CN115084614A - Solid oxide fuel cell stack - Google Patents
Solid oxide fuel cell stack Download PDFInfo
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- CN115084614A CN115084614A CN202210995731.9A CN202210995731A CN115084614A CN 115084614 A CN115084614 A CN 115084614A CN 202210995731 A CN202210995731 A CN 202210995731A CN 115084614 A CN115084614 A CN 115084614A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
- H01M8/2425—High-temperature cells with solid electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0297—Arrangements for joining electrodes, reservoir layers, heat exchange units or bipolar separators to each other
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/0432—Temperature; Ambient temperature
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/04537—Electric variables
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/04537—Electric variables
- H01M8/04544—Voltage
- H01M8/04552—Voltage of the individual fuel cell
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2465—Details of groupings of fuel cells
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention provides a solid oxide fuel cell stack, comprising: the electric pile integral structure is formed by stacking a plurality of electric pile repeating units; conducting posts are respectively led out from the cathode side and the anode side of the whole galvanic pile structure; the electric pile repeating unit comprises a single cell, a first metal net, a connecting plate and a second metal net from bottom to top in sequence; the lower side of the single cell is an anode, and the upper side of the single cell is a cathode; an air flow channel is arranged at the lower side of the connecting plate, and the upper side of the connecting plate is a plane; and conductive leads are respectively led out of the first metal net, the air flow channel on the lower side of the connecting plate and the second metal net. Compared with the prior art, the solid oxide fuel cell stack provided by the invention adopts a specific structure to realize better integral interaction under a specific connection relation, improves the interface contact among modules in the stack, can realize in-situ monitoring of the electrical properties of each cell, a connecting plate and other components in the stack, and simultaneously detects the temperature field and gas phase distribution of the stack in real time.
Description
Technical Field
The invention relates to the technical field of galvanic piles, in particular to a solid oxide fuel cell galvanic pile.
Background
The hydrogen energy and fuel cell technology is an important innovative technology for promoting economic society to realize low-carbon environmental protection development, and is a strategic choice for China to deal with global climate change, ensure national energy supply safety and realize sustainable development. In recent years, hydrogen energy and fuel cell technology have become important development directions of energy strategies in China. The fuel cell is classified into a proton exchange membrane fuel cell, a solid oxide fuel cell, an alkaline fuel cell, and the like. Solid Oxide Fuel Cells (SOFCs), as a kind of all-Solid Fuel cell, are a highly efficient and clean energy technology, and can directly convert chemical energy of fuels such as methane and hydrogen into electric energy or heat energy without generating any harmful substances. The SOFC has the advantages of adjustable power, continuity and stability, low exhaust emission, high combined power generation efficiency, low battery cost and the like, and is suitable for the fields of small household power supplies, distributed power stations, military portable power supply systems and the like. Under the background of energy shortage in the 21 st century and strict requirements on environmental protection, the SOFC has important research value on a new energy technology without environmental pollution and is widely concerned in various fields.
The SOFC pile mainly comprises a flat plate type, a circular tube type and a flat tube type. The flat SOFC has high space utilization rate and relatively simple preparation, but has longer start and stop; the circular tube type SOFC has strong thermal shock resistance, short start-up and shut-down, but low space utilization rate and volume power density; the flat-tube SOFC has the structural advantages of both flat plates and round tubes, is one of important development directions of SOFC technology, and the thick support anode greatly improves the mechanical strength of the cell, has strong thermal shock resistance and also improves the long-term operation stability of the cell. However, the single cells have low power, the Open Circuit Voltage (OCV) is only 1.23V at most, and the application field is limited, so that a plurality of single cells and a connecting plate are required to be assembled into a stack between kilowatt and megawatt, and a flat-tube type high-power stack is required. The SOFC electric pile has harsh operation environment, the working temperature is 650-850 ℃, and the whole electric pile is sealed and isolated from external air. The analysis of the voltage of the monocell inside the electric pile, the resistance of the connecting plate and the interface contact resistance between the monocell and the connecting plate needs to be carried out under the condition of not damaging the internal structure of the electric pile and simultaneously not influencing the normal operation of the electric pile. However, the problems that the performance of the elements inside the galvanic pile cannot be detected in real time or the detection signals are unstable and the like exist at present, if the performance of the galvanic pile suddenly drops, the testing can be stopped by cooling, the galvanic pile is disassembled for analysis, the disassembled galvanic pile can not be reused, the resource waste is caused, and the galvanic pile cost is greatly increased.
