CN114824403B - Module combined type high fault tolerance reversible battery stack - Google Patents
Module combined type high fault tolerance reversible battery stackInfo
- Publication number
- CN114824403B CN114824403B CN202110068686.8A CN202110068686A CN114824403B CN 114824403 B CN114824403 B CN 114824403B CN 202110068686 A CN202110068686 A CN 202110068686A CN 114824403 B CN114824403 B CN 114824403B
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- Prior art keywords
- reversible
- gas
- hydrogen
- cell stack
- cells
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Links
- 230000002441 reversible effect Effects 0.000 title claims abstract description 173
- 239000007789 gas Substances 0.000 claims abstract description 143
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000001257 hydrogen Substances 0.000 claims abstract description 88
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 88
- 238000009826 distribution Methods 0.000 claims abstract description 76
- 239000000446 fuel Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000004020 conductor Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 11
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- 239000002002 slurry Substances 0.000 claims description 3
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- 239000007787 solid Substances 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
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- 238000010248 power generation Methods 0.000 description 2
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- 238000005245 sintering Methods 0.000 description 2
- DJOYTAUERRJRAT-UHFFFAOYSA-N 2-(n-methyl-4-nitroanilino)acetonitrile Chemical compound N#CCN(C)C1=CC=C([N+]([O-])=O)C=C1 DJOYTAUERRJRAT-UHFFFAOYSA-N 0.000 description 1
- 101150058765 BACE1 gene Proteins 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
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- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
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- IGPAMRAHTMKVDN-UHFFFAOYSA-N strontium dioxido(dioxo)manganese lanthanum(3+) Chemical compound [Sr+2].[La+3].[O-][Mn]([O-])(=O)=O IGPAMRAHTMKVDN-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Abstract
A module combined type high fault tolerance reversible cell stack is an energy conversion device for mutually and reversibly converting chemical energy and electric energy of hydrogen fuel; the reversible cell stack includes: a plurality of electric pile units, each of which comprises a plurality of reversible cells, the plurality of reversible cells comprising hydrogen electrodes and air electrodes, and the plurality of reversible cells in the electric pile units being arranged in parallel in such a manner that the hydrogen electrodes are connected to each other to form a hydrogen electrode side, and the air electrodes are connected to each other to form an air electrode side; a pair of stack gas distribution plates for conducting and collecting gas to the plurality of stack units; a hydrogen electrode wire; an air electrode wire; the plurality of electric pile units are arranged between a pair of electric pile gas distribution plates in a serial connection mode; the air electrode wire and the hydrogen electrode wire are respectively connected with the air electrode side of the electric pile unit positioned at the head end and the hydrogen electrode side of the electric pile unit positioned at the tail end in the electric pile units.
Description
Technical Field
The invention belongs to the technical field of hydrogen energy and fuel cells, and particularly relates to a module combined type high-fault-tolerance reversible cell stack.
Background
The reversible solid battery can utilize hydrogen fuel and other high-efficiency power generation to input into a power grid within the temperature range of 400-700 ℃, and can reversely utilize garbage power and other electrolytic water to produce hydrogen, so that the reversible solid battery is a novel and high-efficiency energy conversion device. The reversible solid battery is a basic energy device in a hydrogen energy system and an energy internet because of the high-efficiency and high-temperature operation characteristics of the reversible solid battery, and the reversible solid battery can effectively connect a heat pipe network, a power grid, a gas network and the like, so that the reversible solid battery is widely paid attention to.
The tubular reversible battery has the characteristics of good pressure resistance and thermal shock resistance, and is one of the more widely adopted solid reversible battery configurations; the current and voltage of the single tube type reversible battery are lower, and the single tube type reversible battery is generally combined into a reversible battery stack in a reasonable series-parallel manner to achieve higher power.
