On the other hand, the electrode must be porous to allow the gas to diffuse well and have high electron conductivity.

Many attempts have been made to improve the power density by improving the characteristics required of the electrolyte membrane or electrode constituting the unit cell.

The present invention provides a unit cell for a fuel cell and a method for manufacturing the same, which can increase the power density by increasing the rate of oxidation reaction of hydrogen.

To this end, a method for manufacturing a unit cell for a fuel cell includes the steps of: i) fabricating a negative electrode sheet, a hydrogen-activated layer sheet, a negative electrode functional layer sheet, and an electrolyte membrane sheet using tape casting; ii) Forming a stack by sequentially laminating a hydrogen-activated layer sheet, an anode functional layer sheet, and an electrolyte membrane sheet, iii) pressing the stack to produce a green body, iv) sintering the green body to form a cathode support, Forming a hydrogen-activating layer, a negative electrode functional layer, and an electrolyte membrane; and v) forming an anode on the electrolyte membrane.

The manufacturing method may further include forming a buffer layer between the electrolyte membrane and the anode.

The buffer layer forming step may be performed by preparing a buffer layer sheet, stacking the buffer layer sheet on the electrolyte membrane sheet in the stack formation, and then subjecting to a green body manufacturing and a green body sintering process.

The hydrogen-activated layer sheet comprises i) a transition metal oxide of Ni, Fe, Cu, Co, or a mixture thereof, ii) a hydrogen ion conductor comprising Zr, Ce, Ba, Sr as a main component, and iii) .

Proton conductor may be formed by _{SrCeO 3, BaCeO 3, BaZrO 3} , BaTbO 3, Ba 2 SnYO 5.5, SrTiO 3, BaThO 3, Ba 3 CaNb least any one selected from ₂ O _9. The hydrogen ion conductor may have a particle size of 0.1 to 10 um.

The buffer layer sheet is formed from a mixture of i) an oxygen ion conductor containing Ce as a main component and ii) a group consisting of Al, Co, Zn, Ni, Fe, Ca, K, Li, Mg, Mn, Na, Zn, And a sintering aid which is added in the form of a nitride, an acetate, or a chloride.

The oxygen ion conductor may be formed of Gd or Y-doped Ce oxide. The oxygen ion conductor may have a particle size of 50 nm to 200 nm.

The sintering aid may be included in the buffer layer in the range of 0.1a / o to 10a / o.

In the step of manufacturing the green body, the stack can be uniaxially pressed or isostatically pressed in an atmosphere of 50 ° C to 200 ° C. The sintering temperature of the green body may be 1,200 ° C to 1,500 ° C.

The hydrogen activation layer can be formed with a pore size of 5 to 70%. The hydrogen-activating layer may be formed to a thickness of 10 to 200 탆.

On the other hand, the unit cell for a fuel cell includes a negative electrode support, a hydrogen activation layer, a negative electrode functional layer, an electrolyte membrane, and a positive electrode.

The hydrogen activation layer may comprise i) a transition metal oxide of Ni, Fe, Cu, Co, or a mixture thereof, ii) a hydrogen ion conductor comprising Zr, Ce, Ba, Sr as a main component, and iii) have.

Proton conductor may be formed by _{SrCeO 3, BaCeO 3, BaZrO 3} , BaTbO 3, Ba 2 SnYO 5.5, SrTiO 3, BaThO 3, at least one selected from Ba ₃ CaNb ₂ O _9. The hydrogen ion conductor may have a particle size of 0.1 to 10 um.

The unit cell may further include a buffer layer between the electrolyte membrane and the anode.

The buffer layer may be formed of a material selected from the group consisting of i) an oxygen ion conductor containing Ce as a main component, and ii) a material selected from the group consisting of Al, Co, Zn, Ni, Fe, Ca, K, Li, Mg, Mn, Na, Zn, And a sintering aid which is added in the form of a nitride, an acetate, or a chloride.

The sintering aid may be included in the buffer layer in the range of 0.1a / o to 10a / o. The oxygen ion conductor may be formed of Gd or Y-doped Ce oxide.