The current detection method for the electric pile mostly focuses on the proton exchange membrane fuel cell pile, because the structure of the proton exchange membrane fuel cell pile is different from that of the solid oxide fuel cell pile, the detection method for the proton exchange membrane fuel cell pile is not suitable. There are many test systems for solid oxide fuel cells, but the specific operation of the test in the stack is not described in detail.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a solid oxide fuel cell stack, which improves the interface contact between modules in the stack, and can implement in-situ monitoring of the electrical performance of each cell, a connection board, and other components in the stack, and simultaneously detect the temperature field and the gas phase distribution of the stack in real time.
The invention provides a solid oxide fuel cell stack, comprising:
the electric pile integral structure is formed by stacking a plurality of electric pile repeating units; conducting posts are respectively led out from the cathode side and the anode side of the whole galvanic pile structure;
the electric pile repeating unit comprises a single cell, a first metal net, a connecting plate and a second metal net from bottom to top in sequence; the lower side of the single cell is an anode, and the upper side of the single cell is a cathode; an air flow channel is arranged at the lower side of the connecting plate, and the upper side of the connecting plate is a plane; and conductive leads are respectively led out of the first metal net, the air flow channel on the lower side of the connecting plate and the second metal net.
Preferably, the number of the pile repeating units is 2-40.
Preferably, the single cell is a single-cathode flat-tube structure solid oxide fuel cell.
Preferably, the single-cathode flat-tube structure solid oxide fuel cell has the structure that:
8YSZ|NiO-8YSZ|NiO-YSZ|NiO-8YSZ|8YSZ|GDC|LSC；
wherein, 8YSZ is electrolyte, NiO-8YSZ is active anode, NiO-YSZ is anode support, GDC is barrier layer, LSC is cathode layer.
Preferably, the thickness of the 8YSZ is 7-9 μm; the thickness of the NiO-8YSZ is 4-6 mu m; the size of the NiO-YSZ is (150-160) mmX (60-62) mmX (4-6) mm, and fuel flow passage holes with the diameter of 0.5-1.5 mm are uniformly distributed in the middle of the NiO-YSZ; the thickness of the GDC is 1-3 mu m; the LSC has a size of (120-130) mmx (60-62) mm and a thickness of 10-20 μm.
Preferably, a rectangle with the thickness of (40-60) mmx (120-140) mm is arranged in the middle of one surface of the single-cathode flat-tube type solid oxide fuel cell and is used as an electron current collecting window, and the other surface of the single-cathode flat-tube type solid oxide fuel cell is a cathode layer.
Preferably, the first metal net is a silver net or a platinum net; the first metal net has a thickness of 0.05mm to 0.15m and a mesh size of (0.2 to 0.4) mmx (0.5 to 0.7) mm.
Preferably, the connecting plate is made of Crofer22 metal, SUS430 metal or SUS441 metal;
the air flow channel of the connecting plate is a groove with the thickness of 1 mm-2 mm.
Preferably, the second metal net is a nickel net; the thickness of the second metal net is 0.05 mm-0.1 m, and the mesh size is (0.1-0.3) mmx (0.3-0.5) mm.
Preferably, the conductive lead is made of Crofer22 metal, SUS430 metal or SUS441 metal;
the diameter of the conductive lead is 0.4 mm-0.6 mm.
The invention provides a solid oxide fuel cell stack, comprising: the electric pile integral structure is formed by stacking a plurality of electric pile repeating units; conducting posts are respectively led out from the cathode side and the anode side of the whole galvanic pile structure; the electric pile repeating unit comprises a single cell, a first metal net, a connecting plate and a second metal net from bottom to top in sequence; the lower side of the single cell is an anode, and the upper side of the single cell is a cathode; an air flow channel is arranged at the lower side of the connecting plate, and the upper side of the connecting plate is a plane; and conductive leads are respectively led out of the first metal net, the air flow channel on the lower side of the connecting plate and the second metal net. Compared with the prior art, the solid oxide fuel cell stack provided by the invention adopts a specific structure to realize better integral interaction under a specific connection relation, improves the interface contact among modules in the stack, can realize in-situ monitoring of the electrical properties of each cell, a connecting plate and other components in the stack, and simultaneously detects the temperature field and gas phase distribution of the stack in real time.