Japanese Iwahara et al found that certain perovskite-type sintered bodies doped with low oxidation state metal cations have proton conductivity under high temperature hydrogen-containing or water vapor-containing atmosphere, which is defined as a high temperature proton conductor and applied to high temperature water electrolysis for hydrogen production. After that, high temperature proton conductor materials have been studied more and applied to the fields of separation and purification of hydrogen, dehydrogenation or hydrogenation of organic matters, normal pressure synthesis of ammonia and the like. Because the water vapor is on the air side to realize dry hydrogen during operation, the complexity and cost of the system can be greatly reduced, and the proton conductor type reversible solid battery becomes a new research hot spot in recent years.
There is no cell stack based on proton conductor type reversible cell, and the fault tolerance of the cell stack structure in the existing cell stack is poor, and it is also difficult to increase or decrease the capacity of the cell stack according to actual requirements.
Disclosure of Invention
Problems to be solved by the invention:
in view of the above problems, an object of the present invention is to provide an expandable, modular, high fault tolerant, reversible cell stack that can be used for high temperature hydrogen fuel generation and also for high temperature electrolysis of water vapor to produce hydrogen.
Technical means for solving the problems:
In order to solve the problems, the invention provides a module combined type reversible cell stack with high fault tolerance, which is an energy conversion device for mutually and reversibly converting chemical energy and electric energy of hydrogen fuel; the reversible cell stack includes: a plurality of electric pile units each including a plurality of reversible cells including a hydrogen electrode and an air electrode, and the plurality of reversible cells in the electric pile units being arranged in parallel in such a manner that the hydrogen electrodes are connected to each other to a hydrogen electrode side and the air electrodes are connected to each other to an air electrode side; a pair of stack gas distribution plates for gas channeling and gas collecting the plurality of stack units; a hydrogen electrode wire; an air electrode wire; the plurality of electric pile units are arranged between the pair of electric pile gas distribution plates in a serial connection mode; the air electrode wire and the hydrogen electrode wire are respectively connected with the air electrode side of the electric pile unit positioned at the head end and the hydrogen electrode side of the electric pile unit positioned at the tail end of the plurality of electric pile units.
According to the present invention, the reversible cell stack can be switched between the cell mode or the fuel cell mode depending on whether an external load is connected or powered. The plurality of reversible cells are connected in parallel to form a modularized electric pile unit, so that a certain difference in performance of single reversible cells can be tolerated. The modularized electric pile units are arranged between the pair of electric pile gas distribution plates in series to form a reversible battery pile, the reversible battery pile can also be combined into a reversible battery pile with larger power, and the modularized assembly mode has high combination flexibility and strong power expansion flexibility.
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. The air electrode side of the reversible cell is placed in wet air containing water vapor, and the hydrogen electrode side generates dry hydrogen, so that separation and drying are not needed, and the water management is simple.
In the present invention, the pile unit may further include: a gas collector that guides and collects gas from the plurality of reversible cells; a gas distribution current 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 connecting body connecting the air electrodes of the plurality of reversible cells to the air electrode side. Thus, a plurality of reversible cells can be connected in parallel, so that a certain difference in performance of a single reversible cell can be tolerated.
In the present invention, a plurality of stepped holes may be formed in the gas collector so as to correspond to the plurality of reversible cells, the stepped holes including a large diameter portion for inserting the hydrogen electrode of the reversible cell and a small diameter portion as a gas passage for flowing a gas; the gas collector is composed of a ceramic material.
In the present invention, a plurality of stepped holes may be formed in the gas distribution/current collector so as to correspond to 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 a gas flows; the gas distribution current collector is composed of a high temperature resistant metallic material.
In the present invention, the connector may include a vertical wall portion, and first and second horizontal extending portions extending reversely from both side tips of the vertical wall portion; a plurality of through holes are formed on the first horizontal extension part corresponding to the plurality of reversible cells; the connector is composed of a high temperature resistant metallic 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 connector through conductive slurry; the upper end is inserted into the stepped hole of the gas collector and is sealed by a sealing material; the lower end is inserted into the stepped hole of the gas distribution current collector through the exposed hydrogen electrode and connected by the conductive paste, and then sealed by the sealing material.
