KR20160030625A - Method for manufacturing proton conducting solid oxide fuel cell and proton conducting solid oxide fuel cell using the method - Google Patents

Abstract

The present invention relates to a method for manufacturing a proton conducting solid oxide fuel cell and the proton conducting solid oxide fuel cell employing the same. The purpose of the present invention is to manufacture a large-area proton conducting solid oxide fuel cell which can be commercially utilized in an easy method. To achieve the purpose, the main invention point is that an oxygen ion conductor is transformed into a proton conductor through a reaction by performing low-temperature heat treatment in a space with controlled atmosphere. According to the present invention, a uniform and fine fuel electrode structure as well as a compact proton conductor electrolyte with excellent conductivity can be obtained even without going through high-temperature sintering, and a large-area proton conducting solid oxide fuel cell with excellent performance is finally provided.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a proton conductor solid oxide fuel cell and a proton conductor solid oxide fuel cell produced by the method,

More particularly, the present invention relates to a solid oxide fuel cell including an electrolyte layer having proton conductivity and / or an anode layer having proton conductivity, and a method of manufacturing the same. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid oxide fuel cell having proton conductivity and a method for manufacturing the same. .

A solid oxide fuel cell generally has a structure in which a plurality of electricity generating units each comprising a unit cell and a separator plate are laminated. The unit cell includes an electrolyte layer and a cathode (anode) located on one side of the electrolyte layer and an anode (anode) located on the other side of the electrolyte layer.

In general, a solid oxide fuel cell must be operated at a high temperature of 700 to 1000 ° C in order to reduce the ohmic resistance of the electrolyte layer and to reduce the polarization resistance of the fuel electrode and the air electrode. However, operation at a high temperature of 700 to 1000 ° C causes various problems such as coarsening of the fuel electrode microstructure, chrome volatilization in the separator, chromium poisoning of the air electrode, separation plate corrosion, generation of the second phase, ≪ / RTI > In addition, materials for separator plates and BOP (Balance of Plant) equipment for high-temperature operation must be used in high-priced metal materials having excellent oxidation resistance at high temperatures, which is a serious obstacle to the commercialization of solid oxide fuel cells.

For these reasons, studies are underway to lower the operating temperature of the solid oxide fuel cell to 400-600 ° C, which is the mid and low temperature range.

However, it is necessary to use an electrolyte material having a high conductivity even at a low temperature for operation in the middle low temperature region. When a proton conductor using proton (H ⁺ ) having high mobility as a charge transfer material is used as an electrolyte compared to an oxygen ion conductor using oxygen ions (O ^2- ) as a charge transfer material, high electric conductivity is obtained even at a low temperature .

Typical examples of such proton conductors include yttrium doped barium zirconia (BaZr _1-x Y _x O _{3 -d} , 0 <x? 0.2, 0? _D? 0.3, hereinafter referred to as BZY) BZY is a chemical compound that is mechanically and chemically bonded to the surface of a substrate. The BZY is a metal oxide having a chemical formula of BaTiO _{3 -y} Y _y O _{3 -d} , 0 < _y ? 0.2, 0? D? 0.3, It is very promising as a proton conductor for low temperature because of its high stability and very high particle electric conductivity.

However, since BZY is an ozone-depleting substance, densification is difficult even at 1600 DEG C or more, and barium (Ba) is volatilized at a high temperature to deteriorate electric conductivity. Further, when BZY is formed of an electrolyte material through a high-temperature method, it is difficult to be commercially used because it causes coarsening of the anode and thermal mismatching with the anode.

In order to lower the densification temperature of BZY, additives such as zinc oxide (ZnO), copper oxide (CuO) and nickel oxide (NiO) are used for BZY, but these additives cause deterioration of electrical conductivity.

On the other hand, a directional thin film with high electrical conductivity can be obtained through a thin film process such as a pulsed laser deposition (PLD) process, but the conductivity varies greatly depending on processing conditions and substrate conditions. In particular, when a fuel electrode used in a solid oxide fuel cell other than a single crystal substrate is used as a substrate, not only a directional thin film can be obtained, but also a fissile region is a very local region.

Korean Patent Publication No. 2012-0027875

It is an object of the present invention to provide a method for manufacturing a commercially available proton conductor solid oxide fuel cell having a large area and a proton conductor solid oxide fuel cell manufactured by the method, .

