KR102514366B1 - Metal supporter-typed solid oxide fuel cell using co-sintering process and manufacturing method thereof - Google Patents

Abstract

The present invention provides a metal-supported solid oxide fuel cell formed by simultaneous sintering and a manufacturing method thereof. A method of manufacturing a metal support type solid oxide fuel cell according to an embodiment of the present invention includes forming an electrolyte layer on one side of an anode layer; Forming a cathode layer on the electrolyte layer; Adhering a metal support to the other side of the anode layer; and co-sintering the metal support, the anode layer, the electrolyte layer, and the cathode layer to bond the anode layer and the metal support, and at the same time to bond the electrolyte layer and the cathode layer. .

Description

Metal supporter-type solid oxide fuel cell using co-sintering process and manufacturing method thereof

The technical idea of the present invention relates to a solid oxide fuel cell, and more particularly, to a metal support type solid oxide fuel cell formed using simultaneous sintering and a manufacturing method thereof.

A solid oxide fuel cell (SOFC) is currently known as a third-generation fuel cell. The solid oxide fuel cell has advantages such as high efficiency compared to other fuel cells and no additional reformer required. A conventional solid oxide fuel cell uses a nickel-electrolyte alloy as a support for supporting an anode layer ( It is composed of a ceramic support type using Ni-electrolyte cermet). Such a ceramic support type solid oxide fuel cell has very weak mechanical strength and toughness against thermal shock, and has limitations in miniaturization and weight reduction.

As an alternative to this, a metal-supported SOFC has been recently studied. However, in the process of manufacturing a conventional metal support-type solid oxide fuel cell, in order to prevent oxidation of the metal support, the metal support and the anode/electrolyte layer are firstly sintered in a reducing atmosphere, and then the cathode is placed on the electrolyte layer. It consists of a process of performing secondary sintering for attaching the phosphorus cathode layer. A reducing atmosphere may be required to bond the metal support and the anode layer. However, when using a material such as La _1-x Sr _x MnO _3-δ (LSM) or La _1-x Sr _x Co _0.8 Fe _0.2 O _3-δ (LSCF) as the cathode, a high sintering temperature is required, In a reducing atmosphere, the phase of the material collapses and the stability of the cathode cannot be maintained. Therefore, there is a need for a material for a cathode and a manufacturing method for forming a metal-supported solid oxide fuel cell by simultaneous sintering in which the primary sintering and the secondary sintering are performed at once.

US Patent No. 10008726

A technical problem to be achieved by the technical spirit of the present invention is to provide a metal support type solid oxide fuel cell formed using simultaneous sintering and a manufacturing method thereof.

However, these tasks are exemplary, and the technical spirit of the present invention is not limited thereto.

A method for manufacturing a metal support-type solid oxide fuel cell formed using simultaneous sintering according to the technical idea of the present invention for achieving the above technical problem includes forming an electrolyte layer on one side of an anode layer; Forming a cathode layer on the electrolyte layer; Adhering a metal support to the other side of the anode layer; and co-sintering the metal support, the anode layer, the electrolyte layer, and the cathode layer to bond the anode layer and the metal support, and at the same time to bond the electrolyte layer and the cathode layer. .

In one embodiment of the present invention, the forming of the electrolyte layer may be performed by pre-sintering the anode layer and the electrolyte layer.

In one embodiment of the present invention, forming the cathode layer may be performed using screen printing.

In one embodiment of the present invention, before performing the step of forming the cathode layer, the step of forming a buffer layer using screen printing on the electrolyte layer may be further included.

In one embodiment of the present invention, before performing the step of adhering the metal support, further comprising the step of forming an adhesive layer on the metal support, and adhering the metal support to the anode layer using the adhesive layer can do.

In one embodiment of the present invention, the co-sintering may be performed in a reducing atmosphere.

In one embodiment of the present invention, the co-sintering may be performed at a temperature ranging from 800 °C to 1000 °C.

In one embodiment of the present invention, the cathode layer may include a compound of the following formula.

<Formula>

Pr _0.5 Ba _0.5-x Sr _x FeO _3-δ

In the above formula, x is a number ranging from greater than 0 to less than 0.5, and δ is a positive number ranging from greater than 0 to less than 1, and is a value that makes the compound of the formula electrically neutral.

In one embodiment of the present invention, the cathode layer may have a structure in which the iron (Fe) is eluted to the surface in the compound of the above formula.

In one embodiment of the present invention, the cathode layer is a Pr _0.5 Ba _0.2 Sr _0.3 FeO _3-δ compound, a Pr _0.5 Ba _0.15 Sr _0.35 FeO _3-δ compound, a Pr _0.5 Ba _0.1 Sr _0.4 FeO _3-δ compound, and Pr _0.5 Ba _0.05 Sr _0.45 FeO _3-δ compounds.

In an embodiment of the present invention, the cathode layer may include a Pr _0.5 Sr _0.5 FeO _3-δ compound (here, δ is a positive number ranging from greater than 0 to less than 1).

A metal support type solid oxide fuel cell according to the technical idea of the present invention for achieving the above technical problem includes an anode layer; an electrolyte layer located on one side of the anode layer; a cathode layer disposed on the electrolyte layer facing the anode layer and supplied with oxygen; And a metal support located on the other side of the anode layer and supporting the anode layer; including, bonding the anode layer and the metal support, and at the same time bonding the electrolyte layer and the cathode layer, the metal The support, the anode layer, the electrolyte layer, and the cathode layer may be co-sintered.

In one embodiment of the present invention, the cathode layer may include a layered R-P perovskite material.

In one embodiment of the present invention, the cathode layer may include a compound of the following formula.