In the present invention, the plurality of pile units may be arranged in series end to end in such a manner that the second horizontal extension of the connecting body in the previous pile unit is connected to the gas distribution and current collector in the subsequent pile unit. Therefore, a plurality of electric pile units can be connected in series end to end, and the reversible battery pile is formed by the series connection.
In the present invention, the pair of stack gas distribution plates may include a main body having a gas passage formed therein, and a gas guide pipe extending from the main body to one side; a plurality of mounting seats for arranging the pile units are formed on the main body; and air holes are formed in the mounting seat.
In the present invention, the hydrogen electrode wire and the air electrode wire may be high temperature resistant metal wires.
In the present invention, the stack unit may further include a metal deflector that shorts the adjacent two gas distribution current collectors of the stack unit by connecting them. Therefore, when the electrochemical performance of one pile unit is lower or larger attenuation occurs, the pile unit can be flexibly short-circuited and skipped, and high fault tolerance of the 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 high-temperature hydrogen fuel power generation and high-temperature electrolysis of water vapor for hydrogen production.
Drawings
Fig. 1 is a schematic structural view of a module-assembled high fault tolerance reversible cell stack according to an embodiment of the present invention, (a) is a schematic structural view of a 16-pipe reversible cell stack, and (b) is a schematic structural view of a 64-pipe reversible cell stack;
Fig. 2 is a schematic structural view of a cell stack unit in the reversible cell stack shown in fig. 1, (a) is a perspective view of the cell stack unit, (b) is an exploded view of the cell stack unit with a connection body removed, (c) is a sectional view of the cell stack unit, and (d) is a schematic structural view of a reversible cell in the cell stack unit;
Fig. 3 is a schematic structural view of the connector in the cell shown in fig. 2, (a) is a perspective view of the connector, (B) is a plan view of the connector, and (c) is a B-B cross-sectional view of the connector;
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 top view of the stack gas distribution plate, and (c) is a front view of the stack gas distribution plate;
FIG. 5 is a diagram illustrating a failed stack cell in a reversible cell stack using a current guide fin shorting;
symbol description:
100. a reversible cell stack (16-tube reversible cell stack); 200. a reversible cell stack (64-tube reversible cell stack); 10. a galvanic pile unit; 10', a fault galvanic pile 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 connecting body; 5. conducting slurry; 6. a sealing material; 11. a hydrogen electrode wire; 12. an air electrode wire; 13. a deflector; 20. a stack gas distribution plate; 21. a main body; 22. an air duct; 211. a mounting base; 212. air holes; 41. a first horizontal extension; 42. a vertical wall portion; 43. a second horizontal extension; 411. a battery mounting hole; A. wet air direction.
Detailed Description
The invention will be further described with reference to the accompanying drawings and the following embodiments, it being understood that the drawings and the following embodiments are only for illustrating the invention, not for limiting the invention.
Disclosed herein is an expandable, modular, high fault tolerance, reversible cell stack (hereinafter referred to as "reversible cell stack") that can be used for high temperature hydrogen fuel generation, and also for high temperature electrolysis of water vapor to produce hydrogen. 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 100 of 16 tubes will be described below 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 electric energy of hydrogen fuel to each other, and includes a plurality of cell units 10, a pair of cell gas distribution plates 20 located on upper and lower sides of the plurality of cell units 10, and hydrogen electrode leads 11 and air electrode leads 12 led out from the cell units 10.
[ Pile unit ]
Fig. 2 is a schematic structural view of the cell stack unit 10 in the reversible cell stack 100, (a) is a perspective view of the cell stack unit 10, (b) is an exploded view of the cell stack unit 10 with the connection body 4 removed, (c) is a sectional view of the cell stack unit 10, and (d) is a schematic structural view of the reversible cell 1. As shown in fig. 2 (a), (b), and (c), the cell stack unit 10 includes a reversible cell 1, a gas collector 2, a gas distribution and current collector 3, and a connection body 4.