In order to achieve the above object, the present invention provides a solid oxide fuel cell comprising an oxygen ion conductor and an electrolyte layer comprising the oxygen ion conductor, or a solid oxide fuel cell comprising the anode layer, wherein the oxygen ion conductor is changed to a proton conductor through a phase change. A method of manufacturing a solid oxide fuel cell is provided.

In the method according to the present invention, the phase change may be achieved by an atmosphere heat treatment.

In the method according to the present invention, the atmosphere may include an electrolyte layer containing the oxygen ion conductor or a substance capable of reacting with a substance constituting the fuel electrode layer to change into an electrolyte layer containing a proton conductor or an anode layer It can be a weather atmosphere.

In the method according to the present invention, the heat treatment may be performed at 600 to 1400 ° C for 1 to 100 hours.

In the method according to the present invention, the electrolyte layer may be formed by applying at least one of pulsed laser deposition, sputter deposition, sintering after screen printing, aerosol thick film deposition, simultaneous sintering after tape lamination, and the like.

In the method according to the present invention, the anode layer is composed of a composite containing at least one selected from the group consisting of nickel (Ni) and nickel oxide (NiO) and an oxygen ion conductor, Lt; RTI ID = 0.0 &gt; 90% &lt; / RTI &gt;

In the method according to the present invention, the solid oxide fuel cell having an electrolyte layer or an anode layer comprising an oxygen ion conductor further comprises a support layer, wherein the support layer is one of nickel (Ni), nickel oxide (Ni), nickel-iron (Ni-Fe), and cobalt-nickel (Co-Ni) &Lt; / RTI &gt;

In the method according to the present invention, the oxygen ion conductor may be selected from among zirconia (ZrO ₂ ) oxide and ceria (CeO ₂ ) oxide, and the oxygen ion conductor is selected from yttria (Y ₂ O ₃ ) (Sc ₂ O ₃ ) and gadolinium oxide (Gd ₂ O ₃ ) in an atomic ratio of 1 to 30%.

In the method according to the present invention, the atmosphere heat treatment may be a method in which a solid oxide fuel cell having an electrolyte including an oxygen ion conductor or a fuel electrode is covered with a powder for forming an atmosphere and then heated.

In the method according to the present invention, the atmosphere forming powder is preferably at least _{one selected} from the group consisting of yttrium-doped barium zirconate (BaZr _1-x Y _x O _{3 -d} , 0 <x? 0.2, 0? _D? 0.3) rate _{(BaCe 1-y y y O} 3-d, 0 <y≤0.2, 0≤d≤0.3), may be one kind or a mixture thereof selected from the group consisting of barium carbonate (BaCO _3).

In the method according to the present invention, the proton conductor, barium zirconate (BaZrO _3), barium and three rates (BaCeO ₃₎ of the composite of _{BaZr x Ce 1-x O 3} -d (0 <x≤1.0, 0 (Y ₂ O ₃ ), ytterbium (Yb ₂ O ₃ ), niobium oxide (Nd ₂ O ₃ ), praseodymium oxide (Pr ₂ O ₃ ) may be contained at an atomic ratio of 1 to 30%.

According to another aspect of the present invention, there is provided a solid oxide fuel cell comprising an electrolyte or a fuel electrode, wherein at least one of the electrolyte or the anode has a proton conductor in a material containing an oxygen ion conductor Wherein the proton conductor is a solid oxide fuel cell.

The fuel cell according to the present invention may further include a support layer adjacent to the anode.

According to the present invention, it is possible to manufacture a medium-low-temperature-operated proton conductor solid oxide fuel cell having a commercially available size.

Particularly, according to the present invention, since the oxygen-ion conductor solid oxide fuel cell, which is technically complicated and partially utilized, is easily converted into a proton conductor solid oxide fuel cell through simple atmosphere heat treatment, It is possible not only to solve the problems of volatilization and electric conductivity lowering due to sintering but also to eliminate costly sintering process and to secure price competitiveness in cell manufacturing.

In addition, when used to control the microstructure of the fuel electrode, fine proton conductor particles can be uniformly distributed, maximizing the reaction area, and thus reducing the polarization resistance, thereby greatly improving fuel cell performance.

