TWI699028B - Metal-air flow secondary battery - Google Patents

Abstract

A metal-air flow secondary battery includes a discharge positive plate module, an air electrode module, a front case, a charge positive plate module, an intermediate case, a negative plate, and a back case. The discharge positive plate module and the air electrode module are disposed on a first side of the front case, and the charge positive plate module is disposed between a second side of the front case and the intermediate case. The negative plate is disposed between the intermediate case and the back case. Both of the front case and the intermediate case have a holding space for containing an electrolyte solution. The front case consists of a first electrolyte channel module and a second electrolyte channel module, wherein the first electrolyte channel module is disposed between the discharge positive plate module and the second electrolyte channel module.

Description

Metal air flow secondary battery

The present invention relates to a metal-air battery, and particularly relates to a metal-air flow secondary battery.

Recently, metal-air secondary batteries with both charging and discharging functions have gradually attracted attention and started to develop. The cathode of the traditional metal liquid flow air secondary battery must have both catalysts, so that it can carry out the oxygen reduction reaction (ORR) during the discharge process, reducing oxygen (O ₂ ) to hydroxide ions (OH ^-); or oxygen evolution reaction (oxygen evolution reaction, OER) during charging the hydroxide ions (OH ^-) is oxidized to oxygen (O _2).

Because the electrolyte of the traditional metal flow air secondary battery cannot flow, during the charging process, the metal electroplated to the negative electrode side will form a dendrite structure, which makes the metal unable to produce a uniform coating on the surface of the negative electrode. Oxygen (O ₂ ) may cause the disintegration and destruction of the ORR catalyst in the dual-effect electrode; the metal oxide generated during the discharge process will not only cover the surface of the negative electrode metal and cause anode passivation, but also contaminate the electrolyte. Increasing the ion conduction impedance may gradually evaporate and become exhausted under long-term operation, which will affect the performance and life of the battery.

Therefore, it is necessary to provide a metal liquid flow air secondary battery to solve the problems caused by the accumulation of waste heat and the inability of electrolyte to flow.

The invention provides a metal-air flow secondary battery, which can improve the performance and service life of the metal-air flow secondary battery.

The present invention provides another metal-air flow secondary battery, which can greatly reduce the generation of bubbles, so as to improve the performance and life of the metal-air flow secondary battery.

The metal-air flow secondary battery of the present invention includes a front casing, a discharge positive plate module, an air electrode module, a rear casing, a negative plate, a charging positive plate module, and a middle casing. The front shell system is composed of a first electrolyte channel module and a second electrolyte channel module, and has a first accommodating space for accommodating electrolyte. The discharge positive plate module is located on the first side of the front housing, and includes a discharge positive plate with a plurality of first through openings, wherein the first electrolyte channel module is between the discharge positive plate module and the second electrolyte channel module between. The air electrode module is located between the discharge positive plate module and the front housing, includes an oxygen reduction reaction catalyst, and is in contact with the electrolyte. The rear case is located on the second side of the front case. The negative plate is located between the rear casing and the front casing and is in contact with the electrolyte. The charging positive plate module is located between the front case and the negative plate, and includes a charging positive plate with a second through opening and an oxygen evolution reaction catalyst. The middle shell is located between the charging positive plate module and the negative plate, and has a second containing space for containing electrolyte.

Another metal-air flow secondary battery of the present invention includes a front casing, a discharge positive plate module, an air electrode module, a middle casing, a negative plate module, a charging positive plate module, and a charging electrode module. The front shell system is composed of a first electrolyte channel module and a second electrolyte channel module, and has a first accommodating space to accommodate the electrolyte. The discharge positive plate module is located on the first side of the front housing, and includes a discharge positive plate with a plurality of first through openings, wherein the first electrolyte channel module is between the discharge positive plate module and the second electrolyte channel module between. The air electrode module is located between the discharge positive plate module and the front housing, includes an oxygen reduction reaction catalyst, and is in contact with the electrolyte. The middle casing is located on the second side of the front casing and has a second accommodating space to accommodate the electrolyte. The negative plate module is located between the first side of the middle casing and the front casing, and has a third accommodating space to accommodate the deposition of electrolyte and metal. The charging positive plate module is located on the second side of the middle casing and includes a charging positive plate with a second through opening. The charging electrode module is located between the charging positive plate module and the middle casing, and has an oxygen evolution reaction catalyst in contact with the electrolyte.

In order to make the above-mentioned features and advantages of the present invention more comprehensible, the following specific embodiments are described in detail in conjunction with the accompanying drawings.

Please refer to the following embodiments and accompanying drawings in order to understand the present invention more fully, but the present invention can still be practiced in many different forms, and should not be construed as limited to the embodiments described herein. In the drawings, for the sake of clarity, the components and their relative dimensions may not be drawn according to actual scale. In addition, the terms "include", "include", "have" and so on used in the text are all open terms; that is, including but not limited to. Moreover, the directional terms mentioned in the text, such as "up", "down", "left", "right", etc., are only used to refer to the direction of the schema. Therefore, the directional terms used are used to illustrate, but not to limit the present invention.

Reference will now be made in detail to the exemplary embodiments of the present invention, and examples of the exemplary embodiments are illustrated in the accompanying drawings. Whenever possible, the same or similar component symbols are used in the drawings and descriptions to indicate the same or similar parts.

FIG. 1A is a perspective view of an assembly structure of a metal liquid flow air secondary battery according to an embodiment of the present invention. Fig. 1B is a back perspective view of the structure of Fig. 1A.

1A and 1B, the metal flow air secondary battery 10 of this embodiment basically includes a plurality of battery cells 100, and a discharge positive collector plate 102 and a charge positive collector plate 104 extend from the battery cell 100 , Discharge negative current collector plate 106 and charge negative current collector plate 108. In addition, there are positive terminal plates 110a and negative terminal plates 110b at both ends of the battery cell 100, respectively. The above-mentioned battery cell 100 forms a metal-air flow secondary battery 10 with charging and discharging functions.

When the discharge positive collector plate 102 and the discharge negative collector plate 106 are respectively connected to an external load (not shown), the metal-air flow secondary battery 10 can perform a discharge operation. When the charging positive current collecting plate 104 and the charging negative current collecting plate 108 are respectively connected to an external load, the metal-air flow secondary battery 10 can be charged.

In FIG. 1A, the positive terminal 110 a has, for example, an electrolyte outlet 112 penetrating through its body, and discharges the electrolyte from a plurality of battery cells 100. In FIG. 1B, the negative electrode end plate 110 b is configured with an electrolyte inlet 116 penetrating through its body to supply electrolyte to a plurality of battery cells 100.

In addition, the positive terminal plate 110a and the negative terminal plate 110b can also be respectively provided with a plurality of positioning holes 114a penetrating through the body to be used for the assembly and positioning of the metal-air flow secondary battery 10. In this embodiment, four positioning holes are used.孔114a. The peripheries of the positive terminal plate 110a and the negative terminal plate 110b are respectively provided with a plurality of screw holes 114b penetrating through their bodies. In this embodiment, 12 screw holes 114b are used to lock and fix the metal air flow secondary battery 10 For use.

2A is a three-dimensional schematic diagram of a metal-air flow secondary battery according to another embodiment of the present invention. 2B is an exploded view of the front assembly structure of the metal-air flow secondary battery shown in FIG. 2A. 2C is an exploded view of the assembled structure on the back of the metal-air flow secondary battery of FIG. 2B.

2A and 2B, the metal-air flow secondary battery of this embodiment can be the single battery cell 100 in the previous embodiment, which includes a discharge positive plate module 200, an air electrode module 300, and a front housing 400. Rechargeable positive plate module 500, middle casing 600, negative plate 700 and rear casing 800.

In this embodiment, the front housing 400 may be a combination of the first electrolyte channel module 402 and the second electrolyte channel module 404, and has a first accommodating space for accommodating the electrolyte. In other words, the first side 400 a of the front housing 400 is the front surface of the first electrolyte channel module 402, and the second side 400 b of the front housing 400 is the back surface of the second electrolyte channel module 404. The discharge positive plate module 200 is located on the first side 400a of the front housing 400; the air electrode module 300 is located between the discharge positive plate module 200 and the front housing 400; the rear housing 800 is located on the second side of the front housing 400. Side 400b; the negative plate 700 is located between the rear housing 800 and the front housing 400, the charging positive plate module 500 is located between the front housing 400 and the negative plate 700; the middle housing 600 is located between the charging positive plate module 500 and the negative Between the board 700.