<Formula>

Pr _0.5 Ba _0.5-x Sr _x FeO _3-δ

In the above formula, x is a number ranging from greater than 0 to less than 0.5, and δ is a positive number ranging from greater than 0 to less than 1, and is a value that makes the compound of the formula electrically neutral.

In one embodiment of the present invention, the cathode layer may have a structure in which the iron (Fe) is eluted to the surface in the compound of the above formula.

In an embodiment of the present invention, the cathode layer may include a compound in which x is a number ranging from 0.3 or more to less than 0.5.

In one embodiment of the present invention, the cathode layer is a Pr _0.5 Ba _0.2 Sr _0.3 FeO _3-δ compound, a Pr _0.5 Ba _0.15 Sr _0.35 FeO _3-δ compound, a Pr _0.5 Ba _0.1 Sr _0.4 FeO _3-δ compound, and Pr _0.5 Ba _0.05 Sr _0.45 FeO _3-δ compounds.

In an embodiment of the present invention, the cathode layer may include a Pr _0.5 Sr _0.5 FeO _3-δ compound (here, δ is a positive number ranging from greater than 0 to less than 1).

In one embodiment of the present invention, the anode layer, nickel (Ni), cobalt (Co), platinum (Pt), zinc (Zn), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), copper (Cu), or an alloy thereof.

In one embodiment of the present invention, the metal support, iron (Fe), stainless steel, nickel (Ni), cobalt (Co), platinum (Pt), zinc (Zn), vanadium (V), chromium (Cr) ), manganese (Mn), iron (Fe), copper (Cu), aluminum (Al), magnesium (Mg), calcium (Ca), stainless steel (eg, Crofer 22 APU), or alloys thereof. .

In the method for manufacturing a metal support type solid oxide fuel cell according to the technical concept of the present invention, a metal support type solid oxide fuel cell structure may be formed using simultaneous sintering. Conventionally, two sintering processes were performed: high-temperature sintering in a reducing atmosphere for bonding the metal support and anode/electrolyte and sintering of the cathode and buffer layer, whereas the present invention can implement these two sintering as one sintering, It can provide the effect of simplifying the process and preventing component damage.

In addition, by using a material capable of phase change from single perovskite to R-P perovskite that can show oxygen ion conductivity in a reducing atmosphere as a cathode material, it is changed into a stable phase by simultaneous sintering in a reducing atmosphere to improve stability. It can provide an increasing effect. In addition, by the simultaneous sintering, iron metal is eluted onto the surface, thereby providing an effect of increasing catalytic activity.

The effects of the present invention described above have been described by way of example, and the scope of the present invention is not limited by these effects.

1 is a cross-sectional view showing a metal support type solid oxide fuel cell according to an embodiment of the present invention.
2 is a flowchart illustrating a manufacturing method of a metal support type solid oxide fuel cell according to an embodiment of the present invention.
FIG. 3 is cross-sectional views illustrating a manufacturing method of the metal support type solid oxide fuel cell of FIG. 2 according to an embodiment of the present invention according to process steps.
4 is a schematic diagram showing a layered RP perovskite material constituting a cathode layer of a metal support type solid oxide fuel cell according to an embodiment of the present invention.
5 is a schematic diagram illustrating elution of a transition element from a cathode layer of a metal support type solid oxide fuel cell according to an embodiment of the present invention.
6 is a schematic diagram illustrating a metal support type metal-air battery according to an embodiment of the present invention.
7 is a schematic diagram illustrating a metal support type solid oxide water electrolysis cell according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The embodiments of the present invention are provided to more completely explain the technical idea of the present invention to those skilled in the art, and the following examples may be modified in many different forms, The scope of the technical idea is not limited to the following examples. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the spirit of the invention to those skilled in the art. Like reference numerals throughout this specification mean like elements. Further, various elements and areas in the drawings are schematically drawn. Therefore, the technical spirit of the present invention is not limited by the relative size or spacing drawn in the accompanying drawings.

A method for manufacturing a metal support-type solid oxide fuel cell according to the technical idea of the present invention uses a metal support made of a metal material as a support for supporting an anode layer, and in a reducing atmosphere, the metal support, the anode layer/electrolyte layer, and the cathode A metal support type solid oxide fuel cell can be fabricated by using only one in-situ co-sintering of layer bonding. In addition, as a material constituting the cathode layer, an R-P perovskite-based material that elutes particles with high catalytic activity is used.

1 is a cross-sectional view showing a metal support type solid oxide fuel cell 100 according to an embodiment of the present invention.

Referring to FIG. 1 , a metal support type solid oxide fuel cell 100 includes an anode layer 110; An electrolyte layer 120 located on one side of the anode layer 110; a cathode layer 130 disposed facing the anode layer 110 on the electrolyte layer 120 and supplied with oxygen; and a metal support 140 located on the other side of the anode layer 110 and supporting the anode layer 110 .

To bond the anode layer 110 and the metal support 140, and at the same time to bond the electrolyte layer 140 and the cathode layer 130, the metal support 140, the anode layer 110, the electrolyte layer 120 , and the cathode layer 130 may be co-sintered.

In addition, the metal support type solid oxide fuel cell 100 may further include a buffer layer 150 interposed between the electrolyte layer 120 and the cathode layer 130 . In addition, the metal support type solid oxide fuel cell 100 may further include an adhesive layer 160 interposed between the anode layer 110 and the metal support 140 .

The anode layer 110 may function as an anode or fuel electrode. The anode layer 110 may include a material that loses electrons to become a cation, and is not particularly limited as long as it is generally usable in the art. The anode layer 110 may include, for example, a metal, and for example, nickel (Ni), cobalt (Co), platinum (Pt), zinc (Zn), vanadium (V), chromium (Cr), Manganese (Mn), iron (Fe), copper (Cu), or alloys thereof may be included.

