CN104979575A - Porous inert supporting tube type solid oxide fuel battery with two opening ends, galvanic pile and preparation method of fuel battery - Google Patents

Abstract

The invention relates to a porous inert support tubular solid oxide fuel cell with open ends, an electric stack and a preparation method thereof. The battery includes a porous inert support tube with openings at both ends and a porous inert support tube that is electronically connected but airtightly separated. The outer wall is coated with different functional sections: inlet gas isolation section, series battery section, thermal isolation section, and battery connection terminal. The gas isolation section is used to isolate air and fuel. A series battery section is a battery connected in series. The thermal isolation section places the external conductive connection of the battery outside the high temperature area. The battery connection terminal provides an external electrical connection terminal of the battery. The battery of the present invention forms a battery row through the battery connection terminals, and the battery row further forms a battery stack by connecting in series or in parallel. The invention can greatly reduce the cost of the solid oxide fuel cell, avoid the influence of thermal expansion on the battery and the battery stack, reduce the influence of high temperature on the conductive connection, facilitate the series and parallel connection of different batteries, and facilitate the assembly of the battery stack.

Description

Porous inert support tubular solid oxide fuel cell with open ends, stack and preparation method thereof

technical field

The invention relates to a porous inert support tubular solid oxide fuel cell with open ends and a preparation method thereof. The solid oxide fuel cell can be applied to micro power sources, distributed power stations and power plants, can reduce manufacturing costs and improve power generation efficiency.

Background technique

Solid oxide fuel cell (SOFC) is a power generation device that uses solid oxide as the electrolyte diaphragm to efficiently and cleanly convert the chemical energy of the fuel into electrical energy through electrochemical reactions. Its power generation efficiency can reach more than 60%. The total energy efficiency is higher than 80%, and it is a new type of power generation device that reduces carbon dioxide emissions. Solid oxide fuel cells can not only use hydrogen fuel, but also use abundant and cheap natural gas, liquefied petroleum gas, fuel oil, vaporized gas of medium, city gas and biomass gas as fuel.

According to the different configurations of the core components of solid oxide fuel cells - membrane electrodes or single cells, solid oxide fuel cells can be divided into tubular cells, flat cells and monolithic cells. According to different supports of membrane electrodes or batteries, solid oxide fuel cells can be divided into electrolyte-supported, cathode-supported and anode-supported types. Batteries with different battery configurations use different component structures and construction methods in building battery stacks and power station systems, and the structures of battery stacks and power stations are also different. Among various types of batteries, electrolyte-supported batteries were developed relatively early, and the cathode-supported tubular solid oxide fuel cell technology and electrolyte-supported battery technology of Siemens-Westinghouse Corporation of the United States are relatively mature, and the operating temperature of both batteries is 900 Above ℃, the cost of battery preparation is relatively high, and the manufacturing cost of the power generation system is also relatively high. The anode-supported battery technology is a battery technology developed at home and abroad in recent years. The working temperature of the battery is reduced to 650-800°C, and the production cost of the battery can be reduced, but this type of battery requires relatively high sealing technology. Since the monolithic battery uses ceramic materials with more functions, the structure is more complicated, and the preparation technology requirements are relatively high.

