KR20150039586A - Method for manufacturing powder for cathode functional layer of solid oxide fuel cell - Google Patents

Abstract

The present application relates to a manufacturing method of powder for cathode functional layer of solid oxide fuel cell. The powder for cathode functional layer of solid oxide fuel cell produced using the manufacturing method allows cathode substance and electrolyte substance to form a compound structure, and therefore, if applied to cathode functional layer, the fuel cell performance can be improved.

Description

TECHNICAL FIELD [0001] The present invention relates to a cathode active material powder for solid oxide fuel cells,

The present application claims the benefit of Korean Patent Application No. 10-2013-0118199 filed on October 2, 2013 with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.

The present application relates to a method for producing a powder for a cathode functional layer of a solid oxide fuel cell.

Fuel cells are devices that directly convert the chemical energy of fuel and air into electricity and heat by electrochemical reactions. Fuel cells are a new concept of power generation technology that not only causes high efficiency but also causes no environmental problems because existing power generation technology does not involve burning process, driving device, and combustion process of fuel, steam generation, turbine drive, and generator. Such a fuel cell emits almost no air pollutants such as SOx and NOx, and generates less carbon dioxide, which is pollution-free, and has advantages of low noise and no vibration.

There are various types of fuel cells such as a phosphoric acid type fuel cell (PAFC), an alkaline fuel cell (AFC), a polymer electrolyte fuel cell (PEMFC), a direct methanol fuel cell (DMFC), a solid oxide fuel cell (SOFC) Solid oxide fuel cells (SOFCs) are based on low activation polarization and have low overvoltage and low irreversible losses and therefore high power generation efficiency. In addition, since it can be used not only as hydrogen but also as a carbon or hydrocarbon-based fuel, it has a wide fuel selection range and has a high reaction speed at the electrode, so that expensive noble metal is not required as an electrode catalyst. In addition, the heat emitted by the power generation is very high in temperature, which is highly worth using. The heat generated from the solid oxide fuel cell can be used not only for the reforming of the fuel but also as an energy source for industrial use or cooling in cogeneration power generation.

Solid oxide fuel cell (SOFC) is a device that basically generates electricity by the oxidation reaction of hydrogen. In the anode which is a fuel electrode and the cathode which is an air electrode, As shown in Fig.

 [Reaction Scheme 1]

Cathode: (1/2) O ₂ + 2e ^- → O ^2-

^{_{Anode: H 2 + O 2- → H2O}} + 2e -

Overall reaction: H ₂ + (1/2) O ₂ → H ₂ O

That is, the electrons reach the cathode through an external circuit, and at the same time, the oxygen ions generated in the cathode are transferred to the anode through the electrolyte, and hydrogen is combined with the oxygen ions in the anode to generate electrons and water.

In a solid oxide fuel cell, a porous cathode layer and an anode layer are formed as an electrode with a dense electrolyte layer interposed between the electrolyte layer and the electrolyte layer, and an electrode reaction occurs at the interface between the electrolyte layer and the electrode layer. In order to increase the efficiency of the solid oxide fuel cell, it is required to increase the area of the triple phase boundary (TPB: Triple Phase Boundary) at which the gas, the electrolyte and the electrode meet because the reaction site at the interface needs to be increased.

Therefore, the development of a solid oxide fuel cell for increasing the area of the three phase interface has been required.

Korean Patent Publication No. 10-2005-0021027

The problem to be solved by the present application is to provide a method for producing a powder for a cathode functional layer applied between a cathode of a solid oxide fuel cell and an electrolyte. Since the ratio of the cathode material to the electrolyte material is uniform in any portion of the cathode functional layer prepared using the cathode functional layer powder, it is effective to increase the three-phase interface that meets the gas at the interface between the cathode and the electrolyte.

The problems to be solved by the present application are not limited to the above-mentioned technical problems, and other technical problems which are not mentioned can be clearly understood by those skilled in the art from the following description.

One embodiment of the present application relates to a method of forming a mixture comprising: mixing a slurry comprising any one of a cathode material and an electrolyte material with the other dissolved solution to form a mixture; Adding a precipitant to the mixture, or adjusting the pH of the mixture to a pH of more than 7 but not more than pH 14 to form a precipitate; And firing the precipitate to form a composite of particles of the cathode material and particles of the electrolyte material.

Another embodiment of the present application provides a powder for a cathode functional layer of a solid oxide fuel cell produced by the above production method.

Another embodiment of the present application provides a method of manufacturing a solid oxide fuel cell including forming a cathode functional layer using a powder for a cathode functional layer manufactured by the above production method between a cathode and an electrolyte.

