CN114824403A - Module combined reversible battery stack with high fault tolerance - Google Patents

Abstract

A modular combined high fault-tolerant reversible battery stack is an energy conversion device that reversibly converts chemical energy and electrical energy of hydrogen fuel to each other; the reversible battery stack includes: a plurality of stack units, each of which includes a plurality of reversible batteries , a plurality of reversible batteries include hydrogen electrodes and air electrodes, and the plurality of reversible batteries in the stack unit are arranged in parallel in the form that the hydrogen electrodes are connected to each other to form the hydrogen electrode side, and the air electrodes are connected to each other to form the air electrode side; A pair of stack gas distribution plates for the stack unit to conduct gas conduction and gas collection; hydrogen electrode wires; and air electrode wires; a plurality of stack units are arranged in series between a pair of stack gas distribution plates; air The 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 end of the plurality of stack units.

Description

A modular combined high fault-tolerant reversible battery stack

technical field

The invention belongs to the technical field of hydrogen energy and fuel cells, and particularly relates to a modular combined high fault-tolerant reversible battery stack.

Background technique

The reversible solid-state battery can use high-efficiency power generation such as hydrogen fuel to enter the power grid in the temperature range of 400-700 °C, and at the same time, it can reversibly use waste electricity and other electrolyzed water to produce hydrogen. It is a new and efficient energy conversion device. Due to its high efficiency and high temperature operation characteristics, reversible solid-state batteries can effectively connect heat pipe networks, power grids, and gas networks.

The tubular reversible battery has the characteristics of good pressure resistance and thermal shock resistance, and is one of the more widely used solid reversible battery configurations; the current and voltage of a single tubular reversible battery are relatively low, generally through a reasonable series and parallel combination After the reversible battery stack reaches a larger power.

Japanese Iwahara et al. found that some perovskite-type sintered bodies doped with low oxidation state metal cations have proton conductivity in high-temperature hydrogen-containing or water-vapor atmospheres, defined them as high-temperature proton conductors and applied them to high-temperature electrolysis of water. hydrogen. Since then, high-temperature proton conductor materials have been widely studied and applied in the fields of separation and purification of hydrogen, dehydrogenation or hydrogenation of organic matter, and synthesis of ammonia at atmospheric pressure. Due to the realization of "dry hydrogen" when the water vapor is on the air side during operation, the complexity and cost of the system can be greatly reduced.

At present, there is no battery stack based on the proton conductor type reversible battery, and the fault tolerance of the stack structure in the existing battery stack is poor, and it is difficult to increase or decrease the capacity of the battery stack according to the actual demand.

SUMMARY OF THE INVENTION

The problem to be solved by the invention:

In view of the above problems, the purpose of the present invention is to provide a reversible cell stack that can be used for high temperature hydrogen fuel power generation, and also can be used for high temperature electrolysis of water vapor for hydrogen production.

Technical means to solve the problem:

In order to solve the above problems, the present invention provides a modular combined high fault-tolerant reversible battery stack, which is an energy conversion device that reversibly converts the chemical energy and electrical energy of hydrogen fuel to each other; the reversible battery stack includes: a plurality of stack units , each of the stack units includes a plurality of reversible batteries, the plurality of reversible batteries include a hydrogen electrode and an air electrode, and the plurality of reversible batteries in the stack unit are interconnected with the hydrogen electrodes to form a hydrogen electrode side, the air electrodes are connected to each other and arranged in parallel in the form of the air electrode side; a pair of stack gas distribution plates for conducting gas conduction and gas collection for the plurality of stack units; hydrogen electrode wires; and air electrodes lead; the plurality of stack units are arranged in series between the pair of stack gas distribution plates; the air electrode lead and the hydrogen electrode lead are respectively connected to the plurality of stack units in the first the air electrode side of the stack unit at the end and the hydrogen electrode side of the stack unit at the end.

According to the present invention, the reversible cell stack can be switched between electrolytic cell mode or fuel cell mode depending on whether to energize or connect an external load. Multiple reversible batteries are connected in parallel to form a modular stack unit, so the performance of a single reversible battery can be tolerated to some extent. A plurality of modular stack units are arranged in series between a pair of stack gas distribution plates to form a reversible battery stack, which can also be combined into a reversible battery stack with higher efficiency. High combination flexibility and strong power expansion flexibility.

