KR100534022B1 - Unit cell of honeycomb-type solid oxide fuel cell by the method of Mixed Gas Fuel Cell, stack design using thereit, method to work the same - Google Patents

Abstract

In the present invention, a honeycomb SOFC unit cell comprising: a fuel electrode channel having a catalyst for hydrocarbon partial oxidation (oxyreforming), into which a mixed gas of hydrocarbon and air is injected; An anode channel installed independently of the anode channel and having a hydrocarbon inert catalyst and into which a mixed gas of hydrocarbon and air is injected; And an ion conductive solid electrolyte layer formed between the anode channel and the cathode channel. The single cell of the honeycomb SOFC by the MGFC method is further disclosed. The honeycomb type SOFC according to the MGFC method is characterized in that a net-shaped current collector having a pore size having the same size as the pore size of the anode channel and the cathode channel of the battery is installed at the upper end or the lower end of the anode channel and the cathode channel. Disclosed is a stack structure using a single cell, and further comprising the steps of: filling or coating a catalyst powder for hydrocarbon partial oxidation in a cathode channel of a honeycomb SOFC stack structure (S1); Filling or coating a hydrocarbon inert catalyst powder in the cathode channel of the honeycomb SOFC stack structure (S2); And injecting a mixed gas of hydrocarbons and air into the anode channel and the cathode channel at the same time (S3). The method of operating a honeycomb SOFC according to the MGFC method comprises a. In the honeycomb type SOFC according to the unit cell of the honeycomb type solid oxide fuel cell using the mixed gas fuel cell method, the stack structure using the same, and a method of operating the same, in the honeycomb type SOFC, the hydrocarbon and the air mixed gas are directly added to the cathode and the anode. By injecting, it is possible to operate the honeycomb type SOFC battery without the need for gas sealing, and has the advantage of being resistant to thermal shock and easy to stack in the z-axis direction. In addition, it is possible to increase the output density by maximizing the fuel cell reaction area per unit volume, and to improve the conversion of hydrocarbons by the hydrocarbon partial oxidation catalyst charged on the anode side, thereby solving the carbon deposition problem on the anode side. In addition, the catalyst for hydrocarbon partial oxidation formed in the anode side channel can maintain a reducing atmosphere at low temperatures during the heat cycle, thereby minimizing the cell structure change due to oxidation-reduction of the anode. In addition, since the anode channel is formed independently of the cathode channel, anode fuels such as hydrogen and carbon monoxide generated on the anode side can be prevented from mixing with cathode fuel, that is, oxygen, thereby achieving high open circuit voltage and cell performance. In addition, it is possible to reduce the crossover phenomenon between the anode and the cathode than the conventional MGFC-type SOFC stack. In addition, by manufacturing the electrolyte in a honeycomb form, it is possible to use a conventional extrusion process and the like, thereby lowering the manufacturing cost.

Description

Unit cell of honeycomb-type solid oxide fuel cell by the method of Mixed Gas Fuel Cell, stack design using thereit, method to work the same}

The present invention is referred to as a honeycomb-type (hereinafter referred to as honeycomb type) solid oxide fuel cell (SOFC) by a mixed gas fuel cell (hereinafter referred to as MGFC) method. ), A stack structure using the same, and a method of operating the same, and more particularly, a low-cost, stable and direct operation on a hydrocarbon fuel, which can improve gas sealing problems and low thermal shock resistance caused by a conventional SOFC structure. The present invention relates to a unit cell of a honeycomb type SOFC by a MGFC method having a structure, a stack structure using the same, and a method of operating the same.

In general, SOFCs are classified into cylindrical and flat plates according to the shape of the unit cell.

In the case of the cylindrical SOFC, an expensive process such as an electrochemical vapor deposition (EVD) method is required instead of gas sealing, and a current collecting distance between electrodes is large, so that internal resistance is large.

On the contrary, the flat plate type SOFC has advantages in that the manufacturing process cost is low and the current collecting distance is short due to the use of a wet process, but the internal resistance of the stack is large due to difficulty in gas sealing and uneven thickness between cells.

Therefore, various attempts have been made to overcome the shortcomings of the above-described type of SOFC, and various types of SOFC unit cells and stack structures have been developed to improve the performance and light weight of the solid oxide fuel cell. Representative examples are anode-supported SOFCs and honeycomb-type SOFCs capable of reducing the film thickness to 10 µm or less.

