KR20120038946A - Manufacturing method of solid oxide fuel cells and solid oxide fuel cells thereby - Google Patents

Abstract

PURPOSE: A solid electrolyte fuel cell and a manufacturing method thereof are provided to improve capacity per unit volume, thereby enabling miniaturization and weight lightening of the fuel cell. CONSTITUTION: A manufacturing method of a solid electrolyte fuel cell comprises the following steps: preparing a first and a second solid electrolyte tapes; preparing a first and a second supporters; constituting a plurality of unit modules by using the first and second solid electrolyte tapes and the first and second supporters; sintering a module which is formed by laminating the unit modules; forming air electrodes(36) in the module; forming fuel electrodes in the module; forming connect electrodes(40,42) in the module; interlinking the connect electrode to the module connect electrode after forming a module connect electrode; and heat-treating the module.

Description

Manufacturing method of solid electrolyte fuel cell and solid electrolyte fuel cell thereby {MANUFACTURING METHOD OF SOLID OXIDE FUEL CELLS AND SOLID OXIDE FUEL CELLS THEREBY}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a solid electrolyte fuel cell, and is particularly composed of an integrated multi-layered module, which does not use assembling members such as a separator, a connecting member, and a sealing member, thereby significantly improving the capacity per unit volume. The present invention relates to a method for manufacturing a lightweight electrolyte fuel cell.

The present invention also relates to a solid electrolyte fuel cell according to the manufacturing method.

A fuel cell is a device that directly converts chemical energy of reactants such as fuel and oxidant into direct current (DC) electricity. In general, fuel cell technology includes various types of fuel cells, such as a polymer electrolyte fuel cell, a phosphate fuel cell, a molten carbonate fuel cell, a solid electrolyte fuel cell, and an enzyme fuel cell.

In particular, solid oxide fuel cells (SOFCs) operate at a high temperature of 600 ~ 1000 ℃ to directly convert the hydrocarbon fuel into electricity, the highest energy conversion efficiency among the fuel cells developed to date. Typically, such a solid electrolyte fuel cell is a solid electrolyte exhibiting ion conductivity, such as oxygen ions, protons, and the like, a porous air electrode or cathode (or cathode) formed on one side of the solid electrolyte, and the other of the solid electrolyte. It consists of a fuel electrode or a fuel electrode (or anode) formed in the side surface. Thus, oxygen gas or air containing oxygen is supplied to the cathode, and fuel gas containing hydrogen and hydrocarbon gas is supplied to the anode. Then, the reduction reaction of oxygen occurs in the cathode to produce oxygen ions, which move to the anode through the solid electrolyte layer and react with hydrogen supplied thereto to generate water. In this case, since electrons are generated at the anode and electrons are consumed at the cathode, electricity may be produced by connecting the anode and the cathode.

On the other hand, solid electrolyte fuel cells are classified into two types, one of which is a cylindrical type in which the electrode and the solid electrolyte covers the periphery of the cylinder, and the other is a flat type in which the solid electrolyte and the electrode are formed in a flat shape. In particular, such a flat type is difficult to assemble, but has a structure that is advantageous to increase the power density per unit volume by increasing the density, it is promising an application to a home or a vehicle power source.

1 shows a schematic structure of a general planar solid electrolyte fuel cell 1. Referring to FIG. 1, the planar solid electrolyte fuel cell 1 includes a plurality of connecting members 4 having a plurality of fuel passages 2 and air passages 3 formed on a lower surface and an upper surface, respectively, as described in detail below. An electrolyte layer 7 having a stacked structure and having a fuel electrode 5 on the upper surface and an air electrode 6 on the lower surface is inserted between each of the connecting members 4. Then, the sealing material 8 is inserted into the edge portion between the electrolyte layer 7 and the connecting material 4.

