CN114824403A - Module combined reversible battery stack with high fault tolerance - Google Patents
Module combined reversible battery stack with high fault tolerance Download PDFInfo
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- CN114824403A CN114824403A CN202110068686.8A CN202110068686A CN114824403A CN 114824403 A CN114824403 A CN 114824403A CN 202110068686 A CN202110068686 A CN 202110068686A CN 114824403 A CN114824403 A CN 114824403A
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Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- H01M8/243—Grouping of unit cells of tubular or cylindrical configuration
-
- 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
- H01M8/2457—Grouping of fuel cells, e.g. stacking of fuel cells with both reactants being gaseous or vaporised
-
- 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
- H01M8/2465—Details of groupings of fuel cells
Abstract
A module combined reversible cell stack with high fault tolerance is an energy conversion device which can convert chemical energy and electric energy of hydrogen fuel into energy in a reversible way; the reversible cell stack includes: a plurality of stack units each including a plurality of reversible cells including a hydrogen electrode and an air electrode, the plurality of reversible cells in the stack units being arranged in parallel in such a manner that the hydrogen electrode is connected to each other on the hydrogen electrode side and the air electrode is connected to each other on the air electrode side; a pair of stack gas distribution plates for gas diversion and gas collection to the plurality of stack units; a hydrogen electrode lead; and an air electrode lead; the plurality of stack units are arranged between the pair of stack gas distribution plates in series; the air electrode lead and the hydrogen electrode lead are respectively connected with the air electrode side of the stack unit at the head end and the hydrogen electrode side of the stack unit at the tail end in the plurality of stack units.
Description
Technical Field
The invention belongs to the technical field of hydrogen energy and fuel cells, and particularly relates to a module combined reversible cell stack with high fault tolerance.
Background
The reversible solid battery can utilize high-efficiency power generation such as hydrogen fuel and the like to be input into a power grid within the temperature range of 400-700 ℃, and can also reversibly utilize electrolysis water such as garbage electricity to produce hydrogen, so that the reversible solid battery is a novel and high-efficiency energy conversion device. The reversible solid-state battery has attracted much attention because it can effectively connect a heat pipe network, a power grid, a gas network, etc. due to its high-efficiency, high-temperature operating characteristics, and is a basic energy device in a hydrogen energy system and an energy internet.
The tubular reversible battery has the characteristics of pressure resistance and good thermal shock resistance, and is one of the widely adopted solid reversible battery configurations; the current and voltage of a single tubular reversible battery are low, and the single tubular reversible battery generally achieves high power after being combined into a reversible battery stack in a reasonable series-parallel mode.
Iwahara et al, Japan, have found that certain perovskite-type sintered bodies doped with metal cations in a low oxidation state have proton conductivity under a high-temperature hydrogen-or water vapor-containing atmosphere, are defined as high-temperature proton conductors and applied to high-temperature hydrogen production by electrolysis of water. Thereafter, high-temperature proton conductor materials are researched more and applied to the fields of hydrogen separation and purification, organic matter dehydrogenation or hydrogenation, normal-pressure ammonia synthesis and the like. The water vapor is on the air side during the operation of the proton conductor reversible solid battery to realize 'dry hydrogen', so that the complexity and the cost of the system can be greatly reduced, and the proton conductor reversible solid battery becomes a new research hotspot in recent years.
At present, a cell stack based on a proton conductor type reversible cell does not exist, the fault tolerance of a cell stack structure in the existing cell stack is poor, and the capacity of the cell stack is difficult to increase or reduce according to the actual requirement.
Disclosure of Invention
The problems to be solved by the invention are as follows:
in view of the above problems, an object of the present invention is to provide an expandable module-combined reversible cell stack with high fault tolerance, which can be used for high-temperature hydrogen fuel power generation and also can be used for high-temperature hydrogen production by water vapor electrolysis.
The technical means for solving the problems are as follows:
in order to solve the above problems, the present invention provides a module-combined reversible cell stack with high fault tolerance, which is an energy conversion device for converting chemical energy and electric energy of hydrogen fuel into reversible energy; the reversible cell stack includes: a plurality of stack units each including a plurality of reversible cells including a hydrogen electrode and an air electrode, and the plurality of reversible cells in the stack units are arranged in parallel in such a manner that the hydrogen electrode is connected to each other in a hydrogen electrode side and the air electrode is connected to each other in an air electrode side; a pair of stack gas distribution plates for gas diversion and gas collection to the plurality of stack units; a hydrogen electrode lead; and an air electrode lead; the plurality of stack units are arranged between the pair of stack gas distribution plates in series; the air electrode lead and the hydrogen electrode lead are respectively connected to the air electrode side of the stack unit located at the head end and the hydrogen electrode side of the stack unit located at the tail end among the plurality of stack units.
