KR20200083705A - Flat - tubular coelectrolysis cell and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a flat tubular coelectrolysis cell to produce syngas from water and carbon dioxide and a manufacturing method thereof. According to the present invention, the flat tubular coelectrolysis cell comprises: a flat tubular supporter including NiO and yttria stabilized zirconia (YSZ); a cathode layer formed on a surface of the flat tubular supporter and including (Sr_1_-_xLa_x)(Ti_1_-_yM_y)O_3, where M = V, Nb, Co, and Mn; a solid electrolyte layer formed on a surface of the cathode layer; and an anode layer formed on a surface of the solid electrolyte layer. According to the present invention, the flat tubular coelectrolysis cell provides an excellent syngas conversion ratio and can produce syngas at low overvoltage.

Description

FLAT-TUBULAR COELECTROLYSIS CELL AND METHOD FOR MANUFACTURING THE SAME}

The present invention relates to a flat tube type electrolytic cell and a method for manufacturing the same, and more particularly, to a flat tube type electrolytic cell capable of producing syngas from water and carbon dioxide, and a method for manufacturing the same.

With the adoption of the Kyoto Protocol in 1997, various policies have been put in place to reduce carbon emissions worldwide, and technologies to reduce the generation of carbon dioxide are being developed in various aspects.

In order to fundamentally block the emission of carbon dioxide, a technology that generates electricity by reacting hydrogen fuel with oxygen in the air has been developed in the aspect of developing a fuel that does not emit carbon dioxide. It is widely known.

On the other hand, research and development related to the process of converting carbon dioxide into usable fuel by using already generated carbon dioxide is steadily being conducted. Hydrogen production by CO2-based high temperature electrolysis has recently attracted much attention along with green energy technology development and renewable energy research and development. Is getting

The high temperature electrolysis reaction system is a device that produces syngas by electrolysis reaction when carbon dioxide and steam are injected into the cathode, air is injected into the anode, and electricity is maintained while maintaining high temperature. High temperature electrolytic reaction of CO2-H2O The technology for producing syngas by is characterized by effectively combining the reaction and separation processes to simplify the process, increase the reaction efficiency, and efficiently operate by mass-processing, but the high-temperature electrolysis technology of carbon dioxide centers on precious metal electrodes. Only a limited number of studies have been conducted.

In addition, the electrolysis cell for producing syngas by high-temperature electrolytic reaction of CO2-H2O has a low conversion rate of CO2 synthesis gas and poor efficiency, so there is a problem in commercialization, so the synthesis gas conversion rate is superior to the existing high-temperature electrolysis reaction system. An orbiting cell is required.

As a result, various types of orbital cells, such as tubular and flat plates, have been manufactured, but the orbital cells that withstand the harsh operating environment but have low performance, but have poor performance and the disadvantages of the flat cell are vulnerable to harsh operating environments. Is being demanded.

An object of the present invention is to provide a flat tubular orbital cell, which compensates for the disadvantages of the tubular ortographic cell and the planar orbital cell in view of the problems of the prior art.

It is also an object of the present invention to provide a method for manufacturing a flat tubular orbital cell with excellent syngas conversion.

In order to achieve the above object, the present invention is a flat tubular support comprising NIO and YSZ; _{(- x} La _x Sr ₁₎ formed in the flat tubular support _surface including a _{(Ti 1 y M y) O} 3 (M = V, Nb, Co, Mn) a cathode layer; A solid electrolyte layer formed on the surface of the cathode layer; And an anode layer formed on the surface of the solid electrolyte layer.

The flat tubular support may be a plate shape including a plurality of hollow flow paths.

In the flat tubular support, the plurality of hollow flow paths may have a cylindrical shape and be aligned in a predetermined direction.

In the flat tubular support, the diameter of the circular cross section of the cylinder may be 0.1 to 0.2 cm.

The solid electrolyte layers are YSZ (yttria stabilized zirconia), LSGM (lanthanum gallate doped with Sr and Mg), ScSZ (scandia stabilized zirconium oxide), GDC (gadolinia doped ceria) and SDC (samaria doped ceria). It may include one or more substances selected from the group consisting.

The anode layer may include LSCF-GDC or YSZ-LSM and LSM composite.