< Reversible Battery >
In this embodiment, the reversible cell 1 is a proton conductor type reversible cell, and its typical operating temperature range is 500 to 700 ℃. As shown in fig. 2 (d), the reversible cell 1 is formed in a hollow tubular shape including 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 1b. 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 0.9In0.1O3) or BaCe 1-x-yZrxYyO3 (abbreviated as-BCZY, where 0.ltoreq.x.ltoreq.0.8, 0.ltoreq.y.ltoreq.0.2, and 0.ltoreq.x+y.ltoreq.1). The air electrode 1c may be a mixed material of BCZY and one or more of strontium lanthanum cobaltate (LSC material), strontium lanthanum manganate, or strontium lanthanum nickelate.
Thus, the reversible battery 1 may be a hydrogen electrode support tube type proton conductor type reversible battery having a structure of LSC-BCZY (air electrode)/BCZY (electrolyte layer)/NiO-BCZY (hydrogen electrode) of a mixed material of lanthanum strontium cobaltate and a proton conductor material by an "isostatic pressing-dipping-co-sintering" method, for example. In the reversible cell 1, the air electrode 1c is formed to have a shorter length than the hydrogen electrode 1a in the axlebox direction, in other words, the hydrogen electrode 1a protrudes from the lower end.
< Gas collector >
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 cell 1, and serves to guide out and collect gas from the reversible cell 1 and to insulate the same. 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 to the periphery, which can be used for mounting to a mounting seat 211 of the 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 penetrating the gas collector 2 in the up-down direction corresponding to the number of the reversible cells 1 provided in the stack unit 10 are formed in the gas collector 2, and the stepped holes include a large diameter portion in which the above-described reversible cells 1 are mounted, the height of which is slightly smaller than the length of the reversible cells 1 in which the hydrogen electrodes 1a protrude from the lower end (i.e., the length of the reversible motor 1 in which the hydrogen electrodes 1a protrude downward from the air electrodes 1c at the end positions of the reversible motor 1), and a small diameter portion as a gas passage for circulating gas.
< Gas distribution Current collector >
The gas distribution current collector 3 is made of a high temperature resistant metal such as SUS430 stainless steel or Crofer22 stainless steel, and is mainly used for mounting and fixing the reversible cell 1, and introducing and distributing gas to the reversible cell 1. Except for the difference in material, the gas distribution and current collector 3 has the same structure as the gas collector 2, that is, has a boss portion for mounting to the mounting seat 211 of 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 cell 1, and is provided in such a manner that the cavity faces downward and a large diameter portion of the stepped hole faces upward, and the specific structure thereof will not be repeated.
< Linker >
Fig. 3 is a schematic structural view of the connector 4, (a) is a perspective view of the connector 4, (b) is a front view of the connector 4, and (c) is a bottom view of the connector 4. The connector 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 galvanic pile units 10.
As shown in fig. 3 (a) and (b), the connector 4 is formed in a substantially zigzag shape, and includes a vertical wall 42, and a first horizontal extension 41 and a second horizontal extension 43 extending reversely from the upper and lower side tips of the vertical wall 42. A plurality of through holes 411 corresponding to the number of the reversible cells 1 in the electric pile unit 10 are formed on the first horizontal extension 41, and the reversible cells 1 are inserted into the through holes 411, respectively.
As described above, the plurality of reversible cells 1 are inserted into the stepped holes of the gas collector 2 at the upper ends thereof, into the stepped holes of the gas distribution current collector 3 at the lower ends thereof, and are provided between the gas collector 2 and the gas distribution current collector 3 in the form of the through holes 411 of the insertion connection body 4. More specifically, the air electrodes 1c of the plurality of reversible cells 1 are electrically connected to the connecting body 4 through the conductive paste to form the parallel air electrode sides, and the upper ends of the reversible cells 1 are inserted into the stepped holes of the gas collectors 2 and sealed with the stepped holes by the sealing material, and the lower ends are inserted into the stepped holes of the gas distribution current collectors 3 with the exposed hydrogen electrodes 1a and electrically connected to the gas distribution current collectors 3 through the conductive paste to form the parallel hydrogen electrode sides, and then sealed from the outside by the sealing material, whereby the plurality of reversible cells 1 form a parallel structure in the electric pile 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 unit 10 having such a structure is disposed in a pair of stack gas distribution plates 20 in series from end to end, as will be described later.
