CN114824346B - Solid oxide fuel cell/electrolytic cell with one end sealed and conductive flat tube supported and cell stack structure - Google Patents

Abstract

The invention provides a solid oxide fuel cell/electrolytic cell with one sealed end and a cell stack structure, which adopts a conductive flat tube as a support body, and a cell group formed by connecting a plurality of single cells in series is respectively distributed on a first plane and a second plane which are parallel to each other of the support body. The battery packs are connected in series or in parallel through the supporting bodies, and when the battery packs are connected in parallel, the supporting bodies also have the function of current collection, and current generated in the battery packs is transmitted to the opening ends through the supporting bodies, so that drainage of the low-temperature opening ends is realized. Compared with a ceramic support body, the conductive flat tube has higher mechanical strength and faster starting speed of a galvanic pile as the support body, can collect cathode current in a series battery pack under a reducing atmosphere and drain current at a low-temperature open end, so that the purposes of increasing the volume power density of the battery, enhancing the output performance of the battery and reducing the difficulty in current collection are realized. In addition, the serial structure of the single cells can realize small current and high voltage output and reduce ohmic loss.

Description

One-end sealed conductive flat tube supported solid oxide fuel cell/electrolyzer and cell stack structure

Technical Field

The present invention relates to the field of energy structure optimization and solid oxide fuel cell technology, and in particular to a solid oxide fuel cell/electrolyzer supported by a conductive flat tube sealed at one end and a battery stack structure.

Background technique

SOFC is an electrochemical energy conversion device that continuously supplies fuel and oxidant, and has the advantages of fuel flexibility (natural gas, hydrocarbons such as biomass gas and urban garbage can be used), clean and efficient (fuel regeneration rate> 70%), and the comprehensive utilization rate can be increased to more than 90% through the combined heat and power device. Therefore, it has great prospects in improving electrical efficiency and improving environmental benefits.

The SOFC single cell structure currently under development is mainly divided into two basic structures: tubular and flat. The main difference lies in the sealing form of the fuel channel and oxidant channel of the cell and the circuit connection method of the single cell in the battery pack. The flat structure has the advantages of short current channel, higher output current density and power density than tubular cells, and more compact battery stacks, but the flat structure has technical difficulties such as high-temperature sealing difficulties and mismatch of high-temperature thermal stress; the tubular structure has the characteristics of no need for high-temperature sealing, less thermal stress, simple single cell assembly, and easy to achieve high power, but it has problems such as a longer path for the collector current and slightly lower power density.

Flat-tube SOFC combines the characteristics of flat-plate SOFC and tubular SOFC, retaining the easy sealing characteristic of tubular SOFC. It has a strong structure, relatively simple battery assembly, and is easy to combine into a high-power battery pack by connecting battery cells in parallel and in series. In the related technology, flat-tube SOFC still has the problems of difficult current collection and low volume power density.

Summary of the invention

In order to solve the technical problems existing in the above-mentioned related technologies, the present application provides a solid oxide fuel cell/electrolyzer supported by a conductive flat tube sealed at one end and a battery stack structure to solve the problems of low volume power density and difficult current collection of flat tube solid oxide fuel cells.

The specific content of the invention is as follows:

In a first aspect, the present invention provides a one-end sealed conductive flat tube supported solid oxide fuel cell/electrolyzer structure, the structure comprising: a conductive flat tube support, a porous insulating layer and a battery pack;

The conductive flat tube support body is composed of an open end, a main body area and a sealed end, wherein the open end is opposite to the sealed end, and the main body area is located between the open end and the sealed end;

The battery group is composed of a plurality of single batteries connected in series through a connector, and the battery groups are distributed on two mutually parallel first and second planes of the main body region to form a first plane battery group and a second plane battery group; the first plane battery group and the second plane battery group are arranged axially symmetrically with respect to the axis of the conductive flat tube support body, or the first plane battery group and the second plane battery group are arranged centrally symmetrically with respect to the axis of the conductive flat tube support body;

The conductive flat tube support is used to transmit the current generated in the conductive flat tube support type solid oxide fuel cell/electrolyzer with one end sealed;

The porous insulating layer is located between the conductive flat tube support and the battery pack.

Optionally, when the first planar battery group and the second planar battery group are arranged axially symmetrically with respect to the axis of the conductive flat tube support body, the first planar battery group and the second planar battery group are connected in parallel, and the cathode layer of the last single cell in the first planar battery group is connected to the conductive flat tube support body through the connector, and the cathode layer of the last single cell in the second planar battery group is connected to the conductive flat tube support body through the connector.