The fuel used in the cathode layer may include H ₂ O, CO ₂ and H ₂ .

In addition, the present invention comprises the steps of mixing the NIO, YSZ and the pore-forming agent, and then mixing with a solvent to prepare a slurry to form a ball mill (step 1); Drying the slurry and then pulverizing it (step 2); Adding an additive to the powdered mixture and kneading to prepare a paste, putting the paste into a flat tube mold, and then extruding to orbit to prepare a support for a cell (step 3); Rolling and drying the support for the extruded orbital cell (step 4); And the rolling by the dry-time after an integral plasticize the cell, the support, the method comprising: coating a cathode, an electrolyte and an anode (5); wherein the said cathode _{(Sr 1 - x La x)} (Ti 1 - y M y )O ₃ (M = V, Nb, Co, Mn) provides a method for manufacturing a flat-type revolution cell.

The pore forming agent may be activated carbon or carbon black, and the additive may include a binder, a plasticizer, and a lubricant.

The plastic sintering may be performed by a stepwise heating up to 300°C to 400°C, and then to 700°C to 800°C, and then to 1000°C to 1200°C.

The cathode and the anode may be coated by a dip coating method or a screen printing method.

After coating the cathode, heat treatment may be performed at 800°C to 1200°C, and after coating the anode, heat treatment may be performed at 900°C to 1400°C.

The electrolyte may be coated by a vacuum slurry coating method.

After coating the electrolyte, heat treatment may be performed at 1200°C to 1600°C.

The fuel used for the cathode may include H ₂ O, CO ₂ and H ₂ .

In addition, the present invention provides a flat cell-based electrolysis module including a flat tube type electrolytic cell manufactured by the manufacturing method and the flat tube type electrolytic cell.

The flat tube type electrolytic cell of the present invention compensates for the shortcomings of the tubular type electrolytic cell and the flat type electrolytic cell, and has an excellent syngas conversion rate and can generate syngas even at low overvoltage.

1 is a view showing the structure of a flat tube cell.
2 is a view showing a mixing process of step 1 of the present invention.
3 is a view showing a process of kneading the mixture of step 3 of the present invention and the process of extruding the paste.
4 is a view showing a process of rolling and drying the support for the extruded orbital cell of step 4 of the present invention.
5 and 6 are views showing a process of coating the cathode of step 5 of the present invention, and then coating the electrolyte and the anode.
7 is a view showing a completed flat tubular revolution cell.
8 is a view showing an end face of a flat tubular orbiting cell.
9 is a view showing an atmospheric pressure high temperature electrolytic module including a flat tubular electrolytic cell.
10 and 11 are graphs showing an IV curve in which a high temperature and high temperature electrolysis cell was operated.
12 is a graph showing the impedance of operating a high-temperature, high-voltage revolution cell.
13 is a graph showing Gas Chromatography driving an atmospheric pressure high temperature electrolysis cell.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings. Terms or words used in the present specification and claims are not limited to interpretation in a conventional or dictionary meaning, and should be interpreted as meanings and concepts consistent with technical aspects of the present invention.

A flat-tubular orbital cell according to an embodiment of the present invention comprises a flat tubular support comprising NiO and YSZ; A cathode layer formed on the flat tubular support surface; A solid electrolyte layer formed on the surface of the cathode layer; And an anode layer formed on the surface of the solid electrolyte layer.

An orbiting cell is a device that produces syngas by electrolysis reaction by injecting carbon dioxide and steam to the cathode, injecting air into the anode, and applying electricity while maintaining high temperature, to obtain reusable fuel from carbon dioxide. It is a new and renewable energy production device. Conventional orbital cells include tubular and flat cells, but the tubular is resistant to harsh operating environments but has low performance, and the flat type is high in performance but vulnerable to harsh operating environments. The flat-type cell has excellent performance for high performance and high capacity, and has strong mechanical strength, so it can be easily configured in a stack.

The flat tubular support may be a plate shape including a plurality of hollow flow paths.

In the flat tubular support, the plurality of hollow flow paths may have a cylindrical shape and be aligned in a predetermined direction.