According to the present embodiment, it is possible to increase the reaction rate at which electrons are emitted while the fuel of the negative electrode is oxidized through the introduction of the hydrogen activation layer. Therefore, the power density of the unit cell can be improved by increasing the fuel oxidation reaction rate.

Since the hydrogen activation layer is formed by sintering simultaneously with the anode support, the anode functional layer and the electrolyte membrane, the manufacturing process can be simplified, the process time can be shortened, and the manufacturing cost can be reduced.

1 is a process flow diagram illustrating a method of manufacturing a unit cell for a fuel cell according to an embodiment of the present invention.
FIG. 2 is a perspective view showing a tape casting apparatus used in the first step shown in FIG. 1. FIG.
3 is a partially enlarged cross-sectional view of the tape casting apparatus shown in Fig.
FIG. 4 is a perspective view showing the anode support sheet, the hydrogen-activated layer sheet, the anode functional layer sheet, the electrolyte membrane sheet, and the buffer layer sheet completed in the first step shown in FIG.
5 is an exploded perspective view showing the stack of the second step shown in Fig.
6 is a perspective view showing the green body of the third step shown in FIG.
7 is a perspective view of the unit cell completed through the fourth step shown in FIG.
8 is an electron micrograph showing a cross section of the unit cell completed according to the manufacturing method of this embodiment.

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. The embodiments described below can be modified into various forms without departing from the concept and scope of the present invention and are not limited to the embodiments described herein. Wherever possible, the same or similar parts are denoted using the same reference numerals in the drawings. It is also noted that the drawings are schematic and are not drawn to scale. The relative dimensions and ratios of the parts in the figures are shown exaggerated or reduced in size for clarity and convenience in the figures, and any dimensions are merely illustrative and not restrictive.

Hereinafter, this embodiment will describe a unit cell and a manufacturing method thereof as a solid oxide fuel cell (SOFC) in a fuel cell.

1 is a process flow diagram illustrating a method of manufacturing a unit cell for a fuel cell according to an embodiment of the present invention.

1, a method of manufacturing a unit cell for a solid oxide fuel cell includes a first step (S100) of manufacturing a cathode support sheet, a hydrogen-activated layer sheet, an anode functional layer sheet, and an electrolyte membrane sheet using a tape casting method, A second step S200 of stacking a negative electrode support sheet, a hydrogen activated layer sheet, a negative electrode functional layer sheet, and an electrolyte membrane sheet in this order to form a stack; and pressing the stack to produce a green body A fourth step S500 of forming a negative electrode support, a hydrogen activation layer, a negative electrode functional layer, and an electrolyte membrane by sintering the green body, a fifth step S500 of forming an anode on the electrolyte membrane, .

Here, the present manufacturing method may further include a barrier layer between the electrolyte membrane and the anode for suppressing the reaction between the electrolyte membrane and the anode. The buffer layer is formed by further forming a buffer layer sheet in the first step (S100), further laminating a buffer layer sheet on the electrolyte membrane sheet in the second step (S200), and then, in the third step (S300) A fourth step S400 is performed to form a buffer layer between the electrolyte membrane and the anode.

In the following description, a manufacturing process of a unit cell having a buffer layer in addition to the hydrogen activation layer will be described.

FIG. 2 is a perspective view showing a tape casting apparatus used in the first step shown in FIG. 1, and FIG. 3 is a partially enlarged cross-sectional view of the tape casting apparatus shown in FIG.

2 and 3, the tape casting apparatus 100 includes a pair of rollers 14 for conveying the backing film 12, a slurry chamber 16 for receiving the slurry and applying the slurry onto the backing film 12, A doctor blade 18 attached to the slurry chamber 16 for pushing the slurry to a uniform thickness and a drying chamber 20 for drying the slurry applied on the backing film 12. [

The cathode support slurry is coated on the base film 12 by using the tape casting apparatus 100 described above and then dried to prepare a cathode support tape. The anode support tape is cut and processed to a desired size, and then the base film 12 Thereby completing the cathode support sheet 22 shown in Fig.