In this embodiment, the discharge positive plate module 200 includes at least one discharge positive plate 202, wherein the discharge positive plate 202 can be a plate made of a highly conductive material with good conductivity and corrosion resistance, such as stainless steel or nickel. (Ni).

The discharge positive plate 202 has a front surface 202a facing the air side and a back surface 202b opposite to the front surface 202a, and the discharge positive plate 202 includes a plurality of first through openings 204, and each first through opening 204 penetrates the front surface 202a of the discharge positive plate 202 With the back surface 202b, the ambient air G can pass through and reach the air electrode module 300.

Please continue to refer to FIG. 2B. On the front surface 202a of the positive discharge plate 202 (the surface away from the air electrode module 300), there are protrusions 206a and 206b, which are respectively provided on the left and right sides of the first through opening 204 to communicate with each other. The first through opening 204 communicates. The protruding portions 206a and 206b can form a plurality of air guide channels for the reaction and heat dissipation air required by the battery cell 100. In this way, the ambient air G can enter the first through opening 204 of the discharge positive plate 202 from the protrusion 206a (or the protrusion 206b) by forced convection to supply the oxygen required for the discharge reaction and take away the reaction The waste heat generated during the process is then discharged from the positive discharge plate 202 by the protrusion 206b (or the protrusion 206a) to the environment.

2C, on the back 202b of the discharge positive electrode plate 202, the first groove 208 and the second groove 210 can be designed according to requirements, and the first groove 208 is provided around the first through opening 204. The second groove 210 is disposed around the first groove 208 to form a space that can accommodate the air electrode module 300. Since the discharge positive plate module 200 may further include a sealing member 212, the first groove 208 can form a space capable of accommodating the sealing member 212, but the structure of the discharge positive plate of the present invention is not limited to this. In addition, the discharge positive plate module 200 may further include a discharge positive collector plate 214, which is arranged on one side of the discharge positive plate 202, wherein the discharge positive collector plate 214 can be connected to the negative plates 700 of the adjacent battery cells 100 to form a series connection. The discharge circuit.

Please continue to refer to FIG. 2B, the air electrode module 300 includes at least one air electrode 302 and a first isolation film 304. The material of the first isolation membrane 304 may be a porous non-metallic material, such as polypropylene (PP), nylon (Nylon), Teflon (PTFE), etc. The air electrode module 300 has a front surface 300 a facing the discharge positive plate module 200 and a back surface 300 b away from the discharge positive plate module 200. The air electrode 302 is located on the front surface 300 a of the air electrode module 300.

The air electrode 302 is composed of, for example, a porous conductive substrate (not shown), a waterproof and breathable membrane (not shown) bonded to one side of the porous conductive substrate, and an oxygen reduction reaction contact surface bonded to the other side of the porous conductive substrate. Medium (discharge reaction catalyst) (not shown). The waterproof and gas-permeable membrane of the air electrode 302 faces the discharge positive plate module 200. The first isolation film 304 is located on the back 300b of the air electrode module 300, and the oxygen reduction reaction catalyst faces the first isolation film 304 to be in contact with the electrolyte. In addition, the first isolation film 304 can isolate the metal generated during the charging reaction, and directly contact the oxygen reduction reaction catalyst of the air electrode 302 to avoid short circuit between the positive and negative electrodes, and can also isolate the oxides generated by the discharge reaction from polluting the air electrode 302. The effective oxygen reduction reaction catalyst can prolong the service life of the air electrode 302.

In this embodiment, when the battery cell 100 is assembled, the porous conductive base material of the air electrode 302 can be in close contact with the first separator 304 and contact with the discharge positive plate 202 of the discharge positive plate module 200 to form An electron conduction path. When the ambient air G diffuses into the oxygen reduction reaction catalyst through the waterproof and gas-permeable membrane of the air electrode 302, the positive electrode discharge reaction can occur. The waterproof and breathable membrane of the air electrode 302 can prevent the electrolyte from leaking into the environment.

Please continue to refer to FIG. 2B. Although the front housing 400 of this embodiment is composed of the first electrolyte channel module 402 and the second electrolyte channel module 404, the present invention is not limited to this. The front case 400 may also include other components. The first electrolyte channel module 402 and the second electrolyte channel module 404 may have an insulating frame structure, such as a square shape, but are not limited thereto. In this embodiment, the first electrolyte channel module 402 is interposed between the discharge positive plate module 200 and the second electrolyte channel module 404, wherein the second electrolyte channel module 404 has a connection with the first electrolyte The channel module 402 has a corresponding appearance, and the first electrolyte channel module 402 and the second electrolyte channel module 404 have substantially coincident transverse cross-sections.

In this embodiment, the first electrolyte channel module 402 has a first opening 406 penetrating through the front surface 402a and the back surface 402b. On the front surface 402a of the first electrolyte channel module 402, there may also be a groove 408, which is arranged around the first opening 406. The size of the groove 408 is approximately equal to the outer boundary of the discharge positive plate 202, and the depth is approximately equal to the discharge positive plate 202. 202 thickness. Therefore, the groove 408 can accommodate the combination of the discharge positive plate module 200 and the air electrode module 300 and can be sealed by a sealing member 410, and the electrolyte contained in the first opening 406 can contact the air electrode module 300, An ion conduction path is formed during the discharge reaction.

2B and 2C, there are a second opening 412 and a third opening 414 above and below the first opening 406, respectively, wherein the second opening 412 and the third opening 414 respectively penetrate the first electrolyte channel module 402 Front 402a and back 402b. In FIG. 2B, two sealing members 416 can be respectively used to set around the second opening 412 and the third opening 414, so as to seal the electrolyte after assembly. On the back surface 402b of the first electrolyte channel module 402, there may be a distribution channel 418 communicating with the first opening 406 and the second opening 412 and communicating with the first opening 406 and the third opening 414.

Please continue to refer to FIG. 2B, the second electrolyte channel module 404 has a fourth opening 420, a fifth opening 422, and a sixth opening 424 corresponding to the respective openings of the first electrolyte channel module 402, wherein the first opening 406 The first middle rectangular opening 426 of the front housing 400 is formed with the fourth opening 420; the first electrolyte discharge manifold 428 of the front housing 400 is formed by the second opening 412 and the fifth opening 422; The six openings 424 constitute the first electrolyte supply manifold 430 of the front case 400. The first electrolyte supply manifold 430 and the first electrolyte discharge manifold 428 are respectively adjacent to the first middle rectangular opening 426, and can supply or discharge the electrolyte to transport the electrolyte in each battery cell 100.

In addition, there may be grooves 432 on the surface of the second electrolyte channel module 404 facing the first electrolyte channel module 402, which are arranged on the outer periphery of the fourth opening 420, the fifth opening 422, and the sixth opening 424, so The groove 432 can accommodate a sealing member 434 for sealing the electrolyte after assembly.

When the first electrolyte channel module 402 and the second electrolyte channel module 404 are combined to form the front housing 400, the first isolation membrane 304, the first electrolyte channel module 402, and the second electrolyte channel module can be used The group 404 and the charging positive plate module 500 are closely connected, and a first accommodating space (not shown) for accommodating the electrolyte is defined in the first middle rectangular opening 426. Moreover, the distribution channel 418 can communicate with the first middle rectangular opening 426 and the first electrolyte discharge manifold 428, and connect the first middle rectangular opening 426 with the first electrolyte supply manifold 430 to supply the first electrolyte to the manifold. The electrolyte in the 430 is transported to the first accommodating space, and the electrolyte in the first accommodating space is output from the first electrolyte discharge manifold 428. Furthermore, the electrolyte located in the first accommodating space can pass through the first middle rectangular opening 426 to contact the first isolation film 304 of the air electrode module 300 and the charging positive plate module 500, thereby providing ions in the battery cell 100 Conduction path for charging and discharging reactions.

In addition, referring to FIG. 2C, a groove 436 corresponding to the middle casing 600 can be selectively provided on the back (second side 400b) of the second electrolyte channel module 404.