Drawings
Fig. 1 is a schematic diagram of an assembled three-dimensional structure of a solid oxide fuel cell stack according to an embodiment of the present invention;
fig. 2 is a schematic diagram of a complex unit structure of a solid oxide fuel cell stack according to an embodiment of the present invention;
fig. 3 is a current-voltage characteristic curve of a solid oxide fuel cell stack according to an embodiment of the present invention;
fig. 4 is a discharge curve of a single cell and a connecting plate in a solid oxide fuel cell stack according to an embodiment of the present invention;
fig. 5 is an interface resistance between a single cell and a connection plate in a constant current discharge process of a solid oxide fuel cell stack according to an embodiment of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a solid oxide fuel cell stack, comprising:
the electric pile integral structure is formed by stacking a plurality of electric pile repeating units; conducting posts are respectively led out from the cathode side and the anode side of the whole galvanic pile structure;
the electric pile repeating unit comprises a single cell, a first metal net, a connecting plate and a second metal net from bottom to top in sequence; the lower side of the single cell is an anode, and the upper side of the single cell is a cathode; an air flow channel is arranged at the lower side of the connecting plate, and the upper side of the connecting plate is a plane; and conductive leads are respectively led out of the first metal net, the air flow channel on the lower side of the connecting plate and the second metal net.
Aiming at the problem that the prior art (1) cannot monitor the performance of components in a high-power electric pile in situ; (2) when the electric pile runs for a long time, the power of the electric pile is reduced due to the increase of interface resistance; (3) the technical problem that signals such as temperature and the like at each position in the stack cannot be monitored and recorded in situ is solved, and the solid oxide fuel cell stack is provided, so that on one hand, the electric signals and the temperature signals of each cell, a connecting plate and other components in the stack can be monitored in situ, and interface resistance data can be obtained through calculation; on the other hand, interface contact between the anode of the battery and the connecting plate and between the cathode of the battery and the connecting plate in the galvanic pile can be improved; the temperature field and the gas phase distribution in the electric pile can be detected in real time, and the electric pile can be fixed at any position of the metal net through a thermocouple or a gas collecting pipe, so that the temperature and the gas phase distribution of each position of the battery can be detected.
In the present invention, the solid oxide fuel cell stack includes: the electric pile integral structure is formed by stacking a plurality of electric pile repeating units; and conductive columns are respectively led out from the cathode side and the anode side of the whole galvanic pile structure.
In the invention, the number of the pile repeating units is preferably 2-40, and more preferably 3-10.
In the invention, the cell stack repeating unit comprises a single cell, a first metal net, a connecting plate and a second metal net from bottom to top in sequence; the lower side of the single cell is an anode, and the upper side of the single cell is a cathode; an air flow channel is arranged at the lower side of the connecting plate, and the upper side of the connecting plate is a plane; and conductive leads are respectively led out of the first metal net, the air flow channel on the lower side of the connecting plate and the second metal net.
In the present invention, the single cell is preferably a single-cathode flat-tube structure solid oxide fuel cell; the structure of the single-cathode flat-tube structure solid oxide fuel cell is preferably as follows:
8YSZ|NiO-8YSZ|NiO-YSZ|NiO-8YSZ|8YSZ|GDC|LSC；
wherein, 8YSZ is electrolyte, NiO-8YSZ is active anode, NiO-YSZ is anode support, GDC is barrier layer, LSC is cathode layer.
In the invention, the thickness of the 8YSZ is preferably 7-9 μm, and more preferably 8 μm; the thickness of the NiO-8YSZ is preferably 4-6 μm, and more preferably 5 μm; the size of the NiO-YSZ is preferably (150-160) mm multiplied by (60-62) mm multiplied by (4-6) mm, more preferably 155mm multiplied by 61mm multiplied by 5mm, and fuel flow channel holes with the diameter of 0.5 mm-1.5 mm are uniformly distributed in the middle; the thickness of the GDC is preferably 1-3 μm, and more preferably 2 μm; the LSC preferably has a size of (120-130) mm x (60-62) mm, more preferably 125mm x 61mm, and a thickness of 10-20 μm, more preferably 15 μm.
In the invention, one surface of the single-cathode flat tube type structure solid oxide fuel cell is preferably provided with a rectangle with a thickness of (40-60) mm multiplied by (120-140) mm (more preferably 50mm multiplied by 130 mm) as an electronic current collecting window, and the other surface is a cathode layer.
In the present invention, the first metal mesh is preferably a silver mesh or a platinum mesh; the thickness of the first metal net is preferably 0.05mm to 0.15m, more preferably 0.1mm, and the mesh size is preferably (0.2 to 0.4) mm x (0.5 to 0.7) mm, more preferably 0.3mm x 0.6 mm.