The hydrogen-activated layer sheet 23 is prepared by using the hydrogen-activated layer slurry in the same manner, the anode functional layer sheet 24 is prepared using the anode functional layer slurry, and the electrolyte membrane sheet 26 ). Further, the buffer layer sheet 28 is prepared using the buffer layer slurry.

The negative electrode slurry contains a transition metal oxide such as Ni, Fe, Cu, Co, etc., an oxygen ion conductor or insulator containing Zr or Ce as a main component, and a pore-forming agent.

The hydrogen-activating layer slurry includes a transition metal oxide such as Ni, Fe, Cu, Co, or a mixture thereof, a hydrogen ion conductor containing Zr, Ce, Ba, or Sr as a main component, and a pore former.

Proton conductor may be formed by _{SrCeO 3, BaCeO 3, BaZrO 3} , BaTbO 3, Ba 2 SnYO 5.5, SrTiO 3, BaThO 3, at least one selected from Ba ₃ CaNb ₂ O _9. The hydrogen ion conductor may have a particle size of 0.1 to 10 um. When the particle size of the hydrogen ion conductor is less than 0.1 탆, sintering shrinkage is severe and it is difficult to form a heterointerface by co-sintering together with the negative electrode support sheet and the negative electrode functional layer sheet. If the particle size of the hydrogen ion conductor exceeds 10 mu m, it is difficult to sinter simultaneously with the negative electrode support sheet and the negative electrode functional layer sheet because the sintering shrinkage is small. Therefore, in both cases, problems may occur in simultaneous sintering together with the negative electrode sheet and the negative electrode functional sheet in the fourth step (S400).

The negative electrode slurry includes transition metal oxides such as Ni, Fe, Cu, and Co, an oxygen ion conductor containing Zr or Ce as a main component, and a pore-forming agent.

The electrolyte membrane slurry includes an oxygen ion conductor containing Zr as a main component.

The oxygen ion conductor can be formed of yttrium stabilized zirconia or scandium stabilized zirconia. The yttrium stabilized zirconia may be doped with 8 mol% Y ₂ O ₃ , and the composition may be Zr _0.84 Y _0.16 O _2-x . The composition of scandium stabilized zirconia may be Zr _0.84 Sc _0.16 O _{2 -x} .

The buffer layer slurry contains an oxygen ion conductor containing Ce as a main component. As the oxygen ion conductor, Gd or Y-doped Ce oxide may be used, and the composition may be Gd _0.1 Ce _0.9 O _{2 -x} or Gd _0.2 Ce _0.8 O _2-x . In the oxygen ion conductor composition of the electrolyte membrane slurry and the buffer layer slurry, x is a value that can be changed according to sintering conditions.

The buffer layer slurry further includes a sintering auxiliary agent serving to control the sintering behavior and the shrinkage ratio of the buffer layer sheet 28. The sintering aid comprises any one selected from the group consisting of Al, Co, Zn, Ni, Fe, Ca, K, Li, Mg, Mn, Na, Zn and mixtures thereof. May be added in the form of chloride.

The oxygen ion conductor included in the buffer layer slurry may have a particle size of 50 nm to 200 nm. If the particle size of the oxygen ion conductor is less than 50 nm, the sintering shrinkage ratio of the buffer layer sheet 28 becomes larger than that of the electrolyte membrane sheet 26. If the particle size of the oxygen ion conductor exceeds 200 nm, The sheet 26 becomes smaller. Therefore, in both cases, there is a difference in shrinkage ratio between the electrolyte membrane sheet 26 and the buffer layer sheet 28 in the fourth step (S400), so that cracking or bending may occur during simultaneous sintering.

The buffer layer sheet 28 has a sintering behavior similar to that of the electrolyte membrane sheet 26 in the sintering process of the fourth step (S400) and a shrinkage ratio (shrinkage ratio) similar to that of the electrolyte membrane sheet 26 due to the function of the sintering aids contained in the buffer layer slurry and the controlled particle size of the above- Lt; / RTI >

5 is an exploded perspective view showing the stack of the second step shown in Fig.