The monolithic battery is prepared by preparing ceramic materials such as the anode, anode, electrolyte and connecting body of the battery together, and has a fuel gas or air channel part, and an electronic conduction channel connecting different batteries. Integral solid oxide fuel cells are available in block type or tube type. Regardless of whether it is a bulk or tubular battery, different monolithic batteries have different structures, material selections, and preparation processes due to different application requirements. For example, in the block-type integrated battery reported by Mitsubishi Heavy Industries disclosed in US Patent No. US06296963, each battery is one section, and different batteries are connected together through ceramic connectors to form a battery stack. Mitsubishi Heavy Industries adopts porous and inert calcia-stabilized zirconia support tubes with openings at both ends, and prepares series-connected batteries on the surface of the support tubes to form a tubular monolithic battery. The gas flows through the middle, and the current is drawn out through the connections at both ends of the battery tube. However, due to the high temperature of the conductive connection, the conductive connection is difficult and difficult to maintain. As another example, U.S. Patent No. 7,892,691 discloses a series-connected tubular battery structure of Rolls-Royce, which uses magnesium-aluminum spinel to support flat-plate batteries. The batteries connected in series are in the middle section, and different battery tubes pass through the two ends. Connect with other battery tubes. The use of cheap raw materials for the battery tube can reduce the manufacturing cost of the battery, but the requirements for the conductive connection between different batteries and the gas supply connection of the battery are relatively high, and it is inconvenient to build a battery stack. Chinese patent CN03114562.0 discloses a structure of a tubular high-temperature solid oxide fuel cell. The tubular high-temperature solid oxide fuel cell is closed at one end and open at one end. There is a layer of ceramic insulating layer, and a plurality of unit cells connected in series are distributed on the ceramic insulating layer, each unit unit is connected in series with each other through connecting poles, and the external connection of the battery tube is arranged at the outlet of the anode gas. On the one hand, the battery has a relatively thin insulating layer, and the diffusion of metal elements can easily cause parallel leakage of the series battery; on the other hand, the battery structure requires wires to lead the current from the high temperature area to the low temperature area.

In the solid oxide fuel cell power generation system, not only the electrochemical reaction of the battery is carried out at high temperature, but also the reforming reaction of fuel and the catalytic combustion reaction of tail gas are carried out at high temperature, especially the combustion reaction of tail gas will cause local high temperature , to generate a large thermal shock to the surrounding materials and components, which may cause the cracking of ceramic components, and may also cause deformation and oxidation of metal components. The temperature of the solid oxide fuel cell is high, and the fuel tail gas needs to be burned in order to recover heat energy and improve the power generation and heat supply efficiency of the system. For example, the outlet of the fuel tail gas is adjacent to the combustion chamber, and its temperature is much higher than the working temperature of the battery, sometimes even reaching above 1000°C. Connecting and taking power from the fuel outlet of the battery tube is easy to cause oxidation of the metal connecting material, and the repeated start-up of the battery system will also cause the connection part to loosen and the conductivity will deteriorate. In the above-mentioned battery structure, the current connection of the battery tube is in a high temperature area, which will affect the reliability and stability of the battery.

At present, the primary problem restricting the development of solid oxide fuel cells is the problem of high cost. The second is the reliability of the battery. Therefore, the structural design and preparation of solid oxide fuel cells should not only reduce the cost, but also improve the reliability of the cell.

Contents of the invention

Electrochemical reactions, fuel reforming, and tail gas combustion of solid oxide fuel cells are all carried out at high temperatures, resulting in relatively high manufacturing costs for battery systems, and some unreasonable battery structures can also cause problems with battery reliability, etc. All of them are restricting the industrial application of solid oxide fuel cells. How to design and prepare a more reasonable battery structure, avoid or reduce the use of expensive alloy materials, reduce manufacturing costs, and improve reliability are important issues in the research and development of solid oxide fuel cells. In response to this requirement, this patent proposes a solid oxide fuel cell supported by porous inert tubes with open ends, an electric stack and a preparation method thereof.

A porous inert support tube type solid oxide fuel cell with two ends open, with a porous inert support tube with two ends open, conductive communication but airtight separation in the tube, the outer wall of which is coated with different functional layers, divided into inlet gas Isolation section, serial battery section, thermal isolation section, battery connection terminal. The gas isolation section has an airtight membrane layer, and the series battery section is composed of anode layer, cathode layer, electrolyte membrane layer and connector layer. The battery connection terminal is the external connection part of the entire battery, including the anode connection terminal and the cathode connection terminal. The different functional sections are prepared on the porous inert support tube by slurry dipping or slurry spraying.

The porous inert support tube is a round tube with two openings and a single channel. There is a conductive but airtight support tube in the middle of the tube between the series battery section and the thermal isolation section. There are one or more points on the wall of one end of the tube Electronically conductive ceramic materials connect internal and external electrical conduction and are used to sinter dense oxide materials. The material of the porous inert support tube is at least one of alumina, yttria-stabilized zirconia, calcium oxide-stabilized zirconia, spinel, cordierite, corundum-mullite and the like. The electronically conductive ceramic material is a composite material composed of one or more of cermets, conductive perovskite composite oxide materials, and porous inert tube materials. The porous inert support tube is a single-hole circular tube with an outer diameter of 3-30mm, a tube length of 63-2650mm, and a porosity of the porous tube wall of 25-50%.