Other embodiments of the present application include a cathode; An anode positioned opposite the cathode; An electrolyte positioned between the cathode and the anode; And a cathode functional layer disposed between the cathode and the electrolyte, the cathode functional layer being produced using the powder for a cathode functional layer manufactured by the manufacturing method.

The powder for a cathode functional layer for a solid oxide fuel cell manufactured by the manufacturing method according to one embodiment of the present application has an advantage that a cathode functional layer having a uniform content ratio can be produced because the cathode material and the electrolyte material form a complex structure have. Accordingly, since the content ratio of the two materials is constant in any portion of the functional layer, the three-phase interface at which the cathode material, the electrolyte material, and the gas meet can be effectively extended, and the performance of the fuel cell can be improved.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows a composite in which electrolyte material particles are distributed around cathode material particles according to one embodiment of the present application, in which the electrolyte material particles surround the cathode material particles.
FIG. 2 shows a composite in which cathode material particles are distributed around electrolyte material particles according to one embodiment of the present application to form a structure in which cathode material particles surround the electrolyte material particles.

Brief Description of the Drawings The advantages and features of the present application, and how to accomplish them, will be apparent with reference to the embodiments described below in conjunction with the accompanying drawings. The present application, however, is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles of the invention as defined in the appended claims. Is provided to fully convey the scope of the invention to those skilled in the art, and this application is only defined by the scope of the claims. The dimensions and relative sizes of the components shown in the figures may be exaggerated for clarity of description.

Unless defined otherwise, all terms, including technical and scientific terms used herein, may be used in a manner that is commonly understood by one of ordinary skill in the art to which this application belongs. Also, commonly used predefined terms are not ideally or excessively interpreted unless explicitly defined otherwise.

Hereinafter, the present application will be described in detail.

One embodiment of the present application includes a step (S10) of mixing a slurry comprising any one of a cathode material and an electrolyte material with the other dissolved solution to form a mixture; Adding a precipitant to the mixture, or adjusting the pH of the mixture to a pH of more than 7 but not more than 14 to form a precipitate (S20); And firing the precipitate to form a composite in which the particles of the cathode material and the particles of the electrolyte material are combined (S30). The present invention also provides a method for producing a powder for a cathode functional layer of a solid oxide fuel cell.

The cathode material and the electrolyte material may each be composed of one or more particles.

The cathode material may include a material that acts as a cathode in the solid oxide fuel cell. In addition, the electrolyte material may include a material that functions as an electrolyte in the solid oxide fuel cell.

The cathode material and the electrolyte material may mean both before and after firing.

The slurry may mean that the cathode material or the electrolyte material is contained in a particle state. Alternatively, the slurry may mean a state in which the cathode material or the electrolyte material is mixed with a solvent and dispersed. Specifically, the slurry may mean that the cathode material or the electrolyte material is dispersed in a particle state in a solvent.

The solution may mean that the cathode material or the electrolyte material is dissolved by the solvent. Specifically, the solution may mean that the cathode material or the electrolyte material is not present in the particle state in the solvent.

The composite may include the cathode material and the electrolyte material bonded to each other. Specifically, the composite may mean that the particles of the cathode material and the particles of the electrolyte material are combined.

The powder for the cathode functional layer of the solid oxide fuel cell may comprise particles of the composite.

The cathode functional layer powder may be composed of a composite material in which one of the cathode material particles and the electrolyte material particles surrounds one of the material particles to surround the one of the material particles.

Specifically, the cathode material particles are formed around the cathode material particles and the cathode material particles are surrounded by the electrolyte material particles. Alternatively, the cathode material particles are positioned around the electrolyte material particles And a composite material in which the electrolyte material particles are surrounded by the cathode material particles.

At this time, since a composite powder having a structure in which different material particles are coated around one of the material particles is formed, the content ratio of the cathode material and the electrolyte material in the powder is always uniform.

If the cathode functional layer formed between the cathode and the electrolyte is simply mixed with the cathode material and the electrolyte material, the uniformity of the two materials in the functional layer is lowered due to the difference in size, density, and shape of the two materials . Therefore, the content ratio of the cathode material and the electrolyte material in each portion of the functional layer is not constant, so that the effect of improving the performance of the fuel cell is less significant than when the functional layer is not used, which is not efficient.

However, since the powder for a cathode functional layer according to the manufacturing method of the present application is a powder composed of a composite of the cathode material and the electrolyte material, the cathode functional layer made of the powder can be formed in any portion of the functional layer, The content ratio of the material becomes constant, and the area of the three-phase interface between the cathode and the electrolyte is uniformly increased, thereby remarkably improving the performance and efficiency of the fuel cell. There is also an effect of improving the durability of the fuel cell. In addition, the cathode functional layer to which the powder for the cathode functional layer according to the manufacturing method of the present application is applied is effective not only in increasing the reaction site at the three-phase interface but also preventing the electrolyte and the cathode from desorbing, thereby increasing the stability of the cathode. When the stability of the cathode is improved, the performance of the fuel cell is improved.