In more detail, in the general planar solid electrolyte fuel cell 1, a plurality of fuel passages 2 through which fuel flows are formed on the lower surface of the connecting member 4, and the fuel passage on the upper surface thereof. A plurality of air flow paths 3 are formed to extend in a direction 90 ° orthogonal to (2), through which air flows, and each fuel flow path 2 and the air flow path 3 are straight between each wall portion 9. It is formed into a groove. In addition, in the case where a plurality of such connecting members 4 are stacked, an electrolyte layer 7 having a fuel electrode 5 formed on the upper surface and an air electrode 6 formed on the lower surface is inserted between the connecting members 4, and the electrolyte layer The sealing material 8 is inserted and arranged in the edge part between 7 and the connection material 4. In this way, the electrolyte layer 7 having the anode 5 on one side of the upper surface and the cathode 6 on the other side of the lower surface thereof, and the anode 5 on the electrolyte layer 7 above the electrolyte layer 7. The connecting member 4 laminated so that the fuel flow passage 2 can be disposed toward the other side, and the other connecting member 4 laminated so that the air passage 3 can be disposed toward the cathode 6 from the lower portion of the electrolyte layer 7. Is combined to form a unit cell which is a basic component. In fact, the planar solid electrolyte fuel cell is completed by stacking a plurality of basic components of such a unit cell.

 Fuel gas and air are respectively introduced through the fuel flow path 2 and the air flow path 3 of each connecting member 4 formed by the wall portion 9 to the two electrode layers, that is, the fuel electrode 5 and the air electrode 6, respectively. Will be reached. These electrode layers, the anode 5 and the cathode 6, have a porous structure to facilitate the electrochemical reaction, and the electrolyte layer 7 has a compact structure so that fuel gas and air do not vent each other. In addition, the sealant 8 is composed of a sealing glass or the like, and keeps airtight so that the two kinds of gases flowing along the flow paths formed on both sides of the connecting member 4 do not mix with each other. Conventional technologies related to such a planar solid electrolyte fuel cell are disclosed in Japanese Patent Application Laid-Open Nos. 2007-200710 and 2007-317594, US Patent 6265095, 6183897 and 4997726, and European Patent Publication Nos. 2019443 and 993059. have.

In such a typical planar solid electrolyte fuel cell 1, a smooth gas supply must be provided at two electrode layers, that is, the anode 5 and the cathode 6, and the airtightness is maintained at the remaining portion of the connecting member 4 which does not come into contact with the unit cell. It should be shaped like the insulating layer or the plate inserted into it. However, in order to construct a laminate of the solid electrolyte fuel cell of the prior art, various components made of different materials are used, thereby ensuring reliability due to various factors such as thermal expansion difference, oxidation reaction, corrosion and deterioration due to high temperature operation. There is a problem that the life of the battery is not long because it cannot be done.

The present invention was devised in view of the drawbacks of the prior art, and is composed of an integrated multi-layered module, which does not use assembling members such as a separator, a connecting member, and a sealing member, thereby significantly improving the capacity per unit volume. The present invention provides a method for producing a lightweight solid electrolyte fuel cell and a solid electrolyte fuel cell thereby.

In order to achieve the above object, according to an aspect of the present invention, a method of manufacturing a solid electrolyte fuel cell in which a plurality of predetermined unit modules are stacked and integrated may include the following steps:

(a) preparing first and second solid electrolyte tapes each having a plurality of anodes having a strip shape on one side thereof at regular intervals;

(b) a plurality of slits each having a closed short side portion and a side edge portion, penetrating up and down at a predetermined interval in parallel in the direction of the side edge portion, and having a plurality of slits having the same strip shape as the fuel electrode, and a plurality of wall portions between the plurality of slits. Preparing a first and a second support;

(c) the first and second solid electrolyte tapes are respectively superimposed on the lower side and the upper side of the first support such that the plurality of fuel electrodes face each other in the plurality of slits of the first support, and the second support is formed of the slits. Constructing a plurality of unit modules by superimposing the lower side of the first or second solid electrolyte tape superimposed on the lower side of the first support so as to be orthogonal to the slits of the first support;

(d) stacking and integrating the plurality of unit modules to form one module, and sintering the modules to densify them;

(e) cutting the short sides of the second support in the module and simultaneously cutting the side portions of the first support, thereby opening the plurality of slits of the second support with the plurality of slits closed; Forming an air path of the air channel, and dipping the module into an electrode slurry to draw the electrode slurry only into the plurality of air paths, thereby forming air electrodes on the entire inner surface of the plurality of air paths;

(f) cutting the short side portions of the first support body from the module and simultaneously cutting the side edge portions of the second support body to open the plurality of slits of the first support body, which are closed and formed on the upper and lower surfaces, respectively, to face each other. Forming a plurality of fuel passages each having a pair of anodes;

(g) forming a connection electrode for connecting the plurality of air electrodes and a connection electrode for connecting the plurality of fuel electrodes in the module, and forming a module connection electrode on the upper and lower surfaces of the module to form the connection electrode for each module connection electrode. Connecting a connection electrode;

(h) heat-treating the module to increase the adhesion strength of each of the cathode, the connection electrode, and the module connection electrode.