According to the present invention, the reversible cell stack can be switched between the electrolytic cell mode or the fuel cell mode depending on whether an external load is connected or electrified. A plurality of reversible batteries are connected in parallel to form a modular electric pile unit, so that certain difference of performances of the single reversible batteries can be tolerated. A plurality of modularized electric pile units are arranged between a pair of electric pile gas distribution plates in series to form a reversible electric pile, and the reversible electric pile can also be combined into a reversible electric pile with higher power.
In the present invention, the reversible battery may be formed in a tubular shape; the hydrogen electrode is formed on the inner side of the reversible battery, the air electrode is formed on the outer side of the reversible battery, and an electrolyte layer is arranged between the hydrogen electrode and the air electrode; at least the hydrogen electrode at the lower end is exposed from the air electrode; the electrolyte layer is a proton conductor material. One side of the air electrode of the reversible battery is placed in wet air containing water vapor, and one side of the hydrogen electrode generates dry hydrogen without separation and drying, so that the water management is simple.
In the present invention, the stack unit may further include: a gas collector that derives and collects gas from the plurality of reversible cells; a gas distribution collector that connects the hydrogen electrodes of the plurality of reversible cells to the hydrogen electrode side, and introduces and distributes gas to the plurality of reversible cells; and a connector connecting the air electrodes of the plurality of reversible cells to the air electrode side. In this way, a plurality of reversible cells can be connected in parallel, so that certain differences in the performance of the individual reversible cells can be tolerated.
In the present invention, the gas collector may be formed with a plurality of stepped holes corresponding to the plurality of reversible cells, the stepped holes including a large diameter portion into which the hydrogen electrode of the reversible cell is inserted and a small diameter portion serving as a gas passage through which gas flows; the gas collector is constructed of a ceramic material.
In the present invention, a plurality of stepped holes may be formed in the gas distribution collector in correspondence with the plurality of reversible cells, the stepped holes including a large diameter portion into which the reversible cells are inserted and a small diameter portion serving as a gas passage through which gas flows; the gas distribution collector is made of a high temperature resistant metal material.
In the present invention, the connecting body may include a longitudinal wall portion, and a first horizontal extending portion and a second horizontal extending portion extending in opposite directions from both side distal ends of the longitudinal wall portion; a plurality of through holes are formed on the first horizontal extension part corresponding to the plurality of reversible batteries; the connecting body is made of a high-temperature-resistant metal material or a conductive oxide material.
In the present invention, the reversible battery may be configured such that: the air electrode is connected with the connecting body through conductive paste; the upper end of the gas collector is inserted into the stepped hole of the gas collector and sealed by a sealing material; the lower end of the hydrogen electrode is inserted into the stepped hole of the gas distribution current collector through the exposed hydrogen electrode, connected by the conductive paste, and sealed by the sealing material.
In the present invention, the plurality of stack units may be connected end to end in series in such a manner that the second horizontal extension portion of the connecting body in the former stack unit is connected to the gas distribution collector in the latter stack unit. Therefore, a plurality of stack units can be connected in series end to form the reversible battery stack.
In the invention, the pair of stack gas distribution plates may include a main body in which a gas channel is formed and a gas guide tube extending from the main body to one side; a plurality of mounting seats for arranging the electric pile units are formed on the main body; an air hole is formed in the mounting seat.
In the present invention, the hydrogen electrode lead and the air electrode lead may be high temperature resistant metal leads.
In the present invention, the gas distribution current collector may be a metal gas distribution current collector, and the gas distribution current collector may be a metal gas distribution current collector. Therefore, when the electrochemical performance of one of the electric pile units is low or large attenuation occurs, the electric pile unit can be flexibly skipped by short circuit, and high fault tolerance of the electric pile structure is realized.
The invention has the following effects:
the invention has strong detachability and power expansion flexibility and high fault tolerance, and can be used for generating power by high-temperature hydrogen fuel and also can be used for producing hydrogen by electrolyzing water vapor at high temperature.