Optionally, when the first planar battery group and the second planar battery group are arranged symmetrically with respect to the axis of the conductive flat tube support body, the first planar battery group and the second planar battery group are connected in series, the cathode layer of the last single battery in the first planar battery group is connected to the conductive flat tube support body through the connector, and the anode layer of the last battery in the second planar battery group is connected to the conductive flat tube support body through the connector.

Optionally, the conductive flat tube support is prepared by extrusion molding.

Optionally, the constituent material of the conductive flat tube support body includes ceramics, and the ceramics are composed of ceramics that cannot be reduced by hydrogen and ceramics that can be reduced by hydrogen;

Wherein, the ceramic that cannot be reduced by hydrogen includes one or more components of magnesium oxide, magnesium aluminum spinel, mullite, violet stone and doped zirconium oxide;

The ceramic that can be reduced by hydrogen includes one or more components selected from the group consisting of nickel oxide, iron oxide, cobalt oxide and copper oxide;

The mass ratio of the ceramic that cannot be reduced by hydrogen to the ceramic that can be reduced by hydrogen is 4:6 to 6:4;

When the ceramic that can be reduced by hydrogen is reduced, a metal is formed, and the content of the metal accounts for 25% to 100% of the total mass of the ceramic.

Optionally, the outer surface of the sealing end and the outer surfaces of the arc structures on both sides of the conductive flat tube support are covered with a dense functional layer;

The dense functional layer is an electrolyte layer or a connector.

Optionally, a fuel gas flow channel is provided inside the conductive flat tube support body, and the fuel gas flow channel is used for the inflow and outflow of fuel gas.

Optionally, the conductive flat tube support has through pores, and the through pore rate is 10% to 40%;

The thickness of the conductive flat tube support is 0.5 mm to 3 mm;

The distance between the first plane and the second plane is 3 mm-15 mm.

Optionally, the porous insulating layer is an electronically insulating porous ceramic material, the through porosity of the porous insulating layer is 10% to 40%, the electronic conductivity of the porous insulating layer is less than 1%, and the thickness of the porous insulating layer is 10 μm to 200 μm;

The electronically insulating porous ceramic material is one or more components of MgAl ₂ O ₄ , MgO, doped zirconia, SrTiO ₃ and SrZrO ₃ .

In a second aspect, the present invention provides a solid oxide fuel cell stack structure supported by a conductive flat tube sealed at one end, the cell stack structure comprising: a cell stack structure consisting of two or more solid oxide fuel cells/electrolyzers supported by a conductive flat tube sealed at one end as described in the first aspect above.

Compared with the related art, the one-end sealed ceramic flat tube supported solid oxide fuel cell/electrolyzer and battery stack structure provided by the present invention have the following advantages:

The present invention provides a new flat tube SOFC structure, which is different from the traditional flat tube SOFC structure. The structure uses a conductive flat tube as a support body, and a battery group consisting of multiple single cells connected in series is distributed on two mutually parallel first and second planes of the support body. The battery groups are connected in series or in parallel through the support body. When the battery groups are in a parallel relationship, the support body also has the function of current collection, and the current generated in the battery group is transmitted to the open end through the support body to achieve low-temperature open end drainage.

In addition, the conductive flat tube used as a support for the solid oxide fuel cell/electrolyzer and its battery stack structure provided by the present invention has higher mechanical strength and faster battery stack startup speed than ceramic support, and can also collect cathode current in the series battery group under a reducing atmosphere and drain it at the low-temperature open end, thereby increasing the battery volume power density, enhancing the battery output performance, and reducing the difficulty of current collection. In addition, the series structure of multiple single cells can achieve low current and high voltage output and reduce ohmic loss.