In this case, the plurality of unit modules of step (d) may be integrated with each other by a binder and thermally bonded at a softening temperature of the binder.

In addition, the sintering temperature may be in the range of 1350 ℃ to 1450 ℃.

In addition, the composition of the first and second solid electrolyte tape may be one or more selected from the group consisting of yttria stabilized zirconia, calcia stabilized zirconia, magnesia stabilized zirconia and lanthangalate. In addition, the first and second solid electrolyte tapes may be cast by molding to a doctor blade.

The composition of the first and second supports may be one or more of zirconia-based yttria partially stabilized zirconia and zirconia-based calcia partially stabilized zirconia.

In addition, the composition of the anode may be made of nickel oxide and yttria stabilized zirconia in a volume ratio of 6: 4 and graphite added by 24% by volume.

In addition, the composition of the air electrode may be one or more of lanthanum strontium manganate and samarium strontium cobaltate, and may further include a stabilized zirconia powder, wherein the stabilized zirconia powder is included in 20% by weight to 40% by weight.

In addition, the composition of the connection electrode and the module connection electrode may be Ag-Pd-based or Ag-Pt-based.

In addition, the heat treatment of step (h) may be performed at a temperature of 1150 ℃ to 1250 ℃.

In addition, the solid electrolyte fuel cell according to another aspect of the present invention is a solid electrolyte fuel cell manufactured by the above-described manufacturing method and at least one predetermined unit module is stacked and integrated, wherein the unit modules are provided on one surface thereof. First and second solid electrolyte layers 22 having a plurality of fuel electrodes 26 having a strip shape spaced apart from each other and first and second having a plurality of slits 28 having the same strip shape, respectively. And a first support and a second solid electrolyte layer 22 such that each of the plurality of fuel electrodes 26 in the plurality of slits 28 of the first support 24 face each other. The second supporter 24 overlaps the lower side and the upper side of the 24, respectively, and the second supporter 24 is formed by overlapping the lower side of the first supporter 24 so that the slit 28 is orthogonal to the slit 28 of the first supporter 24. Overlying one or the second solid electrolyte layer 22, the slit 28 of the first support 24 is upper And a plurality of fuel passages 38 formed on the lower surface and having a pair of fuel electrodes 26 facing each other, and the slit 28 of the second support 24 has a plurality of air electrodes 36 formed on the entire inner surface thereof. To form an air flow path 34.

According to the present invention as described above has the following advantages:

-As it does not use assembling members such as separating plate, connecting material, sealing material, etc., the capacity per unit volume is remarkably improved, so the fuel cell can be miniaturized and light weight, and the efficiency can be greatly increased when used as a mobile battery;

Integration of materials of similar properties without the use of assembly members such as separators, connectors, seals, etc., which greatly increases the reliability and life of the battery;

-There are no parts manufacturing and assembly costs because there is no use of assembling members such as separators, connecting materials, sealing materials, etc., which can greatly reduce manufacturing costs;

-By modularizing the integrated solid electrolyte fuel cell, the capacity of the battery can be easily diversified in connection with its configuration.