The electrolyte layer 120 may be positioned between the anode layer 110 and the cathode layer 130, contain an electrolyte material, and perform a function of moving the electrolyte material. The electrolyte layer 120 is not particularly limited as long as it is generally usable in the art. The electrolyte layer 120 may be, for example, a stabilized zirconia system such as yttria stabilized zirconia (YSZ) or scandia stabilized zirconia (ScSZ); Ceria-types to which rare earth elements are added, such as Samaria-doped ceria (SDC) and Gadolinia-doped ceria (GDC); other LSGM ((La, Sr)(Ga, Mg)O ₃ ) based; etc. may be included.

For example, the anode layer 110 and the electrolyte layer 120 may include nickel and zirconia as zirconia-based electrodes, and may be composed of, for example, Ni—YSZ.

The cathode layer 130 may function as a cathode or an air electrode, and may include, for example, a layered R-P perovskite material. Materials constituting the cathode layer 130 will be described in detail below.

The buffer layer 150 may be positioned between the electrolyte layer 120 and the cathode layer 130 to provide smooth contact. The buffer layer 150 may, for example, mitigate crystal lattice distortion between the electrolyte layer 120 and the cathode layer 130 . The buffer layer 150 may be omitted as an optional component. The buffer layer 150 may include, for example, GDC (Gd _0.1 Ce _0.9 O _2-δ ), LDC (La _0.4 Ce _0.6 O _2-δ ), or both.

The metal support 140 may serve to support the anode layer 110 . The metal support 140 may include a material having rigidity and ductility, and may include, for example, various metal materials, such as iron (Fe), stainless steel, nickel (Ni), and cobalt (Co). , Platinum (Pt), Zinc (Zn), Vanadium (V), Chromium (Cr), Manganese (Mn), Iron (Fe), Copper (Cu), Aluminum (Al), Magnesium (Mg), Calcium (Ca) , stainless steel (eg Crofer 22 APU) or alloys thereof.

The adhesive layer 160 may be interposed between the anode layer 110 and the metal support 140 to adhere the anode layer 110 and the metal support 140 to each other. The adhesive layer 160 may be omitted as an optional component. The adhesive layer 160 may include various materials for bonding the anode layer 110 and the metal support 140 to each other, and may include, for example, inorganic adhesives, sinterable adhesives, organic adhesives, photocurable adhesives, and the like. .

On one side of the anode layer 110, the electrolyte layer 120, the buffer layer 150, and the cathode layer 130 may be disposed, and on the other side opposite to the one side, the adhesive layer 160, and the metal support ( 140) may be placed.

As shown in the following reaction equation, the electrochemical reaction of the metal-supported solid oxide fuel cell 100 is the anode reaction in which oxygen gas O ₂ of the cathode layer 130 is converted into oxygen ion O ^2- and the fuel of the anode layer 110 (H ₂ or hydrocarbon) and oxygen ions that have moved through the electrolyte of the electrolyte layer 120 react with a cathode reaction.

<reaction formula>

Anode reaction: 1/2 O ₂ + 2e ^- -> O ^2-

Cathodic reaction: H ₂ + O ^2- -> H ₂ O + 2e ^-

In the cathode layer 130 of the metal-supported solid oxide fuel cell 100, oxygen adsorbed on the surface of the electrode undergoes dissociation and surface diffusion, whereby the electrolyte layer 120, the cathode layer 130, and pores (not shown) meet in three phases. It moves to the triple phase boundary to obtain electrons and become oxygen ions, and the generated oxygen ions move to the anode layer 110, which is the fuel electrode, through the electrolyte layer 120.

In the anode layer 110 of the metal-supported solid oxide fuel cell 100, oxygen ions that have moved are combined with hydrogen contained in the fuel to generate water. At this time, hydrogen emits electrons to change into hydrogen ions (H ⁺ ) and combine with the oxygen ions. The discharged electrons move to the cathode layer 130 through a wire (not shown) and change oxygen into oxygen ions. Through this movement of electrons, the metal support type solid oxide fuel cell 100 can perform a battery function.

Since the metal support type solid oxide fuel cell 100 can be manufactured using a conventional method known in various literatures in the art, a detailed description thereof will be omitted here. In addition, the metal support type solid oxide fuel cell 100 may be applied to various structures such as a tubular stack, a flat tubular stack, and a planar stack.

The metal support type solid oxide fuel cell 100 may be in the form of a stack of unit cells. For example, unit cells (MEA, Membrane and Electrode Assembly) composed of an anode layer 110, a cathode layer 130, and an electrolyte layer 120 are stacked in series and electrically connected between the unit cells. A stack of unit cells may be obtained by interposing a separator having a separator therebetween.

2 is a flowchart illustrating a method (S100) of manufacturing a metal support type solid oxide fuel cell according to an embodiment of the present invention.

FIG. 3 is cross-sectional views illustrating a manufacturing method (S100) of the metal support type solid oxide fuel cell of FIG. 2 according to an embodiment of the present invention according to process steps.