The anode-supported SOFC is a unit cell structure that forms a thin film electrolyte of 10 μm or less by using porous NiO and YSZ cermet as a support, and many of them exhibit high-performance unit cell performance of 1 W / cm ² or more recently. Although reported <SD Souza, SJ Visco, and LC De Jonghe, Thin-film Solid Oxide Fuel Cell with High Performance at Low-temperature, Solid State Ionics, 98, p.57-61, 1997> The mechanical stress due to the difference in thermal expansion coefficient of the, the electrical conductivity is reduced by the oxidation of the metal separator plate, and the structural stability due to the oxidation-reduction of the anode during the thermal cycle, the battery stability is greatly reduced.

The honeycomb SOFC is a stack structure that helps to improve the output density per unit volume by widening the reaction area of the cell.

However, the honeycomb SOFC also has a drawback in that the current collector and fuel gas supply part are very complicated due to the problem of the existing cell that must separately supply the fuel gas and air <US Patent Nos. 4,499,663, 4,476,198, 4,510,212 4,476,197, 6,551,735, 4,476,196.

As such, in order to commercialize SOFC, a cheap manufacturing process, a structure having stable performance, in particular, a structure capable of thinning and shortening to solve gas sealing problems are essential. It has not been solved, and a process suitable for commercialization of SOFC has not been developed yet.

Meanwhile, new researches on single chamber cells or MGFCs (see US Patent No. 4,248,941) using the catalytic activity difference of hydrocarbons of electrodes have been conducted.

When MGFC technology supplies a mixture of hydrocarbons and air as fuels to the cathode and anode simultaneously, the anode discharges hydrogen and carbon monoxide with catalytic activity for hydrocarbons, and the cathode is inert for hydrocarbons, resulting in a potential difference between the two electrodes. The principle is to operate the battery based on what is generated.

As an example, great Bono (Hibino) such experiment, the output density by using a gas mixture of ethane and air at operating temperatures of 500 ℃ may bar a report that it is possible to manufacture a 0.4W / cm ² in a single chamber of the SOFC <Science vol. 288, p.2031 (2000)>.

However, in the case of the MGFC, the stack structure is very important because the mixed gases generated in the unit cells may be sequentially mixed in the gas flow direction. However, an appropriate stack structure for this MGFC has not been proposed yet.

In addition, in the case of the conventional MGFC has a problem that carbon deposition occurs on the anode side to block the electrochemical reaction site, greatly reducing the battery performance.

Therefore, the present invention has been made to solve the above problems,

It is an object of the present invention to provide a single cell of a honeycomb type SOFC by MGFC method, a stack structure using the same, and a method of operating the same, which have a strong thermal shock resistance and are easy to be laminated as gas sealing is unnecessary.

Another aspect of the present invention, MGFC method that can maintain the reducing atmosphere at low temperatures during the heat cycle to minimize cell structure changes due to oxidation-reduction of the anode, and to simplify the current collector and fuel gas supply portion The present invention provides a honeycomb SOFC unit cell, a stack structure using the same, and a method of operating the same.

Another aspect of the object of the present invention is that the honeycomb by the MGFC method can achieve a high open-circuit voltage and battery performance because it can block the mixing by the diffusion of the reaction gases observed in conventional cells of the MGFC type The present invention provides a single cell of a SOFC, a stack structure using the same, and a method of operating the same.

Another aspect of the present invention is to provide a single cell of a honeycomb type SOFC by the MGFC method, a stack structure using the same, and a method of operating the same, which can solve the problem of carbon deposition in the anode by the unreacted hydrocarbon fuel.

Another aspect of the object of the present invention is the honeycomb SOFC by the MGFC method, which realizes the high mechanical strength of the honeycomb SOFC and can achieve a high power density due to the maximum fuel cell reaction area per unit volume. A single cell, a stack structure using the same, and a method of manufacturing the same are provided.

Another aspect of the object of the present invention is to use an inexpensive process such as extrusion (extrusion) method for manufacturing the electrolyte in a honeycomb type, the unit cell of the honeycomb SOFC by the MGFC method, which can significantly lower the manufacturing cost, this It is to provide a stack structure and a method of operation thereof.

An object of the present invention as described above, in the honeycomb type SOFC unit cell, having a catalyst for hydrocarbon partial oxidation (oxyreforming), the anode channel, a mixed gas of hydrocarbon and air is injected; An anode channel installed independently of the anode channel and having a hydrocarbon inert catalyst and into which a mixed gas of hydrocarbon and air is injected; And an ion conductive solid electrolyte layer formed between the anode channel and the cathode channel.