Alternatively, in the present invention, the reversible battery 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 the hydrogen electrode is connected to the reversible battery. An electrolyte layer is also arranged between the air electrodes; 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 battery is placed in moist air containing water vapor, and the hydrogen electrode side generates dry hydrogen, which does not need to be separated and dried, and the water management is simple.

Alternatively, in the present invention, the stack unit further includes: a gas collector for extracting and collecting gas from the plurality of reversible batteries; connecting the hydrogen electrodes of the plurality of reversible batteries to form the hydrogen electrode a gas distribution current collector for introducing and distributing gas to the plurality of reversible batteries; and connecting the air electrodes of the plurality of reversible batteries into a connector on the air electrode side. As a result, multiple reversible cells can be connected in parallel, so that certain differences in the performance of individual reversible cells can be tolerated.

In the present invention, a plurality of stepped holes may be formed in the gas collector corresponding to the plurality of reversible batteries, and the stepped holes include a large-diameter portion for inserting the hydrogen electrodes of the reversible batteries. and a small diameter portion as a gas passage for circulating gas; the gas collector is made of a ceramic material.

In the present invention, a plurality of stepped holes may be formed on the gas distribution current collector corresponding to the plurality of reversible batteries, and the stepped holes include a large-diameter portion for inserting the reversible batteries and a large diameter portion for inserting the reversible batteries. The small diameter part of the gas passage in which the gas flows; the gas distribution collector is made of a high temperature resistant metal material.

Alternatively, in the present invention, the connecting body includes a vertical wall portion, a first horizontal extending portion and a second horizontal extending portion oppositely extending from both ends of the vertical wall portion; the first horizontal extending portion A plurality of through holes are formed on the portion corresponding to the plurality of reversible batteries; the connecting body is made of a high temperature-resistant metal material or a conductive oxide material.

It can also be that, in the present invention, the reversible battery is configured as follows: the through hole of the connecting body is inserted through and the air electrode is connected to the connecting body through conductive paste; the upper end is inserted into the stepped hole of the gas collector and The sealing material is used for sealing; the lower end is inserted into the stepped hole of the gas distribution current collector through the exposed hydrogen electrode, connected by the conductive paste, and then sealed by the sealing material.

In the present invention, the plurality of stack units may be connected to the gas distribution in the next stack unit by the second horizontal extension of the connecting body in the previous stack unit. The current collectors are arranged end to end in series. As a result, a plurality of stack units can be connected in series in end-to-end, so as to form a reversible battery stack in series.

Alternatively, in the present invention, the pair of stack gas distribution plates includes a main body with a gas channel formed therein and an air duct extending from the main body to one side; A plurality of mounting seats of the stack unit; air holes are formed in the mounting seats.

Alternatively, in the present invention, the hydrogen electrode lead and the air electrode lead are metal leads that are resistant to high temperature.

Alternatively, in the present invention, a metal guide fin may be further included, and the guide fin may be short-circuited by connecting the gas distribution current collectors of the two adjacent stack cells. Therefore, when the electrochemical performance of one of the stack units is low or has a large attenuation, the stack unit can be flexibly short-circuited and skipped, so as to realize the high fault tolerance of the stack structure.

Invention effect:

The invention has strong disassembly and power expansion flexibility, and high fault tolerance, and can be used not only for high-temperature hydrogen fuel power generation, but also for high-temperature electrolysis of water vapor to produce hydrogen.