1 is an exploded perspective view of each component showing a typical solid electrolyte fuel cell of the prior art.
Figure 2 is a perspective view of a solid electrolyte tape which is a basic component of a solid electrolyte fuel cell according to the present invention.
3 is a perspective view of a support which is a basic component of a solid electrolyte fuel cell according to the present invention;
Figure 4 is a perspective view showing a process in which the solid electrolyte tape is disposed overlapping the lower side and the upper side of the support.
5 is a plan view of the solid electrolyte tape is superimposed on the lower side and the upper side of the support.
6 is a cross-sectional view taken along the line VI-VI of FIG. 5.
FIG. 7 is a basic structure in which a support is formed perpendicular to a slot of another support adjacent to each other by being rotated by 90 ° in a configuration in which a solid electrolyte tape is superposed on a lower side and an upper side of the support as shown in FIG. 5. A perspective view illustrating the lamination process of the laminate as a component.
FIG. 8 is a plan view showing a plane of the stacked laminates as shown in FIG. 7 and illustrating that the slits of the support are orthogonal to each other; FIG.
FIG. 9 is a front view seen from the arrow IX direction in FIG. 8; FIG.
FIG. 10 is a plan view illustrating a process of completing a structure of a unit cell based on a laminate, showing openings of an air passage and cutting both sides of the support in the laminate to form an air electrode in the air passage; FIG.
FIG. 11 is a front view seen from the arrow XI direction in FIG. 10; FIG.
FIG. 12 is a front view similar to FIG. 11 showing that an air electrode is formed in the air passage; FIG.
FIG. 13 is a plan view showing cutting of both sides of the support in the laminate to open the fuel passage; FIG.
FIG. 14 is a front view seen from the arrow XIV direction in FIG. 13; FIG.
FIG. 15 is a front view seen from the arrow XV direction in FIG. 13; FIG.
16 is a cross-sectional view taken along the line XVI-XVI in FIG. 13.
17 is a perspective view of a laminate.
18 is a perspective view showing the structure of a fuel cell stack having a multi-layer structure;

First, FIG. 2 shows a solid electrolyte tape which is a basic component of a solid electrolyte fuel cell according to the present invention, and FIG. 3 shows a support which is a basic component of a solid electrolyte fuel cell according to the present invention.

2 and 3, the solid electrolyte fuel cell 20 according to the present invention is a solid electrolyte tape 22 having a plurality of electrode layers and a fuel passage or an air passage, respectively, for the solid electrolyte tape 22. Predetermined modules formed of a support body 24 supporting them by being stacked up and down are configured in the form of a plurality of stacked laminates.

The solid electrolyte tape 22 constituting the solid electrolyte fuel cell of the present invention is formed with a plurality of fuel electrodes 26 spaced at regular intervals in a strip shape on only one side thereof. The strip-shaped fuel electrode 26 is disposed in such a manner that both ends thereof do not extend to the edge of the solid electrolyte tape 22. In addition, the solid electrolyte tape 22 is composed of yttria stabilized zirconia (8 mol% Y ₂ O ₃ -ZrO ₂ ; YSZ), and calcia or magnesia stabilized zirconia (13 mol% CaO-ZrO ₂ ; CSZ or 18 mol% MgO-ZrO ₂ MSZ), and lanthanum gallate (LaGaO ₃ ; LGO) and the like, and may be one or more selected from the group having a good ion, especially yttria stabilized zirconia (8 mol% Y ₂ O ₃ -ZrO ₂ ; YSZ). desirable. In addition, the solid electrolyte tape 22 may be a solvent (for example, a mixed solution of toluene and ethanol) by adding a binder (PVB or acrylic) and / or a dispersing agent (such as BYK-111 or BYK-180 as a common dispersant) to the composition. After dispersing well), it may be molded into a tape in a conventional manner including a doctor blade or the like. This tape formation can be cast at 80 ° C. by casting at a rate of 5 m / min as an example. In addition, the thickness of the solid electrolyte tape 22 is preferably about 10 ~ 30㎛, if the thickness is thinner than this, the strength is low, fear of breakage during production and use, if the thickness is thicker than this, the electrical conductivity is deteriorated may deteriorate characteristics. have.

In addition, the anode 26 formed on one side of the solid electrolyte tape 22 serves to reduce fuel gas and maintain conductivity and porosity for gas permeation. Preferably, the anode 26 is composed of a nickel oxide and yttria stabilized zirconia (YSZ) in a volume ratio of 6: 4 and a composition added with 24 vol% graphite to impart porosity thereto, but the present invention is not limited thereto. All electrode materials known in the art may be used. The anode composition may be made of a paste together with a binder and a solvent and then printed in a plurality of strip patterns on one side of the solid electrolyte tape 22. At this time, the plurality of strip patterns should match the pattern of the fuel passage 28 as described below.

