KR100724120B1 - Single chamber solid oxide fuel cell with barrier rib and the fabrication method thereof - Google Patents

Abstract

Provided is a single-chamber solid oxide fuel cell, which allows electrodes to be disposed separately to inhibit reactant gases from mixing and to prevent a voltage loss, and realizes a micro fuel cell generating a high voltage and high current. The single-chamber solid oxide fuel cell comprises an anode and a cathode(720,725), both electrodes being disposed on one surface of an electrolyte(715). The single-chamber solid oxide fuel cell further comprises a partition formed on the surface of the electrolyte and interposed between two same or other sorts of electrodes. The anode and the cathode are disposed alternately. Each of the anode and the cathode includes a set of two electrodes having the same polarity. The partition has a height equal to or higher than the heights of the anode and the cathode.

Description

SINGLE CHAMBER SOLID OXIDE FUEL CELL WITH BARRIER RIB AND THE FABRICATION METHOD THEREOF

1 is a perspective view showing a configuration of a B-type SC-SOFC having a separation barrier disposed between an anode and a cathode as a first embodiment of the present invention.

FIG. 2 is a cross-sectional view along the line A-A 'of the SC-SOFC shown in FIG.

3 is a flowchart illustrating a method of manufacturing the SC-SOFC shown in FIG.

4 is a perspective view illustrating an A-type SC-SOFC in which a unit cell is embedded as a second embodiment of the present invention.

5 is a plan view illustrating a method of electrically connecting unit cells of the type shown in FIG. 4.

FIG. 6 is a flowchart illustrating a method of manufacturing SC-SOFC shown in FIG. 4.

7 is a cross-sectional view showing the configuration of a B-type SC-SOFC using a porous substrate as a third embodiment of the present invention.

FIG. 8 is a plan view illustrating a method of electrically connecting unit cells of the type shown in FIG. 7.

FIG. 9 is a flowchart illustrating a method of manufacturing SC-SOFC shown in FIG. 7.

FIG. 10 is a cross-sectional view illustrating a configuration of an A-type SC-SOFC using an air gap as a fourth embodiment of the present invention.

FIG. 11 is a plan view illustrating a method of electrically connecting unit cells of the type shown in FIG. 10.

FIG. 12 is a flowchart illustrating a method of manufacturing SC-SOFC shown in FIG. 10.

FIG. 13 is a plan view illustrating another method of electrically connecting unit cells of the type shown in FIG. 10.

The present invention relates to a solid oxide fuel cell, and more particularly, to a solid oxide fuel cell which can be used while effectively preventing gas phase mixing in a single room operating environment, and to manufacture such a solid oxide fuel cell using a thin film process. It is about a method.

Recently, with the development of portable electronic devices, the limitation of the existing portable power source battery has been revealed, and accordingly, interest in the new small power source has increased. The conditions for the new small power supply include high power density, long operating time and long life, and low cost, and fuel cells have been considered as an alternative with these conditions.

A fuel cell basically consists of an electrolyte and two kinds of electrodes called a cathode and an anode. A fuel cell is generally classified as an electrolyte material. A fuel cell using a solid oxide, that is, a ceramic material as an electrolyte is called a solid oxide fuel cell (SOFC). SOFC has been of interest because of its high efficiency and the use of various fuels compared to other fuel cells, but its operating temperature is more than 800 degrees Celsius, which is very high. Performance degradation due to thermal expansion mismatch and the like has been a problem. In particular, the reduction of the operating temperature is a very important problem in the application of small power supply, and it is necessary to study the fuel cell design that is resistant to thermal shock.

In this respect, Single Chamber SOFCs (SC-SOFCs) represent an alternative. In general, SOFC takes the form of dual-chamber in which fuel and oxidant are separated and supplied to cathode and anode, respectively. In single-room type, fuel and oxidant are mixed and supplied to SOFC. Therefore, there is no need to use a sealing material, which simplifies the design and, accordingly, the thermal shock resistance can be improved. In addition, the simplicity of the design makes integration, packaging and production easier.

SC-SOFC is divided into two types. One is the A-type, which has a typical SOFC structure in which the electrolyte is located between the positive and negative electrodes. The other is the B-type, in which the positive electrode and the negative electrode are simultaneously positioned on one side of the electrolyte. The principle of operation is the same for both types. Selective reforming of the hydrocarbon-based fuel occurs at the cathode to produce hydrogen and carbon monoxide through partial oxidation, and the hydrogen and carbon monoxide produced are oxidized. Oxygen is reduced in the positive electrode, and thus a difference in oxygen partial pressure occurs between the negative electrode and the positive electrode to generate an open voltage, and an external circuit is connected to a battery to obtain electricity.