Furthermore, the one-end sealed conductive flat tube supporting the solid oxide fuel cell/electrolyzer and its cell stack structure provided by the present invention has a self-sealing property, reduces the difficulty of sealing, and can also operate at high temperatures, effectively solving the problems of large polarization loss, poor long-term operation stability and low mechanical strength in solid oxide fuel cells.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

FIG1 is a schematic cross-sectional view of a conductive flat tube support provided by an embodiment of the present invention;

FIG2 is a side view schematic diagram showing a one-end sealed conductive flat tube supported solid oxide fuel cell/electrolyzer structure provided by an embodiment of the present invention;

FIG3 shows a side view schematic diagram of another one-end sealed conductive flat tube supported solid oxide fuel cell/electrolyzer structure provided by an embodiment of the present invention;

FIG4 is a schematic top view of a one-end sealed conductive flat tube supported solid oxide fuel cell/electrolyzer structure provided by an embodiment of the present invention;

FIG5 is a schematic top view of another one-end sealed conductive flat tube supported solid oxide fuel cell/electrolyzer structure provided by an embodiment of the present invention;

FIG6 is a cross-sectional schematic diagram showing a one-end sealed conductive flat tube supported solid oxide fuel cell/electrolyzer structure provided by an embodiment of the present invention;

FIG. 7 shows a schematic cross-sectional view of a solid oxide fuel cell/electrolyzer structure supported by a conductive flat tube with one end sealed, provided in an embodiment of the present invention.

Detailed ways

The following examples are provided for a better understanding of the present invention, but are not intended to limit the best mode of implementation, nor to limit the content and protection scope of the present invention. Any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior arts shall fall within the protection scope of the present invention.

If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the prior art can be used. The reagents and other instruments used without specifying the manufacturer are all conventional reagent products that can be purchased commercially.

Since the solid oxide fuel cell and the solid oxide electrolytic cell are a pair of energy conversion devices with the same structure and opposite working processes, the structure of the present invention is also applicable to a solid oxide electrolytic cell structure.

In order to solve the problems of difficult current collection and low volume power density in flat tube solid oxide fuel cells, the technical concept proposed in the present invention is: to provide a solid oxide fuel cell/electrolyzer supported by a conductive flat tube sealed at one end and a battery stack structure, wherein the flat tube support is a metal ceramic structure with a conductive function, one end is open and the other end is sealed; two series battery groups are distributed on two parallel planes of the flat tube support, and the battery groups are connected in series or in parallel through a support with a conductive function. The present invention uses two parallel planes of the flat tube support to increase the arrangement of batteries, thereby improving the volume power of the batteries. In addition, the conductive flat tube as a support can also collect the cathode current in the series battery group under a reducing atmosphere, and drain it at the low-temperature open end to solve the difficulty of current collection. Based on the above technical concept, the present invention provides a solid oxide fuel cell/electrolyzer supported by a conductive flat tube sealed at one end and a battery stack structure, and the specific implementation content is as follows:

In a first aspect, the present invention provides a one-end sealed conductive flat tube supported solid oxide fuel cell/electrolyzer structure, the structure comprising: a conductive flat tube support, a porous insulating layer and a battery group; the conductive flat tube support is composed of an open end, a main body region and a sealed end; the battery group is composed of a plurality of single cells connected in series through a connector, and the battery group is distributed in two mutually parallel first and second planes of the main body region to form a first plane battery group and a second plane battery group; the first plane battery group and the second plane battery group are arranged axially symmetrically with respect to the axis of the conductive flat tube support, or the first plane battery group and the second plane battery group are arranged centrally symmetrically with respect to the axis of the conductive flat tube support; the conductive flat tube support is used to transmit the current generated in the conductive flat tube supported solid oxide fuel cell/electrolyzer with one end sealed; the porous insulating layer is located between the conductive flat tube support and the battery group.

In specific implementation, FIG1 shows a cross-sectional schematic diagram of a conductive flat tube support provided by an embodiment of the present invention. As shown in FIG1 , the structure can be regarded as consisting of an open end, a main body region and a sealed end, the open end is opposite to the sealed end, and the main body region is located between the open end and the sealed end. Among them, the open end corresponds to the open area of the conductive flat tube support, the open area refers to the area from the open side of the support to the first single cell, and the inlet and outlet of the gas flow channel and the collector are located in this area (not shown in the figure); the two mutually parallel surfaces of the main body region are covered with a porous insulating layer and a first plane battery group and a second plane battery group; the sealed end corresponds to the closed area of the conductive flat tube support, and the closed area refers to the area from the tail of the last single cell in the battery group to the closed side of the support. In addition, the conductive flat tube support has a conductive function and can transmit the current generated in the battery/electrolytic cell. Therefore, the first plane battery group and the second plane battery group can realize the series or parallel connection between battery groups through the conductive flat tube support without the help of external wires. After the anode bus layer of the first single cell in the first planar battery group and the anode bus layer of the first single cell in the second planar battery group are extended, a current collector located at the open end is obtained. The current collector together with the conductive flat tube support is used for the introduction and extraction of current, so as to realize the collection of current at the open end (low-temperature end), so that the current generated by the conductive flat tube supported solid oxide fuel cell/electrolyzer provided by the present invention can be simply and easily operated in conduction and collection.