In the present invention, the material of the connecting plate is preferably Crofer22 metal, SUS430 metal or SUS441 metal, and more preferably SUS441 metal; the material is metal with good conductivity and strong oxidation resistance, and the source of the material is not particularly limited.
In the invention, the air flow channel of the connecting plate is preferably a groove with the thickness of 1 mm-2 mm, and more preferably a groove with the thickness of 1.5 mm.
In the present invention, the second metal mesh is preferably a nickel mesh; the thickness of the second metal net is preferably 0.05mm to 0.1m, and the mesh size is preferably (0.1 to 0.3) mm x (0.3 to 0.5) mm, and more preferably 0.2mm x 0.4 mm.
In the present invention, the material of the conductive lead is preferably Crofer22 metal, SUS430 metal, or SUS441 metal, and more preferably SUS441 metal; the diameter of the conductive lead is preferably 0.4 mm-0.6 mm, and more preferably 0.5 mm.
In the invention, as shown in fig. 1-2, fig. 1 is a schematic diagram of an assembled three-dimensional structure of a solid oxide fuel cell stack provided by an embodiment of the invention, wherein 1 is a conductive column, 2 is a repeating unit (i), 3 is a repeating unit (ii), 4 is a lead (i), 5 is a lead (ii), 6 is a lead (iii), 7 is a single cell, 8 is a metal mesh, and 9 is a connecting plate; fig. 2 is a schematic diagram of a multiple-unit structure of a solid oxide fuel cell stack according to an embodiment of the present invention, where 4 is a lead (i), 5 is a lead (ii), 6 is a lead (iii), 7 is a single cell, 8 is a metal mesh, and 9 is a connecting plate; the preparation method of the solid oxide fuel cell stack preferably comprises the following steps:
(1) preparation of the components:
the single cell selects a single-cathode flat-tube type structure solid oxide fuel cell, firstly an anode support body NiO-YSZ is prepared through an extrusion column forming method, a layer of active anode NiO-8YSZ is prepared on the outer side of the anode support body through a screen printing method, a layer of electrolyte 8YSZ is prepared on the outer side of the active anode, a rectangle of (40-60) mmX (120-140) mm is arranged in the middle of one surface of the cell and used as an electronic current collecting window, a blocking layer GDC is continuously screen printed on the outer layer of the electrolyte, and a cathode layer is screen printed on the other surface of the cell.
A thin metal mesh (silver mesh or platinum mesh) with good conductivity is added between the cathode of the single cell and the connecting plate, and the area of the metal mesh is the same as that of the cathode as shown by a metal mesh 8 (below the connecting plate 9) in fig. 2.
A nickel mesh metal net is added between the single cell anode and the connecting plate, the position of the nickel mesh metal net is shown as a metal mesh 8 (above the connecting plate 9) in fig. 2, and the area of the metal mesh is consistent with that of the current collecting window.
The material of the conducting lead is preferably consistent with that of the connecting plate, so that interface contact is improved under high pressure, and test errors are reduced; the contact part of the conductive lead and the galvanic pile is rolled into a thin sheet with the thickness of 0.1-0.3 mu m by a roller press.
Material treatment of the conductive lead: silk-screening a battery cathode material with the thickness of about 10 microns on the surface of the contact part of the conductive lead and the cathode of the cell stack, wherein the battery cathode material can be LSC, LSCF, LSM and the like, and preferably is LSC; the material treatment is consistent with the material of the battery cathode, so that the contact resistance among different parts can be reduced, and the accuracy of signal collection is improved.
(2) Assembling the galvanic pile:
by repeating the unit (i): the battery pack comprises a single battery, a first metal net, a connecting plate and a second metal net; a repeating unit (c): the single cells, the first metal net, the connecting plate and the second metal net are assembled in a continuous stacking mode, the number of the repeating units is three, and the conductive columns are respectively led out from the cathode and the anode of the electric pile and can be used for collecting current and voltage signals.
In the invention, the electric pile is an electric pile assembled by hollow flat tube type batteries; and conductive columns are respectively led out from the cathode and the anode of the electric pile, so that power loss caused by long electronic transmission path is avoided.