FIGS. 1A and 1B show an embodiment of the present invention, schematically illustrating a process in which an oxygen ion conductor solid oxide fuel cell is phase-changed into a proton conductor solid oxide fuel cell.
FIGS. 2A and 2B are graphs showing the results of a component analysis for a cross-section of a solid oxide fuel cell after heat treatment at 1200 ° C. and 1350 ° C., respectively, according to Example 1 of the present invention.
FIGS. 3A to 3C are scanning electron micrographs of cross sections of a solid oxide fuel cell after heat treatment at 1200.degree. C. and 1350.degree. C. before heat treatment according to Embodiment 1 of the present invention, respectively.
FIG. 4 schematically illustrates a process in which an oxygen ion conductor solid oxide fuel cell having the structure according to Embodiment 2 is phase-changed into a proton conductor solid oxide fuel cell.
5 is a graph showing the results of a component analysis on a cross section of a solid oxide fuel cell after heat treatment at 1200 ° C according to Example 2 of the present invention.
6 is a scanning electron micrograph of a cross section of the solid oxide fuel cell before the heat treatment is performed according to the second embodiment of the present invention and after the heat treatment at 1200 ° C.
FIG. 7 is a scanning electron microscope (SEM) image showing that the proton conductor particles of the anode layer are very finely and uniformly distributed on the BZY nickel particles according to the second embodiment of the present invention.
8A and 8B show the results of evaluating the performance of the fuel cell before and after performing the atmosphere heat treatment according to the second embodiment of the present invention.

Hereinafter, the present invention will be described in detail based on representative embodiments of the present invention. However, the technical spirit of the present invention is not limited to the embodiments disclosed below and can be implemented in various forms. It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to provide further explanation only as the scope of the invention mayinpower a person skilled in the pertinent art to a comprehensive understanding. Is defined.

The present invention relates to a fuel cell comprising an oxygen ion conductor or a fuel cell having an anode layer by performing a heat treatment at a relatively low temperature in an atmosphere controlled atmosphere to change the oxygen ion conductor into a proton conductor , And a proton conductor solid oxide fuel cell.

In manufacturing a proton conductor solid oxide fuel cell including a conventional BZY, the BZY fine particles can be densified only at a very high sintering temperature of 1600 DEG C or more. According to the present invention, the densified YSZ layer and BaO are formed in a range of 600 to 1200 The heat treatment at a high temperature is not required in order to ensure the compactness of BZY. Accordingly, problems such as barium (Ba) volatilization due to the high temperature process, coarsening of the fuel electrode, and thermal mismatch with the fuel electrode can be solved.

For example, the electrolyte layer can be formed by the reaction of yttrium stabilized zirconia (YSZ) and barium oxide (BaO), which are typical oxygen ion conductors used in solid oxide fuel cells, and an electrolyte comprising a proton conductor made of BZY Layer can be obtained.

Further, as another example, the proton conductor used for the anode layer can be easily changed in the method according to the present invention. For example, in a typical Ni-YSZ fuel electrode composite, a Ni-BZY composite can be formed by changing YSZ to BZY.

In particular, since the phase-changed BZY is changed into very small fine particles and is uniformly distributed on the Ni particles, it is very useful for maximizing the reaction area. Such maximization of the reaction area greatly reduces the polarization resistance, The performance of the battery can be improved.

The phase change may be performed by an atmosphere heat treatment, and the atmosphere preferably comprises a vapor phase containing a component capable of reacting with the oxygen ion conductor to cause a phase change to a proton conductor.

If the heat treatment temperature is lower than 600 ° C, the reaction between BaO and YSZ is not smooth. If it exceeds 1400 ° C, an undesired second phase other than BZY may be generated. Therefore, And more preferably in the range of 1000 to 1400 ° C. If the heat treatment time is less than 1 hour, the reaction is not sufficient and the desired region can not be sufficiently phase-changed. If the heat treatment time is more than 100 hours, the particles may be coarsened or the second phase may be generated due to over- desirable.

The electrolyte layer may be formed by various film forming methods such as pulsed laser deposition, sputter deposition, sintering after screen printing, aerosol thick film deposition, and simultaneous sintering after tape lamination.

The anode layer may be composed of a composite containing at least one selected from the group consisting of nickel (Ni) and nickel oxide (NiO) and an oxygen ion conductor, and the composite may include the oxygen ion conductor at a molecular ratio of 10 to 90% .