Drawings
Fig. 1 is a schematic structural view of a modular combined reversible cell stack with high fault tolerance according to an embodiment of the present invention, (a) is a schematic structural view of a 16-tube reversible cell stack, and (b) is a schematic structural view of a 64-tube reversible cell stack;
fig. 2 is a schematic structural view of a stack unit in the reversible cell stack shown in fig. 1, (a) is a perspective view of the stack unit, (b) is an exploded view of the stack unit with connectors hidden, (c) is a sectional view of the stack unit, and (d) is a schematic structural view of a reversible cell in the stack unit;
FIG. 3 is a schematic structural view of a connecting body in the cell stack unit shown in FIG. 2, wherein (a) is a perspective view of the connecting body, (B) is a plan view of the connecting body, and (c) is a sectional view of the connecting body taken along line B-B;
fig. 4 is a schematic structural view of a stack gas distribution plate of the reversible cell stack, (a) is a perspective view of the stack gas distribution plate, (b) is a plan view of the stack gas distribution plate, and (c) is a front view of the stack gas distribution plate;
fig. 5 is a diagram showing shorting of a failed stack cell in a reversible cell stack using a flow deflector;
description of the symbols:
100. a reversible cell stack (16 tube reversible cell stack); 200. a reversible cell stack (64 tube reversible cell stack); 10. a stack unit; 10', a faulty stack unit; 1. a reversible battery; 1a, a hydrogen electrode; 1b, an electrolyte layer; 1c, an air electrode; 2. a gas collector; 3. a gas distribution current collector; 4. a linker; 5. conductive paste; 6. a sealing material; 11. a hydrogen electrode lead; 12. an air electrode lead; 13. a flow deflector; 20. a stack gas distribution plate; 21. a main body; 22. an air duct; 211. a mounting seat; 212. air holes; 41. a first horizontal extension; 42. a longitudinal wall portion; 43. a second horizontal extension; 411. a battery mounting hole; A. the direction of the humid air.
Detailed Description
The present invention is further described below in conjunction with the following embodiments and the accompanying drawings, it being understood that the drawings and the following embodiments are illustrative of the invention only and are not limiting thereof.
Disclosed herein is an expandable, modular, high-fault-tolerant reversible cell stack (hereinafter referred to as "reversible cell stack") that can be used for high-temperature hydrogen fuel power generation and also for high-temperature steam hydrogen production by electrolysis. Fig. 1 is a schematic structural view of a reversible cell stack according to an embodiment of the present invention, (a) is a schematic structural view of a 16-tube reversible cell stack 100, and (b) is a schematic structural view of a 64-tube reversible cell stack 200. The structure of the reversible cell stack is described below by taking a 16-tube reversible cell stack 100 as an example.
As shown in fig. 1 (a), the reversible cell stack 100 is an energy conversion device that reversibly converts chemical energy and electrical energy of hydrogen fuel into each other, and includes a plurality of stack units 10, a pair of stack gas distribution plates 20 located at upper and lower sides of the plurality of stack units 10, and a hydrogen electrode lead 11 and an air electrode lead 12 led from the stack units 10.
[ electric pile Unit ]
Fig. 2 is a schematic structural diagram of the stack unit 10 in the reversible cell stack 100, (a) is a perspective view of the stack unit 10, (b) is an exploded view of the stack unit 10 with the connecting body 4 hidden, (c) is a sectional view of the stack unit 10, and (d) is a schematic structural diagram of the reversible cell 1. As shown in fig. 2 (a), (b), and (c), the stack unit 10 includes the reversible cell 1, the gas collector 2, the gas distribution current collector 3, and the connector 4.
< reversible Battery >
In the present embodiment, the reversible cell 1 is a proton conductor type reversible cell, and the typical working temperature range is 500-. As shown in fig. 2 (d), the reversible battery 1 is formed in a hollow tubular shape, and includes a hydrogen electrode 1a located at the innermost side, an air electrode 1c located at the outermost side, and an electrolyte layer 1b located between the hydrogen electrode 1a and the air electrode 1 b. The hydrogen electrode 1a is located at the innermost side of the reversible cell 1, and is mainly a place where hydrogen gas electrochemically reacts and conducts electrons. The electrolyte layer 1b is a proton conductor material, and may be, for example, indium oxide-doped calcium zirconate (CaZr) 0.9 In 0.1 O 3 ) Or BaCe 1-x-y Zr x Y y O 3 (referred to as BCZY, wherein x is more than or equal to 0 and less than or equal to 0.8, y is more than or equal to 0 and less than or equal to 0.2, and x + y is more than or equal to 0 and less than or equal to 1). The air electrode 1c may be a mixed material of one or more of lanthanum strontium cobaltate (LSC material), lanthanum strontium manganate, or lanthanum strontium nickelate and BCZY.