Then in FIG. 2B, the charging positive plate module 500 at least includes a charging positive plate 504 with a second through opening 502 and an oxygen evolution reaction catalyst (not shown). In this embodiment, the charging positive plate 504 may be a plate made of a highly conductive material with good conductivity and corrosion resistance, such as stainless steel or nickel (Ni). The charging positive plate module 500 may further include a second isolation film 506, which is disposed on a side of the charging positive plate 504 away from the front housing 400 and facing the front housing 400 to isolate the metal generated during the charging reaction. The material of the second isolation film 506 is, for example, a porous non-metallic material, such as polypropylene (PP), nylon (Nylon), Teflon (PTFE), and the like.

2C, the oxygen evolution reaction catalyst 508 of the charging positive plate module 500 faces the negative plate 700, and the oxygen evolution reaction catalyst 508 is, for example, a stainless steel mesh. In addition, the charging positive plate module 500 may further include a charging positive collector plate 510 arranged on one side of the charging positive plate 504, and the negative plates 700 of the adjacent battery cells can be connected to form a series charging circuit.

Please continue to refer to FIG. 2B, the middle casing 600 has an appearance corresponding to the second electrolyte channel module 404 of the front casing 400. In this embodiment, the middle casing 600 is, for example, a square insulating frame, and the second electrolyte channel module 404 and the middle casing 600 have substantially overlapping transverse cross-sections. The middle housing 600 includes a second middle rectangular opening 602 for forming a second accommodating space, a second electrolyte discharge manifold 604, and a second electrolyte supply manifold 606, wherein the second electrolyte discharge manifold 604 The second middle rectangular opening 602 is adjacent to the second electrolyte supply manifold 606 respectively. The middle casing 600 is sealed with the charging positive plate module 500 and the negative plate 700, so that the second middle rectangular opening 602 of the middle casing 600 defines a second containing space for containing the electrolyte. The middle housing 600 may further include a groove 608 surrounding the outer edge of the second middle rectangular opening 602 and communicating with the second accommodating space for accommodating the charging positive plate module 500, and in the second middle rectangular opening 602 The electrolyte can contact the charging positive plate module 500 to form an ion conduction path during the charging reaction. The size of the groove 608 is approximately equal to the outer boundary of the positive electrode plate module 500, and the depth is approximately equal to the thickness of the positive electrode plate module 500. Moreover, on the periphery of the groove 608, there is another groove 612 capable of accommodating a sealing member 610, which may correspond to the groove 436 provided on the back of the second electrolyte channel module 404 (please refer to FIG. 2C).

Please continue to refer to FIG. 2B. Two sealing members 614 can be respectively arranged around the second electrolyte discharge manifold 604 and the second electrolyte supply manifold 606, so as to seal the electrolyte after assembly.

In this embodiment, the negative electrode plate 700 is, for example, a plate made of a highly conductive material with good conductivity and corrosion resistance, such as stainless steel, nickel (Ni), tin (Sn), or any combination of the foregoing materials. The negative plate 700 can contact the electrolyte contained in the second middle rectangular opening 602 of the middle casing 600 to perform negative charge and discharge reactions.

In addition, a discharge negative current collector plate 704 and a charge negative current collector plate 702 are provided on the lower side and the upper side of the negative plate 700, respectively. When the charging negative collector plate 702 is connected to the charging positive plate 504 of an adjacent battery cell, a series charging circuit can be formed; when the discharging negative collector plate 704 is connected to the discharging positive plate 202 of an adjacent battery cell, a series discharge can be formed Circuit.

Please continue to refer to FIG. 2B, the rear housing 800 has an appearance corresponding to the middle housing 600. In this embodiment, the rear housing 800 is, for example, a square insulating frame, and the middle housing 600 and the rear housing 800 have substantially overlapping transverse cross-sections. The rear case 800 may include a third electrolyte discharge manifold 802 and a third electrolyte supply manifold 804. In addition, the surface of the rear case 800 facing the negative plate 700 can be provided with a groove 806 for receiving the negative plate 700. The outer boundary of the groove 806 is similar and slightly larger than the negative plate 700, and its depth is approximately equal to the negative plate 700. The thickness. In this way, when the negative electrode plate 700 is combined with the rear case 800, the groove 806 can be closely attached to the negative electrode plate 700.

In this embodiment, two sealing members 808 can be respectively arranged around the third electrolyte discharge manifold 802 and the third electrolyte supply manifold 804, so as to seal the electrolyte after assembly.

That is to say, in the assembled battery cell 100, the positions of the first electrolyte supply manifold 430, the second electrolyte supply manifold 606, and the third electrolyte supply manifold 804 are corresponding and connected, so that the electrolyte It can flow into the first and second accommodating spaces and generate charge and discharge reactions, and the positions of the first electrolyte discharge manifold 428, the second electrolyte discharge manifold 604, and the third electrolyte discharge manifold 802 are also corresponding and connected , So the electrolyte can be discharged through the manifold.

If several battery cells 100 in FIG. 2A are combined, the rear housing 800 of one of the two adjacent battery cells will contact the discharge positive plate module 200 of the other battery cell.

3A is a schematic diagram of the charging reaction mechanism of the metal-air flow secondary battery of FIG. 2B. Taking a zinc-air flow secondary battery as an example, during the charging process, the electrolyte composed of zinc oxide (ZnO), potassium hydroxide (KOH) and water (H ₂ O) will be transported to the battery via an external pump Unit 100.

In FIG. 3A, the electrolyte first enters the third electrolyte supply manifold 804 of the rear housing 800, and then the electrolyte is introduced to the second middle rectangular opening 602 of the middle housing 600 through the second electrolyte supply manifold 606, and It further flows into the second through opening 506 and the first middle rectangular opening 426 of the charging positive plate module 500.

When the electrolyte fills the first middle rectangular opening 426, the second through opening 506, and the second middle rectangular opening 602, the electrolyte can contact the air electrode of the air electrode module 300 and the second isolation film of the charging positive plate module 500 506 and the negative plate 700, and form the conductive ion medium in the battery cell 100. In addition, the electrolyte will also enter the second electrolyte supply manifold 606 of the middle housing 600 through the third electrolyte supply manifold 804, and then enter the first electrolyte supply manifold 430 of the front housing 400 to be supplied to the next Battery unit.

In detail, each battery cell 100 can be charged by applying appropriate current to the metal flow air battery through the charging positive collector plate 510 and the charging negative collector plate 702 from the outside. On the negative electrode side, zinc oxide (ZnO) and water (H ₂ O) in the electrolyte will react with the e ^- introduced from the negative electrode collector plate 702 of the negative electrode plate 700, and zinc oxide (ZnO) is further decomposed into Zinc ions (Zn ²⁺ ) migrate toward the negative plate 700. After zinc ions (Zn ²⁺ ) contact the negative electrode plate 700, the zinc ions (Zn ²⁺ ) can react with e ^- to form metallic zinc (Zn) and be electroplated to the surface of the negative plate 700. At the same time, hydroxide ions (OH ⁻ ) are also generated and migrate toward the second isolation film 506 of the charging positive plate module 500.

Charging the positive electrode side, when the hydroxide ions from the negative electrode (OH ^-) contact the second insulating film 506, hydroxide ions (OH ^-) can be produced by catalytic reaction of a stainless steel net of OER oxygen (O _2), water (H ₂ O) and e ^-. e ^- will be conducted to the charging positive collector plate 510 of the charging positive plate 502 through the stainless steel mesh, and then lead to the charging negative collector plate 702 of the negative plate 700 of the adjacent battery cell 100.

During the charging reaction process, the electrolyte can continue to circulate and flow so that oxygen (O ₂ ) enters the first electrolyte discharge manifold 428 with the electrolyte through the distribution channel 418. Then, the electrolyte and O ₂ will flow into the third electrolyte discharge manifold 802 and the second electrolyte discharge manifold 604 of the next battery cell in sequence.

1A and 1B, the electrolyte and oxygen (O ₂ ) of each battery cell 100 can be discharged to the environment through the electrolyte outlet 112 of the metal flow air battery 10, or can be discharged to the environment by forced convection by a fan In the external environment. The electrolyte discharged from the electrolyte outlet 112 will then be transported to the electrolyte inlet 116 via an external pump, thus completing the circulating flow of the electrolyte.

In addition, because the flowing electrolyte can prevent metallic zinc (Zn) from forming a dendritic structure on the surface of the negative plate 700, the flowing electrolyte will also help the formation of a uniform metallic zinc (Zn) coating.