(S10) of forming a mixture by mixing a slurry containing any one of the cathode material and the electrolyte material with a solution of the other one dissolved in the above-mentioned production method will be described.

The step may be a step of mixing a slurry containing a cathode material with a solution in which an electrolytic material is dissolved to form a mixture or mixing a slurry containing an electrolyte material with a solution in which a cathode material is dissolved to form a mixture Lt; / RTI >

The content of the electrolyte material in the mixture is 20 wt% or more and 80 wt% or less based on the total weight excluding the solvent, and the content of the cathode material is 20 wt% or more and 80 wt% or less, ≪ / RTI >

More specifically, the content of the electrolyte material in the mixture is 30 wt% to 70 wt%, based on the total weight excluding the solvent, and the content of the cathode material is 30 wt% Or more and 70 weight% or less.

A mixture of the electrolytic material particles surrounding the cathode material particles may be formed by performing a precipitation step using a mixture of a slurry containing the cathode material and a solution in which the electrolyte material is dissolved. Alternatively, a composite having a structure in which the cathode material particles surround the electrolyte material particles may be formed by performing a precipitation step using a mixture of a slurry containing the electrolyte material and a solution in which the cathode material is dissolved.

When the slurry containing the cathode material and the solution in which the electrolyte material is dissolved are mixed, the content of the cathode material in the mixture is 20 wt% or more and 80 wt% or less based on the total weight excluding the solvent, The content of the substance may be 20 wt% or more and 80 wt% or less based on the total weight excluding the solvent. If the content of the electrolyte material is 20 wt% or more, the effect of forming the complex surrounding the cathode material particles is good, and if the amount is less than 80 wt%, uniformity of content can be maintained.

When the slurry containing the cathode material is mixed with a solution in which the electrolyte material is dissolved, more specifically, the content of the cathode material in the mixture is 30 wt% or more and 70 wt% or less based on the total weight excluding the solvent , The content of the electrolyte material may be 30 wt% or more and 70 wt% or less based on the total weight excluding the solvent. When the content of the electrolytic material is 30 wt% or more and 70 wt% or less, the effect of the complex formation and the uniformity of the content are more effective.

In this case, the powder for the cathode functional layer may be composed of a composite in which the electrolyte material particles are positioned around the cathode material particles, and the electrolyte material particles surround the cathode material particles. At this time, the diameter of the cathode material particle is 200 nm or more and 10 m or less, more specifically 500 nm or more and 5 m or less, and the diameter of the electrolyte material particle surrounding the periphery of the cathode material particle is 10 nm More preferably less than 500 nanometers, more specifically less than 10 nanometers and less than 200 nanometers. FIG. 1 shows a composite in which electrolyte material particles are disposed around the cathode material particles, and the electrolyte material particles surround the cathode material particles.

When the slurry containing the electrolyte material and the solution in which the cathode material is dissolved are mixed, the content of the electrolyte material in the mixture is 20 wt% or more and 80 wt% or less based on the total weight excluding the solvent, The content of the substance may be 20 wt% or more and 80 wt% or less based on the total weight excluding the solvent. If the content of the cathode material is 20 wt% or more, the effect of forming the complex surrounding the electrolyte material particles is good, and if it is 80 wt% or less, the uniformity of the content can be maintained.

In a case where a slurry containing the electrolyte material and a solution in which the cathode material is dissolved are mixed, more specifically, the content of the electrolyte material in the mixture is 30 wt% to 70 wt% And the content of the cathode material may be 30 wt% or more and 70 wt% or less based on the total weight excluding the solvent. When the content of the cathode material is 30 wt% or more and 70 wt% or less, the effect of the complex formation and the uniformity of the content are more effective.

In this case, the powder for the cathode functional layer may be formed of a composite in which the cathode material particles are positioned around the electrolyte material particles, and the cathode material particles surround the electrolyte material particles. At this time, the diameter of the electrolyte material particles is 200 nm or more and 10 m or less, more specifically 500 nm or more and 5 m or less, and the diameter of the cathode material particles is 10 nm or more and 500 nm or less It may be 10 nanometers or more and 200 nanometers or less. FIG. 2 shows a composite in which the cathode material particles are positioned around the electrolyte material particles, and the cathode material particles surround the electrolyte material particles.

The cathode material is not particularly limited as long as it can be generally used in the art.