Description of drawings

FIG. 1 is a schematic structural diagram of a module combined high fault-tolerant reversible battery stack according to an embodiment of the present invention, (a) is a schematic structural diagram of a 16-tube reversible battery stack, (b) is a 64-tube reversible battery stack structure schematic diagram;

FIG. 2 is a schematic structural diagram of the stack unit in the reversible battery stack shown in FIG. 1 , (a) is a perspective view of the stack unit, (b) is an exploded view of the stack unit with the connectors hidden, (c) is The cross-sectional view of the stack unit, (d) is the schematic structural diagram of the reversible battery in the stack unit;

3 is a schematic structural diagram of the connector in the stack unit shown in FIG. 2 , (a) is a perspective view of the connector, (b) is a top view of the connector, and (c) is a cross-sectional view of the connector along B-B;

Figure 4 is a schematic diagram of the structure of the stack gas distribution plate of the reversible battery stack, (a) is the perspective view of the stack gas distribution plate, (b) is the top view of the stack gas distribution plate, (c) is the stack gas distribution plate. main view;

5 is a diagram illustrating the use of a baffle to short a faulty stack cell in a reversible battery stack;

Symbol Description:

100, reversible battery stack (16-tube reversible battery stack); 200, reversible battery stack (64-tube reversible battery stack); 10, stack unit; 10', fault stack unit; 1, reversible battery; 1a, hydrogen electrode; 1b, electrolyte layer; 1c, air electrode; 2, gas collector; 3, gas distribution current collector; 4, connector; 5, conductive paste; 6, sealing material; 11, hydrogen electrode lead; 12, air electrode Wire; 13, guide plate; 20, stack gas distribution plate; 21, main body; 22, air duct; 211, mounting seat; 212, air hole; 41, first horizontal extension; 42, vertical wall part; 43, The second horizontal extension; 411, the battery mounting hole; A, the direction of the humid air.

Detailed ways

The present invention will be further described below with reference to the accompanying drawings and the following embodiments. It should be understood that the accompanying drawings and the following embodiments are only used to illustrate the present invention, but not to limit the present invention.

Herein is disclosed a scalable, modular combined 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 high-temperature electrolysis of water vapor for hydrogen production. 1 is a schematic structural diagram of a reversible battery stack according to an embodiment of the present invention, (a) is a schematic structural diagram of a 16-tube reversible battery stack 100 , and (b) is a structural schematic diagram of a 64-tube reversible battery stack 200 . The structure of the reversible battery stack will be described below by taking the 16-tube reversible battery stack 100 as an example.

As shown in (a) of FIG. 1 , the reversible cell stack 100 is an energy conversion device that reversibly converts the chemical energy and electrical energy of hydrogen fuel, and includes a plurality of stack units 10 , two upper and lower layers of the plurality of stack units 10 . A pair of stack gas distribution plates 20 on the side, and the hydrogen electrode wires 11 and the air electrode wires 12 drawn out from the stack unit 10 .

[stack unit]

2 is a schematic structural diagram of the stack unit 10 in the reversible battery stack 100 , (a) is a perspective view of the stack unit 10 , (b) is an exploded view of the stack unit 10 with the connector 4 hidden, (c) is a cross-sectional view of the stack unit 10 , and (d) is a schematic structural diagram of the reversible battery 1 . As shown in (a), (b), and (c) of FIG. 2 , the stack unit 10 includes a reversible battery 1 , a gas collector 2 , a gas distribution current collector 3 , and a connecting body 4 .

<Reversible battery>

In this embodiment, the reversible battery 1 is a proton conductor type reversible battery, and its typical operating temperature range is 500-700°C. As shown in (d) of FIG. 2 , 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 1b . The hydrogen electrode 1a is located at the innermost side of the reversible battery 1, and is mainly a place where the hydrogen gas undergoes an electrochemical reaction and conducts electrons. The electrolyte layer 1b is a proton conductor material, such as calcium zirconate doped with indium oxide (CaZr _0.9 In _0.1 O ₃ ) or BaCe _1-xy Zr _x Y _y O ₃ (abbreviated as -BCZY, where 0≤x≤0.8, 0≤y≤0.2, and 0≤x+y≤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 lanthanate nickelate and BCZY.

Thus, the reversible battery 1 can be, for example, LSC-BCZY (air electrode)/BCZY (electrolyte layer) prepared by the "isostatic pressing-dipping-co-sintering" method, which is a mixed material of lanthanum strontium cobaltate and proton conductor material. Hydrogen electrode support tubular proton conductor type reversible battery of NiO-BCZY (hydrogen electrode) mixed material of nickel oxide and proton conductor material. In addition, in the reversible battery 1, the air electrode 1c is formed to be shorter in length in the axle box direction than the hydrogen electrode 1a, in other words, the hydrogen electrode 1a protrudes from the lower end.