[ Pile gas distribution plate ]
Fig. 4 is a schematic structural view of the stack gas distribution plate 20 of the reversible cell stack 100, (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 B-B sectional view of the stack gas distribution plate 20. As shown in fig. 4 (a), (b), and (c), the stack gas distribution plate 20 is formed in a substantially long plate shape, but the present invention is not limited thereto, and the stack gas distribution plate 20 may be formed in any plate shape according to actual needs, 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 (a), (b), and (c) of fig. 4, the stack gas distribution plate 20 includes: a main body 21 having a gas passage formed therein and a gas duct 22 extending from the main body 21 to one side, and a plurality of mounting seats 211 for mounting the cell stack unit 10 are formed in the main body 22.
The gas channels in the body 21 are used for gas diversion and gas collection to each stack unit 10. The mounting seat 211 is formed in a shape recessed downward from the upper surface of the main body 21, and may be provided with a boss portion of the gas collector 2 and the gas distribution and collection plate 3 for supporting the cell stack unit 10 and achieving gas sealing by a sealing material. A gas hole 212 communicating with the gas passage of the main body 21 is formed in the center of the mount 211. The gas guide pipe 22 is mainly used for inputting or outputting hydrogen from or to the outside.
As described above, as shown in fig. 1 (a), the plurality of stack units 10 are mounted on the mounting seats 211 of the stack gas distribution plates 20 with the gas collectors 2 and the distribution current collectors 3, respectively, and the respective cavities are provided between the upper and lower pairs of the stack gas distribution plates 20 in communication with the gas 212. More specifically, the plurality of galvanic pile units 10 are arranged end to end in series in such a manner that the second horizontal extension 43 of the connector body 4 in the former galvanic pile unit 10 is connected to the gas distribution and current collector 3 in the latter galvanic pile unit 10, for example, by using a process such as conductive paste, soldering or laser welding. Thus, the plurality of cell units 10 are arranged in series end to end between the pair of upper and lower cell gas distribution plates 20 to form the reversible cell stack 100. These reversible cell stacks 100 may be used as pile modules, and as shown in fig. 1 (b), a reversible cell stack 200 having a larger series composition specification may be used. More pile modules are connected electrically and pneumatically in parallel to form a pile with higher power.
[ Hydrogen electrode wire and air electrode wire ]
The reversible cell stack 100 also has a hydrogen electrode lead 11 and an air electrode lead 12 respectively led from the connection body 4 of the cell stack 10 at the head end and the gas distribution current collector 3 of the cell stack 10 at the tail end. Specifically, the hydrogen electrode wire 11 is a high temperature resistant metal wire composed of, for example, a ni—cr alloy, and is bonded to the connector 4 of the galvanic pile unit 10, i.e., the hydrogen electrode side, by a conductive paste. The air electrode wire 12 is also a high temperature resistant metal wire composed of, for example, a ni—cr alloy, and is bonded to the gas distribution current collector 3, i.e., the air electrode side, of the galvanic cell 10 by a conductive paste. Thereby supplying power to the reversible cell stack 100 or drawing current generated by the reversible cell stack 100.
[ Flow deflector ]
In addition, in the present invention, the reversible cell stack 100 further includes a metal guide sheet 13, and the guide sheet 13 is adhered between two adjacent cell stack units 10 through conductive paste, so that the cell stack unit 10 having poor or failed performance in the reversible cell stack 100 is shorted to an adjacent one of the cell stack units 10 that normally operates.