In addition, the support body 24 is prepared in order to form the fuel flow path or air flow path mentioned below by laminating | stacking on the upper and lower sides of the solid electrolyte tape 22, respectively. The support 24 is, for example, rectangular in shape and includes a plurality of slits 28 that are divided by the plurality of wall portions 30 to form a plurality of fuel passages or air passages. These slits 28 are vertically penetrating, and both ends thereof are terminated adjacent to both side short sides 24a of the support 24, and are arranged side by side on the side edges 24b of the support 24, respectively. Here, the term "short side portion 24a" of the present invention refers to two opposite side sides of these slits 28 on the basis of the plurality of slits 28 in the support plate 24 which is a plate-shaped quadrangle, The term "side edge 24b" of the present invention refers to two opposite sides parallel to the sides of these slits 28 with respect to the plurality of slits 28 in the support 24, which is a plate-shaped rectangle. Accordingly, these slits 28 arranged side by side at a predetermined interval are enclosed and blocked by the two short sides 24a and the two side portions 24b of the support 24, but as described below, these short sides 24a or the side edges. The portion 24b is later removed so that the plurality of slits 28 form a fuel passage or an air passage, respectively.

In addition, since the support body 24 supports the solid electrolyte tape 22 and has a fuel flow path or an air flow path, a thermal expansion coefficient and a sintering temperature similar to those of the solid electrolyte tape 22 may be used to manufacture the integrated multilayer module. It is desirable to have a similar composition to have. Accordingly, the support 24 is composed of the same zirconia-based yttria partially stabilized zirconia (3 mol% Y ₂ O ₃ -ZrO ₂ ; PSZ) and zirconia-based calcia partially stabilized zirconia (similar to the composition of the solid electrolyte tape 22 described above). 6 mol% CaO-ZrO ₂ ; PSZ) is preferably, but not limited to, any material having a coefficient of thermal expansion and a sintering temperature similar to that of the solid electrolyte tape 22 used in the art. It is possible. In addition, the composition may be molded in the form of a tape or a plate as a slurry, like the solid electrolyte tape 22, wherein the thickness of the support 24 to be formed is preferably about 50 to 200 μm, so that a constant strength is maintained. Its role should be sufficient and the formation of fuel or air flow paths should be easy. In addition, the plurality of slits 28 constituting the fuel flow path or the air flow path are formed into openings on the strip by punching the formed support 24 at a predetermined interval, and the width thereof is preferably about 0.5 to 1 mm, and these slits are preferred. It is preferable that the interval of the 28, that is, the width of the wall portion 30, is also about the width of the slit 28 so as to maintain a constant strength.

In addition, as will be described later, the cathode is formed in one step of manufacturing the fuel cell of the present invention through the lamination of the solid electrolyte tape 22 and the support 24.

4 to 19 illustrate a manufacturing process of the solid electrolyte fuel cell 20 according to the present invention. Hereinafter, the structure and the manufacturing method of the solid electrolyte fuel cell 20 of the present invention will be described with reference to the drawings. .

First, as described above, a solid electrolyte tape 22 having a plurality of strip-shaped fuel electrodes 26 and a support 24 having a plurality of slits 28 are prepared on one side shown in FIG. 2. The number of these solid electrolyte tapes 22 and the support 24 is determined in accordance with the design details of the fuel cell.

Referring to FIG. 4, the first support 24 is oriented so that the plurality of slits 28 are oriented so as to coincide with the directions of these anodes 26 on the first solid electrolyte tape 22 having the plurality of anodes 26 facing upwards. ) To overlap. The second solid electrolyte tape 22 is disposed on the upper side of the first support 24 so as to coincide with the direction of the slit 28 of the first support 24 and the fuel electrode 26 is downward. Accordingly, the first and second solid electrolyte tapes 22 are disposed on the lower side and the upper side of the first support 24 so that the upper surface side fuel electrode 26 of the first solid electrolyte tape 22 on the lower side may be formed. 1 is disposed on the bottom surface side of the slit 28 of the support body 24, and the fuel electrode 26 on the lower surface side of the second solid electrolyte tape 22 on the upper surface side of the slit 28 of the first support body 24. Is placed. As a result, the upper and lower fuel electrodes 26 face each other in the slits 28. Since the plurality of slits 28 constitute the fuel flow path in the subsequent process, the first support 24 becomes the fuel flow path forming support 24.