Referring to FIGS. 2 and 3 , the method of manufacturing a metal-supported solid oxide fuel cell (S100) includes forming an electrolyte layer 120 on one side of an anode layer 110 (S110); Forming a cathode layer 130 on the electrolyte 120 (S120); Adhering the metal support 140 to the other side of the anode layer 110 (S130); And to bond the anode layer 110 and the metal support 140, and at the same time to bond the electrolyte layer 120 and the cathode layer 130, the metal support 140, the anode layer 110, the electrolyte layer 120 ), and co-sintering the cathode layer 130 (S140);

In the step of forming the electrolyte layer 120 (S110), after forming the electrolyte layer 120 on the anode layer 110 by using a method such as, for example, drop coating or sputtering, It can be made by pre-sintering the anode layer 110 and the electrolyte layer 120. The preliminary sintering may be performed at a temperature ranging from 1300° C. to 1500° C. in a vacuum, inert gas atmosphere, or air atmosphere. The anode layer 110 and the electrolyte layer 120 may be solidified by the preliminary sintering, and the inside of the anode layer 110, the inside of the electrolyte layer 120, and the anode layer 110 and the electrolyte layer (120) may have a desired level of bonding force between them.

Forming the cathode layer 130 (S120) may be performed using screen printing. Forming the cathode layer (S120) may be performed by applying a cathode layer material constituting the cathode layer 130 on the electrolyte layer using screen printing. The cathode layer 130 may include a perovskite material described below. The screen printing may be performed at various suitable temperatures, for example at room temperature. The cathode layer 130 formed by the screen printing may be completed by subsequent simultaneous sintering.

Before forming the cathode layer 130 (S120), forming a buffer layer 150 on the electrolyte layer 120 (S115) may be further included. Forming the buffer layer 150 (S115) may be performed using screen printing. Forming the buffer layer (S115) may be performed by applying a material for the buffer layer constituting the buffer layer 150 on the electrolyte layer 120 using screen printing. The screen printing may be performed at various suitable temperatures, for example at room temperature. The buffer layer 150 formed by the screen printing may be completed by subsequent simultaneous sintering.

For example, the buffer layer 150 may be formed on the electrolyte layer 120 using screen printing, and then the cathode layer 130 may be formed on the buffer layer 150 using screen printing.

Before performing the attaching the metal support 140 (S130), forming an adhesive layer 160 on the metal support 140 (S125) may be further included. Subsequently, the metal support 140 may be adhered to the anode layer 110 using the adhesive layer 160 .

In the co-sintering step (S140), the metal support 140, the anode layer 110, the electrolyte layer 120, and the cathode layer 130 are co-sintered. By performing the co-sintering step (S140), the anode layer 110 and the metal support 140 may be bonded, and at the same time, the electrolyte layer 120 and the cathode layer 130 may be bonded. In addition, the cathode layer 130 may form a layered R-P perovskite material by the co-sintering step (S140). The co-sintering step (S140) may be performed in an in-situ manner. The co-sintering step (S140) may be performed in a reducing atmosphere such as a hydrogen gas atmosphere, and may be performed at a temperature ranging from about 800 °C to about 1000 °C.

By co-sintering in such a reducing atmosphere, the material constituting the cathode layer 130 can be changed into a stable phase, such as a layered R-P perovskite material. In addition, stability in which the perovskite phase does not collapse in the reducing atmosphere can be provided. In addition, bonding between the metal support 140 and the anode layer 110 can be effectively achieved by the reducing atmosphere.

Hereinafter, materials constituting the cathode layer 130 of the metal support type solid oxide fuel cell 100 will be described in detail.

4 is a schematic diagram showing a layered R-P perovskite material constituting a cathode layer of a metal support-type solid oxide fuel cell according to an embodiment of the present invention.

Referring to Figure 4, a layered R-P perovskite material is shown. Perovskite materials can be largely classified into single perovskite materials and layered perovskite materials.

The single perovskite material may have a chemical formula of ABO ₃ . In the crystal structure of the single perovskite material, elements with relatively large ionic radii may be located at the A-site, which is a corner position of a cubic lattice, and 12 coordinated by oxygen ions may have a number (CN, Coordination number). For example, rare earth elements, alkaline rare earth elements, and alkaline elements may be positioned at the A-site. Elements having relatively small ionic radii may be located at the B-site, which is the body center position of the cubic lattice, and may have a coordination number of 6 due to oxygen ions. For example, a transition metal such as iron (Fe) or cobalt (Co) may be positioned at the B-site. Oxygen ions may be located at each face center of the cubic lattice. Such a single perovskite structure can generally undergo structural displacement when another material is substituted at the A-site, and its nearest oxygen ion (mainly centered on the element located at the B-site) 6), structural variations can occur in the octahedron of BO ₆ . That is, the perovskite material may exhibit various characteristics depending on which material is doped and occupied at the A-site and the B-site.

The layered RP (Ruddlesden-Popper) perovskite material shown in FIG. 4 may have a crystal lattice structure in which two or more elements are regularly arranged at an A-site. Specifically, ABO ₃ and an AO layer having a rock salt structure above and below are regularly present. The structure can be expressed as [AO]-[ABO ₃ ]-[AO].

When reduction is performed in a reducing atmosphere, for example, a hydrogen atmosphere, a single perovskite material is changed into a layered R-P perovskite material. In this layered R-P perovskite material, the movement of oxygen ions can be accelerated, thermal and chemical stability can be improved, and electrical conductivity can be high.

5 is a schematic diagram illustrating elution of a transition element from a cathode layer of a metal support type solid oxide fuel cell according to an embodiment of the present invention.

Referring to FIG. 5 , the cathode layer may be composed of layered R—P perovskite in which oxygen is deficient by reduction to form vacancy oxygen. In the layered R-P perovskite material, “Vo” represents oxygen vacancy and “T” represents a transition element, such as iron, cobalt or an iron-cobalt alloy. As the vacancy oxygen is formed, the transition element located at the B-site may be reduced together to promote an elution phenomenon. For example, by heat treatment, the vacancy oxygen and the transition element are co-separated and moved to the surface. The energy required for this movement is referred to as cavity separation energy, and the higher the cavity separation energy, the more difficult the cavity separation is. Since the transition element eluted on the surface can accelerate the oxygen reduction reaction, electrical conductivity can be improved.