<Gas collector>

The gas collector 2 is composed of insulating ceramic materials such as alumina, zirconia, etc., and is mainly used to install and fix the reversible battery 1 , and extract and collect gas from the reversible battery 1 , and play an insulating role. The gas collector 2 is formed in a substantially rectangular parallelepiped shape.

More specifically, the upper part of the gas collector 2 is formed with a boss portion protruding to the periphery, and the boss portion can be used for mounting to a mounting seat 211 of the stack gas distribution plate 20 to be described later. The upper surface of the gas collector 2 is recessed downward to form a cavity corresponding to the air hole 212 of the stack gas distribution plate 20 . In addition, the gas collector 2 is formed with a plurality of stepped holes corresponding to the number of reversible batteries 1 provided in the stack unit 10 and penetrating the gas collector 2 in the up-down direction, and the stepped holes include the installation of the above-mentioned reversible batteries 1. The large-diameter portion of the reversible battery 1 and the small-diameter portion serving as a gas passage for circulating gas, the height of the large-diameter portion is slightly smaller than the length of the hydrogen electrode 1a protruding from the lower end in the reversible battery 1 (that is, the hydrogen electrode 1a at the end position of the reversible motor 1). The length of the electrode 1a exposed downward from the air electrode 1c).

<Gas distribution collector>

The gas distribution collector 3 is made of, for example, a high-temperature-resistant metal such as SUS430 stainless steel or Crofer22 stainless steel, and is mainly used to install and fix the reversible battery 1 , and to introduce and distribute gas to the reversible battery 1 . The gas distribution collector 3 has the same structure as the gas collector 2 except that the material is different, that is, it has a boss portion for mounting to the mounting seat 211 of the stack gas distribution plate 20, for distributing with the stack gas The cavity connected with the air holes 212 of the plate 20 and a plurality of stepped holes for installing and fixing the reversible battery 1 are arranged in the form of the cavity facing downward and the large diameter portion of the stepped hole facing upward.

<connector>

3 is a schematic structural diagram 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 connecting body 4 is made of a high-temperature-resistant metal material such as SUS430 stainless steel and Crofer22 stainless steel, or a conductive oxide material such as lanthanum chromate oxide, and is mainly used for connecting adjacent stack cells 10 .

As shown in FIGS. 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 horizontal extension extending oppositely from the upper and lower ends of the vertical wall portion 42 part 41 and the second horizontally extending part 43 . A plurality of through holes 411 corresponding to the number of reversible batteries 1 in the stack unit 10 are formed on the first horizontally extending portion 41 , and the above-mentioned reversible batteries 1 are respectively inserted into these through holes 411 .

In this way, the upper end of the plurality of reversible batteries 1 is inserted into the stepped hole of the gas collector 2, the lower end is inserted into the stepped hole of the gas distribution collector 3, and the through hole 411 through which the connecting body 4 is inserted is provided between the gas collector 2 and the gas collector 2. Gas distribution between collectors 3. More specifically, the air electrodes 1c of the plurality of reversible batteries 1 are electrically connected to the connecting body 4 through conductive paste to form a parallel air electrode side, and the upper ends of the reversible batteries 1 are inserted into the stepped holes of the gas collector 2 and are connected to the stepped holes. It is sealed by a sealing material, the lower end is inserted into the stepped hole of the gas distribution collector 3 with the exposed hydrogen electrode 1a, and is electrically connected to the gas distribution collector 3 through the conductive paste to form a parallel hydrogen electrode side, and then the hydrogen electrode side is formed by the sealing material. Sealing is performed from the outside, whereby the plurality of reversible batteries 1 form a parallel structure in the stack unit 10 . The conductive paste can be Pt paste, Ag paste, etc., and the sealing material can be glass, glass-ceramic or mica, etc.