In addition, in the structure in which the first and second solid electrolyte tapes 22 are overlapped on the lower and upper sides of the first support 24 as described above, as shown in FIG. 7 on the second solid electrolyte tape 24. The second support body 24 in which the slit 28 is disposed in the direction orthogonal to the orthogonal direction by being rotated by 90 ° with the direction of the slit 28 of the first support body 24 overlaps. The second support 24 is an air flow path forming support 24 for forming an air flow path in a subsequent process.

Then, the laminate 32 is formed by repeatedly stacking a structure in which the first and second solid electrolyte tapes 24 are overlapped with each other on the second support 24 under and over the first support 24. In this case, as described above, the slit 28 of the second support 24 and the slit 28 of the first support 24 are stacked to be 90 ° orthogonal. The first and second solid electrolyte tapes 24 having the first and second solid electrolyte tapes 24 superimposed on the lower side and the upper side thereof, the second support 24 overlapping the first and second solid electrolyte tapes 24, and the first and second solid electrolytes on the lower side and the upper side again The laminate 32 in which the first support 24 in which the tape 24 is overlapped is laminated can be bonded to its respective components using a predetermined binder. Such a binder can be used in any composition known in the art, and can be integrated, for example, by applying a pressure of 40 to 70 kg / cm 2 at a temperature of about 60 to 80 ° C. at which the binder can soften. In addition, the integrated laminate 32 may be sintered at a temperature of 1350 to 1450 ° C. to produce a densified solid electrolyte laminate module, wherein the temperature and cooling rate are set as slowly as possible (for example, 5 ° C. / min or less) It is desirable to prevent cracking and deformation of the laminate. In addition, the binder volatilization temperature range (for example, 400 ~ 600 ℃ section) is preferably maintained for a long time (for example, 6 hours or more) so that the binder is sufficiently lost.

In addition, in the manufacturing process of the integrated solid electrolyte laminate module densified as described above, each slit 28 of each support 24 is maintained in a closed state. However, both ends of the slit 28 are opened by cutting the short side portion 24a of the second support body 24 in the laminate 32 to form an air passage thereafter. At this time, the second support 24 has an orthogonal state in which the slit 28 is rotated by 90 ° with respect to the slit 28 of the first support 24, so that the second support 24 in the laminate 32 At the same time as cutting the short side portion 24a of the, only the side portion 24b of the first support body 24 is cut so that the slit 28 of the first support body 24 is not opened (see FIG. 10). In this way, by cutting the short sides 24a of the second support body 24 from the laminate 32, the plurality of slits 28 are opened to constitute the plurality of air flow paths 34. The plurality of air flow paths 34 are respectively disposed in the slit 28 of the second support 24, and the solid electrolyte tape 22 disposed on the inner surface of both wall portions 30 and the upper and lower portions of the slit 28. It is limited to the area of.

In addition, the air electrode (reference numeral “36” in FIG. 12) indicates the inner surface portion of both wall portions 30 defining the air flow path 34 in the slit 28 as described above, and the area of the solid electrolyte tape 22 above and below. Is formed. The cathode 36 is an electrode that oxidizes air or oxygen gas injected therein and needs to have conductivity and porosity for gas permeation similarly to the anode 26, and as a composition thereof, lanthanum strontium manganate (LaSrMnO ₃ ; LSM) and samarium strontium cobaltate (SmSrCoO ₃ ; SSC) may be one or more of the stabilized zirconia (YSZ) powder is preferably added in the range of 20-40% by weight in order to improve the adhesion to the solid electrolyte. In addition, such composition powder may be prepared as a slurry 36 which is prepared as a slurry dispersed in a solvent by adding a binder and / or a dispersant thereto as an example. Also, as an example, by cutting the short side portion 24a of the second support 24, the air flow path 34 is opened in the second support 24 (however, the slit 28 of the first support 24). The cathode 36 may be formed on the entire inner surface of the air flow path 34 by dipping the laminate 32, which is not opened, into the cathode slurry. Such a layer of the cathode 36 is preferably formed two to three times thinner than 5㎛. As a result, the air passage 34 is formed in the second support 24 by the opening of the slit 28, and the cathode 36 is formed therein (see FIG. 12).

In addition, the cathode 36 formed as described above is connected to the connection electrode in order to electrically connect the cathode 36 with each other. Such a connection electrode may be of a known electrode composition in the art, and may be formed, for example, by dipping Ag-Pd-based or Ag-Pt-based electrodes to a certain depth. This connecting electrode is described later with reference to FIG. 18.