In the cathode layer according to the technical idea of the present invention, the sum of praseodymium (Pr), barium (Ba), and strontium (Sr) is placed in a 1:1 content at the A-position, and iron (Fe) is placed at the B-position A layered R-P perovskite material may be disposed. It is also possible to substitute some of the iron with cobalt. This elution phenomenon can stabilize the layered R-P perovskite phase because a material having catalytic activity from the inside to the surface, for example, iron (Fe), is eluted and fixed.

A cathode layer of a metal support type solid oxide fuel cell according to an embodiment of the present invention may include a compound represented by the following chemical formula.

<Formula>

Pr _0.5 Ba _0.5-x Sr _x FeO _3-δ

In the above formula, x is a number ranging from greater than 0 to less than 0.5, and δ is a positive number ranging from greater than 0 to less than 1, and is a value that makes the compound of the formula electrically neutral. The δ represents interstitial oxygen in the perovskite structure, and the value of δ may be determined according to a specific crystal structure.

As described above, the cathode layer may have a structure in which iron (Fe) is eluted to the surface in the compound of the above formula.

The cathode layer may include a compound in which x in the above Chemical Formula is a number ranging from 0.3 or more to less than 0.5. For example, the cathode layer may include Pr _0.5 Ba _0.2 Sr _0.3 FeO _3-δ compound, Pr _0.5 Ba _0.15 Sr _0.35 FeO _3-δ compound, Pr _0.5 Ba _0.1 Sr _0.4 FeO _3-δ compound, and Pr _0.5 Ba _0.05 At least one of Sr _0.45 FeO _3-δ compounds may be included.

In addition, the cathode layer may include a compound in which x is 0.5 in the above formula. That is, the cathode layer may include a Pr _0.5 Sr _0.5 FeO _3-δ compound (here, δ is a positive number ranging from greater than 0 to less than 1). In this case, the compound constituting the cathode may not contain barium (Ba).

Hereinafter, a method for manufacturing a cathode layer in a metal support type solid oxide fuel cell according to the technical idea of the present invention will be described.

The method for producing the cathode layer includes mixing (for example, wet using a solvent) each metal precursor weighed to match the composition of the compound of the above formula, obtaining a solid from the mixture, and removing the solid from the air It includes a step of firing to obtain a fired object and a step of polishing the fired object.

The metal precursor is mixed in a stoichiometric ratio to obtain the compound of the above formula. Examples of the metal precursor include, but are not limited to, nitrides, oxides, halides, and the like of each component constituting the cathode layer of the above formula. For example, the metal precursor in which the compound forming the cathode layer is a Pr _0.5 Ba _0.5-x Sr _x FeO _3-δ compound of the chemical formula is a nitride or an oxide containing at least one of Pr, Ba, Sr, Fe, and the like. , halides, and the like.

In the step of mixing the metal precursor with the solvent, water may be used as the solvent, but is not limited thereto. Any material capable of dissolving the metal precursor may be used without limitation, and examples thereof include lower alcohols having a total carbon number of 5 or less, such as methanol, ethanol, 1-propanol, 2-propanol, and butanol; acidic solutions such as nitric acid, hydrochloric acid, sulfuric acid, and citric acid; water; organic solvents such as toluene, benzene, acetone, diethyl ether, and ethylene glycol; These etc. can be used individually or in mixture.

Mixing the metal precursor with the solvent may be performed at a temperature ranging from about 100 °C to about 200 °C, and may be performed for a predetermined time under stirring so that each component is sufficiently mixed. The mixing process, the removal of the solvent, and the addition of necessary additives for this purpose are well known as, for example, the pechini method, and will not be described in detail here. This allows the formation of a single perovskite material.

After the mixing process, an ultrafine solid material may be obtained by a spontaneous combustion process. Subsequently, the ultrafine solid may be subjected to heat treatment (calcination, sintering) at a temperature ranging from about 400° C. to about 950° C. for a period of about 1 hour to about 5 hours, for example, at about 600° C. for about 4 hours.

If necessary, a second heat treatment (calcination, sintering) may be performed after the firing. The second heat treatment process is a process of calcining in air, for about 1 hour to about 24 hours at a temperature in the range of about 950 ° C to about 1500 ° C, for example, at a temperature in the range of about 950 to about 1500 ° C for about 12 hours. It is carried out to obtain a powdery result.

Subsequently, the calcined product may be ground or pulverized to obtain a fine powder of a predetermined size. Grind and mix, for example, by ball milling in acetone for about 24 hours. Next, the mixed powder may be put into a metal mold and pressed, and then the pressed pellets may be sintered in the air. Sintering may be performed at a temperature ranging from about 950° C. to about 1500° C. for about 12 hours to about 24 hours, for example, at a temperature ranging from about 950° C. to about 1500° C. for about 24 hours, but is not limited thereto. . The calcined product may be ground or pulverized to obtain a material for a cathode layer in the form of fine powder having a predetermined size.

A cathode layer may be manufactured using the material for the cathode layer. For example, the cathode layer may be formed by coating the material for the cathode layer on a substrate and then heat-treating the substrate. The heat treatment may be performed in a reducing atmosphere such as a hydrogen atmosphere. The heat treatment may be performed at a temperature ranging from about 750 °C to about 850 °C, for example. The heat treatment may be performed under a hydrogen pressure of about 3 atm, for example. By the heat treatment in the reducing atmosphere, the material for the cathode layer phase changes from a single perovskite to a layered R-P perovskite, and iron is eluted and disposed on the surface. The heat treatment in the reducing atmosphere may be performed by the above-described simultaneous sintering.