3B is a schematic diagram of the working mechanism of the discharge reaction of the metal-air flow secondary battery of FIG. 2B.

Referring to FIG. 3B, the working mechanism of the discharge reaction of the battery cell 100 is also taken as an example of a zinc-air flow secondary battery. When the charging reaction is completed and the discharging reaction starts, the electrolyte will continue to circulate in the manner described in the charging process to fill the middle rectangular openings and penetrate the openings to form a conductive ionic medium.

The negative electrode side, the metal of the zinc plating to the surface of the negative electrode plate 700 (Zn) will hydroxide ions (OH ^-) from the positive electrode react together. The generated zinc ions (Zn ²⁺ ) migrate from the negative plate 700 to the positive electrode, and e ^-is conducted from the negative plate 700 to the discharge negative collector plate 704, and then introduced into the discharge positive plate 202 of the adjacent battery cell 100 Discharge the positive collector plate 214.

During the discharge reaction, the electrolyte can be continuously circulated so that zinc oxide (ZnO) is discharged with the electrolyte and the metal flow air battery. That is, it is possible to prevent zinc oxide (ZnO) from accumulating and covering the surface of the negative plate 700. In addition, the zinc oxide (ZnO) present in the electrolyte can be removed by external filtration, so that the electrolyte can restore the original ionic conductivity, and then transport to the metal flow air battery.

On the side of the discharge positive electrode, the ambient air G can be introduced into the flow channel formed by the protrusion 206a of the discharge positive plate 202 in a forced convection manner by a fan, enters each of the first through openings 204, and then flows from the protrusion The flow channel formed by 206b is discharged to the environment. At the same time, oxygen (O ₂ ) can diffuse into the waterproof and gas-permeable membrane of the air electrode 302 and then into the catalyst to react with the water (H ₂ O) in the electrolyte and e ^- from the negative electrode to produce toward the negative side migration of hydroxide ions (OH ^-). Because the negative electrode discharge reaction requires sufficient oxygen and generates a large amount of waste heat, the air flow is required to meet the reaction and heat dissipation requirements when supplying air to the negative electrode side to ensure that the metal flow air battery can produce stable performance output.

其中 F_coolant 是反應所需空氣流量、I是電流(A)、F是法拉第常數(96485C/mol)、而 N_cell 則是電池數目。The air flow required for the charge and discharge reaction of the battery cell 100 can be estimated by the following formula:

Among them, F _coolant is the air flow required for the reaction, I is the current (A), F is the Faraday constant (96485C/mol), and N _cell is the number of batteries.

其中，F_coolant 是散熱所需空氣流量、I是電流(A)、V_o 是開路電壓(V)、V是操作電壓(V)、ρ是空氣密度(1.2kg/m³ )、C_P 是空氣比熱(1000J/kg/K)、△T是空氣進出口溫差(K)、而N_cell 則是電池數目。In addition, a large amount of waste heat generated by the discharge reaction of the battery cell 100 can also be discharged by forced convection by a fan. The air flow required for heat dissipation can be estimated as follows:

Among them, F _coolant is the air flow required for heat dissipation, I is the current (A), V _o is the open circuit voltage (V), V is the operating voltage (V), ρ is the air density (1.2kg/m ³ ), and C _P is The specific heat of air (1000J/kg/K), △T is the air inlet and outlet temperature difference (K), and N _cell is the number of batteries.

When the ambient air G is introduced into the first through opening 206 or oxygen (O ₂ ) is discharged out of the first through opening 206 by forced convection by a fan, an air flow field generated on the surface of the discharge positive plate is formed, which reduces air flow resistance and improves The effect of air and heat convection.

4A and 4B are simplified diagrams of the working mechanism of the charging and discharging reactions shown in FIGS. 3A and 3B, respectively.

Please refer to FIG. 4A, which mainly shows the discharge positive plate module 200, the charging positive plate module 500, the negative plate 700 and the space that can accommodate the electrolyte. In terms of zinc-air batteries, for example, during charging of the negative electrode plate 700 with the positive oxidation reduction reaction can be represented by the following chemical formula: negative reduction _{reaction: ZnO + H 2 O + 2e} - → Zn + 2OH - positive oxidation reaction: 2OH _{^{- → 1 / 2O 2 + H}} 2 O + 2e -

It can be seen from the above chemical formula that the zinc oxide (ZnO) water in the electrolyte of the negative plate 700 and the electrons that move from the discharge positive plate module 200 to the negative plate 700 through the external circuit undergo a reduction reaction together, and the resulting zinc (Zn) will be electroplated To the metal surface of the negative plate 700. The charging positive plate module 500 releases hydroxide ions (OH ⁻ ) into the electrolyte and migrates toward the discharge positive plate module 200. Also in the charging of the positive electrode plate modules 500, 700 of hydroxide ions (OH ^-) from the negative electrode plate 500, a reaction catalyst may be generated on the positive electrode plate 500 contact charging module by charging the positive electrode plate modules oxygen (O ₂ ) Water and electronics. The electrons are conducted to the discharge positive plate module 200, and then move to the negative plate 700 through an external circuit. The oxygen (O ₂ ) can be discharged through the charging positive plate module 500.

Still referring to Figure 4B, the oxidation reaction of the positive electrode reduction reaction can be represented in the negative electrode during discharge of the following formula: negative oxidation ^{reaction: Zn + 2OH - → ZnO +} H 2 O + 2e - positive reduction reaction: 1 / 2O ₂ + ^{_{H 2 O + 2e - → 2OH}} -

From the above formula, hydroxide ions (OH ^-) in the negative electrode plate 700 will zinc electrolytic solution together with the oxidation reaction, the negative electrode plate 700 of zinc (Zn) is consumed and simultaneously produce zinc oxide ( ZnO), water and electrons. Wherein, electrons move from the negative plate 700 to the discharge positive plate module 200 through the negative plate 700 through an external circuit. Further discharge of the positive electrode plate module 200, from the oxygen (O ₂₎ with air, the water will be present in the electrolyte and electrons from the negative electrode plate 700 to generate a common reduction reaction of hydroxide ions (OH ^- ), migrate toward the charged positive plate module 500, and use the potassium hydroxide solution in the electrolyte as the ion conductive medium to migrate from the discharged positive plate module 200 to the negative electrode and participate in the above oxidation reaction.

In summary, the present invention has a three-pole metal-air flow secondary battery with a discharge positive electrode, a charging positive electrode, and a negative electrode configuration. Through openings in the discharge positive plate module and the charging positive plate module, Convectively introduce ambient air into the battery cell or exhaust the waste heat formed during the charge and discharge reaction, and there is no need to separately supply ambient air for reaction and heat dissipation, which is beneficial to the lightweight and cost reduction of the metal flow air battery, system and operation Can be more simplified.

In detail, the present invention uses a three-pole metal-air flow battery to help eliminate zinc oxide (ZnO) to avoid negative electrode passivation and electrolyte pollution during the discharge reaction, and uses a common air flow field design to remove air Introducing battery cells and taking away waste heat is conducive to compactness, weight reduction and cost reduction. In addition, during the charging reaction, it is beneficial to produce a uniform metal zinc (Zn) coating on the surface of the negative electrode, remove oxygen (O ₂ ), and avoid the generation of oxygen (O ₂ ) that has a negative effect on the ORR catalyst. Therefore, it can provide good metal-air flow battery performance and life.

In addition, the present invention provides an electrolyte supply manifold and an electrolyte discharge manifold in the front case, the middle case, and the rear case, which can provide a channel to communicate with each battery cell without excessively increasing the size of the battery cell. , To supply and discharge electrolyte. Therefore, it can provide good metal-air flow battery performance and life.

5 is a perspective view of an assembly structure of a metal liquid flow air secondary battery according to another embodiment of the present invention, in which the same component symbols as in FIGS. 1A and 1B are used to represent the same or similar components, and the omitted Part of the technical description, such as the size, material, function, etc. of each module, can refer to the content of Figure 1A and Figure 1B.