The inlet gas isolation section is located on the porous inert support tube on the gas inlet side of the battery, and there is a layer of high temperature resistant and airtight oxide diaphragm layer on the surface of the support tube. The length of the inlet gas isolation section is 10-200mm. The material of the oxide diaphragm layer is at least one of yttrium-stabilized zirconia, perovskite structure material, and alumina, and the diaphragm layer is preferably the same material as the electrolyte. At this time, the oxide film layer can be prepared together with the electrolyte membrane, simplifying Preparation Process. The main function of the gas isolation section is to prevent back-mixing of the gas in the stack, to facilitate the isolation of fuel and air to a suitable area for mixing and reaction, and to avoid the high temperature of the combustion reaction from directly impacting the battery.

The series-connected battery segment is a series-connected battery composed of an anode layer, a cathode layer, an electrolyte membrane layer and a connector layer. Wherein, the thickness of the anode layer is 15-100 μm, the thickness of the electrolyte membrane layer is 5-50 μm, the thickness of the cathode layer is 15-100 μm, and the thickness of the connector layer is 20-100 μm. The electrolyte material in the electrolyte layer is an oxygen ion conductor oxide, which is one of ceria-based oxygen ion conductors, zirconia-based oxygen ion conductors, and lanthanum-gallium-based perovskite oxides. The electrolyte is preferably stable with 8-10mol% yttrium oxide Zirconia. The anode in the anode layer is a metal-electrolyte material composite anode, the raw material of the metal in the anode is a transition metal oxide, or a doped modified transition metal oxide, and the weight content of the metal raw material is 40-60%; the anode is preferably oxidized A composite anode composed of nickel-yttrium stabilized zirconia. The cathode in the cathode layer is a composite cathode composed of a perovskite composite oxide and an electrolyte material, and the weight content of the perovskite composite oxide is 40-60%, preferably strontium lanthanum manganite or calcium lanthanum manganite Composite cathode composed of yttrium-stabilized zirconia. If the cathode layer is exposed on the outside of the tube, on the electrochemical layer of the cathode, there can also be a layer of porous pure perovskite material for current collection and conduction to strengthen the electrical connection between different batteries. The connecting body is made of at least one of strontium lanthanum chromate, strontium lanthanum titanate, strontium lanthanum manganate and strontium lanthanum iron cobaltate, and the connecting body is used for isolating fuel gas and oxidant and connecting batteries in series. Different functional layers are arranged on the porous support tube in a certain order to form a battery connected in series. The length of each battery is 4-50mm, and the number of sections on each battery is 10-50. The battery sections are connected in series. The length is 40-2500mm. Wherein, the thickness of the anode layer is 15-100 μm, the thickness of the cathode layer is 15-100 μm, the thickness of the electrolyte layer is 5-50 μm, and the thickness of the connector layer is 20-100 μm.

In the series battery section, the one directly in contact with an electrode on the porous support tube can be an anode or a cathode, so there are two types of structural batteries, which are called α battery and β battery. The anode of the α battery is directly loaded on the porous inert support tube, and the cathode is exposed outside the tube. Its structure is shown in Figure 1(A). The cathode of the β battery is directly loaded on the porous inert support tube, and the anode is exposed outside the tube. Its structure is shown in Figure 1(B). The inside of the tube of the α battery is a fuel cavity, and the outside of the tube is an air cavity. The inside of the tube of the β battery is an air cavity, and the outside of the tube is a fuel cavity. At the same time, the materials used to extend the conductive connection coating also differ. The current conduction layer in the anode chamber of the α battery can be preferably Ni-YSZ coating, and the cathode current conduction layer exposed to the air is made of perovskite structure materials, such as strontium lanthanum chromate, strontium lanthanum titanate, strontium lanthanum manganate, iron At least one of strontium lanthanum cobaltate and the like. At least one of strontium lanthanum chromate, strontium lanthanum titanate, strontium lanthanum manganate and strontium lanthanum iron cobaltate is used for the current conduction layer in the cathode chamber of the β battery.