The cathode material may specifically be an oxide having a perovskite (ABO ₃ ) type crystal structure. Here, A and / or B is any one or two or more elements selected from a rare earth element, an alkaline earth metal element and a transition element, and O may be a substance having an electric conductivity because it is an oxygen ion. More specifically, the present invention relates to a method for producing a lanthanum-strontium manganese oxide (LSM), lanthanum-strontium iron oxide (LSF), lanthanum-strontium cobalt oxide (LSC), lanthanum-strontium cobalt iron oxide (LSCF) Barium-strontium cobalt iron oxide (BSCF), or a mixture of two or more thereof.

Alternatively, the cathode material may be an oxide having a double perovskite (A ^Ⅲ A ^Ⅱ B ₂ O _{5 + δ} ) type crystal structure, and A ^Ⅲ may be an oxide selected from a rare earth element of +3 And A ^Ⅱ is any one or two or more elements selected from +2 valent alkaline earth metal elements, B is any one or two or more elements selected from transition metals, and O is an oxide ion have.

Alternatively, the cathode material may be an oxide having a Ruddlesden popper structure (A ^Ⅲ _2-x A ^Ⅱ _x BO _4-δ ) type crystal structure, and A ^Ⅲ may be selected among a +3 rare-earth rare earth element And A ^Ⅱ is any one or two or more elements selected from +2 valent alkaline earth metal elements, B is any one or two or more elements selected from transition metals, O is an oxide ion Lt; / RTI >

More specifically, the transition metal of B may be any one or two or more selected from the group consisting of iron, cobalt, nickel, manganese, and copper.

The cathode material may include any one or a mixture of two or more of a perovskite-type oxide, a double perovskite-type oxide, and a ridestepper-type oxide.

The electrolyte material is a material having oxygen ion conductivity and is not particularly limited as long as it can be generally used in the art,

The electrolyte material may specifically be an oxide having a fluorite (AO ₂ ) type crystal structure. Here, A may be any one or two or more elements selected from a rare earth element, an alkaline earth metal element and a transition element, and O may be a substance that is an oxygen ion. More specifically, zirconia-based materials doped or undoped with at least one of gadolinium, yttrium, samarium, scandium, calcium and magnesium; Ceria systems doped or undoped with at least one of gadolinium, samarium, lanthanum, ytterbium, praseodymium and neodymium; And a bismuth oxide system doped with at least one of yttrium, dysprosium, erbium, niobium, and tungsten, or a mixture of two or more thereof.

The electrolyte material may specifically be an oxide having a perovskite (ABO ₃ ) type crystal structure. Here, A and / or B may be any one or two or more elements selected from a rare earth element, an alkaline earth metal element and a transition element, and O may be a substance having an electric conductivity that is an oxygen ion. More specifically, it may be a lanthanum gallate-based oxide doped or undoped with at least one of strontium and magnesium, and the transition metal may be further doped. The transition metal may specifically be any one or two or more selected from the group consisting of iron, cobalt, nickel, manganese, and copper. More specifically, gadolinium-doped ceria (GDC); Samarium-doped ceria (SDC); Lanthanum-doped ceria (LDC); Yttria stabilized zirconia (YSZ); Scandia stabilized zirconia (ScSZ); Strontium and magnesium-doped lanthanum gallate (LSGM); And lanthanum gallate (LSGMC) doped with strontium, magnesium and cobalt.

The electrolyte material may include any one or a mixture of two or more of a fluorite (AO ₂ ) type oxide and a perovskite (ABO ₃ ) type oxide.

The mixture may contain water and an alcohol having 1 to 3 carbon atoms. The alcohol having 1 to 3 carbon atoms may specifically be methanol, ethanol, propanol or isopropanol.

A step S20 of forming a precipitate by adding a precipitant to the mixture or adjusting the pH of the mixture to a pH of more than 7 and a pH of more than 7 is described as follows in the production method according to one embodiment of the present application.

The step S20 may be a step of adding a precipitant to the mixture, or may be a step of adjusting the pH of the mixture to a pH of more than 7 and a pH of 14 or adding a precipitant to the mixture, To adjust the pH of the mixture at the same time.

The precipitant may be selected from the group consisting of ammonium carbonate, sodium carbonate, oxalic acid, ammonium oxalate, NaOH, KOH, and NH ₄ OH, as long as it is generally usable in the related art.

The adjusting the pH can be carried out using NaOH, KOH or NH ₄ OH.

The step of obtaining the precipitate can be carried out by stirring the mixture, discarding the supernatant, and filtering.

The step of forming the precipitate may be performed by stirring at a temperature of 20 ° C or more and 90 ° C or less for 30 minutes to 36 hours or less, followed by filtration.