The conductive lead is placed in the groove in the flow channel, as shown by a lead II (reference numeral 5) in fig. 2, the contact between a monocell and a connecting plate can be avoided, the accuracy is improved, and the conductive lead is fixed on the metal connecting plate through welding, is convenient, stable and cannot be broken, so that test interruption and data loss are avoided; the conductive lead can also be placed at different positions to analyze different performance parameters, such as the anode of the battery and the cathode of the connecting plate, as shown by the lead I (reference numeral 4) in fig. 2, the interface contact resistance between the cathode of the battery and the connecting plate and the interface contact resistance between the anode of the battery and the connecting plate can be respectively analyzed; because the interface contact resistance of the galvanic pile can not be directly tested in the actual operation process, the interface contact resistance can only be tested through a simulation model, but the method can be directly tested in the actual operation process of the galvanic pile; because the components for lead test comprise the battery and the connecting plate, the lead test can not be performed due to the lower resistance of the connecting plate, and meanwhile, the precision of test equipment can be reduced, and the cost is reduced.
Thermocouple or conductive lead wires with the diameter of 0.5mm and the like are fixed on the metal mesh in an inserting mode, as shown by a lead wire (I) (reference numeral 4) in fig. 2, the lead wires can be firmly fixed, and test interruption and data loss caused by lead wire displacement or local fracture in the operation process of the galvanic pile are avoided; the thermocouple can be fixed at the gas inlet, the center of the pile, the outlet and other positions needing to be monitored, such as a lead wire (reference number 6) in FIG. 2; the gas collecting pipe can also be fixed in the air flow channel in an inserting mode, and the gas phase distribution of different areas of the electric pile can be tested by fixing the gas collecting pipe at different positions.
In the invention, the performance of the cell, the connecting plate and other components in the stack can be monitored in real time; the conductive lead is added between the battery and the connecting plate, so that the internal structure of the galvanic pile is not damaged, the normal operation of the galvanic pile is not influenced, the testing method is simple and easy to operate, the cost of the lead is low, and the lead can be used repeatedly; the conductive leads can be fixed at different positions on the connecting plate in a welding mode; the conductive lead can be subjected to surface treatment, so that the influence of the addition of the conductive lead on the normal test of the galvanic pile is avoided.
In the invention, a metal net is additionally arranged between the anode of the battery and the connecting plate, and the cathode of the battery and the connecting plate, and a conductive lead, a thermocouple or a gas collecting pipe can be fixed on the metal net in an inserting way; the device can be fixed at any position on a metal net to monitor the performance of each area in real time; the method can not only detect the performance of each component such as a single cell, a connecting plate and the like in the electric pile, but also obtain the interface contact resistance between the single cell and the connecting plate, improve the interface contact between the cell and the connecting plate and improve the discharge power of the electric pile.
(3) The electric signal processing method comprises the following steps:
the conducting columns of the anode and the cathode of the electric pile can collect data such as current, voltage, power and the like, and the voltage loss of the electric pile caused by too long electronic transmission path in the test process is avoided. The voltage and resistance signal changes among the single batteries, the connecting plates and the component parts of the electric pile in the open circuit and discharge process can be detected through the conductive leads. The voltage of the connecting plate can be obtained by subtracting the voltage of the battery from the voltage of the battery and the voltage of the connecting plate through testing, and then the resistance of the connecting plate is obtained through current data calculation, so that the situation that the resistance of the connecting plate is too small and cannot be detected is avoided.
If the single cell fails in the actual operation of the electric pile, the single cell can be short-circuited by contacting the leads on the two sides of the cathode and the anode of the single cell, and the power output of the single cell is directly abandoned, so that the total power of the electric pile is prevented from being influenced or the electric pile fails, and the electric pile is prevented from being scrapped.
The beneficial effects of the solid oxide fuel cell stack provided by the invention are specifically explained as follows:
(1) in-situ monitoring the electrical properties of each cell, a connecting plate and other components in the pile;
the SOFC (solid oxide fuel cell) stack has higher discharge power and higher assembly cost, and can only detect the total output performance of the stack when being operated in a high-temperature and closed environment after being assembled, so that the operation conditions of an internal single cell, a connecting plate and modules thereof in the stack are difficult to detect, but the performance of one unit module can influence the total output performance of the stack, including current and voltage; the running conditions of each component inside the galvanic pile cannot be obtained through the total current and total voltage data of the galvanic pile, and the performance of the components forming the galvanic pile cannot be evaluated; for example, the failure of one single cell can cause the interface resistance to be large, the current to be reduced, if the reason cannot be analyzed to improve the situation, the operation of the cell stack can only be stopped, and the cell stack cannot be used any more, thereby causing resource waste; therefore, the elements in the electric pile need to be monitored in real time on the premise of not damaging the internal structure; if the abnormal condition is monitored, a specific module with a problem can be analyzed, and operation processing is carried out in time; the performance of each component can be detected by a method of simulating the operating environment of the galvanic pile, and the actual operating environment of the galvanic pile is complex and can be analyzed only by real-time detection.