In a specific implementation, the porous insulating layer is located on two mutually parallel surfaces of the main area of the conductive flat tube support body, and the first planar battery group and the second planar battery group are further covered on the surface of the porous insulating layer. Among them, the battery group is composed of a plurality of single batteries connected in series through a connector, including a first planar battery group and a second planar battery group, and the first planar battery group and the second planar battery group can be arranged axially symmetrically or centrally symmetrically with the axis of the conductive flat tube support body to achieve parallel or series connection of the first planar battery group and the second planar battery group. The battery group formed by the arrangement of single battery units can effectively reduce the gap between each battery, increase the contact area between the battery and the support body, and achieve the purpose of increasing the battery power density. The functional layers that make up the single battery include an anode layer, an electrolyte layer, and a cathode layer, and can also include an anode bus layer, an anode layer, an electrolyte layer, a cathode layer, and a cathode bus layer.

In the one-end sealed conductive flat tube supported solid oxide fuel cell/electrolyzer structure provided by the present invention, a plurality of single cells are arranged on two mutually parallel surfaces of a flat tube support body with a conductive function, thereby increasing the volume power density of the battery, reducing the ohmic loss, and realizing the current output in a small current and high voltage mode, thereby effectively solving the problems of large polarization loss, difficulty in current collection, low battery output performance, poor long-term operation stability, and low mechanical strength in the solid oxide fuel cell/electrolyzer.

In some embodiments, when the first planar battery group and the second planar battery group are arranged axially symmetrically with respect to the axis of the conductive flat tube support body, the first planar battery group and the second planar battery group are connected in parallel, and the cathode layer of the last single cell in the first planar battery group is connected to the conductive flat tube support body through a connector, and the cathode layer of the last single cell in the second planar battery group is connected to the conductive flat tube support body through a connector.

In specific implementation, when the first plane battery group can work in parallel with the second plane battery group, FIG. 2 shows a side view schematic diagram of a one-end sealed conductive flat tube support type solid oxide fuel cell/electrolyzer structure provided by an embodiment of the present invention. As shown in FIG. 2, the first plane battery group is arranged in an axisymmetric structure with the second plane battery group arranged with the axis of the conductive flat tube support body. The cathode layer of the last single cell in the first plane battery group contacts the connector, and the cathode current in the first plane battery group is conducted to the conductive flat tube support body, and then it is conducted to the open end through the conductive flat tube support body, and collected with the help of the anode bus layer extending from the first single cell in the first plane. Similarly, the cathode layer of the last single cell in the second plane battery group contacts the connector, and the cathode current in the second plane battery group is conducted to the conductive flat tube support body, and then it is conducted to the open end through the conductive flat tube support body, and collected with the help of the anode bus layer extending from the first single cell in the second plane battery group. The support body serves as a common current transmission electrode, which can realize the parallel connection of the first plane battery group and the second plane battery group.

In some embodiments, when the first planar battery group and the second planar battery group are arranged centrally symmetrically with respect to the axis of the conductive flat tube support, the first planar battery group and the second planar battery group are connected in series, the cathode layer of the last single battery in the first planar battery group is connected to the conductive flat tube support through a connector, and the anode layer of the last battery in the second planar battery group is connected to the conductive flat tube support through a connector.

In specific implementation, the first planar battery group can also work in series with the second planar battery group. FIG3 shows a side view schematic diagram of another one-end sealed conductive flat tube support type solid oxide fuel cell/electrolyzer structure provided by an embodiment of the present invention. As shown in FIG3, the conductive flat tube support body first planar battery group arrangement and the second planar battery group arrangement are centrally symmetrical with the support body axis. The cathode layer of the last single cell in the first planar battery group is connected and contacted with the conductive flat tube support body through a connector, and the anode layer of the last single cell in the second planar battery group is also connected and contacted with the conductive flat tube support body through a connector. In this way, the conductive flat tube support body (its sealed end) with conductive energy acts as a connector, and the cathode current of the last single cell in the first planar battery group is connected to the anode of the last cell in the second plane through the sealed end of the conductive flat tube support body, so as to realize the series connection of the first planar battery and the second planar battery group. The current generated by the battery/electrolyzer is transmitted to the open end for collection through the series connection of the first planar battery group and the second planar battery group, so that the flat tube battery group has the characteristics of small current and high voltage output, reduces the current transmission polarization loss and is easy to improve the single tube output power density and output power.