However, in the case of SC-SOFC, the difference in oxygen partial pressure between the two electrodes can be reduced due to gas phase mixing including fuel, oxidant, product, etc., and gas fraction change due to direct oxidation of fuel at the cathode, thus opening A decrease in open circuit voltage (OCV) results in cell performance (see S. Ahn et al. Electrochemical and Solid-State Letter, vol. 9, no. 5, pp A228-231). Therefore, in order to prevent cell performance degradation of SC-SOFC, it is important to prevent gas phase mixing to maintain the oxygen partial pressure difference at the two electrodes.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object thereof is to provide a single solid oxide fuel cell having a structure in which an anode and a cathode are effectively disposed to prevent gas phase mixing.

In addition, the use of a thin film process is aimed at reducing the integration cost and the production cost together with the lowering of the operating temperature.

Single chamber solid oxide fuel cell according to the first aspect of the present invention for achieving the above object,

An anode electrode and a cathode electrode are disposed together on one surface of the electrolyte, and are formed on the one surface of the electrolyte, and include a separation barrier positioned between two electrodes of the same or different type.

In addition, the single-solid-type solid oxide fuel cell according to the second aspect of the present invention for achieving the above object,

A substrate having a trench formed on the top surface thereof; An electrolyte located at the center of the trench; Two different electrodes disposed in the trench and disposed separately from the left and right sides of the electrolyte; And a separation barrier formed over at least the electrolyte.

In addition, the single-solid-type solid oxide fuel cell according to the third aspect of the present invention for achieving the above object,

Board; Two different electrodes disposed to be spaced apart from each other on the substrate; And an electrolyte formed between the two electrodes and on the two electrodes, wherein at least a lower portion of the electrode of the substrate has a pore structure, or at least part of the substrate in contact with the bottom surface of the electrode is removed. It is done.

In addition, the single-solid-type solid oxide fuel cell according to the fourth aspect of the present invention for achieving the above object,

A structure in which a substrate, a dielectric, a first electrode, an electrolyte, and a second electrode are sequentially stacked from below, and a portion of the dielectric in contact with the first electrode is removed to form an air gap. It features.

In addition, a method for manufacturing a single solid oxide fuel cell according to a fifth aspect of the present invention for achieving the above object,

Forming a separation barrier material layer over the electrolyte layer; Forming a separation barrier by patterning the separation barrier material layer using a photoresist; Forming a first electrode on one side of the separation barrier; And forming a second electrode on an opposite side of the one side of the separation barrier.

In addition, a method for manufacturing a single solid oxide fuel cell according to a sixth aspect of the present invention for achieving the above object,

Forming a photoresist layer on the electrolyte layer; Patterning the photoresist layer to form a trench; Depositing a separation barrier material in the trench to form a separation barrier; Removing the photoresist layer; Forming a first electrode on one side of the separation barrier; And forming a second electrode on an opposite side of the one side of the separation barrier.

In addition, a method for manufacturing a single solid oxide fuel cell according to a seventh aspect of the present invention for achieving the above object,

Forming a separation barrier material layer over the electrolyte layer; Forming a first trench by patterning the separation barrier material layer using a photoresist; Forming a first electrode in the first trench; Forming a second trench by patterning the photoresist at a position spaced apart from the first electrode; And forming a second electrode in the second trench.

In addition, a method for manufacturing a single solid oxide fuel cell according to an eighth aspect of the present invention for achieving the above object,

Forming a trench in the upper surface of the substrate; Forming a first electrode-electrolyte-second electrode in the trench in a horizontal direction; Forming a dielectric layer over the electrolyte and the first and second electrodes; And forming at least a portion of the upper part of the first and second electrodes while the upper part of the dielectric layer is left, to form an upper gas passage.

In addition, a method for manufacturing a single solid oxide fuel cell according to a ninth aspect of the present invention for achieving the above object,

Forming at least a portion of the substrate into a pore structure; Forming a first electrode on the substrate portion having the pore structure; Forming a second electrode on the substrate portion having the pore structure so as to be spaced apart from the first electrode; And forming an electrolyte between the two electrodes and on the two electrodes.

In addition, a method for manufacturing a single solid oxide fuel cell according to a tenth aspect of the present invention for achieving the above object,

Forming a dielectric layer over the substrate; Forming a trench in the dielectric layer; Filling a sacrificial substance in the trench; Forming a first electrode on the dielectric layer and the sacrificial material; Forming an electrolyte layer on the first electrode; And forming a second electrode on the electrolyte layer, wherein the sacrificial material is thermally decomposed through heat treatment or subsequent heat treatment of the first electrode to form an air gap. .

In addition, the method for manufacturing a single solid oxide fuel cell according to an eleventh aspect of the present invention for achieving the above object,

Forming a sacrificial material layer on the substrate; Patterning the sacrificial material layer to form a sacrificial material at a predetermined interval; Forming a dielectric layer between and over said sacrificial material; Planarizing the dielectric layer; Forming a first electrode on the dielectric layer and the sacrificial material; Forming an electrolyte layer on the first electrode; And forming a second electrode on the electrolyte layer, wherein the sacrificial material is thermally decomposed through heat treatment or subsequent heat treatment of the first electrode to form an air gap. .

Various embodiments presented in the present invention represent a SOFC manufacturing method using a thin film process and a separate arrangement structure of the electrode to minimize the mutual mixing of the gas phase. Although the following embodiments have been described with respect to SOFCs operating in a single room environment, they may also be applicable to general SOFCs.