5, the metal flow air secondary battery 10A of this embodiment basically includes a plurality of battery cells 100A, a charging positive collector plate 104, a discharge positive collector plate 102, a charging negative collector plate 108, and a discharge negative collector. The electric board 106, the front-end board 111a and the back-end board 111b. The plurality of battery cells 100A are stacked in series. When the charging positive collector plate 104 and the charging negative collector plate 108 are respectively connected to an external load, the metal liquid flow air secondary battery 10A can be charged. At this time, the charging positive collector plate 510 in each battery unit 110A is connected to The charging negative collector plates 707 of adjacent battery cells 110A are connected in series by external connection (not shown in FIG. 5). When the discharge positive collector plate 102 and the discharge negative collector plate 106 are respectively connected to an external load, the metal liquid air secondary battery 10A can be discharged. At this time, the discharge positive collector plate 214 in each battery cell 110A is connected to The discharge negative collector plates 706 of adjacent battery cells 110A are connected in series by external connection. The front plate 111a is equipped with an electrolyte inlet (not shown) penetrating the body to supply electrolyte to a plurality of battery cells 100A. The rear end plate 111b is provided with an electrolyte outlet 112 penetrating the body to discharge the electrolyte from the plurality of battery cells 100A. In addition, the front end plate 111a and the rear end plate 111b are respectively configured with a plurality of positioning holes 114a penetrating through their bodies for battery assembly and positioning. In this embodiment, four positioning holes 114a are used. The front end plate 111a and the rear end plate 111b are also respectively equipped with a plurality of screw holes 114b penetrating the body. In this embodiment, 12 screw holes 114b are used for locking and fixing the metal flow air secondary battery 10A.

6A is a perspective schematic view of a metal-air flow secondary battery according to another embodiment of the present invention, and FIG. 6B is an exploded view of the front assembly structure of the metal-air flow secondary battery shown in FIG. 6A, and FIG. 6C It is an exploded view of the assembly structure on the back of the metal-air flow secondary battery in FIG. 6B, in which the same component symbols as those in FIGS. 2A, 2B, and 2C are used to represent the same or similar components, and some technical descriptions are omitted. For the size, material, function, etc. of each module, please refer to the contents of Fig. 2A, Fig. 2B and Fig. 2C.

Referring to FIGS. 2A to 2C and FIGS. 6A to 6C, the battery unit 100A of this example is similar to the battery unit 100 of the previous embodiment. However, it should be noted that the relative positions of the discharge positive plate module 200A, the negative plate module 700-1, and the charging positive plate module 500 of the battery cell 100A of this embodiment are the same as those of the discharge positive electrode of the battery cell 100 of the previous embodiment. The relative positions of the plate module 200, the negative plate module 700, and the charging positive plate module 500 are different.

6B and 6C, the battery unit 100A of this embodiment includes a discharge positive plate module 200A. The discharge positive plate module 200A includes a discharge positive plate 202 and a sealing member 212. The discharge positive plate 202 has a front surface 202 a and a back surface 202 b opposite to the front surface 202 a, and the sealing member 212 is disposed on the back surface 202 b of the discharge positive plate 202. A plurality of first through openings 204 penetrate through the front surface 202 a and the back surface 202 b of the discharge positive electrode plate 202. The discharge positive plate 202 has a protruding portion 206a and a protruding portion 206b disposed on the front surface 202a. The protruding portion 206 a and the protruding portion 206 b are respectively disposed on the left and right sides of the adjacent plurality of first through openings 204 to communicate with each of the first through openings 204 respectively. The protruding portion 206a and the protruding portion 206b are provided on a surface away from the air electrode module 300 to form multiple air guide channels for the reaction and heat dissipation air required by the battery cell 100A. In this way, the ambient air G can enter the plurality of first through openings 204 of the discharge positive plate 202 from the protrusion 206a (or the protrusion 206b) by forced convection, so as to supply the oxygen required for the discharge reaction and take it away The waste heat generated during the reaction is then discharged from the discharge positive electrode plate 202 by the protrusion 206b (or the protrusion 206a) to the environment.

The discharge positive plate 202 further has a first groove 208 disposed on the back 202b of the discharge positive plate 202. The first groove 208 is disposed around the plurality of first through openings 204 to form a space that can accommodate the seal 212. The discharge positive plate 202 also has a second groove 210 which is arranged on the back 202 b of the discharge positive plate 202. The second groove 210 is disposed around the first groove 208 to form a space that can accommodate the air electrode module 300. The discharge positive collector plate 214 can be selectively arranged on one side of the discharge positive plate 202, wherein the discharge positive collector plate 214 can be connected to the negative plate module 700-1 of the adjacent battery cell 100A to form a series discharge circuit .

It should be noted that the discharge positive plate module 200A of this embodiment further includes a separator 216, which is disposed on the side of the discharge positive plate 202 away from the front housing 400-1. The separator 216 can separate the discharge positive plate 202 of the discharge positive plate module 200A of one battery cell 100A from the charging positive plate module 500 of the adjacent battery cell 100A, so that the discharge positive plate modules of two adjacent battery cells 100A Group 200A and charging positive plate module 500 are insulated.

The battery cell 100A includes an air electrode module 300 located between the discharge positive plate module 200 and the front case 400-1, and includes an air electrode 302 and a first isolation film 304. The air electrode module 300 has a front surface 300 a facing the discharge positive plate module 200 and a back surface 300 b opposite to the front surface 300 a. The air electrode 302 is disposed on the front surface 300a of the air electrode module 300, and the first isolation film 304 is disposed on the back surface 300b of the air electrode module 300 so as to be located between the air electrode 302 and the front case 400-1 after assembly. The air electrode 302 is composed of a porous conductive substrate (not shown), a waterproof and breathable membrane (not shown) bonded to one side of the porous conductive substrate, and an oxygen reduction reaction on the other side of the porous conductive substrate. Catalyst (discharge reaction catalyst) (not shown). Among them, the waterproof and breathable membrane of the air electrode 302 faces the discharge positive plate module 200A, and the oxygen reduction reaction catalyst faces the first isolation membrane 304 to contact the electrolyte. The aforementioned ambient air G entering the plurality of first through openings 204 of the discharge positive plate 202 can diffuse into the oxygen reduction reaction catalyst through the waterproof and breathable membrane of the air electrode 302 to perform the discharge reaction, and the waterproof and breathable membrane can also avoid electrolyte Leak to the environment. In addition, the first isolation film 304 can isolate the metal generated by the charging reaction and directly contact the oxygen reduction reaction catalyst of the air electrode 302 to avoid short circuit between the positive and negative electrodes, and it can also isolate the oxide generated by the discharge reaction from polluting the air electrode 302. Oxygen reduction reaction catalyst to extend the service life of the air electrode 302.

The battery unit 100A includes a front housing 400-1, which is composed of a first electrolyte channel module 402 and a second electrolyte channel module 404. In this embodiment, the first electrolyte channel module 402 is interposed between the discharge positive plate module 200A and the second electrolyte channel module 404, wherein the second electrolyte channel module 404 has a connection with the first electrolyte The channel module 402 has a corresponding appearance, and the first electrolyte channel module 402 and the second electrolyte channel module 404 have substantially coincident transverse cross-sections.

The first electrolyte channel module 402 in the front housing 400-1 has a first opening 406 passing through the front surface 402a and the back surface 402b. A groove 408 can be arranged on the front surface 402 a of the first electrolyte channel module 402. The groove 408 is provided around the first opening 406. The size of the groove 408 is approximately equal to the outer boundary of the discharge positive plate 202, and the depth is approximately equal to the thickness of the discharge positive plate 202. Therefore, the groove 408 can accommodate the combination of the discharge positive plate module 200A and the air electrode module 300 and can be sealed with the sealing member 410, and the electrolyte contained in the first opening 406 can contact the air electrode module 300. An ion conduction path is formed during the discharge reaction. The first electrolyte channel module 402 further has a second opening 412 and a third opening 414 above and below the first opening 406, wherein the second opening 412 and the third opening 414 respectively penetrate through the first electrolyte channel module 402 Front 402a and back 402b. In FIG. 6B, two sealing members 416 can be respectively used to set around the second opening 412 and the third opening 414, so as to seal the electrolyte after assembly. On the back surface 402b of the first electrolyte channel module 402, there may be a connection between the first opening 406 and the second opening 412 (or the first middle rectangular opening 426 and the first electrolyte discharge manifold 428) and the connection between the first opening 406 and the A plurality of electrolyte distribution channels 418 with three openings 414 (or the first middle rectangular opening 426 and the first electrolyte supply manifold 430).