In some embodiments of the present invention, in order to make the conductive flat tube support body have the function of conducting electricity, the constituent materials of the conductive flat tube support body include ceramics, and the ceramics are composed of ceramics that cannot be reduced by hydrogen and ceramics that can be reduced by hydrogen; wherein the ceramics that cannot be reduced by hydrogen include one or more components of magnesium oxide, magnesium aluminum spinel, mullite, corundum and doped zirconium oxide; the ceramics that can be reduced by hydrogen include one or more components of nickel oxide, iron oxide, cobalt oxide and copper oxide. Moreover, the mass ratio of the ceramics that cannot be reduced by hydrogen to the ceramics that can be reduced by hydrogen is 4:6 to 6:4; when the ceramics that can be reduced by hydrogen are reduced to form metal, the metal content accounts for 25% to 100% of the total mass of the constituent ceramics.

During specific implementation, the reducing gas in the fuel gas flow channel of the conductive flat tube support body will reduce the hydrogen-reducible ceramics that constitute the conductive flat tube support body to form a metal element, so that the support body becomes a composite material of the metal element and ceramic. The presence of the metal element enables the flat tube support body to have a conductive function.

In some embodiments, in order to achieve the structural self-sealing effect of a solid oxide fuel cell/electrolyzer supported by a conductive flat tube sealed at one end, isolate gas leakage, and avoid additional sealing work, when preparing an electrode layer on the surface of the conductive flat tube support, a dense functional layer is prepared on the outer surface of the sealed end and the outer surface of the arc structure on both sides of the conductive flat tube support. The dense functional layer can be an electrolyte layer or a connector.

In specific implementation, Figure 4 shows a schematic diagram of the top view of a solid oxide fuel cell/electrolyzer structure supported by a sealed conductive flat tube at one end provided in an embodiment of the present invention. As shown in Figure 4, the sealed end of the battery/electrolyzer structure and the outer surfaces of the arc structures on both sides of the conductive flat tube are covered with an electrolyte layer.

In a specific implementation, FIG5 shows a schematic diagram of a top view of a solid oxide fuel cell/electrolyzer structure supported by a conductive flat tube with another sealed end provided in an embodiment of the present invention. As shown in FIG5 , the sealed end of the battery/electrolyzer structure and the outer surfaces of the arc structures on both sides of the conductive flat tube are covered with a connector.

In some embodiments, a fuel gas flow channel is disposed inside the conductive flat tube support body, and the fuel gas flow channel is used for the inflow and outflow of fuel gas.

In a specific implementation, FIG6 shows a cross-sectional schematic diagram of a solid oxide fuel cell/electrolyzer structure supported by a conductive flat tube with one end sealed provided in an embodiment of the present invention. As shown in FIG6 , a fuel gas flow channel is provided inside the conductive flat tube.

In specific implementation, FIG7 shows a cross-sectional schematic diagram of a one-end sealed conductive flat tube supported solid oxide fuel cell/electrolyzer structure provided by an embodiment of the present invention. As shown in FIG7 , a fuel gas flow channel is provided inside the conductive flat tube. Different from FIG6 , the outer surfaces of the arc structures on both sides of the conductive flat tube of the battery/electrolyzer structure shown in FIG7 are covered with a connector material, while the outer surfaces of the arc structures on both sides of the conductive flat tube of the battery/electrolyzer structure shown in FIG6 are covered with an electrolyte layer.

In the specific implementation, the conductive flat tube support is prepared by extrusion molding. In order to ensure that the gas in the fuel gas flow channel can be smoothly transmitted to the electrode layer through the conductive flat tube support for electrochemical reaction, the conductive flat tube support has through pores, and the through porosity of the conductive flat tube support needs to be controlled. If the porosity is too small, the gas cannot flow normally, affecting the battery performance; when the porosity is too large, the strength and surface roughness of the conductive flat tube support cannot be guaranteed, and the service life and performance of the battery cannot be optimized. In the embodiment of the present application, the through porosity of the conductive flat tube support is 10% to 40%. In addition, the thickness of the conductive flat tube support can be 0.5mm to 3mm; the spacing between the first plane and the second plane can be 3mm-15mm. The one-end sealed conductive flat tube support type solid oxide fuel cell/electrolyzer structure obtained in this way has excellent mechanical properties and comprehensive power generation performance, and has volume advantages when integrated into a battery stack.