As described above, after the air channel 34 is formed by the opening of the slit 28 in the second support 24 and the air electrode 36 is formed thereon, the air channel 34 is rotated by 90 ° to be perpendicular to the direction of the air channel 34. A fuel flow path is formed. To this end, the fuel passage 38 is formed by cutting the short sides 24a of the first supports 24 in the laminate 32 so that both ends of the slits 28 are opened (see FIG. 13). In addition, since the fuel electrodes 26 of the first solid electrolyte tape 22 and the second solid electrolyte tape 22 are already disposed on the first support 24 at the lower side and the upper side of the slit 28, respectively. 1 The formation of the fuel flow path 38 having the anode 26 is completed only by opening the slit 28 in the support 24 (see FIG. 14).

Thereafter, the fuel electrodes 26 are connected to each other by connecting electrodes in order to connect and collect current. As described above, the connection electrode may be manufactured by the same composition and manufacturing method as in the case of the air electrode 36.

As described above, the laminate 32 in which the air passage 34 having the air electrode 36 is formed and the fuel passage 38 having the fuel electrode 26 is formed has a stack of unit cells for the sake of brevity. Although described in a sieve, those skilled in the art will appreciate that the present invention can be configured as a multi-layer structure according to the design. For example, FIG. 18 illustrates a solid electrolyte fuel cell module having a multilayer structure. Here, a connection electrode 40 to which each cathode 36 is connected and a connection electrode 42 to which each fuel electrode 26 is connected are schematically illustrated. Such solid electrolyte fuel cell modules can be easily diversified in capacity in connection with their series or parallel configurations, and for this purpose, connections between modules should be made simple. Therefore, the module connection electrodes 44 and 46 are formed in an X-shaped pattern at predetermined intervals so that the electrical connection is made by contact between the upper and lower surfaces of the solid electrolyte fuel cell module. The connecting electrode 40 connected to the 36 may be connected to the module connecting electrode 44 and the connecting electrode 42 to which the fuel electrode 26 is connected may be connected to the module connecting electrode 46. The module connection electrodes 44 and 46 may also be electrode compositions known in the art and may be printed, for example, with an Ag-Pd based or Ag-Pt based composition.

As described above, the laminate module of the solid electrolyte fuel cell completed by connecting the connection electrodes 40 and 42 to the module connection electrodes 44 and 46 is heat-treated at a temperature of 1150 to 1250 ° C. (for example, 1 to 3 hours) The integrated solid electrolyte fuel cell of the present invention can be completed.

Preferred embodiments of the present invention described above are disclosed for purposes of illustration, and any person having ordinary skill in the art may make various modifications, changes, additions, etc. within the spirit and scope of the present invention. And additions should be regarded as within the scope of the claims.

1, 20: fuel cell 2, 28: fuel passage
3, 34: air passage 4: connecting material
5, 26: fuel electrode 6, 36: air electrode
7: electrolyte layer 8: sealing material
22: solid electrolyte tape 24: support
28: slit 40, 42: connection electrode
44, 46: module electrode

Claims (17)