Application to metal-air batteries

A case in which the metal support type solid oxide fuel cell and the manufacturing method according to the technical idea of the present invention described above are applied to a metal support type metal air battery are also included in the technical idea of the present invention. For example, the anode of the metal support type solid oxide fuel cell may be applied to the anode of the metal support type metal air battery, and the cathode of the metal support type solid oxide fuel cell may be applied to the cathode of the metal support type metal air battery. there is.

A metal support-type metal-air battery according to the technical idea of the present invention for achieving the above technical problem includes an anode layer; an electrolyte layer located on one side of the anode layer; a cathode layer disposed on the electrolyte layer facing the anode layer and supplied with oxygen; And a metal support located on the other side of the anode layer and supporting the anode layer; including, bonding the anode layer and the metal support, and at the same time bonding the electrolyte layer and the cathode layer, the metal The support, the anode layer, the electrolyte layer, and the cathode layer may be co-sintered.

6 is a schematic diagram illustrating a metal support type metal-air battery 200 according to an embodiment of the present invention.

Referring to FIG. 6 , the metal support type metal-air battery 200 includes an anode layer 210; An electrolyte layer 220 located on one side of the anode layer 210; a cathode layer 230 disposed on the electrolyte layer 220 facing the anode layer 210 and supplied with oxygen; and a metal support 240 located on the other side of the anode layer 210 and supporting the anode layer 210 .

To bond the anode layer 210 and the metal support 240, and at the same time to bond the electrolyte layer 220 and the cathode layer 230, the metal support 240, the anode layer 210, the electrolyte layer 220 , and the cathode layer 230 may be co-sintered.

The metal-supported metal-air battery 200 generates power by using a reaction between metal and oxygen. The greatest advantage of the metal-supported metal-air battery 200 is that it uses oxygen, which is infinitely present in nature, as an active material, has a very high theoretical energy density compared to other secondary batteries, and has environmentally friendly characteristics. In addition, since the metal support type metal-air battery 200 does not contain a chemical oxidizer therein, there is no risk of explosion or fire, and the weight can be greatly reduced. In addition, compared to fuel cells using hydrogen or alcohol, they are very economical, have excellent stability, and have excellent operating performance at low temperatures.

The anode layer 210 may include a material that loses electrons and becomes a positive ion during discharge, and may include, for example, a metal, such as lithium (Li), nickel (Ni), or cobalt (Co). , Platinum (Pt), Zinc (Zn), Vanadium (V), Chromium (Cr), Manganese (Mn), Iron (Fe), Copper (Cu), Aluminum (Al), Magnesium (Mg), Calcium (Ca) , or alloys thereof. In particular, lithium exhibits a theoretical energy density of 11,140 Wh/kg, which is almost similar to that of 13,000 Wh/kg of gasoline. For reference, aluminum has a theoretical energy density of 8130 Wh/kg, calcium 4180 Wh/kg, and zinc 1350 Wh/kg.

The electrolyte layer 220 may be positioned between the anode layer 210 and the cathode layer 230, contain an electrolyte material, and perform a function of moving the electrolyte material. The electrolyte layer 220 may include, for example, a sodium hydroxide (NaOH) solution or a calcium hydroxide (KOH) solution. In addition, the electrolyte layer 220 may be composed of a solid medium.

The cathode layer 230 is configured to use oxygen in the air and can collect the oxygen. The cathode layer 230 may include a current collector 250 made of a porous material that collects oxygen and a catalyst body 260 that activates a reduction reaction of oxygen. The cathode layer 230, for example, the catalyst body 260 may include the above-described layered R-P perovskite material. The cathode layer 230 may include a compound of the following chemical formula.

<Formula>

Pr _0.5 Ba _0.5-x Sr _x FeO _3-δ

In the above formula, x is a number ranging from greater than 0 to less than 0.5, and δ is a positive number ranging from greater than 0 to less than 1, and is a value that makes the compound of the formula electrically neutral.

The metal support 240 may serve to support the anode layer 210 . The metal support 240 may include a material having rigidity and ductility, and may include, for example, various metal materials, such as iron (Fe), stainless steel, nickel (Ni), and cobalt (Co). , Platinum (Pt), Zinc (Zn), Vanadium (V), Chromium (Cr), Manganese (Mn), Iron (Fe), Copper (Cu), Aluminum (Al), Magnesium (Mg), Calcium (Ca) , or alloys thereof.

Since the metal-supported metal-air battery 200 can use oxygen in the air for the cathode layer 230, the weight of the cathode layer 230 can theoretically be reduced to zero or dramatically. Therefore, since the weight of the anode layer 210 can be increased as the weight of the cathode layer 230 is reduced, the weight ratio of the anode layer 210 to the total weight of the metal-supported metal-air battery 200 is increased, resulting in a high energy density per unit weight of the battery.

Hereinafter, power generation in the metal support type metal-air battery 200 will be described. A discharge reaction and a charge reaction may be performed in the anode layer 210 and the cathode layer 230 . A discharge reaction in the anode layer 210 and the cathode layer 230 is as follows. The charge reaction is directed in the opposite direction to the following reactions. In the reaction formula below, “M” may be a metal as a material constituting the anode layer 210 .

<Anode reaction>

M -> M ⁺ + e ^-

<Cathode Reaction>

2( M ⁺ + e ^- ) + O ₂ -> M ₂ O ₂

Positive ions 270 formed in the anode layer 210 by this discharge reaction pass through the electrolyte layer 220 and are directed to the cathode layer 230 . At this time, the electrons lost by the positive ions 270 pass through the load 290 through a separate conducting wire, thereby supplying power to the load 290 as a result.