Thus, the reversible cell 1 may be, for example, a hydrogen electrode-supported tubular proton conductor type reversible cell having a configuration of LSC-BCZY (air electrode)/BCZY (electrolyte layer)/NiO-BCZY (hydrogen electrode) of a mixed material of nickel oxide and a proton conductor material prepared by an "isostatic pressing-impregnation-co-sintering" method. In the reversible battery 1, the air electrode 1c is formed to have a length shorter than that of the hydrogen electrode 1a in the axle box direction, in other words, the hydrogen electrode 1a extends from the lower end.
< gas trap >
The gas collector 2 is made of an insulating ceramic material such as alumina or zirconia, and is mainly used for mounting and fixing the reversible battery 1, guiding and collecting gas from the reversible battery 1, and performing an insulating function. The gas collector 2 is formed in a substantially rectangular parallelepiped shape.
More specifically, the gas collector 2 is formed at an upper portion with a boss portion protruding toward the periphery, which can be used for mounting to a mounting seat 211 of a stack gas distribution plate 20 described later. The upper surface of the gas collector 2 is recessed downward to form a cavity corresponding to the gas holes 212 of the stack gas distribution plate 20. Further, a plurality of stepped holes corresponding to the number of the reversible cells 1 provided in the stack unit 10 and penetrating the gas collector 2 in the vertical direction are formed in the gas collector 2, and each of the stepped holes includes a large diameter portion to which the reversible cell 1 is attached and a small diameter portion serving as a gas passage for flowing gas, and the height of the large diameter portion is slightly smaller than the length of the reversible cell 1 in which the hydrogen electrode 1a protrudes from the lower end (i.e., the length of the reversible motor 1 in which the hydrogen electrode 1a is exposed downward from the air electrode 1c at the end position).
< gas distribution collector >
The gas distribution collector 3 is made of a high-temperature-resistant metal such as SUS430 stainless steel or Crofer22 stainless steel, and is mainly used for fixing the reversible battery 1 and introducing and distributing gas into the reversible battery 1. The gas distribution collector 3 has the same structure as the gas collector 2 except for the difference in material, that is, has a boss portion provided with the mounting seat 211 for mounting to the stack gas distribution plate 20, a cavity for communicating with the gas holes 212 of the stack gas distribution plate 20, and a plurality of stepped holes for mounting and fixing the reversible battery 1, and is provided in such a manner that the cavity faces downward and the major diameter portion of the stepped hole faces upward, and the detailed structure thereof will not be described again.
< connecting body >
Fig. 3 is a schematic structural view of the connecting body 4, where (a) is a perspective view of the connecting body 4, (b) is a front view of the connecting body 4, and (c) is a bottom view of the connecting body 4. The connecting body 4 is made of a high-temperature resistant metal material such as SUS430 stainless steel, Crofer22 stainless steel, or a conductive oxide material such as lanthanum chromate oxide, and is mainly used for connecting adjacent cell stack units 10.
As shown in fig. 3 (a) and (b), the connecting body 4 is formed in a substantially zigzag shape, and includes a vertical wall portion 42, and a first horizontally extending portion 41 and a second horizontally extending portion 43 extending in opposite directions from upper and lower distal ends of the vertical wall portion 42. A plurality of through holes 411 corresponding to the number of the reversible cells 1 in the stack unit 10 are formed in the first horizontal extension portion 41, and the reversible cells 1 are inserted into the through holes 411, respectively.
In this way, the plurality of reversible cells 1 are arranged between the gas collector 2 and the gas distribution collector 3 in such a manner that the upper ends thereof are inserted into the stepped holes of the gas collector 2 and the lower ends thereof are inserted into the stepped holes of the gas distribution collector 3, and the through holes 411 of the connecting body 4 are inserted therethrough. More specifically, the air electrodes 1c of the plurality of reversible cells 1 are electrically connected to the connecting body 4 by conductive paste to form air electrode sides connected in parallel, and the upper ends of the reversible cells 1 are inserted into the stepped holes of the gas collector 2 and sealed with the stepped holes by a sealing material, and the hydrogen electrodes 1a with the lower ends exposed are inserted into the stepped holes of the gas distribution current collector 3 and electrically connected to the gas distribution current collector 3 by conductive paste to form hydrogen electrode sides connected in parallel, and are sealed from the outside by a sealing material, whereby the plurality of reversible cells 1 form a parallel structure in the stack unit 10. The conductive paste may be Pt paste, Ag paste, or the like, and the sealing material may be glass, glass ceramics, mica, or the like.