Substrates that can be used as a support in the present invention include an electronic insulator, an electronic non-conducting material, a semi-conducting material, an oxygen ion conducting material, and a proton conductor. Any one selected from a category covering conducting materials, etc. may be used. For example, the substrate may be silicon (Si), silicon oxide (SiO _x ), silicon nitride (Si _x N _y ), aluminum oxide (Al _x O _y ), magnesium oxide (Mg _x O _y ), titanium oxide (Ti _x O _y). ), Zirconium oxide (Zr _x O _y ), cerium oxide (Ce _x O _y ), lanthanum galate, barium cerate, barium zirconate, bismuth oxide, or Any one selected from the category encompassing various doping phases, etc. of the materials can be used.

In addition, when a semiconductor material such as a silicon (Si) wafer or a non-insulating material is used as the support, an insulating and thermal expansion buffer layer may be further included on the support. Here, the thermal expansion buffer layer refers to a buffer layer for suppressing stress due to thermal expansion. For example, the insulating and buffer layers include silicon oxide (SiO _x ), silicon nitride (Si _x N _y ), aluminum oxide (Al _x O _y ), magnesium oxide (Mg _x O _y ), titanium oxide (Ti _x O _y ), Zirconium Oxide (Zr _x O _y ), Cerium Oxide (Ce _x O _y ), Lanthanum Gallate, Barium Cerate, Barium Zirconate, Bismuth-based Oxide, or the Material Any one selected from a category covering various doping phases may be used.

As such a support, a substrate is not necessarily required, and an electrolyte may be prepared to an appropriate thickness or more to serve as a support.

On the other hand, the positive electrode (also referred to as cathode electrode, air electrode, or reducing electrode) used in the present invention is platinum (Pt), gold (Au), silver (Ag), lanthanum-strontium manganese oxide (LSM), lanthanum-strontium iron Lanthanum oxide-based perovskite such as oxide (LSF), lanthanum-strontium cobalt iron oxide (LSCF), or bismuth-ruthenium oxide-based electrode may be used.

In addition, a cathode (also called an anode electrode, a fuel electrode, or an oxide) used in the present invention is a metal such as nickel (Ni), ruthenium (Ru), palladium (Pd), rhodium (Rd), and these YSZ, GDC Cermet composites, alloys of these metals, ruthenium oxide and the like can be used.

In addition, the electrolyte used in the present invention is a zirconium oxide (Zr _x O _y ), cerium oxide (Ce _x O _y ), lanthanum galate (Lanthanum Gallate), barium Cerate (barium Cerate), barium zirconate ), Bismuth-based oxides or ionic conductors such as oxygen ion conducting materials such as various doping phases of the above materials, and proton conducting materials.

In addition, the material of the separation barrier used in the present invention may be the same or different materials from the electrolyte. For example, the material of the separation barrier is silicon oxide (SiO _x ), silicon nitride (Si _x N _y ), aluminum oxide (Al _x O _y ), magnesium oxide (Mg _x O _y ), titanium oxide (Ti _x O _y). ), Zirconium oxide (Zr _x O _y ), cerium oxide (Ce _x O _y ), lanthanum galate, barium cerate, barium zirconate, bismuth-based oxide or the Various doping phases of materials can be selected and used.

As a method of forming the substrate, the anode, the cathode, the electrolyte, and the separation barrier material, various vapor deposition methods such as chemical vapor deposition, sputtering, physical vapor deposition, and sol-gel, spray, and spin-on methods are used. Can be. All the materials and deposition methods presented above can be applied to all the methods presented in the present invention, and the contents of the present invention are not limited to the materials listed above.

Hereinafter, with reference to the accompanying drawings will be described in detail an embodiment of a single solid oxide fuel cell and a method for manufacturing the same according to the present invention.

One method of preventing gas phase mixing in the present invention is to arrange a separation barrier between two electrodes, which is shown in FIGS.

In the case of the B-type SC-SOFC in which two kinds of electrodes are alternately positioned on one surface of the electrolyte, the performance degradation due to gas phase mixing is more severe. In this embodiment, by separating the separation barrier between the two electrodes, the performance of the battery is maintained by preventing the mixing of the fuel, oxidant, gas generated by the reaction between the two electrodes to maintain the oxygen partial pressure difference.

In addition, the cathode and the anode of the SC-SOFC may be formed in various combinations with separation barriers interposed therebetween, in order to show different cell characteristics. For example, different electrodes may be alternately arranged, such as 'cathode-anode-anode-anode', or a bundle of the same second electrode unit such as 'cathode-anode-anode-anode-anode-anode-anode' In this way, different electrode sets may be alternately arranged to form an electrode.

In addition, the shape, width and height of the separation barrier can be adjusted according to the system design, the height of the separation barrier is preferably equal to or higher than the height of the cathode and anode in order to faithfully perform the role of preventing gas phase mixing.