The thermal isolation section is to extend the connection area between the battery and the metal to the low temperature area to improve the reliability and stability of the battery connection. In order to extend the conductive connection, the thermal isolation section is coated with an electronic conductive layer on the inner and outer walls of the porous inert support tube. One end of the electronic conductive layer is connected to the electrode of the battery, and the other end is connected to the corresponding electrode connection terminal of the battery. The material of the electronic conduction layer in the thermal isolation section is at least one of strontium lanthanum chromate, strontium lanthanum titanate, strontium lanthanum manganate and strontium lanthanum iron cobaltate. The length of the thermal insulation section is 10-300mm.

The battery connection terminal is the external connection part of the whole battery, including the anode connection terminal and the cathode connection terminal, which are used for serial or parallel connection between different battery tubes through metal parts. One battery connection terminal is connected to the corresponding electrode terminal of the whole battery through the electron conduction layer on the outer wall or inner wall of the porous inert support tube, and the other battery connection terminal is connected to the other electrode terminal of the whole battery through the electron conduction layer on the inner wall . The length of the battery connection terminal section is 3-50mm.

Figure 2 shows two tubular battery structures described in this patent: α battery and β battery; the anodes of the series-connected battery sections of α batteries are directly loaded on the porous inert support tube, and the cathode is exposed outside the tube; the β battery The cathodes of the series-connected battery segments are directly supported on the porous inert support tube, and the anodes are exposed outside the tube. There is an internal severed but electrically connected block between the series-connected cell section of an alpha cell or a beta cell and the thermally isolated section.

As shown in Figure 2(A) and Figure 2(B), although the structure of the α battery and the β battery are different, and the coating sequence of each functional layer is different, the preparation process of the two is similar, including the following steps:

(1) Preparation of porous inert support tubes with open ends:

The raw material of the support tube, the organic binder, the pore-forming agent and the deionized water are mixed, and the green body of the porous inert support tube with openings at both ends is prepared by extrusion or grouting. Wherein, the organic binder is at least one of polyvinyl alcohol, methyl cellulose, and polyvinyl alcohol, and the pore-forming agent is at least one of starch, activated carbon, and cellulose acetate. A conductive but sinterable dense oxide material is used to seal the green tube at a suitable position in the support tube green body, and then a hole is opened at a suitable position on the tube wall to fill the conductive connecting material. Finally, the green tube is calcined at high temperature for a certain period of time to obtain a porous inert support tube with openings at both ends. The calcination temperature is 1100-1450°C, and the calcination time is 2-50h.

(2) Preparation of each functional section on the porous inert support tube:

Add organic binders and organic solvents to the materials that make up each functional section to prepare functional layer slurry. According to the composition of each functional section and its position in the porous inert support tube, the porous inert support tube is sprayed or dipped sequentially on the porous inert support tube. The tube is coated with the slurry of the corresponding functional section, and then calcined at a high temperature to obtain the corresponding functional section. After multiple steps of slurry coating and calcination, all the functional sections loaded on the support tube are obtained. The organic binder added in the slurry can increase the bonding strength and thickness of the coating material on the pipe wall. The organic binder is at least one of polyvinyl alcohol, methyl cellulose, and polyvinyl alcohol; the pore-forming agent is starch , activated carbon, and cellulose acetate; the organic solvent is at least one of ethanol, ethylene glycol, glycerol, isobutanol, acetone, and methyl ethyl ketone. The preferred method of coating the functional layer slurry on the support tube is the dip coating method. The thickness of the slurry can be controlled by adjusting the concentration of the slurry to obtain the thickness of the dipping coating each time, and the thickness of the wall layer can also be increased through multiple dipping-drying processes. The thickness of the inlet gas isolation section, thermal isolation section, and battery connection terminal section is controlled between 2-100 microns, preferably 6-50 microns, the thickness of the anode in the series-connected battery section is 15-100 μm, and the thickness of the electrolyte membrane is 5 -50μm, the thickness of the cathode is 15-100μm, and the thickness of the connector film is 20-100μm.