The stirring may be performed for 30 minutes or more, more specifically 3 hours or more, 36 hours or less, more specifically 24 hours or less. Further, it can be carried out at a temperature of 20 ° C or more and 90 ° C or less.

The method according to one embodiment of the present application may further comprise, after the step of forming the precipitate, drying the precipitate at a temperature of 100 ° C or more and 200 ° C or less.

A manufacturing method according to one embodiment of the present application will be described as follows (S30) of forming a composite in which particles of the cathode material and particles of the electrolyte material are combined by firing the precipitate.

The composite may include the electrolyte material particles on at least a part of the surface of the cathode material particle, or the cathode material particles may be provided on at least a part of the surface of the electrolyte material particle.

Specifically, the composite material may include the electrolyte material particles in 70% or more of the surface of the cathode material particle, or the cathode material particles may be provided in 70% or more of the surface of the electrolyte material particle.

More specifically, the composite may include the electrolyte material particles at 85% or more of the surface of the cathode material particle, or the cathode material particles may be provided at 85% or more of the surface of the electrolyte material particle.

The step of forming the composite may be performed at a temperature of 400 ° C or higher and 1,600 ° C or lower, and may be performed for 30 minutes or more, more specifically 2 hours or more, 24 hours or less, more specifically 12 hours or less.

The manufacturing method according to one embodiment of the present application may further include ball milling the composite.

It is preferable that the ball mill is performed for 6 hours to 72 hours at a rotation speed of 10 rpm or more and 500 rpm or less.

The manufacturing method according to one embodiment of the present application may further include filtering the sintered precipitate after ball milling to obtain a powder for a cathode functional layer.

One embodiment of the present application provides a powder for a cathode functional layer of a solid oxide fuel cell produced by the above production method.

The description of the powder is the same as described above.

One embodiment of the present application provides a method of manufacturing a solid oxide fuel cell comprising forming a cathode functional layer using a powder for a cathode functional layer manufactured by the above manufacturing method between a cathode and an electrolyte.

The method includes forming a cathode functional layer on the electrolyte layer, forming a cathode layer on the cathode functional layer, and forming the anode layer on the opposite side of the electrolyte layer. And forming the anode functional layer between the electrolyte layer and the anode layer.

Alternatively, the manufacturing method includes forming the electrolyte layer on the anode layer, forming the cathode functional layer on the electrolyte layer, and forming the cathode layer on the cathode functional layer. And forming the anode functional layer between the anode layer and the electrolyte layer.

In the above manufacturing method, the cathode layer, the cathode functional layer, the electrolyte layer, the anode layer, and optionally, the anode functional layer may be formed by a typical slurry coating method such as dip-coating, painting, Vacuum deposition methods such as a printing method, a wet spray method, a chemical vapor deposition method, and a physical vapor deposition method may be used.

One embodiment of the present application includes a cathode; An anode positioned opposite the cathode; An electrolyte positioned between the cathode and the anode; And a cathode functional layer disposed between the cathode and the electrolyte, the cathode functional layer being produced using the powder for a cathode functional layer manufactured by the manufacturing method.

The cathode refers to a layer where an electrochemical reaction occurs in the fuel cell by an oxygen reduction catalyst. The oxygen gas is reduced to oxygen ions, and the air is continuously supplied to the cathode to maintain a constant oxygen partial pressure.

The oxygen reduction catalyst included in the cathode may be the same as the cathode material included in the cathode functional layer.

The oxygen reduction catalyst may specifically be an oxide having a perovskite (ABO ₃ ) type crystal structure. Here, A and / or B is any one or two or more elements selected from a rare earth element, an alkaline earth metal element and a transition element, and O may be a substance having an electric conductivity because it is an oxygen ion. More specifically, the present invention relates to a method for producing a lanthanum-strontium manganese oxide (LSM), lanthanum-strontium iron oxide (LSF), lanthanum-strontium cobalt oxide (LSC), lanthanum-strontium cobalt iron oxide (LSCF) Barium-strontium cobalt iron oxide (BSCF), or a mixture of two or more thereof.

Alternatively, the oxygen reduction catalyst may be an oxide having a double perovskite (A ^Ⅲ A ^Ⅱ B ₂ O _{5 + δ} ) type crystal structure, and A ^Ⅲ may be selected among rare earth elements of +3 And A ^Ⅱ is any one or two or more elements selected from +2 valent alkaline earth metal elements, B is any one or two or more elements selected from transition metals, and O is an oxide ion .

Alternatively, the oxygen reduction catalyst may be an oxide having a Ruddlesden popper structure (A ^Ⅲ _2-x A ^Ⅱ _x BO _4-δ ) type crystal structure, and A ^Ⅲ may be an oxide of rare earth element A ^Ⅱ is any one or two or more elements selected from +2 valent alkaline earth metal elements, B is any one or two or more elements selected from transition metals, O is an oxygen ion Oxide.