The solid oxide fuel cell may have a support layer. The support layer may be a composite including at least one selected from the group consisting of nickel (Ni) and nickel oxide (NiO) and an oxygen ion conductor, a stainless steel, nickel (Ni) (Ni-Fe), and cobalt-nickel (Co-Ni).

Preferably, the oxygen ion conductor is at least one selected from the group consisting of zirconia (ZrO ₂ ) oxide and ceria (CeO ₂ ) oxide, yttrium oxide (Y ₂ O ₃ ), scandia (Sc ₂ O ₃ ) and gadolinium oxide Gd ₂ O ₃ ) in an amount of 1 to 30 atomic%. However, the present invention is not limited to the above-mentioned oxygen ion conductor, and any oxygen ion conductor can be used without limitation as long as it is a material capable of phase-changing into a proton conductor through an atmosphere heat treatment.

The atmosphere heat treatment may be performed by a solid oxide fuel cell having an anode including an oxygen ion conductor or a fuel electrode including an oxygen ion conductor or a solid oxide fuel cell further comprising the support layer, A method of covering a solid oxide fuel cell with a powder containing a reaction component capable of phase-changing into a conductor and then heating the solid oxide fuel cell so that a reaction gas generated in the powder penetrates and reacts with the solid oxide fuel cell.

At this time, the atmosphere forming powder may be at least one selected from the group consisting of yttrium doped barium zirconia (BaZr _1-x Y _x O _{3 -d} , 0 <x? 0.2, 0? _D? 0.3), yttrium doped barium sulfate _{doped barium cerate: BaCe 1-y} y y O 3-d, 0 <y≤0.2, 0≤d≤0.3), it may be one kind or a mixture thereof selected from the group consisting of barium carbonate (BaCO _3). However, the atmosphere-forming powder of the present invention is not limited to the above-mentioned material, and any material including a reaction material which reacts with the oxygen ion conductor to change its phase to the proton conductor can be used without limitation.

Further, the proton conductor is preferably (BaZr _x Ce _1-x O _{3 -d,} 0 < _x ? 1.0, 0? D? 0.3) which is a complex of barium zirconate (BaZrO ₃ ) and barium cerate (BaCeO ₃ ) Wherein the composite is at least one selected from yttria (Y ₂ O ₃ ), ytterbium (Yb ₂ O ₃ ), nioxide (Nd ₂ O ₃ ), and praseodymium oxide (Pr ₂ O ₃ ) The additive may be included at 1 to 30% atomic ratio.

[Example 1]

FIG. 1 schematically shows a process in which an oxygen ion conductor solid oxide fuel cell having the structure according to Example 1 is phase-changed to a proton conductor solid oxide fuel cell.

The oxygen ion conductor solid oxide fuel cell comprises an electrolyte layer 1, an anode layer 2, and a support layer 3 for securing mechanical strength in contact with the electrolyte layer 1.

The electrolyte layer 1 is a layer made of zirconia (ZrO ₂ ) doped with yttrium (Y), and a thin sheet produced by a tape casting method is squeezed together with the anode layer and the support layer sheet and sintered simultaneously at 1350 ° C &Lt; / RTI &gt;

In the first embodiment of the present invention, the electrolyte layer 1 is formed of zirconia (ZrO ₂ ) (Zr _0.84 Y _0.16 O _{2 -d} ) doped with yttrium (Y), but other than zirconia (ZrO ₂ ) such as (CeO ₂₎ based oxide and the like may be used, in order to improve the thermal stability and ionic conductivity at high temperatures, the yttria (Y ₂ O _3), scandia (Sc ₂ O ₃₎ and gadolinium oxide (Gd ₂ O ₃₎ Some stabilizers may be included. If the addition amount of the stabilizer is less than 1 atomic%, the ionic conductivity becomes very low, which is difficult to use as the electrolyte layer. When the amount is more than 30 atomic%, the second phase is formed or the ionic conductivity is similarly low. %.

In addition, although the electrolyte layer 1 is formed by simultaneous sintering after the tape lamination in the first embodiment of the present invention, it may be formed by various methods such as pulse laser film deposition, sputtering film deposition, aerosol thick film deposition, screen printing, have.

The anode layer 2 is composed of a composite containing 35% of electrolyte material in nickel oxide (NiO) particles.