FIG. 1 shows the structure of a B-type SC-SOFC in which the separation barrier 110 is positioned between the two electrodes 100 and 105, and FIG. 2 is a cross-sectional view taken along line A-A 'of FIG. The two types of electrodes are designated 200 and 205, and the separation barrier is designated 210, and both are positioned on the surface of the electrolyte 215. The insulator and / or buffer layer 225 may be formed on the substrate 220 according to the type of substrate.

The method of forming the structure shown in FIGS. 1 and 2 is shown in the flowchart shown in FIG. 3.

In some cases, an insulating layer is formed on the substrate (300), and an electrolyte layer is formed thereon (301). If the electrolyte layer is thick, the substrate may be unnecessary because it may serve as a support.

A barrier layer material layer is then formed over this electrolyte layer (305). The method of forming the separation barrier material layer may use a suitable thin film deposition technique, and the shape, width and height of the separation barrier may be adjusted according to the system design.

In FIG. 3, the method of patterning the barrier layer material layer first compared to the electrode is indicated from step 305. The barrier material layer is patterned using a photoresist. Patterning consists of photoresist spin-on coating, lithography, photoresisting, and selective etching of the barrier material layer. In this case, the photoresist removal process is performed after the etching process is finished. As a result, a separation barrier is formed.

Alternatively, as another method of forming the separation barrier, it may be patterned by selective deposition instead of etching. That is, a photoresist layer is formed on the electrolyte layer, the photoresist is patterned, and a separation barrier material is deposited in trenches or vias formed after the development process is completed. The separation barrier is patterned by removing the separation barrier material layer deposited thereon.

Then, in some cases, in step 315 of FIG. 3, a trench is formed to form the first electrode through patterning of the dielectric. It is also possible to use the space between adjacent separation barriers formed in the previous step without forming a separate trench. Here, the first electrode is a cathode or an anode.

Next, in step 320, the first electrode is deposited in the trench to one side of the separation barrier, and then heat treatment is performed in step 325. Accordingly, the first electrode can be changed into a porous structure. For heat treatment, heat treatment is performed at a temperature of 300 to 1200 degrees Celsius depending on the material, and in some cases, a reducing atmosphere is used.

Next, a trench for the second electrode is formed after the heat treatment of the first electrode is completed (330). The second electrode is the opposite electrode of the first electrode. In operation 335, the second electrode is deposited on the opposite side of the inner side of the trench to the side of the separation barrier, and then heat treatment to obtain a porous microstructure (340).

Next, a current collector is formed by patterning using a photoresist and connected to both electrodes, respectively (345). After that, the connecting line may be formed according to the necessity of connecting individual cells. The material of the current collector and the connecting wire is an oxidation-resistant metal current collector such as gold (Au), platinum (Pt), silver (Ag), nickel (Ni), palladium (Pd), rhodium (Rh), or ruthenium (Ru). Alternatively, a ceramic-metal composite material having high electrical conductivity may be used. By using the current collector and the connection line, the electrodes can be connected in a series or parallel combination to form a high voltage, high power micro power device. In addition, a metal material coated with a nonmetallic material to be stable in an oxygen and fuel atmosphere may be used. For example, copper (Cu) or aluminum (Al) may be a material such as titanium nitride (TiN) or tantalum nitride (TaN). The case where it is wrapped is mentioned. As a method of depositing a current collector or a connecting line, a deposition method such as sputtering, electroplating, electroless plating, sol-gel, or spin-on process may be used. All the materials and deposition methods presented above can be applied in all cases of the invention.

Meanwhile, in FIG. 3, a method different from the above process in which the separation barrier is patterned after electrode formation is described from step 350.

In this case, patterning and forming of the first electrode are started in step 355. By trenching the isolation barrier material layer with a photoresist, trenches are formed in which the first electrode is to be formed. After removal of the photoresist, a first electrode is formed 360 in the trench and then subjected to heat treatment 365. There may be two methods for forming the first electrode in the trench. The first is to leave the photoresist used as an etch mask when patterning the isolation barrier material layer and use it again as a mask for selective deposition of the first electrode. After selective deposition, the photoresist is removed and the first electrode material deposited thereon is also removed, leaving only the first electrode in the trench. In the second method, after removing the photoresist used as an etch mask, the first electrode material is entirely deposited to cover both the trench and the separation barrier and then planarized through a CMP process to make the first electrode trench. Change it until you are in the form. However, the content of the present invention is not limited to the above two methods.

Next, a trench to form the second electrode is formed in the patterning process of step 370. As in the case of the first electrode, the trench of the second electrode is formed in the separation barrier material layer. A second electrode is deposited in the trench in step 375 and heat treated in step 380.

The current collector connected to the electrode is then formed by patterning the barrier material layer in step 385 to form a trench, and depositing a conductive material in the trench.

The remaining barrier layer material in the preceding process can be used as a separation barrier by itself, but if an individual block is needed as the separation barrier, the separated barrier material layer remaining in step 395 is separately separated using a photoresist. Patterned as a barrier.

