CN115084614B - Solid oxide fuel cell stack - Google Patents
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- CN115084614B CN115084614B CN202210995731.9A CN202210995731A CN115084614B CN 115084614 B CN115084614 B CN 115084614B CN 202210995731 A CN202210995731 A CN 202210995731A CN 115084614 B CN115084614 B CN 115084614B
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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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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M8/02—Details
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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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- 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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- 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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- H01M8/04552—Voltage of the individual fuel cell
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- H01M8/2465—Details of groupings of fuel cells
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- 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) are a full Solid Fuel cell, are a high-efficiency 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 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 round 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 voltage of the monocells in the electric pile, the resistance of the connecting plate and the interface contact resistance between the monocells and the connecting plate need to be analyzed under the condition that the internal structure of the electric pile is not damaged and the normal operation of the electric pile is not influenced. 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 to 40.
Preferably, the single cell is a Shan Yinji flat tube type structure solid oxide fuel cell.
Preferably, the Shan Yinji flat tube type 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, and LSC is cathode layer.
Preferably, 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 to 160) mmX (60 to 62) mmX (4~6) mm, and fuel flow passage holes with the diameter of 0.5 to 1.5mm are uniformly distributed in the middle of the NiO-YSZ; the thickness of the GDC is 1~3 μm; the LSC has the size of (120 to 130) mmX (60 to 62) mm and the thickness of 10 to 20 mu m.
Preferably, a rectangle with the diameter of (40 to 60) mm multiplied by (120 to 140) mm is opened in the middle of one surface of the Shan Yinji flat tube type structure solid oxide fuel cell to be used as an electronic current collecting window, and the other surface of the solid oxide fuel cell is a cathode layer.
Preferably, the first metal net is a silver net or a platinum net; the thickness of the first metal net is 0.05mm to 0.15m, and the mesh size is (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 of 1mm to 2mm.
Preferably, the second metal mesh is a nickel mesh; the thickness of the second metal net is 0.05mm to 0.1m, and the mesh size is (0.1 to 0.3) mmX (0.3 to 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 a diagram illustrating the interface resistance between the single cell and the connection plate in the constant current discharge process of the solid oxide fuel cell stack according to the 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 galvanic pile integral structure is formed by stacking a plurality of galvanic 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 present invention, the number of the pile repeating units is preferably 2 to 40, and more preferably 3 to 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 invention, the single cell is preferably a Shan Yinji flat tube type structure solid oxide fuel cell; the Shan Yinji flat tube type solid oxide fuel cell preferably has the following structure:
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 present invention, the thickness of the 8YSZ is preferably 7~9 μm, 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 to 160) mmX (60 to 62) mmX (4~6) mm, more preferably 155mm X61 mm X5 mm, and fuel flow passage holes with the diameter of 0.5mm to 1.5mm are uniformly distributed in the middle; the thickness of the GDC is preferably 1~3 μm, more preferably 2 μm; the LSC preferably has a size of (120 to 130) mmX (60 to 62) mm, more preferably 125mm X61 mm, and a thickness of preferably 10 to 20 μm, more preferably 15 μm.
In the invention, the Shan Yinji flat tube type solid oxide fuel cell preferably has a rectangle with one surface opened with a thickness of (40 to 60) mm × (120 to 140) mm (more preferably 50mm × 130 mm) in the middle, and the other surface is a cathode layer as an electronic current collecting window.
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) mmx (0.5 to 0.7) mm, more preferably 0.3mm x 0.6mm.
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 of 1mm to 2mm, and more preferably a groove 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) mmX (0.3 to 0.5) mm, and more preferably 0.2mm X0.4 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 0.4mm to 0.6mm, and more preferably 0.5mm.
In the present invention, refer to fig. 1~2, where 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, where 1 is a conductive pillar, 2 is a repeating unit (1), 3 is a repeating unit (2), 4 is a lead (1), 5 is a lead (2), 6 is a lead (3), 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 (1), 5 is a lead (2), 6 is a lead (3), 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 method comprises the steps of selecting a Shan Yinji flat tube type structure solid oxide fuel cell as a single cell, firstly preparing an anode support NiO-YSZ by an extrusion column forming method, preparing a layer of active anode NiO-8YSZ outside the anode support through a screen printing method, preparing a layer of electrolyte 8YSZ outside the active anode, forming a rectangle with the thickness of (40 to 60) mm multiplied by (120 to 140) mm in the middle of one surface of the cell to serve as an electronic current collecting window, continuously screen printing a blocking layer GDC on the outer layer of the electrolyte, and screen printing a cathode layer on the other surface of the cell.