In the flat tubular support, the diameter of the circular cross section of the cylinder may be 0.1 to 0.2 cm. When the diameter of the cross-section is less than 0.1 cm, sufficient flow paths are not formed to degrade the performance of the cell, and when the diameter of the cross-section is 0.2 cm or more, it is difficult to maintain the shape of the support.

The flat tubular support may be NiO, YSZ may be a cermet of nickel (NiO)/Yttria Stabilized Zirconia (YSZ), but is not limited thereto.

The cathode layer is a metal-ceramic composite of Ni-YSZ, a perovskite-based ceramic cathode in _{LSCM (... (La 0.75} , Sr 0 25) 0.95 Mn 0 5 Cr 0 5 O 3), the LST-based ceramic cathode (Sr _{1 - x} La _x )(Ti _{1 - y} M _y )O ₃ (M = V, Nb, Co, Mn) may be used, but is not limited thereto.

In particular, it is preferable to use (Sr _{1 - x} La _x )(Ti _{1 - y} M _y )O ₃ (M = V, Nb, Co, Mn) as the cathode layer. The LST-based ceramic cathode (Sr _{1 - x} La _x ) (Ti _{1 - y} M _y )O ₃ (M = V, Nb, Co, Mn) has excellent redox resistance and contains a high concentration of H ₂ O in the fuel Even if the redox cycling does not occur, the electrical conductivity and mechanical strength can be kept constant.

The anode layer may use what is commonly known in the art to which the present invention pertains, and for example, LSCF-GDC, YSZ/LSM and LSM composite may be used, but is not limited thereto.

The solid electrolyte layer includes YSZ (yttria stabilized zirconia), LSGM (lanthanum gallate doped with Sr and Mg), ScSZ (scandia stabilized zirconium oxide), GDC (gadolinia doped ceria), SDC (samaria doped ceria), etc. It may include.

Hereinafter, a method of manufacturing a flat tube type electrolytic cell of the present invention will be described with reference to FIGS. 2 to 6.

Figure 2 is a view showing a mixing process of step 1 of the present invention, Figures 2 and 3 are views showing a process of kneading the mixture of step 3 of the present invention and extruding the paste, Figure 4 is the present invention It is a view showing a process of rolling and drying the support for the extruded orbital cell of step 4 of the step. 5 and 6 are views showing a process of coating the cathode of step 5 of the present invention, and then coating the electrolyte and the anode.

First, the present invention Flat Orbital cell used Flat As a step of mixing the raw materials to prepare a support, NIO, YSZ and a pore-forming agent are mixed, followed by ball milling (step 1).

NIO, YSZ may be a cermet of nickel (NIO)/Yttria Stabilized Zirconia (YSZ), and the pore-forming agent is for forming the flat tubular support porously, and as a pore-forming agent Carbon black, activated carbon, and the like can be used.

The mixture of NIO, YSZ and activated carbon or carbon black can be homogenized by ball milling, and in order to increase uniformity, ethanol is added as a solvent to prepare a slurry to perform a ball milling process.

At this time, the pore-forming agent is preferably included in 3 to 10 parts by weight relative to the raw material powder NIO, YSZ.

Next, the mixture prepared in step 1 is dried and screened in a hot plate (step 2).

Drying may be performed at 80°C to 100°C for 12 hours to 48 hours.

Screening is a process for sorting powders having a uniform particle size from a mixture having different particle sizes through sieving, and it is preferable to use a sieve of 80 to 120 mesh.

Next, an additive is added to the mixed powder prepared in step 2 above. Kneaded Paste Manufactured, put into a flat tube mold, and then extruded to prepare a support for a flat tube type electrolytic cell (step 3).

The flat tube mold includes a plurality of protrusions, and the protrusions are in the form of cylinders, and may be aligned in a predetermined direction.

Additives may include binders, plasticizers and lubricants. Each material may use what is commonly known in the art to which the present invention pertains. For example, methyl cellulose, hydroxypropyl methyl cellulose, etc. may be used as the binder, and the plasticizer may be used. As the furnace, propylene carbonate, polyethylene glycol, dibutyl phthalate, etc. may be used, and stearic acid may be used as the lubricant.

The binder is preferably added in an amount of 15 to 20 parts by weight based on 100 parts by weight of the NIO, YSZ mixed powder, which is a raw material powder, and when the binder is added in less than 15 parts by weight, the moldability of the cell support is reduced and the pore formation rate is reduced. When the binder is added in excess of 20 parts by weight, the pores are excessively formed, and the strength is lowered and cracks may occur in the sintering process.