It should be noted that in this embodiment, the first electrolyte channel module 402 also has a groove 413, which is disposed on the back surface 402b. The groove 413 is disposed around the first opening 406, the second opening 412, and the third opening 414 to form a space that can accommodate the seal 415.

The second electrolyte channel module 404 has a fourth opening 420, a fifth opening 422, and a sixth opening 424 respectively corresponding to the first opening 406, the second opening 412, and the third opening 414 of the first electrolyte channel module 402. . The first opening 406 and the fourth opening 420 constitute a first middle rectangular opening 426 of the front housing 400-1 to form a first accommodating space. The second opening 412 and the fifth opening 422 constitute the first electrolyte discharge manifold 428 of the front housing 400-1. The third opening 414 and the sixth opening 424 constitute a first electrolyte supply manifold 430 of the front housing 400-1. The first electrolyte supply manifold 430 and the first electrolyte discharge manifold 428 are respectively adjacent to the first middle rectangular opening 426, and can transport the electrolyte in the first electrolyte supply manifold 430 to the first container The electrolyte in the first accommodating space is output from the first electrolyte discharge manifold 428 to transport the electrolyte in each battery cell 100A.

It should be noted that, in this embodiment, the front surface 404a of the second electrolyte channel module 404 facing the first electrolyte channel module 402 may not be provided with the groove 432 and the sealing member 434 of FIG. 2B.

In addition, a groove 436 can be selectively provided on the back surface 404b (second side 400b) of the second electrolyte channel module 404. The groove 436 is arranged around the fourth opening 420. It should be noted that the groove 436 can accommodate a sealing member 417 for sealing the electrolyte after assembly. The size of the groove 436 is approximately equal to the outer boundary of the negative plate module 700-1, and its depth is approximately equal to half the thickness of the negative plate module 700-1. In this way, the groove 436 can accommodate the negative plate module 700-1, and the electrolyte in the groove 436 can contact the negative plate module 700-1 to form an ion conduction path during charge and discharge reactions. In addition, in FIG. 6B, two grooves 439 can be selectively provided on the back 404b (second side 400b) of the second electrolyte channel module 404, which are respectively provided around the fifth opening 422 and the sixth opening 424. around. The two sealing members 438 are respectively arranged in the two grooves 439 for sealing the electrolyte after assembly.

When the first electrolyte channel module 402 and the second electrolyte channel module 404 are combined to form the front housing 400-1, the first electrolyte channel module 402, the second electrolyte channel module 404 and the negative electrode The plate module 700-1 is tightly closed, a gap is formed between the first isolation film 304 and the negative plate module 700-1 to allow the electrolyte to flow, and a first middle rectangular opening 426 is defined to accommodate the electrolysis The first accommodating space of the liquid (not shown). In addition, the electrolyte distribution channel 418 can communicate with the first middle rectangular opening 426 and the first electrolyte discharge manifold 428, and communicate with the first middle rectangular opening 426 and the first electrolyte supply manifold 430 to supply the first electrolyte The electrolyte in the manifold 430 is delivered to the first accommodating space, and the electrolyte in the first accommodating space is output from the first electrolyte discharge manifold 428. Furthermore, the electrolyte located in the first accommodating space can pass through the first middle rectangular opening 426 to contact the first isolation film 304 of the air electrode module 300 and the negative plate module 700-1, and then be in the battery cell 100A. Provide ion conduction path for charge and discharge reaction.

The battery unit 100A includes a negative plate module 700-1. The negative plate module 700-1 is located between the first side of the middle casing 600-1 and the front casing 400-1, and has a third accommodating space for accommodating the deposition of electrolyte and metal produced. In this embodiment, the negative plate module 700-1 includes a negative plate 700A and a porous metal material 701. The negative plate 700A has a front surface 700a facing the second electrolyte channel module 404 and a back surface 700b opposite to the front surface 700a. The middle rectangular opening 700c penetrates the front surface 700a and the back surface 700b of the negative electrode plate 700A, and the middle rectangular opening 700c can accommodate the porous metal material 701. The negative plate 700A has a first flange 700d and a second flange 700e, which are disposed around the middle rectangular opening 700c, and are respectively disposed on the front surface 700a and the back surface 700b of the negative plate 700A. The outer boundaries of the first flange 700d and the second flange 700e are approximately equal to the fourth opening 420 of the second electrolyte channel module 404 and the opening 630c of the third electrolyte channel module 630, respectively. The height between the first flange 62 and the second flange 63 is approximately equal to the thickness of the porous metal material 701. The porous metal material 701 has a plurality of pores to serve as the third accommodating space of the negative plate module 700-1. The negative plate module 700-1 further includes a clip 703 and a clip 705, which are respectively coupled to the first flange 700d and the second flange 700e of the negative plate 700A. The distance between the clip 703 and the clip 705 is smaller than the thickness of the porous metal material 701. In this way, the porous metal material 701 can be fixed and clamped by the two clips 703 and 705 to form a good electron conduction path between the negative electrode plate 700A and the porous metal material 700.

The negative plate module 700-1 also includes a discharge negative current collector plate 706, which is disposed on one side of the negative plate 700A (for example, but not limited to: the upper right side). The discharge negative collector plate 706 can be connected to the discharge positive collector plate 214 of the adjacent battery cell 100A to form a series discharge circuit. The negative plate module 700-1 also includes a charging negative current collector plate 707, which is arranged on one side of the negative plate 700A (for example, but not limited to: the lower right side). The charging negative collector plate 707 can be connected to the charging positive collector plate 510 of the adjacent battery cell 100A to form a series charging circuit.

In addition, the first flange 700d and the second flange 200e of the negative plate 700A are respectively disposed on the first pseudo-plane (not shown) and the second pseudo-plane (not shown). The front case 400-1, the negative plate 700A, and the middle case 600-1 are stacked in a stacking direction, and the first pseudo-plane (not shown) and the second pseudo-plane (not shown) are in the stacking direction The distance is approximately equal to the sum of the depth of the groove 436 of the second electrolyte channel module 404 and the depth of the groove 634 of the third electrolyte channel module 630. When the electrolyte enters the porous metal material 701 through the first middle rectangular opening 426 of the front case 400, the metal (such as but not limited to: zinc) generated during the charging process can be deposited in the pores of the porous metal material 701 (ie, the negative electrode). The third accommodating space of the board module 700-1) is used as a metal for later discharge.

The battery unit 100A includes a middle case 600-1, which is located on the second side 400b of the front case 400-1, and has a second accommodating space to accommodate the electrolyte. Specifically, the middle housing 600-1 of this embodiment includes a third electrolyte channel module 630 and a fourth electrolyte channel module 640.

The third electrolyte channel module 630 has a front surface 630a facing the negative plate module 700-1 and a back surface 630b opposite to the front surface 630a. The third electrolyte channel module 630 has a seventh opening 630c, an eighth opening 630d, and a ninth opening 630e, which all penetrate through the front surface 630a and the back surface 630b of the third electrolyte channel module 630. The seventh opening 630c can contain electrolyte. The eighth opening 630d and the ninth opening 630e are respectively located above the seventh opening 630c and below the seventh opening 630c. On the front surface 630a of the third electrolyte channel module 630, the groove 634 is disposed around the seventh opening 630c (or the second middle rectangular opening 602) and is approximately equal to the peripheral boundary of the negative plate module 700-1, and the groove The depth of 634 is approximately equal to half the thickness of the negative plate 700A. In this way, the groove 634 can accommodate the negative plate module 700-1 and communicates with the second accommodating space, and the electrolyte in the seventh opening 630c can contact the negative plate module 700-1 to form a battery Ion conduction path during discharge reaction.

The third electrolyte channel module 630 further includes a seal 631, a seal 632 and a seal 633. On the front surface 630 a of the third electrolyte channel module 630, the groove 635 is disposed on the outer boundary of the groove 634 to form a space that can accommodate the sealing member 631. On the front surface 630a of the third electrolyte channel module 630, the groove 636 and the groove 637 are respectively arranged around the eighth opening 630d and the ninth opening 630e to form a seal 632 and a seal 633 that can be accommodated respectively Space.