In the embodiment of the present invention, a composite made of 35% of electrolyte material is used for nickel oxide (NiO) particles, but metal particles such as nickel oxide (NiO) besides nickel particles may also be used. Ionic conductors or proton conductors. When the concentration is less than 10%, the ionic conductivity drops sharply due to insufficient connection between the particles. When the ionic conductivity exceeds 90%, the connection between NiO particles is not smooth. There is a problem that it falls rapidly, so it is preferable that it is included in the range of 10 to 90%. The fuel electrode layer 2 can form pores for smooth flow of the fuel gas, and the porosity of the anode layer 2 is preferably 50% or less.

The support layer 3 is made of a composite of zirconia (ZrO ₂ ) and nickel oxide (NiO) doped with yttrium (Y), and may have a porosity of 30%.

In the embodiment of the present invention, a composite of zirconia (ZrO ₂ ) and nickel oxide (NiO) in which yttrium (Y) is doped is used as the support layer 3, but a composite of 300 series stainless steel, 400 series stainless steel, nickel (Ni), nickel-iron (Ni-Fe), and cobalt-nickel (Co-Ni). When the porosity of the support layer 3 is less than 20%, the gas is not smoothly flowed into the support layer 3, resulting in resistance due to insufficient fuel supply. When the support layer 3 is more than 50%, the mechanical strength of the support layer 3 is low, 50% is preferable.

As shown in Fig. 1, the oxygen-ion conductor solid oxide fuel cell having the above-described structure is charged into the high-temperature vessel 5 by covering the powder 4 for forming the atmosphere. At this time, it is preferable that the atmosphere forming powder 4 is sufficiently covered so that the electrolyte layer 1 is not directly exposed to air. Also, the high-temperature container 5 can be performed in a vacuum atmosphere, an inert atmosphere, etc., in addition to the air atmosphere as in the first embodiment.

In the first embodiment of the present invention, the atmosphere forming powder 4 is made of yttrium-doped barium zirconia (BaZr _{1 -x} Y _x O _{3 -d,} 0 &lt; x? 0.2, 0? _D? 0.3) Respectively. Yttrium-doped barium zirconia _{(Yttrium doped barium zirconia: BaZr 1} -x Y x O 3-d, 0 <x≤0.2, 0≤d≤0.3) In addition, barium carbonate (BaCO which may be a source of barium oxide (BaO) ₃ ), barium zirconate (BaZrO ₃ ), barium cerate (BaCeO ₃ ), yttrium doped barium cerate (BaCe _{1 -x} Y _x O _{3 -d,} 0 <x? 0.2, d? 0.3) can be used. The use of the mixed powder of the above materials is preferable because the vapor pressure of the volatilized barium Ba can be kept more constant and barium carbonate (BaCO ₃ ), barium sulfate (BaCeO ₃ ) _3), yttrium-doped barium zirconia _{(yttrium doped barium zirconia: BaZr 1} -x Y x O 3-d, 0 <x≤0.2, 0≤d≤0.3) or yttrium doped barium three rates (yttrium doped barium cerate: BaCe _{1 -x} Y _x O _3-d, 0 &lt; x? 0.2, 0? _d? 0.3).

It is sufficient that the high-temperature vessel 5 is provided with a clearance and an outlet for discharging gas such as CO ₂ generated in the inside of the high-temperature vessel 5 to prevent strong airflow from being generated on the upper portion of the atmosphere- .

After the powder 4 for forming the atmosphere was covered with the oxygen ion conductor solid oxide fuel cell, heat treatment was performed at 1200 ° C and 1350 ° C for 5 hours, respectively.

Meanwhile, in Example 1 of the present invention, the heat treatment was performed under the same conditions as described above, but the heat treatment conditions may be performed at 600 to 1400 ° C, preferably at 1000 to 1400 ° C, depending on the materials used. If the heat treatment time is less than 1 hour, the reaction is not sufficient and the desired region can not be sufficiently phase-changed. If the heat treatment time is more than 100 hours, the particles may be coarsened or the second phase may be generated due to over- desirable. Since the thickness of the phase change reaction can be controlled according to the heat treatment temperature and time, only the electrolyte layer may be phase-changed or the electrolyte layer and the anode layer may be phase-changed by adjusting the above conditions.