Oxygen 280 is provided to the cathode layer 230 from the outside, and positive ions 270 react with the oxygen 280 in the cathode layer 230 to form an oxide. At this time, electrons passing through the load 290 are provided to the cathode layer 230 to form the oxide together.

On the other hand, during charging, the oxide is decomposed, and the positive ions 270 acquire electrons and return to the anode layer 210 from the cathode layer 230 via the electrolyte layer 220.

Application to Solid Oxide Water Electrolysis Cell

A case in which the metal support type solid oxide fuel cell and the manufacturing method according to the technical idea of the present invention described above are applied to a metal support type solid oxide water electrolysis cell are also included in the technical idea of the present invention. For example, the cathode of the metal support type solid oxide fuel cell may be applied to the anode of the metal support type solid oxide water electrolysis cell, and the anode of the metal support type solid oxide water electrolysis cell may be applied to the metal support type solid oxide water electrolysis cell. can be applied to the cathode.

A metal support type solid oxide water electrolysis cell according to the technical idea of the present invention for achieving the above technical problem is a metal support type solid oxide water electrolysis cell that generates hydrogen and oxygen, and discharges hydrogen gas formed by decomposition of water cathode layer; an electrolyte layer located on one side of the cathode layer; an anode layer disposed on the electrolyte layer facing the cathode layer and discharging oxygen gas formed by decomposition of the water; And a metal support located on the other side of the cathode layer and supporting the cathode layer; including, bonding the cathode layer and the metal support, and at the same time bonding the electrolyte layer and the anode layer, the metal The support, the cathode layer, the electrolyte layer, and the anode layer may be co-sintered.

7 is a schematic diagram illustrating a metal support type solid oxide water electrolysis cell 300 according to an embodiment of the present invention.

Referring to FIG. 7 , the metal support type solid oxide water electrolysis cell 300 includes a cathode layer 330 that generates hydrogen and oxygen and discharges hydrogen gas formed by decomposition of water; An electrolyte layer 320 located on one side of the cathode layer 330; an anode layer 310 disposed on the electrolyte layer 320 facing the cathode layer 330 and discharging oxygen gas formed by decomposition of the water; and a metal support 340 located on the other side of the cathode layer 330 and supporting the cathode layer 330 .

To bond the cathode layer 330 and the metal support 340, and at the same time to bond the electrolyte layer 320 and the anode layer 310, the metal support 340, the cathode layer 330, the electrolyte layer 320 , and the anode layer 310 may be co-sintered.

Since the cathode layer 330 is in contact with hydrogen gas, it may be referred to as a hydrogen electrode, and the anode layer 310 may be referred to as an oxygen electrode since it is in contact with oxygen gas. Electrolyte 330 may be composed of an oxygen ion conducting solid oxide.

Anode layer 310 may be configured to release oxygen into the air. The anode layer 310 may include the layered R-P perovskite material described above. The anode layer 310 may include a compound of the following chemical formula.

<Formula>

Pr _0.5 Ba _0.5-x Sr _x FeO _3-δ

In the above formula, x is a number ranging from greater than 0 to less than 0.5, and δ is a positive number ranging from greater than 0 to less than 1, and is a value that makes the compound of the formula electrically neutral.

The electrolyte layer 320 is located between the anode layer 310 and the cathode layer 330, can perform the function of moving the oxygen, and is not particularly limited as long as it is generally usable in the art. The electrolyte layer 320 may include the same material as or have the same structure as the electrolyte layer 120 of the metal support type solid oxide fuel cell 100 described above.

The cathode layer 330 may include a metal, for example, lithium (Li), nickel (Ni), cobalt (Co), platinum (Pt), zinc (Zn), vanadium (V), It may include chromium (Cr), manganese (Mn), iron (Fe), copper (Cu), aluminum (Al), magnesium (Mg), calcium (Ca), or an alloy thereof.

The metal support 340 may serve to support the cathode layer 330 . The metal support 340 may include a material having rigidity and ductility, and may include, for example, various metal materials, such as iron (Fe), stainless steel, nickel (Ni), and cobalt (Co). , Platinum (Pt), Zinc (Zn), Vanadium (V), Chromium (Cr), Manganese (Mn), Iron (Fe), Copper (Cu), Aluminum (Al), Magnesium (Mg), Calcium (Ca) , or alloys thereof.

As shown in the following reaction equation, the electrochemical reaction of the metal support type solid oxide water electrolysis cell 300 is that the water (H ₂ O) of the cathode layer 330 reacts with hydrogen gas (H ₂ ) and oxygen ions (O ^2- ). It consists of a cathode reaction that changes to and an anode reaction that changes the oxygen ions that have moved through the electrolyte layer 320 into oxygen gas (O ₂ ). This reaction is contrary to the reaction principle of conventional fuel cells.

<reaction formula>

Cathodic reaction: H ₂ O + 2e ^- -> O ^2- + H ₂

Anode reaction: O ^2- -> 1/2 O ₂ + 2e ^-

When power is applied to the metal support type solid oxide water electrolysis cell 300 from the external power supply 350 , electrons are supplied from the external power supply 350 to the metal support type solid oxide water electrolysis cell 300 . The electrons react with water supplied to the cathode layer 330 to generate hydrogen gas and oxygen ions. The hydrogen gas is discharged to the outside, and the oxygen ions pass through the electrolyte layer 320 and move to the anode layer 310 . The oxygen ions moved to the anode layer 310 lose electrons and are converted into oxygen gas and discharged to the outside. The electrons flow to the external power source 350. Through this movement of electrons, the metal support type solid oxide water electrolysis cell 300 may electrolyze water to form hydrogen gas in the cathode layer 330 and oxygen gas in the anode layer 310 .