The invention can analyze the voltage of a single cell in the galvanic pile and the voltage of a connecting plate under the condition of not influencing the normal operation of the galvanic pile, and then calculate the power of the cell and the resistance of the connecting plate according to the current signal; different performance parameters can be analyzed by placing the conductive lead at different positions, such as the anode of the battery and the cathode of the connecting plate, and the interface contact resistance between the cathode of the battery and the connecting plate and between the anode of the battery and the connecting plate can be analyzed; because the interface contact of the galvanic pile can not be directly tested in the actual operation process, the galvanic pile can only be tested through a simulation model, and the method can be directly tested in the actual operation process of the galvanic pile; if a single cell in the electric pile is detected to be out of work in actual operation, the single cell can be short-circuited by contacting the conductive leads on the two sides of the cathode and the anode of the single cell, so that the influence of the out-of-work of the single cell on the total output power of the electric pile is avoided, and the stop of the electric pile operation is also avoided.
(2) Interface contact among modules in the galvanic pile is improved;
the reasons for influencing the overall output performance of the electric pile are many, including the performance of each component and the contact between the components; the operation life requirement of the cell stack is usually more than 100000h, the assembly of components is also an important factor influencing the output performance of the cell stack during the long-term discharge operation of the cell stack, and if the contact between the battery and the connecting plate is poor, the interface contact resistance is increased, so that the output current of the cell stack is reduced.
By adding a thin metal mesh with good conductivity such as silver mesh between the single cell and the connecting plate, the contact area between the flow channel side of the connecting plate and the cathode of the cell can be increased due to high conductivity and low hardness, so that the interface contact resistance is reduced, and the discharge power of the cell stack is increased.
(3) Detecting the temperature field and gas phase distribution of the electric pile in real time;
the SOFC galvanic pile has larger discharge power and higher assembly cost, and the SOFC galvanic pile runs in a high-temperature and closed environment after being assembled, so that the running conditions of the internal monocells and the connecting plate modules in the galvanic pile are difficult to detect, and meanwhile, the performance of one unit module can influence the total output performance of the galvanic pile, including current and voltage; for example, the failure of one single cell causes the interface resistance to be suddenly large and the current to be reduced; therefore, the elements in the electric pile need to be monitored in real time on the premise of not damaging the internal structure; if the abnormal condition is monitored, the specific module with the problem can be analyzed, and the operation treatment can be carried out in time.
By adding the metal mesh between the battery and the connecting plate, the metal mesh can be used as an electronic collecting layer to improve the interface contact between the cathode of the battery and the connecting plate and between the anode of the battery and the connecting plate, and can also firmly fix the thermocouple at any position between the battery and the connecting plate, realize the temperature detection at any position in the electric pile and analyze the temperature field distribution in the electric pile; many other conductive leads can be added into the metal mesh, including a gas collecting pipe and the like, so that gas components at different positions can be collected, and the operation condition of the cells in the electric pile can be analyzed. The performance of different parts in different areas can be analyzed by placing the conductive leads at different positions.
The invention provides a solid oxide fuel cell stack, comprising: the electric pile integral structure is formed by stacking a plurality of electric pile repeating units; conducting posts are respectively led out from the cathode side and the anode side of the whole galvanic pile structure; the electric pile repeating unit comprises a single cell, a first metal net, a connecting plate and a second metal net from bottom to top in sequence; the lower side of the single cell is an anode, and the upper side of the single cell is a cathode; an air flow channel is arranged at the lower side of the connecting plate, and the upper side of the connecting plate is a plane; and the first metal net, the air flow channel on the lower side of the connecting plate and the second metal net are respectively led out with a conductive lead. Compared with the prior art, the solid oxide fuel cell stack provided by the invention adopts a specific structure to realize better integral interaction under a specific connection relation, improves the interface contact among modules in the stack, can realize in-situ monitoring of the electrical properties of each cell, a connecting plate and other components in the stack, and simultaneously detects the temperature field and gas phase distribution of the stack in real time.
To further illustrate the present invention, the following examples are provided for illustration.
Examples
Referring to fig. 1-2, fig. 1 is a schematic diagram of an assembled three-dimensional structure of a solid oxide fuel cell stack according to an embodiment of the present invention; fig. 2 is a schematic diagram of a complex unit structure of a solid oxide fuel cell stack according to an embodiment of the present invention.
By adding the conductive lead in the electric pile assembled by three single batteries, the collection of electric signals of the battery, the connecting plate and other components can be realized in the discharging process of the electric pile.