More specifically, the transition metal of B may be any one or two or more selected from the group consisting of iron, cobalt, nickel, manganese, and copper.

The oxygen reduction catalyst may be any one or a mixture of two or more of a perovskite-type oxide, a double perovskite-type oxide, and a ridestepper-type oxide.

As the composition for forming the cathode, a noble metal such as platinum, ruthenium, or palladium may be used in addition to the oxygen reduction catalyst. The above-mentioned cathode materials may be used singly or in combination of two or more. It is possible to form a cathode having a multi-layer structure by using a single layer cathode or a different cathode material.

The cathode composition may optionally further comprise an inorganic oxide, a binder resin and / or a solvent having oxygen ion conductivity.

The inorganic oxide having oxygen ion conductivity may be a substance contained in the electrolyte.

The binder resin is not limited as long as it is a binder resin capable of imparting adhesion, and may be, for example, ethyl cellulose.

The solvent may be any one or more selected from the group consisting of butyl carbitol, terpineol and butyl carbitol acetate, as long as it can dissolve the binder resin.

The cathode composition may be sintered by heat treatment. The heat treatment temperature may be 800 ° C or higher and 1,200 ° C or lower. At 800 ° C or higher, the oxygen reduction catalyst can be sintered together with the inorganic oxide, and at 1,200 ° C or lower, the oxygen reduction catalyst can be sintered without reaction with the electrolyte.

The thickness of the cathode layer may be generally from 1 to 1,000 micrometers. More specifically, it may be 5 micrometers or more and 100 micrometers or less.

The thickness of the cathode functional layer formed between the cathode and the electrolyte may be in a range of 0.5 micrometers to 50 micrometers, for example, 1 micrometer to 10 micrometers.

The electrolyte should be dense so that air and fuel do not mix, have high oxygen ion conductivity and low electron conductivity. In addition, since the anode and the cathode having a great difference in oxygen partial pressure exist on both sides of the electrolyte, it is necessary to maintain the above properties in a wide range of oxygen partial pressure.

The material contained in the electrolyte may be the same as the electrolyte material contained in the cathode functional layer.

The thickness of the electrolyte may be generally 10 nanometers or more and 100 micrometers or less. More specifically, it may be 100 nanometers or more and 50 micrometers or less.

The electrolyte may be sintered by heat treatment. The heat treatment temperature may be 800 占 폚 or higher and 1,600 占 폚 or lower.

The anode serves to electrochemically oxidize the fuel and to transfer electrons.

The material contained in the anode is not particularly limited as long as it can be generally used in the art.

Specifically, the anode may comprise a metal oxide. The metal contained in the metal oxide may be at least one selected from the group consisting of Zr, Ce, Ti, Mg, Al, Si, Mn, Fe, Co, Ni, Cu, Cr, Zn, Mo, Y, Nb, Sn, Nd, and the like. Preferably, Ni can be used. Ni has a high electrical conductivity and adsorbs hydrogen and hydrocarbon fuels, and can exhibit high electrode catalyst activity. In addition, it is advantageous as an electrode material in terms of low cost compared to platinum.

Specifically, the anode may comprise a mixture of a metal and an inorganic oxide having ionic conductivity. The metal may be mixed with an inorganic oxide having an ion conductivity in the form of a metal oxide, but may be reduced to a metal under a reducing atmosphere, which is a fuel cell operating condition, to exhibit electrical conductivity. For example, a metal such as Zr, Ce, Ti, Mg, Al, Si, Mn, Fe, Co, Ni, Cu, Cr, Zn, Mo, Y, Nb, Sn, La, Ta, V, and Nd. The ionic conductive inorganic oxide may include a material used as the following electrolyte material, and examples thereof include a fluoride (AO ₂ ) type oxide and a perovskite (ABO ₃ ) type oxide And may include any one or a mixture of the two.

In particular, the anode may comprise a mixed ionic and eletronic conductor material having both electrical and ionic conductivity.

The anode may comprise a metal oxide; A mixture of a metal and an inorganic oxide having ionic conductivity; And a mixed conducting material having both electrical conductivity and ionic conductivity at the same time.

The anode may further optionally comprise a binder resin and / or a solvent.