A stack constructed of porous inert support tube-type solid oxide fuel cells with openings at both ends. Firstly, the solid oxide fuel cells supported by the porous inert tubes are connected in parallel through the cathode common electrical connection metal strip and the anode common electrical connection metal strip. A battery tube row is formed, and then different tube rows are connected in parallel or in series to form a stack. The gas entering the battery tube is introduced through the metal or ceramic distribution tube, and the gas outside the battery tube is supplied to the battery through the gap of the battery tube. The gas entering the porous inert support tube of the cell stack of the α-structure battery is introduced through the fuel distribution tube, the gas entering the porous inert support tube of the cell stack of the β-structure cell is introduced through the air distribution tube, and the gas outside the porous inert support tube is introduced through the porous inert support tube Tube clearance supply.

Aiming at the problems of traditional batteries in current collection, gas distribution, connection between batteries, selection of high-temperature materials, and manufacturing of power generation systems, the invention proposes a series-connected solid oxide battery supported by porous inert tubes, a stack and a preparation method thereof. The main features are as follows: (1) Using cheap inert materials as the support tube material greatly reduces the cost of battery materials; (2) Using the support tube structure improves battery strength and battery reliability; (3) will The batteries are connected in series on the support tube to increase the output voltage of a single battery and reduce the current of a single battery, which is beneficial to reduce the current loss; (4) A thermal isolation section is designed in the battery tube, and the non-conductive porous Conductive connection coatings are prepared on the inner and outer surfaces of the support tubes, and the connection of the battery tubes is placed in a low-temperature area, and the electrical connection between the battery tubes is placed in a low-temperature area, avoiding the high-temperature area, which is conducive to the stability of the connection between the batteries and improves the reliability of the battery. Reliability of conductive connection; (5) Place the current lead-out part of the battery tube at the other end of the gas inlet, which facilitates the electrical connection, improves the reliability of the connection, and facilitates the construction of the battery stack; (6) The opening at both ends In the middle of the inert support tube, a conductive but airtight plug is designed and prepared, which realizes electrical communication but does not allow gas to flow out from the other port; (7) The gas isolation section at the inlet is designed to prevent The cathode air is mixed with the anode fuel for direct combustion, which facilitates the construction of the stack.

Description of drawings

Figure 1(A), a schematic plan view of the α battery structure of the tandem solid oxide battery supported by porous inert tubes with openings at both ends;

Figure 1(B), a schematic plan view of the β battery structure of the tandem solid oxide battery supported by porous inert tubes with openings at both ends;

Figure 2 (A), a schematic diagram of the 60-section α-structure battery structure of a series-connected solid oxide battery supported by porous inert tubes with openings at both ends;

Figure 2(B), Schematic diagram of the 60-section β-structure battery structure of the tandem solid oxide battery supported by porous inert tubes with openings at both ends;

Figure 3. The stack structure of the α-structure battery;

Figure 4. The stack structure of the β-structure battery;

Among them, 1-cathode layer; 2-electrolyte layer; 3-anode layer; 4-porous inert support tube; 5-connector layer; 61-current conducting layer in the anode cavity; 62-current conducting layer in the cathode cavity; 71-fuel cavity; 72-air cavity; 8-cathode connection terminal; 9-anode connection terminal; 10-middle plugging of support tube; 11-inlet gas isolation section; 12-serial battery section; 13-heat Isolation section; 14-battery connection terminal; 15-single battery; 16-internal cut but electrical connection blocked; 17-cathode connection terminal; 18-anode connection terminal; 191-fuel distribution pipe; 192- Air distribution pipe; 201-a tubular battery of α structure; 202-a tubular battery of β structure; 21-the common electrical connection metal belt of the cathode; 22-the common electrical connection metal belt of the anode.

Detailed ways

Below by embodiment the present invention is described in further detail and concretely.