In the embodiment of the invention, three flat tube type SOFC monocells are selected to be assembled into a galvanic pile, and the monocell is a single-cathode flat tube type structure solid oxide fuel cell, and the structure is as follows:
8YSZ|NiO-8YSZ|NiO-YSZ|NiO-8YSZ|8YSZ|GDC|LSC；
wherein the anode support NiO-YSZ has the size of 155mm multiplied by 61mm multiplied by 5mm, and fuel flow passage holes with the diameter of 1mm are uniformly distributed in the middle; the outer side of the anode support body is provided with a layer of active anode NiO-8YSZ with the thickness of about 5 mu m; a layer of electrolyte, 8YSZ, with the thickness of about 8 μm is arranged at the outer side of the active anode, and a rectangle of 50mm multiplied by 130mm is arranged in the middle of one surface of the battery and is used as an electronic current collection window; a barrier layer GDC with the thickness of about 2 μm is arranged on the outer layer of the electrolyte; on the other side of the cell was a cathode layer of LSC material, 125mm x 61mm, approximately 15 μm thick.
The connecting plate material is SUS441 metal, one side of the connecting plate material, which is in contact with the cathode of the battery, is provided with an air flow channel, the air flow channel is a groove with the thickness of 1.5mm, and the other side of the connecting plate material, which is in contact with the anode of the battery, is a plane.
A thin metal net (platinum net) with good conductivity is added between the cathode of the single cell and the connecting plate, the position of the metal net is shown as a metal net 8 (below the connecting plate 9) in figure 2, the thickness is 0.1mm, the mesh is 0.3mm multiplied by 0.6mm, the area of the metal net is the same as that of the cathode, and because of the higher conductivity and the lower hardness, the contact area between the flow channel side of the connecting plate and the cathode of the cell can be increased, so that the interface contact resistance is reduced, and the discharge power of the cell stack is increased.
A nickel net metal net is added between the monocell anode and the connecting plate, the position of the nickel net metal net is shown as a metal net 8 (above the connecting plate 9) in figure 2, the thickness of the nickel net metal net is 0.05 mm-0.1 mm, the mesh is 0.2mm multiplied by 0.4mm, and the area of the metal net is consistent with that of the current collecting window.
The conductive lead is made of SUS441 with the diameter of 0.5mm, and the contact part of the conductive lead and the galvanic pile is rolled into a sheet with the thickness of 0.1-0.3 mu m by a roll squeezer; and screen printing the battery cathode material on the surface of the contact part of the conductive lead and the cathode of the stack battery, wherein the thickness of the battery cathode material is about 10 mu m.
When assembled according to the configuration of fig. 1, six conductive leads are placed at the cathode and anode of the battery # 1#2#3 (first conductive lead | anode of battery # 1 | second conductive lead | cathode of battery # 1 | third conductive lead | anode of battery # 2 | fourth conductive lead | cathode of battery # 2 | fifth conductive lead | anode of battery #3 | sixth conductive lead | battery #3 cathode) respectively for collecting voltage signals, the conductive leads being fixed by a metal mesh.
After the three cells were assembled according to the structure shown in fig. 1, the cells were placed in a heating furnace to maintain the stack at 750 ℃. And 0.6SLM hydrogen is introduced to the anode side of the cell for reduction, and 1.8SLM air is introduced to the cathode side of the cell. After 4 hours of reduction, the transient discharge test was started, hydrogen was introduced into 2SLM, and air was introduced into 6SLM, to obtain the voltammetry characteristics of the cell stack as shown in fig. 3.
Fig. 3 is a current-voltage-power curve of a three-unit cell stack during transient discharge, with current and voltage signals collected by conductive pillars on the cathode and anode sides of the stack, with a voltage of 3V and a power of 64.8W.
While the data of fig. 3 can only be obtained by a general stack test, the solid oxide fuel cell stack provided by the present invention can simultaneously obtain the data of the single cell and the connecting plate shown in fig. 4 during the discharging process.
The discharge test method is the same as the electric pile, so that the discharge curves of the single battery and the connecting plate in the three-unit electric pile in the figure 4 are obtained, the I-V data of the battery # 1 are obtained through the first conductive lead and the second conductive lead on the two sides of the battery, and the power P is obtained through I multiplied by V calculation; the same is true for battery # 2#3, while the data for battery # 1+ connection plate is obtained through the first and third conductive leads.