The anode may be used singly or as a mixture of two or more kinds. The anode may be formed solely or separately on the anode support. Alternatively, Another anode having a multi-layer structure may be further formed using another anode material. Or the anode support may use a metal oxide as a starting material and an inorganic oxide having hydrogen ion conductivity as coarse particles of several micrometers or more in order to delay the densification of the anode support during sintering. In this case, a triple phase boundary (TPB: Triple Phase Boundary) in which a gas reaction occurs inside the sintered anode may not be sufficiently formed. Therefore, a functional layer FL having the same composition as the anode support and having a small particle size between the anode support and the electrolyte, Functional Layer).

The thickness of the anode layer may be generally from 1 to 5,000 micrometers. More specifically, it may be 10 micrometers or more and 1,000 micrometers or less.

The thickness of the anode functional layer may range from 0.5 micrometers to 50 micrometers, for example, from 1 micrometer to 10 micrometers.

The solid oxide fuel cell can be manufactured by a conventional method known in the art. In addition, the solid oxide fuel cell can be applied to various structures such as a tubular stack, a flat tubular stack, and a planar type stack.

Hereinafter, the present invention will be described in detail by way of examples and comparative examples in order to specifically explain the present application. However, the embodiments according to the present application can be modified into various other forms, and the scope of the present application is not construed as being limited to the embodiments described below. Embodiments of the present application are provided to more fully describe the present application to those of ordinary skill in the art.

≪ Example 1 >

A cathode material slurry prepared by dispersing 40 g of LSCF (La _0.6 Sr _0.4 Co _0.2 Fe _0.8 ) as a cathode material in 200 g of distilled water was prepared and 13.7 g of Gd (NO ₃ ) ₃ 6H ₂ O and Ce (NO ₃ ) ₃ 6H ₂ O dissolved in 200 g of distilled water was prepared, and then the electrolyte material solution was slowly added to the cathode material slurry, followed by thorough stirring and mixing. 5% NH ₄ OH was added dropwise to the mixed solution slurry to adjust the pH to 9.0, followed by stirring for 12 hours. At this time, the temperature of the hot plate was raised to adjust the temperature of the slurry to 50 ° C. Then, stirring was stopped, the supernatant was discarded, and the filtrate was filtered, and then the filtered cake was dried at 120 ° C. The dried powder was fired at 800 ° C for 3 hours, ball milled, and sieved to form a cathode functional layer powder using a 325 mesh.

At this time, the cathode material content and the electrolyte material content were 60:40 by weight.

≪ Example 2 >

A powder for a cathode functional layer was prepared in the same manner as in Example 1 except that ethanol was used instead of water as a solvent in Example 1. At this time, the cathode material content and the electrolyte material content were 60:40 by weight.

≪ Comparative Example 1 &

The cathode active material powder and the cathode active material powder were mixed by a ball mill so that the cathode material content and the electrolyte material content ratio were the same as in Example 1 to complete the cathode functional layer powder. At this time, the cathode material content and the electrolyte material content were 60:40 by weight.

The weight percentages calculated from the EDS analysis results of the powders prepared in Examples 1 and 2 and Comparative Example 1 are shown in Table 1 below.

Example 1 Example 2 Comparative Example 1 Spot 1 Spot 2 Spot 1 Spot 2 Spot 1 Spot 2 GDC 40.8% 40.6% 39.4% 39.7% 41.2% 27.8% LSCF 59.2% 59.4% 60.6% 60.3% 58.8% 72.2%

The results are shown in Table 1. The results are shown in Table 1. In Examples 1 and 2, even though the spot to be analyzed is different, the content ratio is uniform. In Comparative Example 1, however, the content ratio varies depending on the spot.

While the present invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It is to be understood that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. It is therefore to be understood that the above-described embodiments are illustrative and non-restrictive in every respect.

100: cathode material particle
200: Electrolyte material particle

Claims (22)