A thin metal net (silver net or 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 area of the metal net is the same as that of the cathode, and because of higher conductivity and 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 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 conducting lead and the galvanic pile is rolled into a sheet with the thickness of 0.1 to 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 processing 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 unit (1): the battery pack comprises a single battery, a first metal net, a connecting plate and a second metal net; repeating unit (2): 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 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 in a lead (2) (reference numeral 5) in fig. 2, the contact between a monocell and the connecting plate can be avoided, the accuracy is improved, and the conductive lead is fixed on the metal connecting plate by welding, is convenient and 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, for example, the conductive lead is placed at the anode of the battery and the cathode of the connecting plate, as shown by the lead (1) (reference numeral 4) in fig. 2, 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 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 (1) (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 breakage 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 (3) (reference numeral 6) in FIG. 2; the gas collecting pipe can also be fixed in the air flow channel in an inserting mode, and the gas collecting pipe can be fixed at different positions to test the gas phase distribution of different areas of the galvanic pile.
In the invention, the performance of the cell, the connecting plate and other components in the galvanic pile 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 components of the pile in the open circuit and discharge process can be detected through the conductive leads. The voltage of the battery can be subtracted from the voltage of the battery to obtain the voltage of the connecting plate through testing the voltage of the battery and the voltage of the connecting plate, 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 galvanic pile can not be directly tested due to interface contact in the actual operation process, the testing can only be carried out 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 electric pile is usually more than 100000h, the assembly among the components is also an important factor influencing the output performance of the electric pile in the long-term discharge operation process of the electric pile, 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 electric pile 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 thermoelectric couple 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 be firmly fixed at any position between the battery and the connecting plate, so that the temperature detection at any position in the galvanic pile is realized, and the temperature field distribution in the galvanic pile is analyzed; many other conductive leads can be added into the metal net, including a gas collecting pipe and the like, so as to collect gas components at different positions and analyze the operation condition of the cells in the electric pile. 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 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.
To further illustrate the present invention, the following examples are provided for illustration.
Examples
Referring to fig. 1~2, wherein 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 Shan Yinji flat tube type structure solid oxide fuel cell, which has the structure that:
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 side of the battery to be used as an electronic current collecting 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, 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, 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 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 net 8 (above the connecting plate 9) in figure 2, the thickness of the nickel mesh metal net is 0.05mm to 0.1mm, the mesh is 0.2mm multiplied by 0.4mm, and the area of the metal mesh 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 roller press; and screen-printing a 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, the six conductive leads are placed at the cathode and anode of cell # 1#2#3 (first conductive lead | cell # 1 anode | second conductive lead | cell # 1 cathode | third conductive lead | cell # 2 anode | fourth conductive lead | cell # 2 cathode | fifth conductive lead | cell #3 anode | sixth conductive lead | cell #3 cathode) respectively to collect voltage signals, and the conductive leads are 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 cell # 2#3, while the data for cell # 1+ connection board 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, a 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 (1)
1. A solid oxide fuel cell stack is characterized in that the stack is of an integral structure formed by stacking a plurality of stack 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; 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;
the single cell is a Shan Yinji flat tube type structure solid oxide fuel cell; the Shan Yinji flat tube type solid oxide fuel cell has the structure that:
8YSZ|NiO-8YSZ|NiO-YSZ|NiO-8YSZ|8YSZ|GDC|LSC；
wherein 8YSZ is an electrolyte, niO-8YSZ is an active anode, niO-YSZ is an anode support body, GDC is a barrier layer, and LSC is a cathode layer;
the thickness of the 8YSZ is 7-9 mu m; the thickness of the NiO-8YSZ is 4-6 mu m; the NiO-YSZ has the size of (150-160) mmX (60-62) mmX (4-6) mm, and fuel flow channel holes with the diameter of 0.5-1.5 mm are uniformly distributed in the middle; the thickness of the GDC is 1-3 mu m; the LSC has the size of (120-130) mmx (60-62) mm and the thickness of 10-20 mu m;
the number of the electric pile repeating units is 2-40;
the Shan Yinji flat tube type structure solid oxide fuel cell is characterized in that a rectangle with the thickness of (40-60) mmX (120-140) mm is arranged in the middle of one surface of the solid oxide fuel cell and is used as an electronic current collecting window, and the other surface of the solid oxide fuel cell is a cathode layer;
the first metal net is a silver net or a platinum net; the thickness of the first metal net is 0.05 mm-0.15 m, and the mesh size is (0.2-0.4) mmX (0.5-0.7) mm;
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;
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;
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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