An example of another method for preventing mixing of the reactant and product gases in the present invention is shown in FIGS. 4 to 6.

This method adopts a structure in which a mixed gas of fuel gas and an oxidant is injected into the entire cell stack at the same time, but is formed by supplying a separate passage to each electrode.

Specifically, FIG. 4 illustrates an embedded A-type SC-SOFC in which air and fuel passages 440 and 445 exist under each electrode 430 and 450. In the Embedded A-type, both electrodes 430 and 450 and the electrolyte 451 are formed side by side in the substrate 435. Dielectrics 400, such as oxides or nitrides, are deposited on the electrolyte and the electrodes to form an upper isolation barrier. The dielectric is patterned to form the upper gas passages 410 and 420 and the current collector 405.

5 illustrates a series connection of single cells. FIG. 5 illustrates an upper shape of the unit cell illustrated in FIG. 4, a current collector 525, and a connection line 535. In order to fabricate an SOFC stack in which several cells are connected, two or more individual unit cells 500 may be manufactured in one row, and two or more rows may be manufactured to increase integration.

The method of forming the structure shown in FIGS. 4 and 5 is shown in the flowchart of FIG. 6. A trench is first formed 600 to create an SOFC structure in the substrate. As the substrate, a material such as silicon (Si) may be used.

An insulating material, such as silicon oxide, silicon nitride, or silicon oxy-nitride, is then deposited to cover the walls in the trench but not completely fill it (605).

Next, through patterning using a photoresist, a portion on which the electrolyte is to be coated is formed and the electrolyte is deposited (610 and 615). After deposition of the electrolyte, the portion where the first electrode (anode or cathode) is to be formed is made through photoresist patterning (620), and the first electrode is fabricated through thermal deposition after deposition (625, 630). After fabrication of the first electrode, a second electrode (the electrode opposite to the first electrode) is deposited and heat-treated to be manufactured (640, 645). As such, the deposition of the electrolyte and the two electrodes may be in the order of electrolyte-first electrode-second electrode, but may also be in order of first electrode-second electrode-electrolyte, or the first electrode-electrolyte-second It may be made in order of electrode.

A dielectric is then deposited over the electrolyte and the electrode and then patterned to form the upper gas passageway and current collector (670, 675). The connecting line can be made at the same time as the current collector or in the subsequent process.

Then, in order to form an air / fuel passage on the opposite side of the substrate, that is, on the opposite side of the surface on which the current collector is formed, the substrate is thinned (680) and then a lower gas passage is formed through the etching process under each electrode. (685). The size of the lower gas passage can be similar to the electrode size or can be made larger for smooth flow of gas. On the other hand, several small passages may be formed to mechanically support the electrode structure. Alternatively, it may be advantageous to use a porous substrate to support and maintain the mechanical strength of the electrode and electrolyte structure without forming a lower gas passage. That is, at least a gas passage below the electrode of the substrate may have a pore structure.

7 to 9 show examples of B-type SC-SOFCs formed using a porous substrate.

When using separate gas passages leading to the electrodes, it may be advantageous to use a porous substrate to support the electrodes and the electrolyte structure while maintaining mechanical strength. The porous passage may be a pore structure of only the electrode portion or the entire support.

7 illustrates an SOFC using a porous substrate. Unlike FIG. 1, both electrodes 720 and 725 are formed below the electrolyte 715. In addition, a current collector 730 is formed at the lower portions of the electrolyte 715 and the electrodes 720 and 725.

One method of making a porous substrate is to use frit, which is to trench and fill trenches 740 and 750 with frit. Frit is a porous material obtained by sintering small spherical particles of a suitable material. The deposition of frits can be accomplished using chemical vapor deposition (CVD) or other nanoparticle deposition methods.

As another method, for example, when the substrate is silicon, the porous substrate can be manufactured by using a method of manufacturing the porous silicon. The porous silicon has a structure in which gas passages are connected in an interconnected silicon matrix. Electrochemical etching of a silicon substrate in a hydrofluoric acid (HF) -based solution is the most common method, and the pore size may vary from several nanometers to several microns depending on the manufacturing method and the characteristics of the silicon substrate.

Instead of using a porous substrate, however, as shown in FIG. 4, a method of forming a lower gas passage may be used by removing the lower side of the electrode through an etching process or the like.

The series connection of the individual cells is shown in FIG. 8. FIG. 8 shows the arrangement of the upper surface, the connecting line 815 and the current collector 810 of FIG. 7. The electrolyte 820 may be manufactured to cover the entire cell or to cover the cell rows arranged horizontally or vertically. In order to fabricate an SOFC stack in which several cells are connected, two or more individual unit cells 800 may be manufactured in one column, and two or more rows may be manufactured to increase integration.

The manufacturing method of the structure shown in FIGS. 7 and 8 is shown in more detail in the flowchart of FIG. 9. If necessary, an insulating isolation structure 745 of FIG. 7 is formed to prevent electrical shorts between the anode and cathode electrodes (900).