Mixing the slurry comprising any one of the cathode material and the electrolyte material with the other dissolved solution to form a mixture;
Adding a precipitant to the mixture, or adjusting the pH of the mixture to a pH of more than 7 but not more than pH 14 to form a precipitate; And
And firing the precipitate to form a composite of particles of the cathode material and particles of the electrolyte material. The method according to claim 1,
The method for producing a powder for a cathode functional layer of a solid oxide fuel cell according to claim 1, further comprising ball milling the composite. The method according to claim 1,
Wherein the composite material has the electrolyte material particles on at least a part of the surface of the cathode material particle or the cathode material particles at least a part of the surface of the electrolyte material particle. Gt; The method according to claim 1,
Wherein the composite material comprises the electrolyte material particles at 70% or more of the surface of the cathode material particle or the cathode material particles at 70% or more of the surface of the electrolyte material particle. Gt; The method according to claim 1,
Based on the total weight of the mixture excluding the solvent,
The content of the electrolyte material is 20 wt% or more and 80 wt% or less,
Wherein the content of the cathode material is 20 wt% or more and 80 wt% or less. The method according to claim 1,
Based on the total weight of the mixture excluding the solvent,
The content of the cathode material is 30 wt% to 70 wt%
Wherein the content of the electrolyte material is 30 wt% or more and 70 wt% or less. The method according to claim 1,
Wherein the cathode material has a diameter of 200 nm or more and 10 μm or less and a diameter of the electrolyte material is 10 nm or more and 500 nm or less. . The method according to claim 1,
Wherein the particle diameter of the electrolyte material is 200 nm or more and 10 μm or less and the diameter of the particles of the cathode material is 10 nm or more and 500 nm or less. The method according to claim 1,
The cathode material may include a perovskite (ABO ₃ ) type oxide, a double perovskite (A ^III A ^II B ₂ O _{5 + delta} ) type oxide and a Ruddlesden popper structure _2-x a _x BO ^{ⅱ ⅲ} _4-δ) the method of the cathode functional layer is a powder of a solid oxide fuel cell characterized in that it comprises one or a mixture of two or more selected from the group consisting of type oxide. The method of claim 9,
A ^Ⅲ is any one or two or more elements selected from the +3 rare earth elements, A ^Ⅱ is any one or two or more elements selected from +2 alkali earth metal elements, B is iron, cobalt, nickel, manganese and copper Wherein the transition metal is one or more transition metals selected from the group consisting of transition metal and transition metal. The method of claim 9,
The perovskite-type oxide may be selected from the group consisting of lanthanum-strontium manganese oxide (LSM), lanthanum-strontium iron oxide (LSF), lanthanum-strontium cobalt oxide (LSC), lanthanum-strontium cobalt iron oxide (LSCF) A solid oxide fuel cell (SSC), barium-strontium cobalt iron oxide (BSCF), and bismuth-ruthenium oxide. By weight based on the total weight of the cathode functional layer. The method according to claim 1,
Wherein the electrolyte material comprises one or a mixture of two or more selected from the group consisting of a fluoride (AO ₂ ) type oxide and a perovskite (ABO ₃ ) type oxide. A method for producing a powder for a cathode functional layer. The method of claim 12,
Wherein the fluorite-type oxide is zirconia-based, doped or undoped with at least one of gadolinium, yttrium, samarium, scandium, calcium and magnesium; Ceria systems doped or undoped with at least one of gadolinium, samarium, lanthanum, ytterbium, praseodymium and neodymium; And a bismuth oxide system doped with at least one of yttrium, dysprosium, erbium, niobium, and tungsten. The method for producing a powder for a cathode functional layer of a solid oxide fuel cell according to claim 1, The method of claim 12,
The perovskite-type oxide may include gadolinium-doped ceria (GDC); Samarium-doped ceria (SDC); Lanthanum-doped ceria (LDC); Yttria stabilized zirconia (YSZ); Scandia stabilized zirconia (ScSZ); Strontium and magnesium-doped lanthanum gallate (LSGM); And lanthanum gallate (LSGMC) doped with strontium, magnesium and cobalt. The method for producing a powder for a cathode functional layer of a solid oxide fuel cell according to claim 1, The method according to claim 1,
Wherein the mixture comprises water or an alcohol having 1 to 3 carbon atoms. ≪ RTI ID = 0.0 > 11. < / RTI > The method according to claim 1,
The precipitating agent The method of ammonium carbonate, sodium carbonate, oxalic acid, ammonium oxalate, NaOH, KOH and the solid oxide fuel cell cathode functional layer of powder, characterized in that selected from the group consisting of NH ₄ OH. The method according to claim 1,
Wherein the step of forming the precipitate is performed by stirring at a temperature of 20 ° C or more and 90 ° C or less for 30 minutes to 36 hours or less, followed by filtration. The method according to claim 1,
The method of claim 1, further comprising, after the step of forming the precipitate, drying the precipitate at a temperature of 100 ° C or more and 200 ° C or less. The method according to claim 1,
Wherein the step of forming the composite comprises firing at a temperature of 400 ° C or higher and 1,600 ° C or lower. A powder for a cathode functional layer of a solid oxide fuel cell produced by the method of any one of claims 1 to 19. A method of manufacturing a solid oxide fuel cell, comprising forming a cathode functional layer made of a powder for a cathode functional layer manufactured by the method of any one of claims 1 to 19 between a cathode layer and an electrolyte layer. Cathode;
An anode positioned opposite the cathode;
An electrolyte positioned between the cathode and the anode; And
A solid oxide fuel cell comprising a cathode functional layer, which is disposed between the cathode and the electrolyte, and is manufactured using the powder for a cathode functional layer manufactured by the manufacturing method according to any one of claims 1 to 19.

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