Through this process, a solid oxide fuel cell having a fuel electrode layer 22 and an electrolyte layer 11, which is phase-changed to a proton conductor, is obtained, as shown on the right side of Fig.

FIG. 2 (a) is a graph showing the results of the component analysis on the cross section of the solid oxide fuel cell after heat treatment at 1200 ° C. according to Example 1 of the present invention, and FIG. 2 Sectional view of an oxide fuel cell according to an embodiment of the present invention.

As shown in FIG. 2A, when heat treatment was performed at 1200 ° C for 5 hours, the YSZ of the solid fuel cell showed a phase change from the upper part to the BZY part, but the lower part of YSZ showed a considerable amount of phase change Of the total population.

On the other hand, as shown in FIG. 2B, when the heat treatment was performed at 1350 ° C. for 5 hours, it can be seen that all the YSZ contained in the material constituting the solid fuel cell was phase-changed into BZY.

From this, it can be seen that the phase change degree can be controlled by controlling the heat treatment process conditions such as the heat treatment temperature and the heat treatment time.

FIGS. 3A to 3C are scanning electron microscopic photographs of cross sections of the solid oxide fuel cells before heat treatment according to the first embodiment of the present invention, respectively, and cross-sectional views of solid oxide fuel cells after heat treatment at 1200 ° C. and 1350 ° C., respectively Lt; / RTI &gt;

As shown in FIGS. 3B and 3C, it can be seen that the electrolyte layer, which is phase-changed from the oxygen ion conductor to the proton conductor by the phase change, is composed of a dense thin film.

[Example 2]

FIG. 4 schematically illustrates a process in which an oxygen ion conductor solid oxide fuel cell having the structure according to Embodiment 2 is phase-changed into a proton conductor solid oxide fuel cell.

In the solid oxide fuel cell according to Example 2, an electrolyte layer 1 'including a proton conductor is formed on a fuel electrode layer 2 including an oxygen ion conductor, and below the fuel electrode layer 2, (3) are formed.

At this time, the electrolyte layer 1 'may be composed of barium zirconate (BaZrO ₃ ), barium cerate (BaCeO ₃ ) or the above two complexes (BaZr _x Ce _1-x O _{3 -d} ). In addition, in the composite, yttria (Y ₂ O ₃ ), ytterbium (Yb ₂ O ₃ ), niobium oxide (Nd ₂ O ₃ ), praseodymium oxide (Pr ₂ O ₃ ) May be added in an amount of 1 to 30 at%.

The electrolyte layer 1 'may be formed by various methods such as pulsed laser deposition, sputtering thin film deposition, aerosol thick film deposition, screen printing, sintering, tape lamination and simultaneous sintering to form an electrolyte layer 1' Any method can be used without limitation.

The anode layer 2 and the support layer 3 except for the electrolyte layer 1 'are made of the same material as that of the first embodiment.

A solid oxide fuel cell having such a structure was produced in the same manner as in Example 1, except that yttrium-doped barium zirconia (BaZr _1-x Y _x O _{3 -d,} 0 &lt; x & ) Powder was coated, and heat treatment was performed at 1200 ° C for 5 hours.

As a result, a solid oxide fuel cell having a fuel electrode layer 22 phase-changed to a proton conductor was obtained as shown on the right side of Fig.

FIG. 5 is a graph showing the result of a component analysis on a cross section of a solid oxide fuel cell after heat treatment at 1200 ° C. according to Example 2 of the present invention. FIG. 6 is a graph showing the result of analysis of components before and after heat treatment according to Example 2 of the present invention, &Lt; RTI ID = 0.0 &gt; ° C. &Lt; / RTI &gt;

As shown in Figs. 5 and 6, according to the second embodiment of the present invention, the anode layer 2 made of an oxygen ion conductor is converted into a proton conductor while the electrolyte layer 1 'is kept as a proton conductor.

According to Example 2 of the present invention, when used for controlling the microstructure of the fuel electrode, it is possible to uniformly distribute fine proton conductor particles, thereby maximizing the reaction area, thereby reducing the polarization resistance and greatly improving the fuel cell performance have. As shown in Fig. 7, it is shown that the proton conductor particles of the anode layer are very finely and uniformly distributed on the BZY nickel particles.