The plasticizer is preferably added in 4 to 8 parts by weight based on 100 parts by weight of the NIO, YSZ mixed powder as the raw material powder. When the plasticizer is added in less than 4 parts by weight, deformation and cracking of the extruded body may occur, and the plasticizer When is added in excess of 8 parts by weight, the ductility of the extruded body is excessively increased, so that a warp phenomenon may occur after sintering.

The lubricant is preferably added in 2 to 6 parts by weight based on 100 parts by weight of the NIO, YSZ mixed powder as the raw material powder, and when the lubricant is added in less than 2 parts by weight, a surface peeling problem of the extruded body may occur. When the lubricant is added in excess of 6 parts by weight, stripes may be formed on the surface by adhesive force between the extruded body and the mold.

Prepared in step 3 Flat After the support is rolled and dried to minimize damage to the surface, Plastic Go through the process (step 4).

The process of rolling and drying is shown in FIG. 4, and the process of plasticizing is preferably performed through a stepwise temperature increase.

Specifically, the plastic sintering process, the temperature of the flat tubular support prepared in step 3 is raised for 8 hours to 12 hours, and then maintained at 300°C to 400°C for 3 hours to 7 hours, and again for 3 hours to 7 hours. The temperature is maintained for 2 hours to 4 hours at 700°C to 800°C. Finally, the temperature may be increased for 3 to 7 hours to maintain the temperature for 2 to 4 hours at 1000°C to 1200°C.

If, instead of going through a stepwise temperature rise, it is immediately heated to 1000°C to 1200°C to perform plastic sintering, the pore forming agent rapidly forms pores, and thus cracks are generated in the support by pores, and the durability of the support is reduced due to cracks. do.

Finally, in step 4 Sintered Flat Orbital cell support Cathode , Electrolyte, Anode Coating (step 5).

Orbital to the cathode which can be used in the cell is a metal-ceramic composite of Ni-YSZ, a perovskite-based ceramic cathode _{LSCM ((La 0 .75, Sr} 0 25) 0.95 Mn 0 5 Cr 0 5 O 3... ), LST series ceramic cathode (Sr _{1 - x} La _x ) (Ti _{1 - y} M _y )O ₃ (M = V, Nb, Co, Mn) may be used.

In particular, it is preferable to use (Sr _{1 - x} La _x ) (Ti _{1 - y} M _y )O ₃ (M = V, Nb, Co, Mn), which is an LST-based ceramic cathode, where LST-based ceramic cathode is hydrogen. This is because, even when the CO reducing gas flow is used in an unsatisfied condition, it does not oxidize and thus does not impair the properties of the cathode.

That is, since the LST-based ceramic cathode has excellent redox resistance, even when a high concentration of H2O is contained in the fuel, redox cycling does not occur, so that electrical conductivity and mechanical strength can be kept constant.

On the other hand, if the cathode has a P-type conduction mechanism in which charge moves through the hole, it induces a strong reduction potential, which causes resistance to polarize the electrode. That is, a cathode having a P-type conduction mechanism causes a chemical and structural change of the cathode, and thus has a short lifespan because it is easily damaged.

However, the LST-based ceramic cathode has an N-type conduction mechanism that induces a negatively charged free electron carrier to induce current, so it exhibits relatively stable behavior under reducing conditions without the problem of electrode polarization, such as P type. It can exhibit excellent life and electrode characteristics.

In addition, to improve the efficiency of the chemical and electrochemical reactions of the cathode, a process of improving the activity of the cathode surface may be further included.

The process of coating the cathode on the support may be performed by a dip coating method as shown in FIG. 6, and after coating, the temperature is raised at a heating rate of 80° C./h to 120° C./h, and then 800° C. to 1200 It may include the step of heat treatment for 2 to 3 hours at ℃, and may further include the step of cooling at a rate of 200 ℃ / h to 300 ℃ / h after heat treatment. However, the coating method is not limited to this, and any applicable coating method such as a screen printing method can be used.