Example 1

After mixing magnesia-aluminum spinel, polyvinyl alcohol, starch and deionized water, a porous inert support tube 4 green body with open ends is prepared by extrusion or grouting, and the porous inert support tube 4 green body is suitable Add strontium lanthanum titanate to plug the green body, then open a hole at a suitable position on the tube wall, fill with NiO-YSZ (nickel oxide-strontium doped lanthanum manganite) conductive connection material, and finally put the green body at 1450 ° C Calcined for 5 hours to obtain a porous magnesium-aluminum spinel support tube with both ends open, electronically conductively connected in the tube but airtightly separated. The outer diameter of the tube is 15mm, and the porosity of the tube wall is 42%.

Add the powder material of each functional section to methyl cellulose and ethylene glycol to prepare corresponding slurry, according to the composition of each functional section and its position in the porous inert support tube 4, in the appropriate position of the porous inert support tube 4 Corresponding slurry is dip-coated, and then the corresponding functional layer is obtained by high-temperature calcination, and all functional segments loaded on the support tube are obtained through multiple slurry coating and calcination steps. Among them, the length of the inlet gas isolation section 11 is 150 mm, and the surface is coated with 8 mol% yttria-stabilized zirconia dense film. The length of the battery segment 12 connected in series is 1200mm, and the length of each battery is 20mm, and a total of 60 batteries are prepared. The anode is NiO-YSZ (nickel oxide-strontium doped lanthanum manganite), the thickness is 45 μm, the electrolyte is 8mol% yttria stabilized zirconia, the thickness is 20 μm, the connecting body is strontium lanthanum titanate, the thickness is 25 μm, the cathode It is LSM-YSZ (strontium-doped lanthanum manganite-yttria stabilized zirconia), the electrochemical reaction layer of the cathode is 32 μm, and the thickness of the current-collecting conductive layer of the cathode is 50 μm. The length of the thermal isolation section is 200mm, the bottom layer of the outer wall of the support tube is coated with strontium lanthanum titanate, and the outer layer is coated with lanthanum cobaltate. The length of the battery connection terminal is 50mm, wherein the length of the cathode connection terminal is 20mm, the length of the anode connection terminal is 20mm, and the interval between them is 10mm.

The above battery tubes were assembled into 60 α batteries, the outer tube was ventilated with air 10L min ^-1 , and the tube was vented with hydrogen gas 800ml min ^-1 , and the electrical output performance at 800°C was tested. Under normal pressure, when the output voltage of the battery tube is 51V, the output current is 1.2A, and the output power is 61.2W.

Example 2

According to the method described in Example 1, 80 α-cells were prepared. Wherein, the porous inert support tube 4 is a porous alumina tube with an outer diameter of 10 mm and a porosity of the tube wall of 35%. The inlet gas isolation section 11 has a length of 100mm, and the surface is coated with 8mol% yttria-stabilized zirconia dense film. The length of the battery segment 12 connected in series is 1200mm, and the length of each battery is 15mm. The anode is NiO-YSZ (nickel oxide-strontium doped lanthanum manganite), the thickness is 45 μm, the electrolyte is 8mol% yttria stabilized zirconia, the thickness is 20 μm, the connecting body is strontium lanthanum titanate, the thickness is 25 μm, the cathode It is LSM-YSZ (strontium-doped lanthanum manganite-yttria stabilized zirconia), the electrochemical reaction layer of the cathode is 32 μm, and the thickness of the current-collecting conductive layer of the cathode is 50 μm. The heat isolation section 13 has a length of 200 mm, and the bottom layer of the outer wall of the porous inert support tube 4 is coated with strontium lanthanum titanate, and the outer layer is coated with lanthanum cobaltate. The length of the battery connection terminal is 50mm, wherein the length of the cathode connection terminal is 20mm, the length of the anode connection terminal is 20mm, and the interval between them is 10mm.

During the battery test, the outer tube was ventilated with 12L min ^-1 of air, and the inner tube was ventilated with hydrogen gas of 1000ml min ^-1 , to test its electrical output performance at 800°C. Under normal pressure, when the output voltage of the battery tube is 64V, the output current is 1.1A, and the output power is 70.4W.