In the unit cell, it is preferable that the anode channel and the cathode channel have a structure formed alternately while being adjacent to each other with an ion conductive solid electrolyte layer interposed therebetween.

The hydrocarbon inert catalyst is preferably alumina, silica or zirconia.

And the anode material is Pt; Ag; Au; Rh; Ir; Pd; Ru; Ni; And Cu; at least one metal selected from the group consisting of: and a cermet of an ion conductive ceramic material.

And, the cathode material, Pt; Ag; Au; Rh; Ir; Pd; Ru; (La _1-X Sr _X ) MnO ₃ wherein x is 0.5 or less; (La _1-X Car _X ) MnO _{3 wherein} x is 0.5 or less; x is 0.6 or less (La _1-X Sr _X ) CoO ₃ ; And at least one metal or oxide selected from the group consisting of (La _1-X Sr _X ) (Co _1-y Fe _y ) O _3, wherein x is 0.4 or less and y is 0.8 or less.

An object of the present invention as described above is also, a plurality of unit cells are stacked, the net current collector having a pore size having the same size as the pore size of the anode channel and the cathode channel of the unit cell is the anode channel and the cathode channel. It is achieved by a stack structure using a single cell of a honeycomb SOFC by the MGFC method, characterized in that it is installed at the upper end or the lower end of.

In addition, the current collector is preferably made of metal, and preferably made of Pt, Ag, Au, Ni, Cu, or an alloy thereof.

In accordance with another aspect of the present invention, there is also provided a method of operating a honeycomb SOFC, comprising: filling or coating a catalyst powder for hydrocarbon partial oxidation in an anode channel of a honeycomb SOFC stack structure (S1); Filling or coating a hydrocarbon inert catalyst powder in the cathode channel of the honeycomb SOFC stack structure (S2); And simultaneously injecting a mixed gas of a hydrocarbon and air into the anode channel and the cathode channel (S3). The method of operating a honeycomb type SOFC according to the MGFC method comprises a.

And, the hydrocarbon is preferably methane, ethane, propane, butane, light oil or gasoline.

Hereinafter, a single cell of a honeycomb type SOFC by the MGFC method according to the present invention, a stack structure using the same, and a method of operating the same will be described in detail.

The honeycomb SOFC by the MGFC method according to the present invention is prepared by filling or coating a honeycomb SOFC anode channel with a catalyst for POX suitable for hydrocarbon partial oxidation, and injecting a mixture of hydrocarbon gas, that is, methane, ethane, butane, propane and air. On the anode side, partial oxidation reforming of the hydrocarbon fuel produces hydrogen and carbon monoxide and minimizes carbon deposition. On the cathode side, the potential difference between the two electrodes occurs due to inertness to the catalytic reaction. Will work.

1 is a conceptual diagram illustrating an electrolyte, an electrode, and a stack structure of a unit cell according to an embodiment of the present invention.

As shown in FIG. 1, in the unit cell according to the exemplary embodiment of the present invention, the cathode 20 channel and the anode 10 channel are formed with the electrolyte 30 interposed therebetween. It holds a hydrocarbon inert catalyst 25 and the anode 10 channel holds a catalyst 15 suitable for hydrocarbon partial oxidation.

As the material of the anode 10, Pt; Ag; Au; Rh; Ir; Pd; Ru; Ni; And Cu; and a cermet of any one metal selected from the group consisting of Cu and an ion conductive ceramic material, wherein the cathode 20 material comprises: Pt; Ag; Au; Rh; Ir; Pd; Ru; (La _1-X Sr _X ) MnO ₃ wherein x is 0.5 or less; (La _1-X Car _X ) MnO _{3 wherein} x is 0.5 or less; x is 0.6 or less (La _1-X Sr _X ) CoO ₃ ; Preference is given to using at least one metal or oxide selected from the group consisting of (La _1-X Sr _X ) (Co _1-y Fe _y ) O ₃ ; wherein x is 0.4 or less and y is 0.8 or less.

At this time, a method of allowing the channel to have a catalyst includes, for example, a method of filling a catalyst into the channel, or a method of surface coating the surface of the channel with the catalyst.

As the hydrocarbon partial oxidation catalyst 15 held in the anode 10 channel, for example, a catalyst such as Ni, Co, Pt, or Pd may be used, and methane, ethane, propane, butane, or the like may be used. Commercially available hydrocarbon partial oxidation catalysts suitable for the respective hydrocarbons can be used.