The fourth electrolyte channel module 640 has a front surface 640a facing the negative plate module 700-1 and a back surface 640b opposite to the front surface 640a. The fourth electrolyte channel module 640 has a tenth opening 640c, an eleventh opening 640d, and a twelfth opening 640e, all of which pass through the front surface 640a and the back surface 640b of the fourth electrolyte channel module 640, and respectively correspond to and communicate with the The seventh opening 630c, the eighth opening 630d and the ninth opening 630e of the three electrolyte channel module 630. The tenth opening 640c can contain electrolyte. The eleventh opening 640d and the twelfth opening 640e are respectively located above the tenth opening 640c and below the tenth opening 640c. The seventh opening 630c of the third electrolyte channel module 630 and the tenth opening 640c of the fourth electrolyte channel module 640 form a second middle rectangular opening 602 of the middle housing 600-1 to define a second middle rectangular opening 602 for accommodating electrolysis. The second accommodating space of the liquid (not shown). The eighth opening 630d of the third electrolyte channel module 630 and the eleventh opening 640d of the fourth electrolyte channel module 640 form a second electrolyte discharge manifold 604 located above the second middle rectangular opening 602. The ninth opening 630e of the third electrolyte channel module 630 and the twelfth opening 640e of the fourth electrolyte channel module 640 form a second electrolyte supply manifold 606 under the second middle rectangular opening 602. The second electrolyte supply manifold 606 and the second electrolyte discharge manifold 604 may be respectively adjacent to the second middle rectangular opening 602, and form electrolyte supply and discharge channels to transport the electrolyte. The positions of the first electrolyte supply manifold 430 and the second electrolyte supply manifold 606 are corresponding and connected, and the positions of the first electrolyte discharge manifold 428 and the second electrolyte discharge manifold 604 are corresponding and connected. of.

On the front face 640a of the fourth electrolyte channel module 640, the distribution flow channel 648 is provided between the opening 640c and the opening 640d and between the opening 640c and the opening 640e. In this way, the electrolyte can enter the second middle rectangular opening 602 from the electrolyte supply manifold 606 through the distribution flow channel 648 and then to the electrolyte discharge manifold 604 through the distribution flow channel 648.

On the front side 640a of the fourth electrolyte channel module 640, the groove 644 is arranged around the tenth opening 640c, the eleventh opening 640d, and the twelfth opening 640e to form a space for accommodating the sealing member 646. On the reverse side 640b of the fourth electrolyte channel module 640, the groove 645 is arranged around the tenth opening 640c and is approximately equal to the peripheral boundary of the charging electrode 910 of the charging electrode module 900, and the depth of the groove 645 is approximately equal to The thickness of the charging electrode 910. In this way, the groove 645 can accommodate the combination of the charging electrode 910 and the isolation film 920, and the electrolyte in the tenth opening 640c can contact the charging electrode module 900 to form an ion conduction path during the charging reaction. In addition, on the back surface 640b of the fourth electrolyte channel module 640, the groove 647, the groove 649a and the groove 649b are respectively arranged around the tenth opening 640c, the eleventh opening 640d and the twelfth opening 640e to form Spaces that can accommodate the seal 641, the seal 642, and the seal 643, respectively.

The charging positive plate module 500-1 of this embodiment is located on the second side of the middle casing 600-1, and includes a charging positive plate 504 with a second through opening 501 and a sealing member 508a. The charging positive plate 504 has a reverse surface 500 b facing the air side and a front surface 500 a opposite to the reverse surface 500 b, and the sealing member 508 a is arranged on the front surface 500 a of the charging positive plate 504. The plurality of second through openings 501 penetrate through the front side 500a and the back side 500b of the positive electrode plate 504. The reverse surface 500b of the charging positive plate 504 has a protruding portion 503a and a protruding portion 503b, which are respectively disposed on the left and right sides of the second through opening 501 to communicate with each second through opening 501, respectively. The protruding portion 503a and the protruding portion 503b are provided on a surface away from the charging electrode module 900, and can form a guide channel for the oxygen generated by the battery cell 100A. The oxygen exiting from the plurality of second through openings 501 of the positive electrode plate 504 can be discharged from the protrusion 503a (or the protrusion 503b) to the environment by forced convection. In other words, the oxygen generated by the charging reaction can be smoothly discharged out of the battery cell 100A, and bubbles are unlikely to accumulate inside the battery cell 100A, which reduces the reaction area. In this way, the performance of the battery unit 100A can be improved.

On the surface of the charging positive plate 504 facing the middle housing 600-1 (ie the front surface 500a of the charging positive plate 504), a groove 505 of the charging positive plate 504 is arranged around the plurality of second through openings 501 to form A space that can accommodate the seal 508a. On the front side 500a of the charging positive plate 504, the groove 507 of the charging positive plate 504 is arranged around the groove 505 to form a space that can accommodate the charging electrode module 900. The charging positive collector plate 510 is arranged on one side of the charging positive plate 504 (for example, but not limited to: the lower right side), and the charging positive collector plate 510 of one battery cell 100A can be connected to another adjacent battery cell 100A. The negative collector plate 707 is charged and connected with the negative plate module 700-1 to form a series-connected charging circuit.

The charging electrode module 900 is located between the charging positive plate module 500-1 and the middle casing 600-1. The charging electrode module 900 includes a charging electrode 910, a third isolation film 920, and an oxygen evolution reaction catalyst (not shown). The charging electrode module 900 has a back side 900b facing the charging positive plate module 500-1 and a front side 900a opposite to the back side 900b. The charging electrode 910 is disposed on the reverse side 900 b of the charging electrode module 900, and the third isolation film 920 is disposed on the front side 900 a of the charging electrode module 900. The charging electrode 910 is composed of a porous conductive material for charging reaction and a waterproof and breathable membrane bonded to one surface of the porous conductive material, wherein the waterproof and breathable membrane of the charging electrode 910 faces the charging positive plate module 500- 1. The oxygen generated by the charging electrode 910 can diffuse into the plurality of second through openings 501 of the charging positive plate 504 through the waterproof and breathable membrane to be discharged to the environment, and the waterproof and breathable membrane of the charging electrode 910 can also prevent electrolyte leakage to the environment. In addition, the third isolation film 920 can isolate the metal (such as but not limited to: zinc) generated by the charging reaction from directly contacting the porous conductive material of the charging electrode 910, so as to avoid short circuit between the positive and negative electrodes. In addition, the third isolation film 920 can also isolate the oxide generated by the discharge reaction from polluting the porous conductive material of the charging electrode 910, so as to prolong the service life of the charging electrode 910. The oxygen evolution reaction catalyst is disposed between the charging electrode 910 and the fourth electrolyte channel module 640 to contact the electrolyte to catalyze the charging reaction.

FIG. 7A is a schematic diagram of the charging reaction mechanism of the metal-air flow secondary battery of FIG. 6B. FIG. 8A is a simplified diagram of the working mechanism of the charging reaction shown in FIG. 7A. Taking the zinc-air flow secondary battery as an example, during the charging process, the electrolyte composed of zinc oxide (ZnO), potassium hydroxide (KOH) and water (H ₂ O) will be transported to the molten metal via an external pump The electrolyte inlet (not shown) of the air-flow secondary battery 10A is then distributed to each battery cell 100A in sequence. In each battery cell 100A, the electrolyte first enters the second electrolyte supply manifold 606 of the middle housing 600-1, and the electrolyte also enters the first electrolyte supply manifold 430 of the front housing 400-1 through The distribution channel 648 of the fourth electrolyte channel module 640 and the distribution channel 418 of the first electrolyte channel module 402 are introduced into the second middle rectangular opening 602 of the middle housing 600-1 and the front housing 400-1 Next, it flows to the middle rectangular opening 700c of the negative plate 700A of the negative plate module 700-1, and then flows into the pores of the porous metal material 701. When the electrolyte fills the second middle rectangular opening 602 of the middle casing 600-1, the first middle rectangular opening 426 of the front casing 400-1 and the middle rectangular opening 700c of the negative plate 700A, the electrolyte can contact the air electrode module The air electrode 302 of 300, the charging electrode 910 of the charging electrode module 900 and the porous metal material 701 of the negative plate module 700-1, and the conductive ion medium formed in the battery cell 100A.