The stack units 10 of this structure are arranged in series end-to-end in a pair of stack gas distribution plates 20, as will be described later.
[ gas distribution plate for a pile ]
Fig. 4 is a schematic structural view of the stack gas distribution plate 20 of the reversible cell stack 100, where (a) is a perspective view of the stack gas distribution plate 20, (B) is a plan view of the stack gas distribution plate 20, and (c) is a sectional view of the stack gas distribution plate 20 taken along line B-B. As shown in fig. 4 (a), (b), and (c), the stack gas distribution plate 20 is formed in a substantially elongated plate shape, but the present invention is not limited thereto, and the stack gas distribution plate 20 may be formed in any plate shape as needed, for example, may be formed in a square plate shape as shown in fig. 1 (b).
The stack gas distribution plate 20 is made of a ceramic material such as alumina or zirconia, and can perform an insulating function. As shown in fig. 4 (a), (b), and (c), the stack gas distribution plate 20 includes: a main body 21 having a gas passage formed therein and a gas guide tube 22 extending from the main body 21 to one side, and a plurality of mounting seats 211 for mounting the stack unit 10 are formed on the main body 22.
The gas passages in the main body 21 are used for gas diversion and gas collection to the respective stack units 10. The mounting seat 211 is formed in a shape recessed downward from the upper surface of the main body 21, and boss portions of the above-described gas collector 2 and gas distribution header 3 may be provided for supporting the stack unit 10 and achieving gas sealing by a sealing material. A gas hole 212 communicating with the gas passage of the body 21 is formed in the center of the mounting seat 211. The gas guide tube 22 is mainly used for inputting hydrogen from the outside or outputting hydrogen to the outside.
As such, as shown in fig. 1 (a), a plurality of stack units 10 are respectively mounted on the mounting seats 211 of the stack gas distribution plates 20 with the gas collectors 2 and the distribution collectors 3, and the respective cavities are disposed between the upper and lower pairs of stack gas distribution plates 20 in such a manner as to communicate with the gas 212. More specifically, the plurality of stack units 10 are arranged end to end in series in such a manner that the second horizontal extension portion 43 of the connecting body 4 of the previous stack unit 10 is connected with the gas distribution current collector 3 of the next stack unit 10, and the connection can be performed by using a conductive paste, soldering, laser welding or other processes. Thus, the plurality of stack units 10 are arranged end to end in series between the pair of upper and lower stack gas distribution plates 20, thereby forming the reversible cell stack 100. These reversible cell stacks 100 can also be used as a stack module, and can be connected in series to form a reversible cell stack 200 with a larger scale as shown in fig. 1 (b). More electric pile modules are electrically and electrically connected in parallel to form a battery pile with higher power.
[ Hydrogen electrode lead and air electrode lead ]
The reversible cell stack 100 also has a hydrogen electrode lead 11 and an air electrode lead 12 led out from the connecting body 4 of the stack unit 10 at the head end and the gas distribution collector 3 of the stack unit 10 at the tail end, respectively. Specifically, the hydrogen electrode lead 11 is a high-temperature resistant metal lead composed of, for example, a Ni — Cr alloy, and is bonded to the connection body 4 of the stack unit 10, i.e., the hydrogen electrode side, by conductive paste. The air electrode lead 12 is also a high-temperature resistant metal lead composed of, for example, a Ni — Cr alloy, and is bonded to the gas distribution collector 3, i.e., the air electrode side, of the stack unit 10 by conductive paste. Thereby supplying power to the reversible cell stack 100 or drawing current generated by the reversible cell stack 100.
[ guide vane ]
In addition, in the present invention, the reversible cell stack 100 further includes a metal current-guiding plate 13, and the current-guiding plate 13 is bonded between two adjacent cell stack units 10 through a conductive paste, so that the cell stack unit 10 with poor performance or failure in the reversible cell stack 100 is shorted with an adjacent cell stack unit 10 that normally operates.