Example 3

According to the method described in Example 1, 80 β batteries were prepared. Wherein, the porous inert support tube 4 is a magnesium aluminum spinel tube with a diameter of 15 mm and a porosity of the tube wall of 42%. The inlet gas isolation section 11 has a length of 100mm, and the surface is coated with 8mol% yttria-stabilized zirconia dense film. The length of the battery segment 12 connected in series is 1200mm, and the length of each battery is 15mm. The anode is NiO-YSZ (nickel oxide-strontium doped lanthanum manganite), the thickness is 45 μm, the electrolyte is 8mol% yttria stabilized zirconia, the thickness is 20 μm, the connecting body is strontium lanthanum titanate, the thickness is 25 μm, the cathode It is LSM-YSZ (strontium-doped lanthanum manganite-yttria stabilized zirconia), the electrochemical reaction layer of the cathode is 32 μm, and the thickness of the current-collecting conductive layer of the cathode is 50 μm. The heat isolation section 13 has a length of 200 mm, and the bottom layer of the outer wall of the porous inert support tube 4 is coated with strontium lanthanum titanate, and the outer layer is coated with lanthanum cobaltate. The length of the battery connection terminal is 50mm, wherein the length of the cathode connection terminal is 20mm, the length of the anode connection terminal is 20mm, and the interval between them is 10mm.

During the battery test, 10L min ^-1 of air was passed through the inner tube, and 800ml min ^-1 of hydrogen gas was passed through the outer tube to test its electrical output performance at 800°C. Under normal pressure, when the output voltage of the battery tube is 64V, the output current is 0.72A, and the output power is 46.1W.

Example 4

For the 80 α batteries prepared by the method described in Example 2, 5 80 α batteries are connected in parallel to form a battery tube row through the cathode common electrical connection metal strip and the anode common electrical connection metal strip, and then 10 battery tubes are connected in parallel. row to form a stack. The gas entering the battery tube is introduced through the fuel distribution tube, and the gas outside the battery tube is supplied to the battery through the gap of the battery tube.

During the stack test, 500L min ^-1 of air was passed through the outer tube, and 40L min ^-1 of hydrogen gas was passed through the inner tube, and its electrical output performance at 800°C was tested. Under normal pressure, the stack output power is 3000W.

Claims (10)

1. the porous inert of both ends open supports a tubular solid oxide fuel cells, it is characterized in that, comprises in a both ends open, pipe and has electron conduction to be communicated with but the porous inert stay pipe (4) of airtight partition; Load has functional sections different successively on described porous inert stay pipe: inlet gas distance piece (11), Stringing cells section (12), hot distance piece (13), battery terminal connections head (14), described difference in functionality section is prepared on porous inert stay pipe (4) by slurry dip-coating or pulp spraying coating method.

2. battery as claimed in claim 1, is characterized in that:

Described porous inert stay pipe (4) is the pipe of both ends open, one channel, and the external diameter of porous inert stay pipe is 3-30mm, and length is 63-2650mm, and the porosity of tube wall is 25-50%; The raw material of porous inert stay pipe is at least one in aluminium oxide, yttria-stabilized zirconia, stable calcium oxide zirconia, spinelle, violet cyanines stone, corundum-mullite.

3. battery as claimed in claim 1, is characterized in that:

In porous inert stay pipe (4), have a conduction and the middle shutoff (10) of airtight stay pipe, the middle shutoff (10) of porous inert stay pipe is positioned between Stringing cells section (12) and hot distance piece (13), for the oxide material of densified sintering product.

4. battery as claimed in claim 1, is characterized in that:

Described inlet gas distance piece (11) is positioned on the porous inert stay pipe of described cell gas inlet side, inlet gas distance piece length is 10-200mm, inlet gas distance piece has airtight membrane layer, and membrane layer material is at least one in yttria-stabilized zirconia, perovskite structure oxide, aluminium oxide.