In addition, a low-cost ceramic powder such as alumina, silica, zirconia, or the like may be used as the hydrocarbon inert catalyst 25 held in the cathode 20 channel.

In addition, the packing density of the catalyst per unit volume of each channel is the same.

Meanwhile, as shown in FIG. 1, in the unit cell, the anode 10 channel and the cathode channel 20 are alternately formed while being adjacent to each other with the ion conductive solid electrolyte layer 30 interposed therebetween, that is, In the case of any one of the anode 10 channels, the anode 20 channel is interposed between the cathode conductive solid electrolyte layer 30 and, for example, a channel having a rectangular pillar shape as shown in FIG. 1. It is formed so as to adjoin on four sides, three sides, or two sides.

Likewise, in the unit cell, any one cathode channel 20 is formed in the form of a rectangular pillar as shown in FIG. 1 and a cathode 10 channel with an ion conductive solid electrolyte layer 30 interposed therebetween. In the case of a channel, it is formed to be adjacent on four, three, or two sides of the periphery.

In the stack structure in which a plurality of unit cells are stacked, as illustrated in FIG. 1, the size of a hole of each channel may be formed at an upper end or a lower end of the anode 10 channel and the cathode 20 channel of the unit cell. A mesh-shaped metal current collector 40 having a hole size of a size is installed. In this case, the current collector 40 may use a general metal, or may use Pt, Ag, Au, Ni, Cu, or an alloy thereof.

A mixed gas of hydrocarbon and air is injected into each channel of the stack structure, and unreacted fuel passed outside of the stack can be burned in a device such as a boiler or gas turbine to supply heat to SOFC or generate power separately. The other heat becomes available as waste heat.

Fabrication of a stack structure of a honeycomb SOFC by the MGFC method according to the present invention is as follows.

First, in order to thin the electrolyte, the porous honeycomb anode support is manufactured by extrusion method, and then calcined at a predetermined temperature and time to be primary molded.

At this time, the support to have a 30% or less of the Gd is doped is CeO _2, Sm of not more than 30% doped CeO _2, 30 with a Y% or less doping of CeO _2, less than 20% Y ₂ O ₃ doped At least one selected from ZrO ₂ , 20% or less Sc ₂ O ₃ doped ZrO ₂ and LaGaO ₃ series ion conductive ceramics, and a cermet consisting of 50% or more NiO may be used.

Thereafter, the selected channel region in the primary molded body is masked, and the electrolyte is coated but the electrolyte is not coated inside the masked channel.

As the masking material, using a paraffin or a polymer material that can be removed during heat treatment can prevent coating of unwanted portions during electrode coating.

Thereafter, for example, a Yttria-stabilized zirconia (YSZ) slurry is coated on the entire support, and the honeycomb anode support in which the electrolyte is formed into a thin film is finally baked at a predetermined temperature and a predetermined time to complete the anode support.

Thereafter, a cathode-forming material such as LaSrMnO ₃ powder is slurry-coated again on the electrolyte-coated portion and calcined at a predetermined temperature and time to form a cathode to fabricate a unit cell.

Thereafter, a stack is fabricated by collecting and laminating using a metal mesh of, for example, nickel or silver, suitable for the size of the anode and cathode channel and the inter-channel.

The anode channel in the stack structure manufactured as described above is filled with a commercial catalyst powder having high catalytic activity with respect to hydrocarbons (S1), while the cathode channel is filled with, for example, alumina, silica, zirconia and the like which are inert to hydrocarbons. (S2).

At this time, as described above, instead of filling the catalyst in each channel, it is also possible to coat the respective channels.

After filling the catalyst in each channel as described above, and injecting a mixture gas of hydrocarbons and air, such as methane, ethane, butane, propane, etc. (S3), in this way, the hydrocarbon and air mixed gas directly injected into the cathode and anode This eliminates the need for sealing the reactor body. As a result, the SOFC is resistant to thermal shock, and the structure has an advantage of being easily laminated in the z-axis direction.

In addition, it is possible to increase the output density by maximizing the fuel cell reaction area per unit volume, and to solve the problem of carbon deposition on the anode side by increasing the conversion of hydrocarbons by the hydrocarbon partial oxidation catalyst formed on the anode side.