Fig. 5 is a diagram illustrating shorting of a cell stack unit 10 in which a problem occurs in the reversible cell stack 100 using a current guide plate 13. As shown in fig. 5, when the second cell stack unit 10, i.e. the faulty cell stack unit 10 ' in the reversible cell stack 100 has poor performance and severely reduces the overall cell stack performance output, the gas distribution current collectors 3 of the cell stack units 10 and the gas distribution current collectors 3 of the faulty cell stack units 10 ' are connected by the flow deflectors 13, so that the current path bypasses the faulty cell stack unit 10 ', and the performance output of the reversible cell stack 100 is the electrochemical performance of 12 cells.
The reversible cell stack 100 of the present invention can be obtained by first preparing the reversible cell 1 of the hydrogen electrode supporting tube type proton conductor, connecting a plurality of reversible cells 1 in parallel to form the cell stack unit 10, connecting a plurality of cell stack units 10 in series, sealing and integrating, and then generating electricity or producing hydrogen by using the reversible cell stack 100 of this structure.
In operation, the reversible cell stack 100 may be heated to an operating temperature, hydrogen may be introduced from the gas duct 22 of one stack gas distribution plate 20 (e.g., the lower stack gas distribution plate 20) and introduced from the gas duct 22 of the other stack gas distribution plate 20 (e.g., the upper stack gas distribution plate 20), and the whole reversible cell stack 100 may be placed in a humid air atmosphere or wet air may be passed through the reversible cell stack 100 along the direction of arrow a as shown in fig. 1 (a), where the external output of electric power from the reversible cell stack 100 is a fuel cell mode, and the supply of electric power to the reversible cell stack 100 and the electrolysis of water vapor are an electrolytic cell mode. In the fuel cell mode, the reversible cell stack 100 is connected to an external load through the hydrogen electrode lead 11 and the air electrode lead 12, and reversely inputs hydrogen gas as fuel, and after losing electrons near the hydrogen electrode 1a inside the reversible cell 1, the hydrogen gas is converted into protons and is conducted to the air electrode 1c outside through the electrolyte layer 1b, electrons are obtained at the air electrode 1c, and water is generated after reaction with oxygen of air and then discharged. In the electrolytic cell mode, the hydrogen passing electrode lead 11 and the air electrode lead 12 are energized to the reversible cell stack 100, water in the wet air outside the reversible cell 1 loses electrons at the air electrode 1c to decompose protons, the protons are conducted to the hydrogen electrode 1a inside through the electrolyte layer 1b to obtain electrons of an external circuit and generate hydrogen gas to be discharged, and at this time, the hydrogen gas input from the outside to the reversible cell stack 100 through one gas duct 22 is used for providing power to push the generated hydrogen gas to be discharged from the other gas duct 22.
Compared with the prior battery stack, the invention has the advantages that:
(1) the modules are combined: the reversible cell stack is formed by serially connecting and combining the electric stack units formed by connecting a plurality of reversible cells in parallel, is convenient for batch preparation and quality control, can carry out performance test on the electric stack units firstly and then serially connecting the electric stack units with similar performance to form the reversible cell stack, and can improve the electrochemical performance of the integrated reversible cell stack;
(2) the battery stack has strong combination flexibility: the power of the reversible battery stack can be flexibly adjusted and the replacement of a damaged unit can be realized by increasing and decreasing the electric stack units;
(3) water management is easy: in the invention, the whole reversible battery stack is mixed with wet air containing water vapor at the outer side (namely the air electrode side), the hydrogen electrode side is dry hydrogen, separation and drying are not needed, and the water management is simple;
(4) the air resistance of the electric pile is small: the invention adopts a straight-through type tubular reversible battery structure, the gas flow path is short, and the gas resistance in the electric pile is small;
(5) the safety is good: the reversible battery pile is of an all-solid-state structure and has no danger of leakage, corrosion, explosion and the like.
The following examples are provided to further illustrate the invention.