In some embodiments, the porous insulating layer is an electronically insulating porous ceramic material, the electronic conductivity of the porous insulating layer is less than 1%, and the thickness is 10-200 μm, so as to ensure the insulation between the support body separated by the ceramic insulating layer and the anode bus layer and the connector in the battery pack; the through porosity of the porous insulating layer is 10-40%, so as to ensure that the reducing atmosphere gas can fully diffuse into the anode layer.

The electronically insulating porous ceramic material is one or more components of MgAl ₂ O ₄ , MgO, doped zirconia, SrTiO ₃ and SrZrO ₃ .

In a second aspect, the present invention provides a solid oxide fuel cell stack structure supported by a conductive flat tube with one end sealed, the stack structure comprising: a stack structure consisting of two or more solid oxide fuel cells/electrolyzers supported by a conductive flat tube with one end sealed according to the first aspect.

In order to further understand the present invention, a one-end sealed conductive flat tube supported solid oxide fuel cell/electrolyzer and a battery stack structure of the present invention are further described below in combination with specific examples. At the same time, the electrolyzer and the fuel cell are mutually inverse energy conversion devices and have the same functional layer distribution. Therefore, the embodiments of the present application are described by taking the fuel cell as an example.

Example 1

Please refer to Figures 2, 4 and 6. A metal ceramic flat tube with one end self-sealed is prepared by extrusion molding and sintering. The thickness of the flat tube is 6 mm. The length and width of the upper and lower parallel plane areas are 50 cm and 8 cm respectively. The first plane battery group and the second plane battery group are respectively composed of 30 single cells connected in series, wherein the anode length is 60 mm, the width is 10 mm, and the interval between adjacent anodes is 2 mm; the electrolyte width is 10 mm, and the interval between adjacent electrolytes is 2 mm, wherein the anode not covered by the electrolyte along the length direction of the support body is 1 mm; the contact area between the electrolyte and the insulating layer is 1 mm wide, and the contact area between the connector and the cathode bus layer is 1 mm wide.

The porosity of the support body is 35% by controlling the content of the pore-forming agent. The outer area of the semi-cylinder is a dense electrolyte material (5YSZ). The material constituting the flat tube is a mixed powder of CSZ and NiO with a mass ratio of 6:4. The insulating layer is prepared by wet spraying on the first plane and the second plane. The insulating layer uses CaO-stabilized _ZrO2 ceramic material. The porosity of the insulating layer surface covering the battery area is 40%; the dense electrolyte material (5YSZ) is prepared on the rest of the support body, including the arc part of the sealing end and the arc parts on both sides. On the first plane and the second plane insulating layer, 30 single cells of anode bus layer (NiO/3YSZ, mass ratio 6:4), anode (NiO/ScSZ, mass ratio 6:4), electrolyte (ScSZ), connector (La _0.7 Sr _0.3 TiO ₃ ), cathode (La _0.8 Sr _0.2 MnO ₃ /8YSZ, mass ratio 8:2) and cathode bus layer (La _0.6 Sr _0.4 Co _0.2 Fe _0.8 O _3-δ /Mn _1.5 Co _1.5 O ₄ , mass ratio 1:1) were prepared by screen printing in sequence, wherein the last single cell connector on the first plane and the last single cell connector on the second plane were connected to the support. The battery pack formed by the first plane 30 single cells connected in series and the battery pack formed by the second plane 30 single cells connected in series were parallel structures, and then co-fired at 1450°C for 4 hours.

Note: Figures 2, 4 and 6 are for structural reference only and do not limit the relevant numerical information in the embodiments of the present invention.

Example 2

Please refer to Figures 3, 4 and 6. A metal ceramic flat tube with one end self-sealed is prepared by extrusion molding and sintering. The thickness of the flat tube is 0.8 cm. The length and width of the upper and lower parallel plane areas are 30 cm and 5 cm respectively. The first plane battery group and the second plane battery group are respectively composed of 15 single cells connected in series, wherein the anode length is 60 mm, the width is 10 mm, and the interval between adjacent anodes is 2 mm; the electrolyte width is 10 mm, and the interval between adjacent electrolytes is 2 mm, wherein the anode not covered by the electrolyte along the length direction of the support body is 1 mm; the contact area between the electrolyte and the insulating layer is 1 mm wide, and the contact area between the connector and the cathode bus layer is 1 mm wide.