The stack unit 10 of such a structure is provided in a pair of stack gas distribution plates 20 in series end-to-end, the details of which will be described later.

[Stack gas distribution plate]

4 is a schematic structural diagram of the stack gas distribution plate 20 of the reversible battery stack 100 , (a) is a perspective view of the stack gas distribution plate 20 , (b) is a top view of the stack gas distribution plate 20 , (c) is the stack B-B sectional view of the gas distribution plate 20 . As shown in (a), (b) and (c) of FIG. 4 , the stack gas distribution plate 20 is formed in a substantially elongated plate shape, but is not limited to this, and the stack gas distribution plate 20 may be formed in any shape according to actual needs. The plate shape may be formed in a square plate shape as shown in FIG. 1( b ), for example.

The stack gas distribution plate 20 is made of ceramic materials such as alumina, zirconia and the like, and can play an insulating role. As shown in FIGS. 4( a ), ( b ) and ( c ), the stack gas distribution plate 20 includes a main body 21 with a gas channel formed therein and a gas duct 22 extending from the main body 21 to one side, and A plurality of mounts 211 for installing the stack unit 10 are formed on the main body 22 .

The gas channels in the main body 21 are used for gas conduction 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 the bosses of the gas collector 2 and the gas distribution collector 3 can be provided to support the stack unit 10 and achieve 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 mounting seat 211 . The gas conduit 22 is mainly used for inputting hydrogen from the outside or outputting the hydrogen to the outside.

In this way, as shown in FIG. 1( a ), the plurality of stack units 10 are respectively mounted on the mounting seat 211 of the stack gas distribution plate 20 with the gas collector 2 and the distribution current collector 3 , and the respective concave cavities The form in communication with the gas 212 is provided between the upper and lower pair of stack gas distribution plates 20 . More specifically, the plurality of stack units 10 are arranged end to end in series in the form that the second horizontal extension 43 of the connecting body 4 in the former stack unit 10 is connected to the gas distribution current collector 3 in the latter stack unit 10, for example The connection can be made by process methods such as conductive paste, brazing or laser welding. As a result, the plurality of stack cells 10 are arranged end to end in series between the upper and lower pair of stack gas distribution plates 20 to form the reversible battery stack 100 . These reversible battery stacks 100 can also be used as stack modules, and are connected in series as shown in FIG. 1( b ) to form a larger-scale reversible battery stack 200 . More stack modules can be connected in parallel to form a higher power battery stack.

[Hydrogen electrode lead and air electrode lead]

In the reversible battery stack 100, the hydrogen electrode lead 11 and the air electrode lead 12 are respectively drawn from the connecting body 4 of the stack unit 10 at the head end and the gas distribution current collector 3 of the stack unit 10 at the end. Specifically, the hydrogen electrode wire 11 is a high-temperature-resistant metal wire made of Ni—Cr alloy, for example, and is bonded to the connecting body 4 of the stack unit 10 , ie, the hydrogen electrode side, by means of a conductive paste. The air electrode wire 12 is also a high-temperature-resistant metal wire made of Ni-Cr alloy, and is bonded to the gas distribution current collector 3 of the stack unit 10 , ie, the air electrode side, through conductive paste. Thereby, power is supplied to the reversible battery stack 100 or the current generated by the reversible battery stack 100 is drawn.

[deflector]

In addition, in the present invention, the reversible battery stack 100 further includes a metal guide plate 13, the guide plate 13 is bonded between two adjacent stack units 10 through conductive paste, so that the reversible battery stack 100 A stack unit 10 with poor neutral performance or failure is short-circuited 10 with an adjacent stack unit in normal operation.

FIG. 5 is a diagram illustrating a problem in short-circuiting the stack unit 10 in the reversible battery stack 100 using the guide vane 13 . As shown in FIG. 5 , when the performance of the second stack unit 10 in the reversible battery stack 100 , that is, the faulty stack unit 10 ′ is poor, and the performance output of the entire stack is severely reduced, the stack unit 10 is connected by the guide vane 13 . The gas distribution collector 3 of 10 and the gas distribution collector 3 of the faulty stack unit 10', the current path bypasses the faulty stack unit 10', and the performance output of the reversible battery stack 100 is the electrochemical performance of 12 cells. performance.