Example 1
The reversible cell 1 of hydrogen electrode supporting tube type proton conductor type having the structure of LSC-BCZY (air electrode)/BCZY (electrolyte layer)/NiO-BCZY (hydrogen electrode) from outside to inside as shown in fig. 2 (d) was prepared by the "isostatic compaction-impregnation-co-sintering" method. The reversible cell 1 has a wall thickness of about 0.6-0.8mm, an outer diameter of about 1.0 cm and an effective length of about 9 cm. As shown in fig. 2 (c), the hydrogen electrodes 1a at the lower ends of the four reversible cells 1 are bonded to the inside of the stepped holes of the gas distribution current collector 3 made of metal by a conductive paste such as Ag paste, and are sealed with a sealing material such as glass ceramics at the outside. Next, the four reversible batteries 1 are inserted into the battery mounting holes 411 of the metal connecting body 4, and the outer air electrode 1c is bonded to the battery mounting holes 411 with a conductive paste such as Ag paste. And finally, respectively inserting the upper ends of the four tubular reversible batteries 1 into the stepped holes of the gas collector 2 and sealing and bonding the upper ends by using microcrystalline glass, thus integrating the pile units 10 in a parallel structure.
Four stack units 10 are sealed to a stack gas distribution plate 20 having a mounting block 211 and gas holes 212. The stack units 10 are connected end to end as described above, and the hydrogen electrode 1a and the air electrode 1c of the adjacent stack units 10 are connected together with the connecting body 4 by laser welding via the gas distribution current collector 3 to form a series structure. The current of the entire reversible cell stack 100 is led out from the gas distribution collector 3 of the end cell stack unit 10 and the connection body 4 of the head cell stack unit 10, respectively, using a bundle of Ni — Cr alloy wires, thereby completing the reversible cell stack 100 composed of 16 reversible cells 1 as shown in fig. 1 (a).
In addition, for example, when the second cell stack unit 10, i.e., the faulty cell stack unit 10 ' in the reversible cell stack 100 has poor performance and severely reduces the overall cell stack performance output, as shown in fig. 5, the gas distribution current collector 3 of the cell stack unit 10 is shorted with the gas distribution current collector 3 of the faulty cell stack unit 10 ' by using the metal flow deflector 13, so that the current path bypasses the faulty cell stack unit 10 ', and the performance output of the reversible cell stack 100 is the electrochemical performance of 12 reversible cells 1.
Example 2
The same procedure as in example 1 is used to integrate the stack units 10 of four reversible cells 1 in parallel. 16 stack units 10 are sealed to a stack gas distributor having a gas distribution groove. The electric pile units 10 are connected end to end, and the hydrogen electrodes and the air electrodes of the adjacent units are connected together with the connecting bodies 4 through the gas distribution current collectors 3 by laser welding to realize series connection. As shown in fig. 1 (b), the position arrangement of the stack units 10 adopts a 4 × 4 ″ square arrangement, and the last stack unit 10 in the previous row and the corresponding stack unit 10 in the next row are electrically connected in a serpentine shape. More specifically, the last stack unit 10 in the previous row is electrically connected to the connecting body 4 of the adjacent stack unit 10 in the same row at the gas distribution collector 3 (for example, in the left-right direction in fig. 1 (b)), while its own connecting body 4 is disposed in the front-rear direction in fig. 1 (b), thereby connecting the gas distribution collectors 3 of the stack units 10 in the next row. Thereby, a reversible cell stack 200 composed of 64 tubes of reversible cells 1 is integrated.
Similarly, when the performance of the failed cell stack unit 10 'is poor in the reversible cell stack 200, the gas distribution current collectors 3 of the adjacent cell stack units 10 and the failed cell stack unit 10' can be short-circuited by the metal flow deflectors 13 in the same manner as in embodiment 1, and the cell stack can be bypassed, so as to achieve high fault tolerance of the cell stack.
The reversible cell stack according to the present invention and the stack unit 10 constituting the reversible cell stack have been described above, but the present invention is not limited thereto. The stack unit 10 is not limited to the four reversible cells 1 arranged in parallel, and may be provided with four or more or four or less. Further, the structure of the connecting body 4 is not limited to the zigzag shape described above, and may be formed in other shapes as long as it can be ensured that the air electrodes 1c of all the reversible cells 1 in one stack unit 10 are connected to the air motor side without being short-circuited to the gas distribution current collectors 3.
The invention adopts modular assembly, and has stronger detachability and flexibility of power expansion; the parallel structure in the electric pile units can tolerate a certain difference of the performances of the single reversible cells, and the structure that the electric pile units are connected in series can allow that when the electrochemical performance of one electric pile unit is low or large attenuation occurs, the electric pile unit can be flexibly short-circuited and skipped, so that high fault tolerance of the electric pile structure is realized.