The porosity of the support body is 40% by controlling the content of the pore-forming agent. The outer area of the semi-cylinder is a dense electrolyte material (5YSZ). The material constituting the flat tube is a mixed powder of 3YSZ and NiO with a mass ratio of 1:1. The insulating layer is prepared by wet spraying on the first plane and the second plane. The insulating layer uses CaO-stabilized _ZrO2 ceramic material. The porosity of the insulating layer surface covering the battery area is 40%; the dense electrolyte material (5YSZ) is prepared by screen printing on the rest of the support body, including the arc part of the sealing end and the arc parts on both sides. On the first plane and the second plane insulating layer, 15 single cells of anode bus layer (NiO/5YSZ, mass ratio 6:4), anode (NiO/8YSZ, mass ratio 6:4), electrolyte (8YSZ), connector (La _0.7 Sr _0.3 TiO ₃ ), cathode (La _0.8 Sr _0.2 MnO ₃ /8YSZ, mass ratio 1:1) and cathode bus layer (La _0.6 Sr _0.4 Co _0.2 Fe _0.8 O _3-δ /Mn _1.5 Co _1.5 O ₄ , mass ratio 1:1) were prepared by screen printing in sequence, wherein the last single cell connector on the first plane and the last single cell connector on the second plane were connected to the support. The battery pack formed by the 15 single cells connected in series on the first plane and the battery pack formed by the 15 single cells connected in series on the second plane were a series structure, and then co-fired at 1450°C for 4 hours.

Note: Figures 3, 4 and 6 are for structural reference only and do not limit the relevant numerical information in the embodiments of the present invention.

Example 3

Please refer to Figures 2, 5 and 7. A metal ceramic flat tube with one end self-sealed is prepared by extrusion molding and sintering. The thickness of the flat tube is 1.5 cm. The length and width of the upper and lower parallel plane areas are 100 cm and 10 cm respectively. The first plane battery group and the second plane battery group are respectively composed of 60 single cells in series, wherein the anode length is 60 mm, the width is 10 mm, and the interval between adjacent anodes is 2 mm; the electrolyte width is 10 mm, and the interval between adjacent electrolytes is 2 mm, wherein the anode not covered by the electrolyte along the length direction of the support body is 1 mm; the contact area between the electrolyte and the insulating layer is 1 mm wide, and the contact area between the connector and the cathode bus layer is 1 mm wide.

The porosity of the support body is 40% by controlling the content of the pore-forming agent, the outer area of the semi-cylinder is a dense connector material (La _0.7 Sr _0.3 TiO ₃ ), and the material constituting the flat tube is FeCr powder. The insulating layer is prepared by injection molding on the first plane and the second plane. The main component of the insulating layer is 35wt% SrZrO ₃ +Al ₂ O ₃ (the content of Al ₂ O ₃ is 3mol% of SrZrO ₃ ), and the porosity of the battery area covered by the insulating layer surface is 40%; the dense connector material (La _0.7 Sr _0.3 TiO ₃ ) is prepared by screen printing on the rest of the support body, including the arc part of the sealing end and the arc parts on both sides. On the first plane and the second plane insulating layer, 60 single cells of anode bus layer (NiO/Sr _0.7 La _0.3 TiO ₃ , mass ratio 7:3), anode (NiO/GDC, mass ratio 6:4), electrolyte (GDC), connector (La _0.7 Sr _0.3 TiO ₃ ), cathode (La _0.8 Sr _0.2 MnO ₃ /8YSZ, mass ratio 1:1) and cathode bus layer (La _0.6 Sr _0.4 Co _0.2 Fe _0.8 O _3-δ /Mn _1.5 Co _1.5 O ₄ , mass ratio 1:1) were prepared by screen printing in sequence, wherein the last single cell on the first plane and the last single cell on the second plane were connected to the support. The battery pack formed by the 60 single cells in series on the first plane and the battery pack formed by the 60 single cells in series on the second plane were parallel structures, and then co-fired at 1450°C for 4 hours.