The instantaneous single cell performance in the cell stack and the resistance of the connecting plate can be analyzed in situ through the data; meanwhile, the power sum of the three batteries and the connecting plate is 69.5W, which is slightly larger than the power of the electric pile by 64.8W. It is therefore speculated that the contact between the cells is optimized and the interfacial resistance loss is reduced by testing with the stack of the present invention.
The three-unit cell stack was subjected to constant current discharge for 107 hours at a current of 14A, and fig. 5 shows the interface resistance between the single cell and the connecting plate during the constant current discharge, including the interface resistance between the cell anode and the connecting plate, and between the cell cathode and the connecting plate. It can be seen that the interface resistance change of the galvanic pile in the long-term discharge process can be obtained through the galvanic pile, and the interface resistance values in the figure are all less than 0.3m omega.
In conclusion, the solid oxide fuel cell stack provided by the invention has the following beneficial effects:
(1) the solid oxide fuel cell stack provided by the invention can realize in-situ monitoring of the electrical properties of each cell, the connecting plate and other components in the stack, and the interface resistance between the cell and the connecting plate does not damage the internal structure of the stack and influence the discharge property output of the stack;
(2) the electric performance of each cell, a connecting plate and other components in the galvanic pile can be detected, and the interface contact between the cell anode and the connecting plate and between the cell cathode and the connecting plate in the galvanic pile can be improved;
(3) detecting the temperature field and gas phase distribution in the galvanic pile in real time; the thermocouple or the gas collecting pipe can be fixed at any position of the metal mesh, so that the temperature and gas phase distribution of each position of the battery can be detected.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A solid oxide fuel cell stack, comprising:
the electric pile integral structure is formed by stacking a plurality of electric pile repeating units; conducting posts are respectively led out from the cathode side and the anode side of the whole galvanic pile structure;
the electric pile repeating unit comprises a single cell, a first metal net, a connecting plate and a second metal net from bottom to top in sequence; the lower side of the single cell is an anode, and the upper side of the single cell is a cathode; an air flow channel is arranged at the lower side of the connecting plate, and the upper side of the connecting plate is a plane; and conductive leads are respectively led out of the first metal net, the air flow channel on the lower side of the connecting plate and the second metal net.
2. The solid oxide fuel cell stack of claim 1, wherein the number of stack repeating units is 2 to 40.
3. The solid oxide fuel cell stack of claim 1, wherein the single cell is a single cathode flat tube structure solid oxide fuel cell.
4. The solid oxide fuel cell stack of claim 3, wherein the single-cathode flat tube structure solid oxide fuel cell has a structure of:
8YSZ|NiO-8YSZ|NiO-YSZ|NiO-8YSZ|8YSZ|GDC|LSC；
wherein 8YSZ is electrolyte, NiO-8YSZ is active anode, NiO-YSZ is anode support, GDC is barrier layer, and LSC is cathode layer.
5. The solid oxide fuel cell stack of claim 4, wherein the 8YSZ has a thickness of 7-9 μm; the thickness of the NiO-8YSZ is 4-6 mu m; the size of the NiO-YSZ is (150-160) mmX (60-62) mmX (4-6) mm, and fuel flow passage holes with the diameter of 0.5-1.5 mm are uniformly distributed in the middle of the NiO-YSZ; the thickness of the GDC is 1-3 mu m; the LSC has a size of (120-130) mmx (60-62) mm and a thickness of 10-20 μm.
6. The solid oxide fuel cell stack of claim 4, wherein the single-cathode flat tube solid oxide fuel cell has a rectangle with a diameter of (40-60) mm x (120-140) mm formed in the middle of one surface thereof to serve as an electron current collecting window, and a cathode layer formed on the other surface thereof.
7. The solid oxide fuel cell stack of claim 1, wherein the first metal mesh is a silver mesh or a platinum mesh; the first metal net has a thickness of 0.05mm to 0.15m and a mesh size of (0.2 to 0.4) mmx (0.5 to 0.7) mm.
8. The solid oxide fuel cell stack according to claim 1, wherein the material of the connection plate is Crofer22 metal, SUS430 metal, or SUS441 metal;
the air flow channel of the connecting plate is a groove with the thickness of 1 mm-2 mm.
9. The solid oxide fuel cell stack of claim 1, wherein the second metal mesh is a nickel mesh; the thickness of the second metal net is 0.05 mm-0.1 m, and the mesh size is (0.1-0.3) mmx (0.3-0.5) mm.
10. The solid oxide fuel cell stack of claim 1, wherein the conductive lead is made of Crofer22 metal, SUS430 metal or SUS441 metal;
the diameter of the conductive lead is 0.4 mm-0.6 mm.
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