8 shows the results of evaluating the performance of the fuel cell before and after performing the atmosphere heat treatment according to the second embodiment of the present invention. FIG. 8A shows the power performance without the atmosphere heat treatment, and FIG. 8B shows the power performance with respect to the cell in which the microstructure of the anode layer is controlled through the atmosphere heat treatment, showing that the performance is drastically improved.

1: oxygen ion conductor electrolyte layer
1 ', 11: proton conductor electrolyte layer
2: oxygen ion conductor anode layer
22: proton conductor anode layer
3: Support layer
4: Atmosphere forming powder
5: high temperature vessel

Claims (14)

A solid oxide fuel cell comprising an electrolyte layer comprising an oxygen ion conductor or an anode layer, wherein the oxygen ion conductor is converted into a proton conductor through a phase change. The method according to claim 1,
Wherein the phase change is performed by an atmosphere heat treatment. 3. The method of claim 2,
Wherein the atmosphere is a gas atmosphere in which the electrolyte layer containing the oxygen ion conductor or the electrolyte layer containing the proton conductor or the phase changeable material by the anode layer material reacts with the substance constituting the anode layer, Oxide fuel cell. 3. The method of claim 2,
Wherein the heat treatment is performed at 600 to 1400 ° C for 1 to 100 hours. The method according to claim 1,
Wherein the electrolyte layer is formed by applying at least one of pulsed laser deposition, sputter deposition, sintering after screen printing, aerosol thick film deposition, tape lamination, and simultaneous sintering. The method according to claim 1,
Wherein the anode layer is made of a composite of at least one of nickel (Ni) and nickel oxide (NiO) and an oxygen ion conductor, and the oxygen ion conductor is a proton conductor solid oxide fuel cell having a molecular ratio of 10 to 90% &Lt; / RTI &gt; The method according to claim 1,
The solid oxide fuel cell having the electrolyte layer or the anode layer including the oxygen ion conductor further comprises a support layer,
Wherein the support layer is made of a composite having at least one of nickel (Ni) and nickel oxide (NiO) and an oxygen ion conductor having a molecular ratio of 10 to 90%, stainless steel, Ni Wherein the proton conductor is selected from the group consisting of oxygen, 3. The method of claim 2,
The oxygen-ion conductor, zirconia (ZrO ₂₎ based oxide, ceria (CeO ₂₎ system is one selected of the oxide, yttria (Y ₂ O _3), scandia (Sc ₂ O _3), and gadolinium (Gd ₂ O oxide ₃ ) is contained in an amount of 1 to 30 atomic%, based on the total weight of the proton conductive solid oxide fuel cell. 9. The method of claim 8,
Wherein the atmosphere heat treatment is performed by a method in which a solid oxide fuel cell having an electrolyte layer containing an oxygen ion conductor or a fuel electrode layer is covered with a powder for forming an atmosphere and then heated. 10. The method of claim 9,
The atmosphere for forming powders, yttrium doped barium zirconate _{(BaZr 1-x Y x O} 3-d, 0 <x≤1,0≤d≤1), yttrium-doped barium three rates (BaCe _{1-y Y y} O _3-d , 0 <y _{? 1} , 0? D? 1) and barium carbonate (BaCO ₃ ) or a mixture thereof. The method according to claim 1,
Wherein either one of the electrolyte layer or the anode layer constituting the solid oxide fuel cell before the phase change comprises a proton conductor. 12. The method of claim 11,
The proton conductor is a composite of barium zirconate (BaZrO ₃ ) and barium cerate (BaCeO ₃ ) (BaZr _x Ce _{1 -x} O _{3 -d,} 0 _{? X? 1 ,} 0 _{? D?} 0.3) triazole as (Y ₂ O _3), oxide ytterbium (Yb ₂ O _3), oxide you audio di _{(Nd 2 O 3), 1} ~ 30 atomic% of one or more additives selected from the group consisting of praseodymium oxide (Pr ₂ O ₃₎ &Lt; / RTI &gt; wherein the proton conductor is a solid oxide fuel cell. A solid oxide fuel cell comprising an electrolyte or a fuel electrode, wherein the electrolyte or the anode has a proton conductor in a material containing an oxygen ion conductor, by the method according to any one of claims 1 to 11 Phase - transformed, proton - conducting solid oxide fuel cell. 14. The method of claim 13,
Further comprising a support layer adjacent to the anode.

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