The above embodiments are intended to illustrate and not to limit the scope of the invention, which is defined by the claims, but rather by the claims, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims (11)
1. A modular, high fault tolerant, reversible cell stack,
the energy conversion device is used for converting chemical energy of hydrogen fuel and electric energy into energy in a mutually reversible way;
the reversible cell stack includes:
a plurality of stack units each including a plurality of reversible cells including a hydrogen electrode and an air electrode, and the plurality of reversible cells in the stack units are arranged in parallel in such a manner that the hydrogen electrode is connected to each other in a hydrogen electrode side and the air electrode is connected to each other in an air electrode side;
a pair of stack gas distribution plates for gas diversion and gas collection to the plurality of stack units;
a hydrogen electrode lead; and
an air electrode lead;
the plurality of stack units are arranged between the pair of stack gas distribution plates in series;
the air electrode lead and the hydrogen electrode lead are respectively connected to the air electrode side of the stack unit located at the head end and the hydrogen electrode side of the stack unit located at the tail end among the plurality of stack units.
2. The modular combined high fault-tolerant reversible cell stack according to claim 1,
the reversible cell is formed in a tubular shape;
the hydrogen electrode is formed on the inner side of the reversible battery, the air electrode is formed on the outer side of the reversible battery, and an electrolyte layer is arranged between the hydrogen electrode and the air electrode;
at least the hydrogen electrode at the lower end is exposed from the air electrode;
the electrolyte layer is a proton conductor material.
3. The modular combined high fault-tolerant reversible cell stack according to claim 1 or 2,
the stack unit further includes:
a gas collector that derives and collects gas from the plurality of reversible cells;
a gas distribution collector that connects the hydrogen electrodes of the plurality of reversible cells to the hydrogen electrode side, and introduces and distributes gas to the plurality of reversible cells; and
connecting the air electrodes of the plurality of reversible cells to a connector on the air electrode side.
4. The modular combined high fault-tolerant reversible cell stack according to claim 3,
a plurality of stepped holes are formed in the gas collector corresponding to the plurality of reversible cells, the stepped holes including a large diameter portion into which the hydrogen electrode of the reversible cell is inserted and a small diameter portion serving as a gas passage through which gas flows;
the gas collector is constructed of a ceramic material.
5. The modular combined high fault-tolerant reversible cell stack according to claim 3,
a plurality of stepped holes are formed in the gas distribution collector in correspondence with the plurality of reversible cells, the stepped holes including a large diameter portion for inserting the reversible cells and a small diameter portion serving as a gas passage for flowing gas;
the gas distribution collector is made of a high temperature resistant metal material.
6. The modular combined high fault-tolerant reversible cell stack according to claim 3,
the connecting body comprises a longitudinal wall part, a first horizontal extending part and a second horizontal extending part, wherein the first horizontal extending part and the second horizontal extending part oppositely extend from the tip ends of the two sides of the longitudinal wall part;
a plurality of through holes are formed on the first horizontal extension part corresponding to the plurality of reversible batteries;
the connecting body is made of a high-temperature-resistant metal material or a conductive oxide material.
7. The modular combined high fault-tolerant reversible cell stack according to one of claims 2 to 6,
the reversible battery is configured to:
the air electrode is connected with the connecting body through conductive paste;
the upper end of the gas collector is inserted into the stepped hole of the gas collector and sealed by a sealing material;
the lower end of the hydrogen electrode is inserted into the stepped hole of the gas distribution current collector through the exposed hydrogen electrode, connected by the conductive paste, and sealed by the sealing material.
8. The modular combined high fault-tolerant reversible cell stack according to one of claims 1 to 7,
the plurality of stack units are arranged end to end in series in such a manner that the second horizontal extension portion of the connecting body in the former stack unit is connected with the gas distribution collector in the latter stack unit.
9. The modular combined high fault-tolerant reversible cell stack according to claim 1,
the pair of pile gas distribution plates comprise a main body and a gas guide pipe, wherein a gas channel is formed in the main body, and the gas guide pipe extends out of the main body to one side;
a plurality of mounting seats for arranging the electric pile units are formed on the main body;
an air hole is formed in the mounting seat.
10. The modular combined high fault-tolerant reversible cell stack according to claim 1,
the hydrogen electrode lead and the air electrode lead are high-temperature-resistant metal leads.
11. The modular combined high fault-tolerant reversible cell stack according to claim 1,
the gas distribution current collector is characterized by further comprising a metal flow deflector which is used for short-circuiting two adjacent electric pile units through the gas distribution current collectors connecting the electric pile units.
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