As the electrolyte, those known in the art to which the present invention pertains can be used. For example, yttria stabilized zirconia powder (YSZ powder), Sr and Mg doped lanthanum gallate powder (LSGM powder), scandia stabilized zirconium oxide powder (ScSZ powder), gadolinia doped ceria powder (GDC powder), Samaria doped ceria powder (SDC powder) may be used, but is not limited thereto, and may be coated by a vacuum slurry coating method.

After coating the electrolyte by a vacuum slurry coating method on a cathode-coated support, heating at a heating rate of 80°C/h to 120°C/h and heat-treating at 1200°C to 1600°C for 3 to 7 hours. After the heat treatment, it may further include a step of cooling at a rate of 200°C/h to 300°C/h.

After coating and heat-treating the electrolyte, an anode may be coated on the cathode and the electrolyte-coated support by the immersion coating method. The anode may use what is commonly known in the art to which the present invention pertains, for example, LSCF-GDC may be used, but is not limited thereto. It can also be coated by screen printing.

After the anode is immersed and coated, it is heated at a rate of 80°C/h to 120°C/h and heat-treated at 1000°C to 1300°C for 2 to 4 hours, and after heat treatment is 200°C/h to 300°C Cooling at a rate of /h may further include.

The flat tube type electrolysis cell manufactured by the above method can simultaneously convert carbon dioxide and steam to convert to syngas fuel with high efficiency, and is excellent in durability as well as easy in high temperature and pressurized operation.

<Example 1> Production of flat tubular revolution cell

1) Preparation of support

8YSZ (8 mol% yttria-stabilized zirconia) powder and NiO (JT Baker Co., USA) powder were mixed in a volume ratio of NiO:8YSZ=40:60 to make a mixed powder, mixed with carbon black, ball milled and homogenized. , Dried and sieved to obtain a uniform mixed powder.

After adding an additive such as an organic binder, distilled water, a plasticizer, a lubricant to the produced NIO/YSZ powder, kneading and pasting, the paste is put into a flat tube mold, then extruded and dried to produce a flat tube support. Did. The diameter of the circular cross-section of the protrusion of the flat tube mold is 0.16 cm, and the flat tube mold includes 14 protrusions.

The support was heated for 10 hours and maintained at 350°C for 5 hours, again heated for 5 hours and maintained at 750°C for 3 hours, and finally heated for 5 hours and held at 1100°C for 3 hours to sinter.

2) Cathode coating

The pre-sintered support was screen-printed with NI-YSZ to form a cathode, heated to 100° C./h, maintained at 1000° C. for 3 hours, and then cooled at a rate of 250° C./h to heat treatment.

3) Electrolytic coating

This was coated with an electrolyte using a vacuum slurry coating method, heated to 100° C./h, maintained at 1400° C. for 5 hours, and then cooled at a rate of 250° C./h to heat treatment.

4) Anode coating

After the heat treatment, an anode was formed by screen printing with YSZ/LSM and LSM composite, heated to 100° C./h, maintained at 1150° C. for 3 hours, and then cooled at a rate of 250° C./h to heat treatment.

The flat tubular orbital cell prepared in the above manner is illustrated in FIG. 7, and the reaction area of the flat tubular orbital cell was 10 cm ² .

On the other hand, Figure 8 is a picture taken by SEM of the cross section of the flat-type orbital cell, referring to Figure 8, the cathode layer and the electrolyte layer prepared by the above method are 12 um, 9 um, respectively, the anode layer It can be seen that it has a thickness of 25 um.

<Experiment> Current collection before the experiment of flat tubular cell

The cell cap is fixed on the inlet and outlet sides to seal it completely. Upon sealing, the temperature is raised to 120°C for 50 minutes, maintained for 1 hour, then heated to 750°C for 6 hours, and then maintained for 3 hours, and then cooled to 100°C/h. After that, the sealed cell is fixed to both ends using Ag paste on both sides of the cathode and anode using Ag and Pt wire.