The reversible battery stack 100 of the present invention can be obtained by first preparing a reversible battery 1 with a hydrogen electrode supporting a tubular proton conductor, connecting a plurality of reversible batteries 1 in parallel to form a stack unit 10, connecting the plurality of stack units 10 in series, sealing and then integrating, The reversible cell stack 100 of this structure can then be used for power generation or hydrogen production.

During operation, the reversible battery stack 100 can be heated up to the working temperature, and hydrogen gas is introduced into the gas duct 22 of one stack gas distribution plate 20 (for example, the lower stack gas distribution plate 20 ) and distributed from the other stack gas The gas duct 22 of the plate 20 (eg, the stack gas distribution plate 20 located above) leads out the hydrogen gas, and the entire reversible battery stack 100 is placed in a humid air atmosphere or in the direction of arrow A as shown in FIG. 1( a ). Moist air passes through the reversible cell stack 100 , and the reversible cell stack 100 outputs electrical power to the outside, which is the fuel cell mode, and the electrolytic cell mode is the electrolytic cell mode that provides power to the reversible cell stack 100 and electrolyzes water vapor to produce hydrogen. In the fuel cell mode, the reversible cell stack 100 is connected to an external load through the hydrogen electrode wire 11 and the air electrode wire 12 and reversely inputs hydrogen as fuel. After the hydrogen loses electrons near the hydrogen electrode 1a inside the reversible cell 1, it is converted into protons and Conducted through the electrolyte layer 1b to the air electrode 1c on the outside, electrons are obtained at the air electrode 1c, react with the oxygen in the air, and generate water, which is then discharged. In the electrolytic cell mode, the hydrogen peroxide electrode lead 11 and the air electrode lead 12 are energized to the reversible battery stack 100, the water in the humid air outside the reversible battery 1 loses electrons at the air electrode 1c and decomposes protons, and the protons are conducted through the electrolyte layer 1b After reaching the inner hydrogen electrode 1a, the electrons of the external circuit are obtained and hydrogen gas is generated and discharged. At this time, the hydrogen input from the outside to the reversible battery stack 100 through one air conduit 22 is used to provide power, and the generated hydrogen is pushed from the other air conduit. 22 discharge.

Compared with the previous battery stack, the advantages of the present invention are mainly manifested in the following aspects:

(1) Modular combined type: The reversible battery stack is composed of multiple reversible batteries connected in series, which is convenient for batch preparation and quality control. Similar stack units are connected in series to form a reversible battery stack, which can improve the electrochemical performance of the integrated reversible battery stack;

(2) The flexibility of the battery stack combination is strong: through the increase or decrease of the stack unit, the power of the reversible battery stack can be flexibly adjusted and the replacement of damaged units can be realized;

(3) Easy water management: In the present invention, the entire reversible battery stack is mixed with moist air containing water vapor on the outside (ie, the air electrode side), and the hydrogen electrode side is "dry hydrogen", which does not need to be separated and dried, and the water management is simple;

(4) Small stack gas resistance: The present invention adopts a straight-through tubular reversible battery structure, the gas flow path is short, and the gas resistance inside the stack is small;

(5) Good safety: the reversible battery stack is an all-solid structure, and there is no danger of leakage, corrosion, explosion, etc.

The following examples are provided to further illustrate the present invention.

Example 1

The structure shown in (d) in Figure 2 is prepared by the "isostatic pressing-dipping-co-sintering" method. The structure from outside to inside is LSC-BCZY (air electrode)/BCZY (electrolyte layer)/NiO-BCZY (hydrogen electrode) The hydrogen electrode supports a tubular proton conductor type reversible battery 1. The wall thickness of the reversible battery 1 is about 0.6-0.8 mm, the outer diameter is about 1.0 cm, and the effective length is about 9 cm. As shown in FIG. 2( c ), the hydrogen electrodes 1 a at the lower ends of the four reversible batteries 1 are bonded into the stepped holes of the metal gas distribution current collector 3 through conductive paste such as Ag paste, while on the outside Seal with a sealing material such as glass-ceramic. Next, the four reversible batteries 1 are respectively inserted through the battery mounting holes 411 on the metal connector 4, and the outer air electrodes 1c are bonded to the battery mounting holes 411 using 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 with glass-ceramic, thus the stack unit 10 in the parallel structure is integrated.