5. battery as claimed in claim 1, is characterized in that:

Described Stringing cells section (12) is the battery of successively connecting be made up of anode layer (3), cathode layer (1), dielectric substrate (2) and connector layer (5), the length of every batteries is 4-50mm, on porous inert stay pipe, battery number is 10-50 joint, and the length of Stringing cells section is 40-2500mm;

Wherein, the electrolyte material in dielectric substrate is the one in cerium oxide base oxygen ion conductor, zirconia base oxygen ion conductor, lanthanum gallium based perovskite type oxide;

Anode in anode layer is the composite anode of metal-electrolyte, and in anode, raw metal is transition metal oxide, or is the transition metal oxide of doping vario-property, and the weight content of raw metal is 40-60%;

Negative electrode in cathode layer is the composite cathode of perovskite composite oxide and electrolyte used, the weight content of perovskite composite oxide is 40-60%, and connector material is at least one in lanthanum strontium chromate, strontium titanate lanthanum, strontium lanthanum manganese oxide, lanthanum strontium cobalt iron oxide;

Wherein, anode layer thickness is 15-100 μm, and cathode electrode layer thickness is 15-100 μm, and dielectric substrate thickness is 5-50 μm, and connector layer thickness is 20-100 μm.

6. battery as claimed in claim 1, is characterized in that:

Described hot distance piece (13) scribbles electronic conductive layer on the inside and outside wall of porous inert stay pipe, electronic conductive layer one end connects the electrode of battery, the other end connects corresponding battery terminal connections head, the length of hot distance piece is 10-300mm, and electronic conductive layer material is at least one in lanthanum strontium chromate, strontium titanate lanthanum, strontium lanthanum manganese oxide, lanthanum strontium cobalt iron oxide.

7. battery as claimed in claim 1, is characterized in that:

Described battery terminal connections head comprises anode connection end (18) and cathode connection terminal head (17), battery terminal connections head connects the corresponding termination electrode of whole battery by the electronic conductive layer on porous inert stay pipe outer wall or inwall, and the length of battery terminal connections head section is 3-50mm.

8. battery as claimed in claim 1, is characterized in that:

Described Solid Oxide Fuel Cell comprises the battery of 2 kinds of structures: AEC and BEC beta electric cell;

The direct load of anode of the Stringing cells section (12) of AEC is on porous inert stay pipe, and negative electrode is exposed to outside pipe;

The direct load of negative electrode of the Stringing cells section (12) of BEC beta electric cell is on porous inert stay pipe, and anode is exposed to outside pipe.

9. the preparation method of the porous inert pipe support solid oxide fuel cell of a kind of both ends open as described in above-mentioned any one claim, it is characterized in that, concrete steps comprise:

(1) preparation of the porous inert stay pipe of both ends open: after stay pipe raw material, organic binder bond, pore creating material and deionized water are mixed, by to extrude or slip casting method prepares the porous inert stay pipe green compact of both ends open, the middle shutoff (10) of stay pipe is added in stay pipe green compact, then punch on tube wall, filled conductive connecting material, finally green compact are calcined at 1100-1450 DEG C, obtain the porous inert stay pipe of both ends open;

(2) preparation of each functional section on porous inert stay pipe: the material forming each functional section is added organic binder bond, organic solvent obtains functional layer slurry, according to the composition of each functional section and the position at porous inert stay pipe thereof, the slurry of corresponding function section is applied according to the order of sequence by spraying or dip-coating method, then at high temperature calcine, obtain corresponding function section, through the coating of repeatedly slurry and calcining step, obtain all functions section of load on porous inert stay pipe;

Wherein, organic binder bond is polyvinyl alcohol, at least one in methylcellulose, polyvinyl alcohol; Pore creating material is at least one in starch, active carbon, cellulose acetate; Organic solvent is at least one in ethanol, ethylene glycol, glycerol, isobutanol, acetone, butanone.

10. the porous inert of a kind of both ends open as claimed in claim 1 supports the pile that tubular solid oxide fuel cells builds, and it is characterized in that:

The Solid Oxide Fuel Cell being connected in parallel the support of porous inert pipe by negative electrode common electrical bonding ribbon (21) and anode common electrical bonding ribbon (22) forms cell tube row, and then different pipe is arranged in parallel or is connected in series formation pile;

The gas entered in the porous inert stay pipe of the pile of α structure battery is introduced by fuel rail (191), in the porous inert stay pipe entering the pile of beta structure battery, gas is introduced by air distribution (192), and the gas outside porous inert stay pipe is by the supply of porous inert stay pipe gap.