Fig. 5 is a diagram showing a cell stack unit 10 in which a problem occurs in the reversible cell stack 100 using the current guide sheet 13. As shown in fig. 5, when the performance of the second cell 10, i.e., the failed cell 10', in the reversible cell 100 is poor and the overall cell performance output is severely reduced, the gas distribution current collector 3 of the cell 10 and the gas distribution current collector 3 of the failed cell 10' are connected by the current guide sheet 13, so that the current path bypasses the failed cell 10', and the reversible cell 100 performance output is the electrochemical performance of 12 cells.
The reversible cell stack 100 of the present invention can be obtained by preparing the reversible cells 1 of the hydrogen electrode support tube type proton conductor, connecting a plurality of the reversible cells 1 in parallel to form the cell stack unit 10, connecting a plurality of the cell stack units 10 in series, sealing and integrating, and then generating electricity or producing hydrogen by using the reversible cell stack 100 of the structure.
In operation, the reversible cell stack 100 may be warmed to an operating temperature, hydrogen gas is introduced from the gas-guide tube 22 of one of the stack gas distribution plates 20 (e.g., the lower stack gas distribution plate 20) and hydrogen gas is introduced from the gas-guide tube 22 of the other of the stack gas distribution plates 20 (e.g., the upper stack gas distribution plate 20), and the entire reversible cell stack 100 is placed in a humid air atmosphere or humid air is passed through the reversible cell stack 100 in the direction of arrow a as shown in fig. 1 (a), the external power output of the reversible cell stack 100 being the fuel cell mode, and the electrolytic cell mode being the electrolytic cell mode for supplying power to the reversible cell stack 100 and producing hydrogen by electrolysis of water vapor. 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 as a fuel, and the inside of the reversible cell 1 loses electrons near the hydrogen electrode 1a, turns into protons and is conducted to the outside air electrode 1c through the electrolyte layer 1b, and electrons are obtained at the air electrode 1c, and after reacting with oxygen of air, water is generated and discharged. In the electrolytic cell mode, the hydrogen electrode lead 11 and the air electrode lead 12 are energized to the reversible cell stack 100, water in the humid air outside the reversible cell 1 loses electrons at the air electrode 1c and then breaks down protons, the protons are conducted to the hydrogen electrode 1a inside through the electrolyte layer 1b, electrons of an external circuit are obtained and hydrogen gas is generated and then discharged, and at this time, hydrogen gas which is externally input to the reversible cell stack 100 through one gas guide pipe 22 is used for supplying power to push the generated hydrogen gas to be discharged from the other gas guide pipe 22.
The advantages of the present invention with respect to the prior art stacks are mainly represented by the following aspects:
(1) Module combination type: the reversible cell stack is formed by serially connecting and combining the cell stack units formed by connecting a plurality of reversible cells in parallel, is convenient for batch preparation and quality control, and can be used for performing performance test on the cell stack units and then serially connecting the cell stack units with similar performance to form the reversible cell stack, so that the electrochemical performance of the integrated reversible cell stack can be improved;
(2) The cell stack combination flexibility is strong: the power of the reversible cell stack can be flexibly adjusted and the replacement of the damaged unit can be realized through the increase and decrease of the cell stack unit;
(3) Water management is easy: in the invention, the whole reversible cell 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 stack air resistance is small: the invention adopts a straight-through tubular reversible battery structure, the gas circulation path is short, and the gas resistance in the electric pile is small;
(5) The safety is good: the reversible cell stack is of an all-solid-state structure, and has no risks of leakage, corrosion, explosion and the like.
The following examples are provided to further illustrate the invention.