<Experimental Example 1> Atmospheric pressure electrolysis experiment of a flat tube type electrolysis cell

Ag, Pt wire was used as a current collector to collect the flat tube type electrolytic cell prepared in Example 1, and a normal pressure using an atmospheric pressure type electrolytic evaluation system composed of a water pump, DC power supply, and GC as shown in FIG. 9. An orbital experiment was carried out at. When setting up the experiment, fuel flows through the tube in the cell interior without the need for a flow line that was used in the existing flat plate. When adding hydrogen, CO ₂ , and H ₂ O during idle, the volume of the gas increases as the temperature of the gas rises, and a vaporizer is placed in front of the cell to increase the gas mixing and stability. Thereafter, the temperature was raised to 400°C for 3 hours, and then maintained for 1 hour. After heating to 650°C at 100°C/h, the flow rates of the cathode and the anode were reduced to 200 ml/min for H ₂ and 300 ml/min for air, respectively, and reduced for 15-18 h. . After sufficiently reducing, it is heated up to 100°C/h to 800°C. Thereafter, the flow rates of the cathode and the anode were changed to the flow rate by orbiting, and the flow rates were respectively 200 ml/min. For comparison with the water electrolysis, the flow rate ratio was measured by increasing H ₂ O = 60% and increasing CO ₂ from 0 to 30% in 10% increments. The performance data measured at this time is shown in FIG. 10.

As a result of the experiment, it was confirmed that the overvoltage of the entire reaction decreased as carbon dioxide was added. This is thought to be because hydrogen and carbon dioxide were added to the fuel to react and hydrogen and carbon dioxide participated in a reverse water gas shift (RWGS).

<Experimental Example 2> IV Curve Experiment of Flat Tubular Electrolysis Cell

After fixing the total flow rate at 200 ml/min, H ₂ O: CO ₂ = 1: 1, 2: 1, 3: 1 was injected to measure the voltage change according to each current density. The performance data measured at this time is shown in FIG. 11. As a result of the experiment, it was found that the electrochemical performance increased as the injection fraction increased, but in the case of the injection fraction 2,3, the difference in electrochemical performance was not large, about 6.5%. At low current densities, it increases linearly due to the electrolysis of steam, and at high current densities, steam is consumed, and the CO ₂ composition having a relatively high activation potential becomes dominant.

<Experimental Example 3> Impedance experiment of flat tube type electrolytic cell

After fixing the total flow rate at 200 ml/min, each impedance was measured in the OCV state where no current was applied by injecting H ₂ O: CO ₂ = 1: 1, 2: 1, 3: 1 in a fraction. The measured performance data at this time is shown in FIG. 12. As a result of the experiment, there was no significant difference because the ohmic resistance was the current resistance according to each injection fraction, but the polarization resistance was highest when the H ₂ O/CO ₂ ratio was 1 and decreased in the order of 2,3. . In the case of the injection fraction 1, the polarization resistance was the highest because the partial pressure of CO2 having a relatively low diffusion rate and high potential for decomposition was the highest. It can be seen that the polarization resistance is significantly reduced at the injection fractions 2 and 3 having a relatively low partial pressure of CO ₂ .

<Experimental Example 4> Gas Chromatography experiment of flat tube type electrolytic cell

After fixing the total flow rate at 200ml/min, inject H2O:CO2 = 1:1, 2:1, 3:1 into fractions starting from OCV with a current density of 0, and perform gas chromatography on each off-gas at a constant current density. Analysis. (When the ratio of H ₂ and CO of off-gas is close to 2, it is the ideal value for producing synthetic fuel.) The measured performance data is shown in FIG. 13. As a result of the experiment, it can be seen that as the current density increases, the slope of CO production compared to hydrogen is small. Also, at all current densities, injection fraction 1 with high CO2 partial pressure had the highest CO production. It can be seen that H ₂ decomposed from steam inside the anode activates the CO ₂ and RWGS reactions and contributes to CO production, thus reducing the production of H ₂ . In the injection fraction 3, since the proportion of steam is relatively high, CO production is suppressed and H2 production increases. In particular -2800 mA / cm ² of the high became close to the ideal value measured at a current density in a 2.15 ratio of H ₂ / CO 2 produced in the injection fraction and the increase of the H ₂ reduction in the current density and the production of CO Increased. The injection fractions 1 and 3 have off-gas ratios of 1.60 and 3.64, and a separate hydrogen reprocessing process is additionally required during the synthesis fuel production process. Accordingly, it was confirmed that the injection fraction 2 was the most suitable injection fraction.