Note: Figures 2, 5 and 7 are for structural reference only and do not limit the relevant numerical information in the embodiments of the present invention.

The above is a detailed introduction to a one-end sealed conductive flat tube supported solid oxide fuel cell/electrolyzer and a battery stack structure provided by the present invention. Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core idea. At the same time, for a person skilled in the art, according to the idea of the present invention, there will be changes in the specific implementation methods and application scope. In summary, the content of this specification should not be understood as a limitation on the present invention.

Claims (7)

1. A solid oxide fuel cell/electrolyser structure supported by a sealed conductive flat tube at one end, said structure comprising: a conductive flat tube support body, a porous insulating layer and a battery pack;

the conductive flat tube support body consists of an opening end, a main body area and a sealing end, wherein the opening end is opposite to the sealing end, and the main body area is positioned between the opening end and the sealing end;

The battery pack is formed by connecting a plurality of single cells in series through a connecting body, and the battery pack is distributed on a first plane and a second plane which are parallel to each other in the main body area to form a first plane battery pack and a second plane battery pack; the first planar battery pack and the second planar battery pack are arranged in an axisymmetric manner by the axis of the conductive flat tube support body, or the first planar battery pack and the second planar battery pack are arranged in a centrosymmetric manner by the axis of the conductive flat tube support body;

The conductive flat tube support body is used for transmitting current generated in the conductive flat tube support type solid oxide fuel cell/electrolytic cell with one sealed end;

the porous insulating layer is positioned between the conductive flat tube support body and the battery pack;

The outer surface of the sealing end and the outer surfaces of the circular arc structures on the two sides of the conductive flat tube support body are covered with compact functional layers; the compact functional layer is an electrolyte layer or a connector;

When the first plane battery pack and the second plane battery pack are arranged in an axisymmetric way by the axis of the conductive flat tube support body, the first plane battery pack is connected with the second plane battery pack in parallel, the cathode layer of the last single cell in the first plane battery pack is connected with the conductive flat tube support body through the connector, and the cathode layer of the last single cell in the second plane battery pack is connected with the conductive flat tube support body through the connector;

When the first plane battery pack and the second plane battery pack are arranged in a central symmetry mode by the axis of the conductive flat tube support body, the first plane battery pack is connected with the second plane battery pack in series, the cathode layer of the last single cell in the first plane battery pack is connected with the conductive flat tube support body through the connector, and the anode layer of the last cell in the second plane battery pack is connected with the conductive flat tube support body through the connector;

The conductive flat tube support comprises ceramic, wherein the ceramic consists of ceramic which can not be reduced by hydrogen and ceramic which can be reduced by hydrogen;

wherein the ceramic which can not be reduced by hydrogen comprises one or more components of magnesia, magnesia-alumina spinel, mullite, bluestone and doped zirconia;

The ceramic capable of being reduced by hydrogen comprises one or more components of nickel oxide, iron oxide, cobalt oxide and copper oxide;

the conductive flat tube support body is provided with a through air hole.

2. The structure of claim 1, wherein the conductive flat tube support is prepared by extrusion molding.

3. The structure of claim 1, wherein the mass ratio of the non-hydrogen reducible ceramic to the hydrogen reducible ceramic is 4:6~6:4, a step of;

And when the ceramic which can be reduced by hydrogen is reduced to form metal, the metal content accounts for 25% -100% of the total mass of the ceramic.

4. The structure according to claim 1, wherein the conductive flat tube support body is internally provided with a fuel gas flow passage for inflow and outflow of fuel gas.

5. The structure of claim 1, wherein the through porosity is 10% -40%;

The thickness of the conductive flat tube support body is 0.5 mm-3 mm;

The distance between the first plane and the second plane is 3mm-15mm.

6. The structure according to claim 1, wherein the porous insulating layer is an electronically insulating porous ceramic material, the through porosity of the porous insulating layer is 10% -40%, the electronic conductivity of the porous insulating layer is lower than 1%, and the thickness of the porous insulating layer is 10 μm-200 μm;

the electronically insulating porous ceramic material is one or more of MgAl ₂O₄, mgO, doped zirconia, srTiO ₃ and SrZrO ₃.

7. A solid oxide fuel cell stack structure supported by a conductive flat tube with one end sealed, the stack structure comprising: a stack structure comprising two or more solid oxide fuel cells/electrolysers supported by a sealed conductive flat tube at one end as claimed in any one of claims 1 to 6.