One method of making a porous substrate is to fabricate porous silicon, in which a portion of the silicon substrate to be made into a porous structure is defined as a photoresist (905), and the specified portion is made into a porous structure through electrochemical etching. (910). Another method is formed by digging a trench into a substrate (907) and filling it with frit (912) using a porous frit material.

After the porous substrate is made, the current collector is formed by patterning 915 a portion where the current collector is to be formed using a photoresist and depositing a conductor thereon 920. In this embodiment, when a silicon substrate is used, silicide may be used as the current collector.

Next, the first electrode (anode or cathode) is formed through photoresist patterning on the portion of the substrate having a pore structure (925), and is formed through deposition and heat treatment (930, 935).

Then, after formation of the first electrode, a second electrode (the opposite electrode of the first electrode) is formed through photoresist patterning 940, deposition 945, and heat treatment 950.

After both electrodes are clad, dielectric 700 may be deposited (953). However, if the insulation is not required between the electrolyte and the connecting line, this process is not necessary because the electrolyte can be patterned and used.

Then, after the region on which the electrolyte is to be coated is patterned (955), the electrolyte is coated over the positive electrode and between the positive electrode (960). In this case, another material may be filled between the two electrodes, and an electrolyte may be coated on the both electrodes.

The bottom of the substrate, opposite the electrolyte, is then ground until it exposes the porous structure to form a passage through which the gas phase of air / fuel flows (975).

In addition, in a typical A-type structure in which the electrodes are disposed above and below the electrolyte, a gas passage may be formed in the support for supporting the lower electrode so that the supply / reaction gas of both electrodes may not be mixed with each other in a single room environment. 10 to 12 illustrate one example.

FIG. 10 is a diagram illustrating a structure of an SC-SOFC using an air gap 1025. The most commonly used method for forming the air gap is as follows. First, spin-fill the sacrificial substance, for example Unity ^™ , which is later removed in the trench made at the site where the air gap is to be formed. An insulating layer, such as a dielectric or polymer, is deposited on the coated material. Depending on the system or design, the sacrificial material is first deposited and patterned, and then an insulating layer is deposited thereon. In this process, the planarization of the insulating layer may be further required. After deposition of the insulating layer, the sacrificial material is heated to its decomposition temperature and disappears through thermal decomposition and diffusion of decomposition products, leaving an embedded air gap in the original area. As shown in FIG. 10, trenches 1025 filled with sacrificial material are formed in dielectric material over the substrate.

Thereafter, a first electrode 1015 is deposited prior to thermal decomposition of the sacrificial material. Subsequent heat treatment is performed for the decomposition of the sacrificial material material as well as the electrode heat treatment. Through this process, an air gap 1025 is formed below the first electrode. After this, the electrolyte 1010 is deposited on the surface of the first electrode 1015, and the second electrode 1005 is formed thereon.

The series connection of the individual cells is shown in FIG. FIG. 11 shows the upper structure, the connecting line 1115 and the current collector 1105 of FIG. 10. It is also shown that electrolyte 1120 may be deposited on multiple unit cells at one time. The electrolyte 1120 may be manufactured to cover the entire cell or to cover cell portions horizontally or vertically arranged. In order to manufacture an SOFC stack in which several cells are connected, two or more individual unit cells 1100 may be manufactured in one column, and two or more rows may be manufactured to increase integration.

The manufacturing method of the structure shown in FIGS. 10 and 11 is shown in more detail in the flowchart of FIG. 12. A dielectric, such as silicon oxide, is deposited on the substrate (1200). The trench in which the air gap will be formed in the dielectric layer is then patterned with photoresist (1205). A sacrificial layer is coated 1210 after the formation of the trench. A first electrode (cathode or anode) is patterned with photoresist and deposited on the dielectric and sacrificial material (1215, 1220), and then an air gap is formed through heat treatment 1225 (1227). An electrolyte is formed over the first electrode through photoresist patterning 1230 and deposition 1235. The heat treatment of the first electrode mentioned in step 1225 may be performed after electrolyte deposition 1235. This heat treatment sequence can be used when the sacrificial material can be diffused and removed from the trench through pyrolysis when heat treated under both the electrolyte and the electrode. After depositing the electrolyte, a second electrode (the opposite electrode of the first electrode) is formed through photoresist patterning 1240 and deposition 1245 and completed through heat treatment (1250). Dielectric 1001 is deposited on the second electrode in step 1255 and subjected to planarization through chemical mechanical polishing (CMP) at 1260. The current collector is formed by patterning into a dielectric in step 1265 and depositing a conductor in step 1270.

5, 8, and 11 illustrating a structure in which a stack is formed by connecting a plurality of unit cells, electrodes may be alternately arranged in adjacent rows in order to facilitate series connection. That is, the first column is arranged in the form of a cathode-electrolyte-anode-anode-electrolyte-anode to form a series connection between neighboring cells, and in the second column, they are arranged in series connection in the order of anode-electrolyte-cathode-anode-electrolyte-cathode do. In this way, connecting lines 535, 815 and 1115 for series connection can be made very easily at the end of each column.