In the above, the technical idea for the present invention has been described together with the accompanying drawings, but this is a preferred embodiment of the present invention and is not intended to limit the present invention. In addition, it is obvious that anyone who has ordinary knowledge in this technical field can make various modifications and imitation without departing from the scope of the technical idea of the present invention.

Claims (19)

A flat tubular support comprising NIO and YSZ;
_{(- x} La _x Sr ₁₎ formed in the flat tubular support _surface including a _{(Ti 1 y M y) O} 3 (M = V, Nb, Co, Mn) a cathode layer;
A solid electrolyte layer formed on the surface of the cathode layer; And
An anode layer formed on the surface of the solid electrolyte layer; comprising a flat tubular electrolytic cell. According to claim 1,
The flat tubular support is a flat tubular orbiting cell, characterized in that it is a plate-like shape including a plurality of hollow flow paths. According to claim 2, In the flat tube support,
The plurality of hollow flow paths are in the form of cylinders, and a flat tubular orbiting cell, characterized in that arranged in a predetermined direction. According to claim 3, In the flat tube support,
A flat tubular orbiting cell, characterized in that the diameter of the circular cross section of the cylinder of the plurality of hollow flow paths is 0.1 to 0.2 cm. According to claim 1,
The solid electrolyte layers are YSZ (yttria stabilized zirconia), LSGM (lanthanum gallate doped with Sr and Mg), ScSZ (scandia stabilized zirconium oxide), GDC (gadolinia doped ceria) and SDC (samaria doped ceria). A flat tubular orbital cell, comprising at least one material selected from the group consisting of. According to claim 1,
The anode layer is a LSCF-GDC or YSZ-LSM and a flat tubular orbital cell, characterized in that it comprises an LSM complex. According to claim 1,
The fuel used for the cathode layer is H ₂ O, CO ₂ and H ₂ flat tubular electrolysis cell, characterized in that it comprises. After mixing NIO, YSZ and pore former, mixing with a solvent to prepare a slurry to perform ball milling (Step 1);
Drying the slurry and then pulverizing it (step 2);
Adding an additive to the powdered mixture and kneading to prepare a paste, putting the paste into a flat tube mold, and then extruding to orbit to prepare a support for a cell (step 3);
Rolling and drying the support for the extruded orbital cell (step 4); And
Including the step of plasticizing the support for the rolled dry electrolytic cell, coating the cathode, electrolyte and anode (step 5); includes,
The cathode (Sr _{1 - x} La _x ) (Ti _{1 - y} M _y ) O ₃ (M = V, Nb, Co, Mn) comprises a flat tubular electrolytic cell manufacturing method. The method of claim 8,
The pore forming agent is a flat tube type electrolytic cell manufacturing method, characterized in that at least one selected from the group consisting of activated carbon and carbon black. The method of claim 8,
The additive is a flat tube type electrolytic cell manufacturing method comprising a binder, a plasticizer and a lubricant. The method of claim 8,
The plastic sintering method of manufacturing a flat-type orbital cell made by a stepwise heating up to 300°C to 400°C, heating to 700°C to 800°C, and then heating to 1000°C to 1200°C. The method of claim 8,
The cathode and the anode is a flat tube type electrolytic cell manufacturing method characterized in that the coating by a dip coating (dip coating) or screen printing method. The method of claim 12,
A method of manufacturing a flat tube type electrolytic cell, wherein the cathode is coated and then heat-treated at 800°C to 1200°C. The method of claim 12,
A method of manufacturing a flat tube type electrolytic cell, characterized in that, after coating the anode, heat treatment is performed at 900°C to 1400°C. The method of claim 8,
The electrolyte is a flat slurry type electrolytic cell manufacturing method characterized in that it is coated by a vacuum slurry coating method (vacuum slurry coating). The method of claim 15,
A method of manufacturing a flat tube type electrolytic cell, characterized in that heat treatment is performed at 1200°C to 1600°C after coating the electrolyte. The method of claim 8,
The fuel used in the cathode is H ₂ O, CO ₂ and H ₂ method for manufacturing a flat-type revolution cell, characterized in that it comprises. A flat tubular orbital cell produced by any one of claims 8 to 17. A flat cell based electrolysis module comprising the flat cell of claim 18.

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