The four stack cells 10 are sealed to the stack gas distribution plate 20 with mounting seats 211 and air holes 212 . The stack units 10 are connected end to end as described above, and the hydrogen electrodes 1a and air electrodes 1c of adjacent stack units 10 are connected together via the gas distribution current collector 3 and the connector 4 by laser welding to form a series structure. Using a wire harness of Ni-Cr alloy wire, the current of the entire reversible battery stack 100 is drawn from the gas distribution current collector 3 of the stack unit 10 at the end and the connector 4 of the stack unit 10 at the head end respectively, so as to be as follows: As shown in FIG. 1( a ), a reversible battery stack 100 composed of 16 reversible batteries 1 is completed.

In addition, for example, when the second stack unit 10 in the reversible battery stack 100, that is, the faulty stack unit 10', has poor performance and seriously reduces the performance output of the entire stack, as shown in FIG. Sheet 13 short-circuits the gas distribution current collector 3 of the stack unit 10 and the gas distribution current collector 3 of the faulty stack unit 10', so that the current path bypasses the faulty stack unit 10', and the reversible battery stack 100 The performance output is the electrochemical performance of 12 reversible cells 1.

Example 2

The same process as in Example 1 was used to integrate four parallel stack units 10 of reversible batteries 1 . The 16 stack cells 10 were sealed to a stack gas distributor with gas distribution grooves. The stack units 10 are connected end to end, and the hydrogen electrodes and 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 (b) of FIG. 1 , the positional 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 latter row are serpentine. Electrical connection. More specifically, the last stack unit 10 in the previous row is electrically connected to the connecting body 4 of the stack unit 10 adjacent to the same row at the gas distribution collector 3 (for example, along the left and right sides of FIG. 1(b) direction), and its own connecting body 4 is arranged in the front-rear direction in FIG. 1(b), thereby connecting the gas distribution current collectors 3 of the next row of stack cells 10. Thus, the integration consists of 64-tube reversible cells 1 The reversible battery stack 200.

Similarly, when the performance of the faulty cell stack 10 ′ is poor in the reversible cell stack 200 , the same method as in Embodiment 1 can be used to remove the gas from the adjacent cell stack 10 and the faulty cell stack 10 ′. The distribution current collector 3 is short-circuited with a metal guide plate 13 to bypass the unit, so as to realize the high fault tolerance of the stack.

The reversible battery stack according to the present invention and the stack unit 10 constituting the reversible battery stack have been described above, but the present invention is not limited thereto. The stack unit 10 is not limited to four reversible batteries 1 provided in parallel, and may be four or more or less than four. In addition, the structure of the connecting body 4 is not limited to the above-mentioned zigzag shape, and can also be formed in other shapes, as long as it can ensure that the air electrodes 1c of all the reversible batteries 1 in one stack unit 10 are connected to the air motor side, and are not connected to the gas distribution collector. The flow device 3 can be short-circuited.

The invention adopts modular assembly, and has strong disassembly and power expansion flexibility; the parallel structure in the stack unit can tolerate a certain difference in the performance of a single reversible battery, and the structure of the stack units in series can allow when one of the battery cells is connected in series. When the electrochemical performance of the stack unit is low or has great attenuation, the stack unit can be flexibly short-circuited and skipped, so as to realize the high fault tolerance of the stack structure.

The above specific embodiment further describes the purpose, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above is only a specific embodiment of the present invention, and is not limited to the protection scope of the present invention. The present invention can be embodied in various forms without departing from the spirit of the essential characteristics of the present invention, so the embodiments in the present invention are for illustration rather than limitation, since the scope of the present invention is defined by the claims rather than by the description, and All changes that come within the ranges defined by the claims, or equivalents to the ranges defined by the claims, should be construed as being included in the claims. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within 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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