Example 1
A hydrogen electrode supporting tube type proton conductor type reversible battery 1 having a structure of LSC-BCZY (air electrode)/BCZY (electrolyte layer)/NiO-BCZY (hydrogen electrode) from outside to inside as shown in fig. 2 (d) was produced by an "isostatic pressing-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 9cm. 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 metal gas distribution current collector 3 with 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 respectively inserted into the battery mounting holes 411 of the metal connector 4, and the outside air electrode 1c is bonded to the battery mounting holes 411 by using a conductive paste such as Ag paste. Finally, the upper ends of the four tubular reversible batteries 1 are respectively inserted into the stepped holes of the gas collector 2 and sealed and bonded by microcrystalline glass, thus integrating the pile unit 10 with a parallel structure.
Four stack units 10 are sealed to a stack gas distribution plate 20 having mounting seats 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 unit 10 are connected together with the connecting body 4 by laser welding via the gas distribution current collector 3, forming a series structure. The current of the entire reversible cell stack 100 was drawn from the gas distribution current collector 3 of the cell stack unit 10 located at the end and the connection body 4 of the cell stack unit 10 located at the head end, respectively, using a wire harness 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 performance of the second cell 10 in the reversible cell stack 100, that is, the failed cell 10', is poor and the overall cell performance output is severely reduced, as shown in fig. 5, the gas distribution current collector 3 of the cell 10 and the gas distribution current collector 3 of the failed cell 10' are shorted by the metal flow guide sheet 13, and the current path bypasses the failed cell 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 was used to integrate four cells 1 in parallel with a stack unit 10. The 16 galvanic pile units 10 are sealed to a galvanic pile gas distributor with gas distribution grooves. The galvanic pile units 10 are connected end to end, and the hydrogen electrodes and the air electrodes of adjacent units are connected together by laser welding through the gas distribution current collector 3 and the connecting body 4 to realize series connection. As shown in fig. 1 (b), the position arrangement of the pile units 10 adopts 4*4 "square arrangement, and the last pile unit 10 in the previous row and the pile unit 10 corresponding to the next row are in serpentine electrical connection. More specifically, the last cell 10 of the previous row is electrically connected to the connection body 4 of the cell 10 adjacent to the same row (for example, in the left-right direction in fig. 1 (b)) at the gas distribution current collector 3, while its own connection body 4 is disposed in the front-rear direction in fig. 1 (b), thereby connecting the gas distribution current collectors 3 of the cells 10 of the next row. Thereby, the reversible cell stack 200 composed of the 64-tube reversible cells 1 is integrated.
Similarly, when the performance of the failed cell 10 'in the reversible cell stack 200 is poor, the gas distribution and current collectors 3 of the adjacent cell 10 and the failed cell 10' may be shorted by the metal flow guide sheet 13 in the same manner as in example 1, bypassing the cell, and achieving high fault tolerance of the cell stack.
The reversible cell stack according to the present invention and the cell stack unit 10 constituting the same are described above, but the present invention is not limited thereto. The stack unit 10 is not limited to the four reversible cells 1 provided in parallel, and may be provided with four or more or four or less. The structure of the connector 4 is not limited to the zigzag shape described above, and may be formed in other shapes as long as it is ensured that the air electrodes 1c of all the reversible cells 1 in one cell stack 10 are connected to the air motor side without shorting to the gas distribution current collector 3.
The invention adopts modularized assembly, and has strong detachability and flexibility of power expansion; the parallel structure in the pile units can tolerate a certain difference of the performances of the single reversible cells, and the structure that the pile units are connected in series with each other can allow the pile units to be flexibly short-circuited and skipped when the electrochemical performance of one pile unit is low or large attenuation occurs, so that the high fault tolerance of the pile structure is realized.