5, in the second step S200, the cathode support sheet 22, the hydrogen activation layer sheet 23, the anode functional layer sheet 24, the electrolyte membrane sheet 26, and the buffer layer sheet 28 Are stacked in this order to form the stack 30. In the stack 30, a plurality of cathode support sheets 22 are stacked, and the number of stacked layers can be adjusted according to the thickness of a desired cathode support. The hydrogen-activating layer sheet 23, the negative electrode functional layer sheet 24, the electrolyte membrane sheet 26 and the buffer layer sheet 28 are also laminated one or more, so that the number of layers can be adjusted to a desired thickness.

In the third step (S300), the green body 32 shown in Fig. 6 is manufactured by press-molding the stack 30. The stack 30 may be uniaxial pressing or isostatic pressing at a temperature of 50 ° C to 200 ° C. Uniaxial pressing is a method in which a mold is pressed in a single axial direction and isotropic pressure pressing is a method in which a mold is pressed in all directions up, down, left, and right using water pressure. The green body 32 can form a dense tissue structure by press molding. When the green body is made by uniaxial pressing, it is easy to peel between the sheet layers as the cell size increases. However, it is possible to prevent peeling between the sheets by isotropic pressing.

If the pressure forming temperature is less than 50 캜, the green body 32 may lose the formability of the green body 32, which may result in delamination after sintering due to difficulty in joining the sheets. If the press forming temperature exceeds 200 캜, . The green body 32 can form a dense tissue structure by press molding. Particularly, in the case of isostatic pressing, it is possible to effectively suppress peeling between sheets in the green body 32.

The thus formed green body 32 is cut into a desired size and shape and then the green body 32 is sintered in the fourth step S400 to form the anode support 34 and the hydrogen activation layer 35 A negative electrode functional layer 36, an electrolyte film 38, and a buffer layer 40 are formed.

The sintering can proceed at 1,200 ° C to 1,500 ° C. When the sintering temperature is less than 1,200 ° C, sufficient mechanical sintering is not achieved and mechanical strength is lowered. When the sintering temperature exceeds 1,500 ° C, the members having pores such as the anode support 34 and the hydrogen activation layer 35, The performance of the anode support 34, the hydrogen activation layer 35, and the anode functional layer 36 may be deteriorated because the porosity of the anode functional layer 36 is lowered.

In the sintering process of the fourth step S400, the buffer layer sheet 28 has a sintering behavior and a shrinkage ratio similar to those of the electrolyte membrane sheet 26, depending on the function of the sintering auxiliary agent contained in the buffer layer slurry and the controlled particle size of the oxygen ion conductor . As a result, in the completed unit cell 200, the buffer layer 40 has excellent adhesion to the electrolyte film 38, and no deformation occurs in the sintering process.

The buffer layer 40 may contain the above-described sintering aids in the range of 0.1 to 10 a / o. If the sintering aid content is less than 0.1 a / o, the sintering behavior and the shrinkage ratio control effect due to the sintering assistant agent can not be obtained. If the content of the sintering agent exceeds 10 a / So that the electric conductivity is lowered and the power density of the unit cell is reduced.

Finally, in the fifth step S500, a cathode material is coated on the buffer layer 40 and then heat-treated to form the anode 42, thereby completing the unit cell 200 for a solid oxide fuel cell.

8 is an electron micrograph of the unit cell according to the present embodiment, which is completed according to the above-described method.

As shown in FIG. 8, the unit cell is provided with a hydrogen activation layer between the anode support and the anode functional layer. Both the cathode support, the anode functional layer and the hydrogen diffusion layer have predetermined pores to facilitate the movement of fuel gas and water vapor. The porosity of the anode support may be 20 to 70%, and the porosity of the anode functional layer may be 5 to 50%. The porosity of the hydrogen-activated layer may be between 5 and 70%.

In this embodiment, the hydrogen-activating layer has a thickness of 10 to 200 mu m. When the thickness of the hydrogen activation layer is less than 10 탆, the effect of improving the oxidation rate of hydrogen is not sufficiently obtained.

The buffer layer forms a dense structure with little pores on the surface.

Thus, in the present embodiment, a hydrogen-activating layer is formed between the anode support and the anode functional layer sheet.