In addition, the hydrocarbon partial oxidation catalyst formed in the anode side channel can maintain the reducing atmosphere at low temperatures during the heat cycle, thereby minimizing the cell structure change due to oxidation-reduction of the anode.

In addition, the anode channel is formed independently of the cathode channel, so that anode fuel such as hydrogen and carbon monoxide generated on the anode side can be prevented from mixing with the cathode fuel, that is, oxygen.

In addition, by supporting the hydrocarbon partial oxidation catalyst on the anode channel side, it is possible to increase the conversion of the hydrocarbon, thereby suppressing carbon deposition in the anode, which has been a problem in the direct reforming of the existing SOFC.

In addition, the honeycomb SOFC stack structure in which the catalyst for hydrocarbon partial oxidation is carried in the anode channel has a crossover between the anode and the cathode than the SOFC stack of the MGFC type of the conventional SOFC, for example, Louis et al. (See USP 4,248,941). (cross-over) phenomenon can be reduced.

In addition, by manufacturing the electrolyte in a honeycomb form, it is expected that the manufacturing cost can be significantly lowered as the existing extrusion process can be used.

Hereinafter, the present invention will be described in more detail by explaining preferred embodiments of the present invention. However, the present invention is not limited to the following examples, and various forms of embodiments can be implemented within the scope of the appended claims, and the following examples are only common in the art while making the disclosure of the present invention complete. It is intended to facilitate the implementation of the invention to those with knowledge.

EXAMPLE

Porous honeycomb anode support (70wt% NiO + 30wt% YSZ cermet) was prepared by extrusion method for thinning of electrolyte and molded by primary firing at 1200 ° C for 4 hours.

Mask each channel by skipping the primary molded body one by one, prevent the electrolyte from being coated inside the masked channel, and then coat the YSZ (8 mol%) slurry on the entire anode support, which is finally baked at 1400 ° C. for 4 hours. The anode support was completed.

At this time, the channel not coated with the YSZ electrolyte was operated as the anode, and the slurry coated LaSrMnO ₃ powder on the electrolyte-coated portion again and calcined at 1100 ° C. for 2 hours to form an cathode.

The unit cell size was 10cm × 10cm × 1cm (thickness), and one module was manufactured with a structure of 10 stacked cells.

In the stack, nickel and silver meshes were selected and stacked according to the size of the anode and cathode channels and the interchannels.

In addition, the catalyst channel (Ni-CeO ₂ and Pt-CeO ₂ ) having high catalytic activity against methane is filled in the anode side channel in the stack structure to increase the hydrogen and carbon monoxide conversion of the fuel gas, and the inert powder (alumina) on the cathode side. Was filled to prevent fuel and air gas from channeling only toward the cathode channel.

2 is a graph showing the performance of a single cell according to an embodiment of the present invention.

As shown in FIG. 2, in the case of a single cell, high performance of 0.2W / cm ² or more was obtained under a 700 ° C., 25% methane and air mixed fuel atmosphere. On the other hand, the stack was able to obtain a performance of 0.5kW / l .

The unreacted hydrocarbon fuel supplied to the cathode was burned to maintain the SOFC stack temperature.

3 is a photograph showing a result of carbon deposition on the anode side after 1000 hours of operation of a fuel cell according to an embodiment of the present invention. FIG. 3A is a photograph showing an anode and an electrolyte interface, and FIG. 3B is an electron probe fine analysis ( The photograph in the case of mapping carbon by electron probe microscopic analysis is shown. In other words, the white point portion indicates the presence of carbon, and in FIG. 3B, it is shown that almost no carbon deposition was formed on the electrolyte and the anode portion.

Therefore, as can be seen in Figure 3b, in the case of a honeycomb solid oxide fuel cell carrying a selective active catalyst for the fuel gas of the present invention, continuous continuous for more than 1,000 hours without carbon deposition on the anode side, which is the biggest problem when using a hydrocarbon fuel You can see that you can drive.