However, even if the electrodes are arranged in other manners, a series connection is possible as shown in FIG. 13. In the case of FIG. 13, the arrangement order of the cathode-electrolyte-anode is the same in both the first column and the second column. In this case, although the connection line may pass long between the rows, the electrical interconnection between the cells may be formed by connecting the current collectors of the cells of one end of the upper row and the other end of the lower row in series.

In addition, parallel connections may be configured by electrically connecting the positive electrodes or the negative electrodes to neighboring single cells. In order to facilitate connection of the connection line according to the design and the connection method, it is possible to freely arrange the electrodes of the adjacent unit cells and the neighboring rows. These serial and parallel connections can be combined in one SC-SOFC stack. That is, within the same row, cells can be connected in series and neighboring rows can be connected in parallel or vice versa.

As described above, a fuel cell having an electrode arrangement structure according to the present invention prevents gas phase mixing and easily solves various disadvantages of the SC-SOFC having a previously proposed coplanar electrode, thereby significantly improving its performance. do. In particular, by presenting an invention that can be realized using a thin film process capable of integration and mass production, the portability, scalability, and versatility to other technologies are also excellent. In addition, the small fuel cell manufactured according to the present invention is a mobile next generation small power supply device, which enables high integration and miniaturization of a fuel cell unit cell, and thus has great economic value.

Although the present invention has been described with reference to the illustrated embodiments, it is merely exemplary, and the present invention may encompass various modifications and equivalent other embodiments that can be made by those skilled in the art. Will understand.

Claims (40)