In the method of manufacturing a solid electrolyte fuel cell in which a plurality of predetermined unit modules are stacked and integrated,
(a) preparing first and second solid electrolyte tapes each having a plurality of anodes having a strip shape on one side thereof at regular intervals;
(b) a plurality of slits each having a closed short side portion and a side edge portion, penetrating up and down at a predetermined interval in parallel in the direction of the side edge portion, and having a plurality of slits having the same strip shape as the fuel electrode, and a plurality of wall portions between the plurality of slits. Preparing a first and a second support;
(c) the first and second solid electrolyte tapes are respectively superimposed on the lower side and the upper side of the first support such that the plurality of fuel electrodes face each other in the plurality of slits of the first support, and the second support is formed of the slits. Constructing a plurality of unit modules by superimposing the lower side of the first or second solid electrolyte tape superimposed on the lower side of the first support so as to be orthogonal to the slits of the first support;
(d) stacking and integrating the plurality of unit modules to form one module, and sintering the modules to densify them;
(e) cutting the short sides of the second support in the module and simultaneously cutting the side portions of the first support, thereby opening the plurality of slits of the second support with the plurality of slits closed; Forming an air path of the air channel, and dipping the module into an electrode slurry to draw the electrode slurry only into the plurality of air paths, thereby forming air electrodes on the entire inner surface of the plurality of air paths;
(f) cutting the short side portions of the first support body from the module and simultaneously cutting the side edge portions of the second support body to open the plurality of slits of the first support body, which are closed and formed on the upper and lower surfaces, respectively, to face each other. Forming a plurality of fuel passages each having a pair of anodes;
(g) forming a connection electrode for connecting the plurality of air electrodes and a connection electrode for connecting the plurality of fuel electrodes in the module, and forming a module connection electrode on the upper and lower surfaces of the module to form the connection electrode for each module connection electrode. Connecting a connection electrode;
and (h) heat treating the module to increase adhesion strength of each of the cathode, the connection electrode, and the module connection electrode. The method of claim 1,
The method of manufacturing a solid electrolyte fuel cell, characterized in that the plurality of unit modules of step (d) are attached to each other by a binder and thermally bonded at a softening temperature of the binder. The method of claim 1,
The sintering temperature is a manufacturing method of a solid electrolyte fuel cell, characterized in that in the range of 1350 ℃ to 1450 ℃. The method of claim 1,
The composition of the first and second solid electrolyte tape is at least one selected from the group consisting of yttria stabilized zirconia, calcia stabilized zirconia, magnesia stabilized zirconia and lanthangalate. The method of claim 1,
Wherein the first and second solid electrolyte tapes are cast and molded by a doctor blade to form a solid electrolyte fuel cell. The method of claim 1,
The thickness of the first and second solid electrolyte tape is a manufacturing method of a solid electrolyte fuel cell, characterized in that the 10㎛ to 30㎛. The method of claim 1,
Wherein the composition of the first and second supports is one or more of zirconia-based yttria partially stabilized zirconia and zirconia-based calcia partially stabilized zirconia. The method of claim 1,
The thickness of the first and second support is a method of manufacturing a solid electrolyte fuel cell, characterized in that the range of 50㎛ to 200㎛. The method of claim 1,
The width of the slit is 0.5mm to 1mm manufacturing method of a solid electrolyte fuel cell, characterized in that. The method of claim 1,
The composition of the anode is a nickel oxide and yttria stabilized zirconia in a volume ratio of 6: 4 and 24% by volume of the graphite added method for producing a solid electrolyte fuel cell. The method of claim 1,
And the composition of the cathode is one or more of lanthanum strontium manganate and samarium strontium cobaltate. The method of claim 11,
The composition of the cathode further comprises a stabilizing zirconia powder. The method of claim 12,
The stabilized zirconia powder is a manufacturing method of a solid electrolyte fuel cell, characterized in that it comprises 20 to 40% by weight. The method of claim 1,
The composition of the connection electrode and the module connection electrode is a method of manufacturing a solid electrolyte fuel cell, characterized in that the Ag-Pd-based or Ag-Pt-based. The method of claim 1,
The method of manufacturing a solid electrolyte fuel cell, wherein the module connection electrode of step (g) is formed in an X-type pattern. The method of claim 1,
The heat treatment of step (h) is a method of manufacturing a solid electrolyte fuel cell, characterized in that carried out at a temperature of 1150 ℃ to 1250 ℃. A solid electrolyte fuel cell manufactured by any one of claims 1 to 16 and integrated with at least one predetermined unit module stacked thereon,
The unit module includes a first and a second solid electrolyte layer 22 having a plurality of strip electrodes 26 having a strip shape spaced apart from each other on one surface thereof, and a plurality of slits 28 having the same strip shape. First and second support 24 each having a,
The first and second solid electrolyte layers 22 are disposed below and above the first support 24 such that the plurality of fuel electrodes 26 thereof face each other in the plurality of slits 28 of the first support 24. Each of the second support 24 overlaps the first or second solid electrolyte layer superimposed on the lower side of the first support 24 such that the slits 28 are orthogonal to the slits 28 of the first support 24. On the lower side of 22),
The slits 28 of the first support 24 are formed on the upper surface and the lower surface, respectively, to form a plurality of fuel passages 38 having a pair of fuel electrodes 26 facing each other, and the slits 28 of the second support 24. ) Is a solid electrolyte fuel cell, comprising a plurality of air passages (34) having a cathode (36) formed on the entire inner surface.

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