The above embodiments further describe the objects, technical solutions and advantageous effects of the present invention in detail, it should be understood that the above is only one embodiment of the present invention and is not limited to the scope of the present invention, and the present invention may be embodied in various forms without departing from the gist of the essential characteristics of the present invention, and thus the embodiments of the present invention are intended to be illustrative and not limiting, since the scope of the present invention is defined by the claims rather than the specification, and all changes falling within the scope defined by the claims or the equivalent scope of the scope defined by the claims should be construed to be included in the claims. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A module combined type reversible battery pile with high fault tolerance is characterized in that,
The energy conversion device is used for mutually and reversibly converting chemical energy and electric energy of hydrogen fuel;
The reversible cell stack includes:
A plurality of electric pile units each including a plurality of reversible cells including a hydrogen electrode and an air electrode, and the plurality of reversible cells in the electric pile units being arranged in parallel in such a manner that the hydrogen electrodes are connected to each other to a hydrogen electrode side and the air electrodes are connected to each other to an air electrode side;
A pair of electric pile gas distribution plates positioned at two ends of the electric pile units and used for conducting gas diversion and gas collection on the electric pile units;
a hydrogen electrode wire; and
An air electrode wire;
the plurality of electric pile units are arranged between the pair of electric pile gas distribution plates in a serial connection mode;
The air electrode wire and the hydrogen electrode wire are respectively connected with the air electrode side of the electric pile unit positioned at the head end and the hydrogen electrode side of the electric pile unit positioned at the tail end of the plurality of electric pile units;
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 made of proton conductor material;
the galvanic pile unit further includes:
a gas collector located at one end of the plurality of reversible cells, for collecting gas from the plurality of reversible cells;
A gas distribution current collector which is positioned at the other end of the plurality of reversible cells, 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
Forming a zigzag shape, connecting the air electrodes of the plurality of reversible cells to the air electrode side, and forming a connecting body of a parallel structure of the plurality of reversible cells in the pile unit;
the gas distribution current collectors of the adjacent two pile units are connected by the metal current guiding sheets so as to be in short circuit;
The connector comprises a longitudinal wall part, a first horizontal extension part and a second horizontal extension part, wherein the first horizontal extension part and the second horizontal extension part extend reversely from the tips of 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 cells;
the plurality of cell units are arranged end to end in series in the form of the second horizontal extension of the connector in a preceding cell unit connecting the gas distribution current collector in a following cell unit.
2. The modular, high fault tolerance, reversible cell stack of claim 1,
A plurality of stepped holes including a large diameter portion for inserting the hydrogen electrode of the reversible cell and a small diameter portion as a gas passage for flowing a gas are formed in the gas collector in correspondence with the plurality of reversible cells;
the gas collector is composed of a ceramic material.
3. The modular, high fault tolerance, reversible cell stack of claim 1,
A plurality of stepped holes including a large diameter portion for inserting the reversible cells and a small diameter portion as a gas passage for circulating gas are formed in the gas distribution and current collector in correspondence with the plurality of reversible cells;
The gas distribution current collector is composed of a high temperature resistant metallic material.
4. The modular, high fault tolerance, reversible cell stack of claim 1,
The connector is composed of a high temperature resistant metallic material or a conductive oxide material.
5. The modular, high fault tolerance, reversible cell stack of claim 1,
The reversible battery is configured to:
the air electrode is connected with the connector through conductive slurry;
the upper end is inserted into the stepped hole of the gas collector and is sealed by a sealing material;
The lower end is inserted into the stepped hole of the gas distribution current collector through the exposed hydrogen electrode and connected by the conductive paste, and then sealed by the sealing material.
6. The modular, high fault tolerance, reversible cell stack of claim 1,
The pair of stack gas distribution plates includes a main body having a gas passage formed therein, and a gas guide tube extending from the main body to one side;
A plurality of mounting seats for arranging the pile units are formed on the main body;
And air holes are formed in the mounting seat.
7. The modular, high fault tolerance, reversible cell stack of claim 1,
The hydrogen electrode wire and the air electrode wire are high-temperature-resistant metal wires.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110068686.8A CN114824403B (en) | 2021-01-19 | Module combined type high fault tolerance reversible battery stack |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110068686.8A CN114824403B (en) | 2021-01-19 | Module combined type high fault tolerance reversible battery stack |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114824403A CN114824403A (en) | 2022-07-29 |
| CN114824403B true CN114824403B (en) | 2024-07-09 |
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