According to a unit cell of a honeycomb solid oxide fuel cell using a mixed gas fuel cell method according to the present invention, a stack structure using the same, and a method of operating the same, in a honeycomb type SOFC, a mixture of hydrocarbons and air is directly applied to the cathode and the anode simultaneously. By injecting, it is possible to operate the honeycomb type SOFC battery without the need for gas sealing, and has the advantage of being resistant to thermal shock and easy to stack in the z-axis direction. In addition, it is possible to increase the output density by maximizing the fuel cell reaction area per unit volume, and to improve the conversion of hydrocarbons by the hydrocarbon partial oxidation catalyst charged on the anode side, thereby solving the carbon deposition problem on the anode side. In addition, the catalyst for hydrocarbon partial oxidation formed in the anode side channel can maintain a reducing atmosphere at low temperatures during the heat cycle, thereby minimizing the cell structure change due to oxidation-reduction of the anode. In addition, since the anode channel is formed independently of the cathode channel, anode fuels such as hydrogen and carbon monoxide generated on the anode side can be prevented from mixing with cathode fuel, that is, oxygen, thereby achieving high open circuit voltage and cell performance. In addition, it is possible to reduce the crossover phenomenon between the anode and the cathode than the conventional MGFC-type SOFC stack. In addition, by manufacturing the electrolyte in a honeycomb form, it is possible to use a conventional extrusion process and the like, thereby lowering the manufacturing cost.

Although the present invention has been described in connection with the above-mentioned preferred embodiments, it is possible to make various modifications or variations without departing from the spirit and scope of the invention. Accordingly, the appended claims will cover such modifications and variations as fall within the spirit of the invention.

1 is a conceptual diagram showing an electrolyte and an electrode, a stack structure of a unit cell according to an embodiment of the present invention;

2 is a graph showing the performance of a unit cell according to an embodiment of the present invention;

3 is a photograph showing a carbon deposition check result of an anode side after 1000 hours of operation of a fuel cell according to an exemplary embodiment of the present invention.

* Short description of the major reference marks *

10: fuel electrode 15: catalyst for hydrocarbon partial oxidation

20: air electrode 25: hydrocarbon inert catalyst

30: ion conductive solid electrolyte 40: current collector (network type)

Claims (9)

In the honeycomb SOFC unit cell, An anode channel having a catalyst for hydrocarbon partial oxidation and into which a mixed gas of hydrocarbon and air is injected; An anode channel installed independently of the anode channel and having a hydrocarbon inert catalyst and into which a mixed gas of hydrocarbon and air is injected; And An ion conductive solid electrolyte layer formed between the anode channel and the cathode channel; honeycomb type SOFC unit cell of the MGFC method comprising a. The method of claim 1, wherein the unit cell, A unit cell of a honeycomb type SOFC according to the MGFC method, wherein the anode channel and the cathode channel are formed adjacent to each other with an ion conductive solid electrolyte layer interposed therebetween. The method of claim 1, wherein the hydrocarbon inert catalyst, A honeycomb SOFC unit cell by the MGFC method, characterized in that it is alumina, silica or zirconia. The method of claim 1, wherein the anode material, Pt; Ag; Au; Rh; Ir; Pd; Ru; Ni; And Cu; at least one metal selected from the group consisting of cermets and a cermet of an ion conductive ceramic material. The method of claim 1, wherein the cathode material, Pt; Ag; Au; Rh; Ir; Pd; Ru; (La _1-X Sr _X ) MnO ₃ wherein x is 0.5 or less; (La _1-X Car _X ) MnO _{3 wherein} x is 0.5 or less; x is 0.6 or less (La _1-X Sr _X ) CoO ₃ ; And at least one metal or oxide selected from the group consisting of (La _1-X Sr _X ) (Co _1-y Fe _y ) O _3, wherein x is 0.4 or less and y is 0.8 or less. Single cell of honeycomb SOFC. A plurality of unit cells according to any one of claims 1 to 5 are stacked, and a net-shaped current collector having a pore size equal to the pore size of the anode channel and the cathode channel of the unit cell includes the anode channel and the cathode. Stack structure using a single cell of a honeycomb SOFC by the MGFC method, characterized in that installed in the upper end or the lower end of the channel. The method of claim 6, wherein the current collector, A stack structure using a single cell of a honeycomb SOFC by the MGFC method, characterized in that it is composed of Pt, Ag, Au, Ni, Cu, or an alloy thereof. In the method of operating honeycomb SOFC, Filling or coating a catalyst powder for hydrocarbon partial oxidation in the anode channel of the honeycomb SOFC stack structure (S1); Filling or coating a hydrocarbon inert catalyst powder in the cathode channel of the honeycomb SOFC stack structure (S2); And And simultaneously injecting a mixed gas of hydrocarbons and air into the anode channel and the cathode channel (S3). The method of claim 8, wherein Method of operating a honeycomb SOFC by the MGFC method, characterized in that the hydrocarbon is methane, ethane, propane, butane, diesel or gasoline.