The technical spirit of the present invention described above is not limited to the foregoing embodiments and the accompanying drawings, and various substitutions, modifications and changes are possible within the scope of the technical spirit of the present invention. It will be clear to those skilled in the art to which it pertains.

100: metal support type solid oxide fuel cell,
110: anode layer, 120: electrolyte layer,
130: cathode layer, 140: metal support,
150: buffer layer, 160: adhesive layer,
200: metal support type metal-air battery,
210: anode layer, 220: electrolyte layer,
230: cathode layer, 240: metal support
250: current collector, 260: catalyst body,
270: cation, 280: oxygen,
290: load,
300: metal support type solid oxide water electrolysis cell,
310: anode layer, 320: electrolyte layer,
330: cathode layer, 340: metal support,
350: external power,

Claims (20)

Forming an electrolyte layer on one side of the anode layer;
Forming a cathode layer on the electrolyte layer;
Adhering a metal support to the other side of the anode layer; and
Co-sintering the metal support, the anode layer, the electrolyte layer, and the cathode layer to bond the anode layer and the metal support, and at the same time to bond the electrolyte layer and the cathode layer,
The cathode layer includes a compound of the following formula,
A method for manufacturing a metal-supported solid oxide fuel cell.
<Formula>
Pr _0.5 Ba _0.5-x Sr _x FeO _3-δ
In the above formula, x is a number ranging from greater than 0 to less than 0.5, and δ is a positive number ranging from greater than 0 to less than 1, and is a value that makes the compound of the formula electrically neutral. The method of claim 1,
The forming of the electrolyte layer is a method of manufacturing a metal support type solid oxide fuel cell made by pre-sintering the anode layer and the electrolyte layer. The method of claim 1,
The step of forming the cathode layer is performed using screen printing, a method of manufacturing a metal support type solid oxide fuel cell. The method of claim 1,
Before performing the step of forming the cathode layer,
The method of manufacturing a metal support type solid oxide fuel cell, further comprising forming a buffer layer on the electrolyte layer using screen printing. The method of claim 1,
Before performing the step of adhering the metal support,
Further comprising forming an adhesive layer on the metal support,
A method of manufacturing a metal support type solid oxide fuel cell, wherein the metal support is adhered to the anode layer using the adhesive layer. The method of claim 1,
The co-sintering step is performed in a reducing atmosphere, a method of manufacturing a metal support type solid oxide fuel cell. The method of claim 1,
The co-sintering step is performed at a temperature in the range of 800 ° C to 1000 ° C, a method for manufacturing a metal support type solid oxide fuel cell. delete The method of claim 1,
The cathode layer has a structure in which the iron (Fe) is eluted to the surface in the compound of the above formula, a method of manufacturing a metal support type solid oxide fuel cell. The method of claim 1,
The cathode layer includes a Pr _0.5 Ba _0.2 Sr _0.3 FeO _3-δ compound, a Pr _0.5 Ba _0.15 Sr _0.35 FeO _3-δ compound, a Pr _0.5 Ba _0.1 Sr _0.4 FeO _3-δ compound, and a Pr _0.5 Ba _0.05 Sr _0.45 FeO ₃ A method of manufacturing a metal-supported solid oxide fuel cell comprising at least one of _-δ compounds. delete anode layer;
an electrolyte layer located on one side of the anode layer;
a cathode layer disposed on the electrolyte layer facing the anode layer and supplied with oxygen; and
Located on the other side of the anode layer, a metal support for supporting the anode layer; includes,
The metal support, the anode layer, the electrolyte layer, and the cathode layer are co-sintered so as to bond the anode layer and the metal support, and at the same time to bond the electrolyte layer and the cathode layer,
The cathode layer includes a compound of the following formula,
Metal-supported solid oxide fuel cell.
<Formula>
Pr _0.5 Ba _0.5-x Sr _x FeO _3-δ
In the above formula, x is a number ranging from greater than 0 to less than 0.5, and δ is a positive number ranging from greater than 0 to less than 1, and is a value that makes the compound of the formula electrically neutral. delete delete The method of claim 12,
The cathode layer has a structure in which the iron (Fe) is eluted to the surface in the compound of the above formula, a metal support type solid oxide fuel cell. The method of claim 12,
The cathode layer, wherein x is a number in the range of 0.3 or more to less than 0.5 containing a compound, a metal support type solid oxide fuel cell. The method of claim 12,
The cathode layer includes a Pr _0.5 Ba _0.2 Sr _0.3 FeO _3-δ compound, a Pr _0.5 Ba _0.15 Sr _0.35 FeO _3-δ compound, a Pr _0.5 Ba _0.1 Sr _0.4 FeO _3-δ compound, and a Pr _0.5 Ba _0.05 Sr _0.45 FeO ₃ A metal-supported solid oxide fuel cell comprising at least one of _-δ compounds. delete The method of claim 12,
The anode layer includes nickel (Ni), cobalt (Co), platinum (Pt), zinc (Zn), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), copper (Cu), Or a metal support type solid oxide fuel cell comprising an alloy thereof. The method of claim 12,
The metal support includes iron (Fe), stainless steel, nickel (Ni), cobalt (Co), platinum (Pt), zinc (Zn), vanadium (V), chromium (Cr), manganese (Mn), iron ( A metal support type solid oxide fuel cell comprising Fe), copper (Cu), aluminum (Al), magnesium (Mg), calcium (Ca), stainless steel or an alloy thereof.

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