The hydrogen activation layer provides a reaction site in which a hydrogen molecule as a fuel of the solid oxide fuel cell is converted into a hydrogen ion while the electronegative reaction occurs under the cathode functional layer. That is, the hydrogen ions can move more smoothly through the hydrogen ion conductors of the hydrogen activation layer. Accordingly, the speed of the fuel oxidation reaction of the cathode is increased by the action of the hydrogen activation layer, so that the power density of the unit cell can be increased.

The hydrogen-activating layer is simultaneously sintered together with a cathode support layer, an anode functional layer, an electrolyte membrane and a buffer layer. Therefore, the manufacturing process can be simplified, the process time can be shortened, and the manufacturing cost can be reduced.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Of course.

22: cathode support sheet 23: hydrogen-activated layer sheet
24: negative electrode function layer sheet 26: electrolyte membrane sheet
28: buffer layer sheet 30: stack
32: Green body 34: Negative electrode support
35: hydrogen-activated layer 36: negative electrode functional layer
38: electrolyte membrane 40: buffer layer

Claims (16)

Preparing a negative electrode support sheet, a hydrogen-activated layer sheet, an anode functional layer sheet, and an electrolyte membrane sheet by tape casting;
Forming a stack by sequentially laminating the negative electrode sheet, the hydrogen-activating layer sheet, the negative electrode functional layer sheet, and the electrolyte membrane sheet in this order;
Pressing the stack to produce a green body,
Sintering the green body to form a cathode support, a hydrogen activation layer, a cathode functional layer, and an electrolyte membrane, and
Forming an anode on the electrolyte membrane
Wherein the method comprises the steps of: The method according to claim 1,
Wherein the hydrogen-
A transition metal oxide of Ni, Fe, Cu, Co, or a mixture thereof,
A hydrogen ion conductor mainly composed of Zr, Ce, Ba, and Sr, and
Credit
Wherein the method comprises the steps of: 3. The method of claim 2,
The proton conductor is _{SrCeO 3, BaCeO 3, BaZrO 3} , BaTbO 3, Ba 2 SnYO 5.5, SrTiO 3, BaThO 3, the manufacturing method of a Ba ₃ CaNb ₂ O Fuel cell unit cells formed by at least one selected from the ₉ . 3. The method of claim 2,
Wherein the hydrogen ion conductor has a particle size of 0.1 to 10 mu m. 3. The method of claim 2,
Wherein the hydrogen-activating layer has a porosity of 5 to 70%. 3. The method of claim 2,
Wherein the hydrogen-activating layer is formed to a thickness of 10 to 200 mu m. 7. The method according to any one of claims 1 to 6,
And forming a buffer layer between the electrolyte membrane and the anode. The method according to claim 1,
Wherein the step of preparing the green body comprises uniaxially pressing or isostatically pressing the stack in an atmosphere of 50 to 200 占 폚. The method according to claim 1,
Wherein the sintering temperature of the green body is 1,200 ° C to 1,500 ° C. A unit cell for a fuel cell comprising a cathode support, a hydrogen activation layer, a cathode functional layer, an electrolyte membrane, and a cathode sequentially stacked. 11. The method of claim 10,
And a buffer layer formed between the electrolyte membrane and the anode. The method according to claim 10 or 11,
The hydrogen-
A transition metal oxide of Ni, Fe, Cu, Co, or a mixture thereof,
A hydrogen ion conductor mainly composed of Zr, Ce, Ba, and Sr, and
Credit
Wherein the fuel cell unit cell is a fuel cell. 13. The method of claim 12,
The proton conductor is _{SrCeO 3, BaCeO 3, BaZrO 3} , BaTbO 3, Ba 2 SnYO 5.5, SrTiO 3, BaThO 3, Ba 3 CaNb 2 O 9 for a fuel cell unit cells formed by at least one selected from. 14. The method of claim 13,
Wherein the hydrogen ion conductor has a particle size of 0.1 to 10 um. 15. The method of claim 14,
Wherein the hydrogen-activated layer has a porosity of 5 to 70%. 16. The method of claim 15,
Wherein the hydrogen-activating layer is formed to a thickness of 10 to 200 mu m.

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