In the single-solid-type solid oxide fuel cell of the type in which the anode electrode and the cathode electrode are disposed together on one surface of the electrolyte, And a separation barrier formed on the one surface of the electrolyte and positioned between two electrodes of the same or different type. The method of claim 1, Single anode type solid oxide fuel cell, characterized in that the anode electrode and the cathode electrode are alternately arranged. The method of claim 1, And the anode electrode and the cathode electrode are alternately arranged in a bundle of identical second electrode pieces. The method of claim 1, Single height solid oxide fuel cell, characterized in that the height of the separation barrier is higher than or equal to the height of the anode and cathode electrode. The method of claim 1, The separation barrier is made of the same kind of material as the electrolyte, or as the material different from the electrolyte, silicon oxide (SiO _x ), silicon nitride (Si _x N _y ), aluminum oxide (Al _x O _y ), magnesium oxide ( Mg _x O _y ), Titanium Oxide (Ti _x O _y ), Zirconium Oxide (Zr _x O _y ), Cerium Oxide (Ce _x O _y ), Lanthanum Gallate, Barium Cerate, Barium Single chamber solid oxide fuel cell comprising a zirconate (Barium Zirconate) or several doped phases of the materials. A substrate having a trench formed on the top surface thereof; An electrolyte located at the center of the trench; Two different electrodes disposed in the trench and disposed separately from the left and right sides of the electrolyte; And And a separation barrier formed over at least the electrolyte. The method of claim 6, And the separation barrier is formed on a portion of the electrode adjacent to the electrolyte. The method of claim 6, At least a lower portion of the electrode of the substrate is a single-solid-type solid oxide fuel cell, characterized in that the pore structure. The method of claim 6, At least part of the substrate in contact with the lower surface of the electrode is removed, characterized in that the solid-state solid oxide fuel cell. The method of claim 6, And a current collector spaced apart from the separation barrier on the electrode. The method of claim 10, A plurality of unit cells (unti cell) is located on the substrate, each unit cell is a solid-state solid oxide fuel cell, characterized in that connected in series or in parallel through a connection line connecting each current collector. The method of claim 6, And a silicon oxide, silicon nitride or silicon oxy-nitride interposed between the substrate and the electrode. Board; Two different electrodes disposed to be spaced apart from each other on the substrate; And An electrolyte formed on the two electrodes; At least a lower portion of the electrode of the substrate has a pore structure, or at least part of the substrate in contact with the lower surface of the electrode is removed, characterized in that the solid-state solid oxide fuel cell. The method of claim 13, And a porous frit is filled in the removed portion of the substrate. The method of claim 13, Single substrate type solid oxide fuel cell, characterized in that the substrate is a porous silicon substrate. The method of claim 13, And a current collector formed on the substrate to be in contact with an outer edge of the lower surface of the electrode. The method of claim 16, A plurality of unit cells (unti cell) is located on the substrate, each unit cell is a solid-state solid oxide fuel cell, characterized in that connected in series or in parallel through a connection line connecting each current collector. The method of claim 13, Single-solid-type solid oxide fuel cell, characterized in that it further comprises an insulating separation structure formed under the electrolyte formed between the two electrodes. A substrate, a dielectric, a first electrode, an electrolyte, and a second electrode are sequentially stacked from below; And a portion of the dielectric in contact with the first electrode is removed to form an air gap. The method of claim 19, The air gap is a single-solid-type solid oxide fuel cell, characterized in that formed at regular intervals. Forming a separation barrier material layer over the electrolyte layer; Forming a separation barrier by patterning the separation barrier material layer using a photoresist; Forming a first electrode on one side of the separation barrier; And And forming a second electrode on an opposite side of the one side of the separation barrier. Forming a photoresist layer on the electrolyte layer; Patterning the photoresist layer to form a trench; Depositing a separation barrier material in the trench to form a separation barrier; Removing the photoresist layer; Forming a first electrode on one side of the separation barrier; And And forming a second electrode on an opposite side of the one side of the separation barrier. Forming a separation barrier material layer over the electrolyte layer; Forming a first trench by patterning the separation barrier material layer using a photoresist; Forming a first electrode in the first trench; Forming a second trench by patterning the photoresist at a position spaced apart from the first electrode; Forming a second electrode in the second trench; Method of manufacturing a single-solid-type solid oxide fuel cell comprising a. The method of claim 23, And forming an individual separation barrier by patterning the separation barrier material layer remaining after the second electrode forming step using a photoresist. The method according to claim 21 or 22 or 23, The electrolyte layer, the separation barrier material layer, and the first and second electrodes are formed by a chemical vapor deposition method, a sputtering method, a sol-gel method, a spraying method, or a spin-on process. Method of manufacturing a fuel cell. Forming a trench in the upper surface of the substrate; Forming a first electrode-electrolyte-second electrode in the trench in a horizontal direction; Forming a dielectric layer over the electrolyte and the first and second electrodes; And And forming at least a portion of the upper part of the first and second electrodes while the upper part of the dielectric layer is left while the upper part of the dielectric layer is formed to form an upper gas passage. . The method of claim 26, Forming the electrolyte and the first and second electrodes, Forming an electrolyte using photoresist patterning at the center of the trench; Forming a first electrode on the side of the electrolyte in the trench by using photoresist patterning; And forming a second electrode on the opposite side of the one side of the electrolyte in the trench by using photoresist patterning. The method of claim 26, Forming the electrolyte and the first and second electrodes, Forming a first electrode on one side of the trench by using photoresist patterning; Forming a second electrode using photoresist patterning at a position spaced apart from the first electrode in the trench; And forming an electrolyte using photoresist patterning between the first electrode and the second electrode. The method of claim 26, Forming the electrolyte and the first and second electrodes, Forming a first electrode on one side of the trench by using photoresist patterning; Forming an electrolyte using photoresist patterning next to the first electrode in the trench; And forming a second electrode using photoresist patterning next to the electrolyte in the trench. The method of claim 26, After forming the first electrode-electrolyte-second electrode, The method of claim 1, further comprising forming a lower gas passage by opening the lower portions of the first and second electrodes, leaving the lower portion of the electrolyte. The method of claim 30, Before forming the lower gas passage, the method of manufacturing a single solid oxide fuel cell characterized in that the process of thinning the overall thickness of the substrate. The method of claim 26, After forming the trench on the upper surface of the substrate, the step of depositing silicon oxide, silicon nitride, or silicon oxy-nitride on the inner surface of the substrate forming the trench further comprising the step of manufacturing a solid oxide fuel cell Way. The method of claim 26, The method of manufacturing a single solid oxide fuel cell according to claim 1, wherein a space in which a whole house is formed to be deposited is formed together when the upper gas passage is formed. Forming at least a portion of the substrate into a pore structure; Forming a first electrode on the substrate portion having the pore structure; Forming a second electrode on the substrate portion having the pore structure so as to be spaced apart from the first electrode; And Forming an electrolyte on the two electrodes; Method of manufacturing a single solid oxide fuel cell comprising a. The method of claim 34, wherein In the method of forming a portion of the substrate into a pore structure, a portion of the substrate to be formed into a pore structure is defined by a photoresist, and the prescribed portion is manufactured by electrochemical etching. Way. The method of claim 34, wherein The method of forming a portion of the substrate in a pore structure comprises forming a trench in the upper surface of the substrate and filling the trench with a porous frit. The method of claim 34, wherein A current collector is formed on the substrate before the first electrode is formed, and the first electrode and the second electrode are formed on a part of the current collector. The method of claim 34, wherein And a pore structure portion of the substrate under the first electrode and a pore structure portion of the substrate under the second electrode are separated from each other. Forming a dielectric layer over the substrate; Forming a trench in the dielectric layer; Filling a sacrificial substance in the trench; Forming a first electrode on the dielectric layer and the sacrificial material; Forming an electrolyte layer on the first electrode; And Forming a second electrode on the electrolyte layer; And thermally decomposing the sacrificial material through heat treatment of the first electrode or subsequent heat treatment to form an air gap. Forming a sacrificial material layer on the substrate; Patterning the sacrificial material layer to form a sacrificial material at a predetermined interval; Forming a dielectric layer between and over said sacrificial material; Planarizing the dielectric layer; Forming a first electrode on the dielectric layer and the sacrificial material; Forming an electrolyte layer on the first electrode; And Forming a second electrode on the electrolyte layer; And thermally decomposing the sacrificial material through heat treatment of the first electrode or subsequent heat treatment to form an air gap.

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