Each battery cell 100A can be charged by passing an appropriate current from the outside through the charging positive collector plate 104 and the charging negative collector plate 108 of the metal flow air secondary battery 10A. On the negative side of the battery cell 100A, the zinc oxide (ZnO) and water (H ₂ O) in the electrolyte will react with the e ^- introduced from the charging negative collector plate 707 of the negative plate 700A, and zinc oxide (ZnO) It is further decomposed into zinc ions (Zn ²⁺ ) and migrates toward the porous metal material 701. After the zinc ion (Zn ²⁺ ) contacts the porous metal material 701, the zinc ion (Zn ²⁺ ) can react with e ^- to form zinc (Zn) and deposit in the pores of the porous metal material 701. At the same time, hydroxide ions (OH ⁻ ) are also generated and migrate toward the charging electrode 910 of the charging electrode module 900. Charging the positive electrode side, from when the hydroxide ion (OH ^-) of the negative side of the charging electrode contact 910, hydroxide ions (OH ^-) The reaction of oxygen (O _2), water (H ₂ O) and e ^- . e ^- will be conducted to the charging positive collector plate 510 of the charging positive plate 504 via the charging electrode 910, and then lead to the charging negative collector plate 707 of the negative plate 700A of the adjacent battery cell 100A.

In particular, the oxygen (O ₂ ) generated by the charging electrode 910 can diffuse into the plurality of second through openings 501 of the charging positive plate 504 through the waterproof and breathable membrane of the charging electrode module 900, and then be discharged by forced convection by a fan To the environment. In this way, the problem that generated oxygen (O ₂ ) may accumulate in the battery cell 100A so that the electrolyte cannot effectively contact the charging electrode 910 can be solved, thereby improving the performance of the metal-air current battery 10A.

The electrolyte in the first middle rectangular opening 426 and the second middle rectangular opening 602 passes through the electrolyte distribution channel 418 of the first electrolyte channel module 402 and the electrolyte distribution channel 648 of the fourth electrolyte channel module 640 The first electrolyte discharge manifold 428 entering the front housing 400-1 and the second electrolyte discharge manifold 604 of the middle housing 600-1. In this way, the electrolyte of each battery cell 100A can be discharged to the outside through the electrolyte outlet 112 of the metal flow air secondary battery 10A. The electrolyte discharged from the electrolyte outlet 112 will be transported to the electrolyte inlet (not shown) via an external pump, and thus the circulating flow of the electrolyte is completed.

7B is a schematic diagram of the working mechanism of the discharge reaction of the metal-air flow secondary battery of FIG. 6B. FIG. 8B is a simplified diagram of the working mechanism of the discharge reaction shown in FIG. 7B. When the charging reaction is completed and the discharging reaction starts, the electrolyte will continuously circulate in the manner described in the charging process to fill the middle rectangular openings 426, 602, 700c, and then form a medium that can conduct ions. The negative electrode side, the deposition material 701 to the pores of the porous metal zinc (Zn) will hydroxide ions (OH ^-) from the positive side common reaction. The generated zinc ions (Zn ²⁺ ) migrate from the porous metal material 701 toward the positive side, and e ^-is conducted from the negative plate 700A to the discharge negative collector plate 706, and then introduced into the discharge positive plate 202 of the adjacent battery cell 100A The discharge positive collector plate 214. Zinc ion (Zn ²⁺⁾ will hydroxide ions (OH ^-) further reaction of zinc oxide (ZnO) and water (H ₂ O), while the part not dissolved in the electrolytic solution of zinc oxide (ZnO) solids will The form exists in the pores of the porous metal material 701 or in the electrolyte. The production of this solid zinc oxide (ZnO) will not only cover the porous metal material 701 to cause negative electrode passivation, but also contaminate the electrolyte to increase ion conduction resistance. These two phenomena respectively cause the negative electrode discharge reaction and ion conduction to deteriorate, so the battery performance will decrease or even stop operating. In order to overcome this problem, during the discharge reaction process, the electrolyte can be continuously circulated so that zinc oxide (ZnO) is discharged with the electrolyte out of the metal flow air secondary battery 10A. In this way, zinc oxide (ZnO) accumulation and negative electrode passivation can be avoided. In addition, the zinc oxide (ZnO) in the electrolyte can be removed by external filtration, so that the electrolyte can restore the original ionic conductivity, and then transport to the metal flow air secondary battery 10A. On the discharge anode side, air can be introduced into the plurality of first through openings 204 of the discharge anode plate 202 by a fan in a forced convection manner, and then discharged to the environment. At the same time, oxygen (O ₂ ) can diffuse into the waterproof and breathable membrane of the air electrode 302 and then into the catalyst to react with the water (H ₂ O) in the electrolyte and e ^- from the negative electrode side to produce the negative electrode the lateral migration of hydroxide ions (OH ^-). Because the negative electrode discharge reaction requires sufficient oxygen and generates a large amount of waste heat, it is necessary to consider whether the air flow can meet the reaction and heat dissipation requirements at the same time when supplying air to the negative electrode side to ensure that the battery cell 100A can produce a stable output.

In summary, in this embodiment, the discharge positive plate module 200A is located on the first side of the front housing 400-1, the middle housing 600-1 is located on the second side of the front housing 400-1, and the negative plate module The group 700-1 is located between the first side of the middle casing 600-1 and the front casing 400-1, the charging positive plate module 500-1 is located on the second side of the middle casing 600-1, and the charging electrode module 900 is located between the rechargeable positive plate module 500-1 and the middle housing 600-1. Therefore, oxygen can be effectively exhausted by the fan, and the electrolyte level can be maintained stable, that is, the reaction area of the battery cell 100A is approximately maintained constant. In this way, the charge voltage of the metal-air flow secondary battery 10A can be stabilized, and the discharge voltage and coulombic efficiency can be improved, as described below in conjunction with FIG. 9.

FIG. 9 shows the relationship between the voltage and time of the metal-air flow secondary battery 10A according to another embodiment of the present invention, wherein the curve S15 shows the voltage and the time of the metal-air flow secondary battery 10A when the charging time is 15 minutes The relationship between time, curve S30 shows the relationship between the voltage and time of the metal-air flow secondary battery 10A when the charging time is 30 minutes, and the curve S60 shows the second metal-air flow when the charging time is 60 minutes The relationship between the voltage of the battery 10A and the time. Please refer to Figure 9, the charging voltage of the metal-air flow secondary battery 10A can be maintained stable between 2.00~2.13 V for a long time; the discharge voltage of the metal-air flow secondary battery 10A can be increased to 0.90~0.55 V; metal air The coulombic efficiency of the flow secondary battery 10A can be increased by 81% to 90%.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field can make slight changes and modifications without departing from the spirit and scope of the present invention. The scope of protection of the present invention shall be subject to those defined by the attached patent scope.

10, 10A‧‧‧Metal air current battery 100, 100A‧‧‧Battery unit 102‧‧‧Discharge positive collector plate 104‧‧‧Charge positive collector plate 106‧‧‧Discharge negative collector plate 108‧‧‧Charge Negative current collector plate 110a‧‧‧Positive terminal plate 110b‧‧‧Negative end plate 111a‧‧‧Front plate 111b‧‧‧Back end plate 112‧‧‧Electrolyte outlet 114a‧‧‧Locating hole 114b‧‧‧Screw hole 116‧‧‧Electrolyte inlet 200, 200A‧‧‧Discharge positive plate module 202‧‧‧Discharge positive plate 202a, 300a, 402a, 404a, 630a, 640a, 500a, 700a, 900a‧‧‧Front 202b, 300b, 402b, 404b, 630b, 640b, 500b, 700b, 900b‧‧‧Back 204‧‧‧First through opening 206a, 206b‧‧‧Protrusion 208‧‧‧First groove 210‧‧‧Second groove 212‧‧‧Seal 214‧‧‧Discharge positive collector plate 216‧‧‧Separator 300‧‧‧Air electrode module 302‧‧‧Air electrode 304‧‧‧First separator 400, 400-1‧‧ ‧Front housing 400a‧‧‧First side 400b‧‧‧Second side 402‧‧‧First electrolyte channel module 404‧‧‧Second electrolyte channel module 406‧‧‧First opening 408, 413 , 432, 436, 439, 608, 612, 634, 635, 636, 637, 644, 645, 647, 649a, 649b, 806‧‧‧ groove 410, 415, 416, 417, 434, 437, 438, 508a , 610, 614, 631, 632, 633, 641, 642, 643, 646, 808‧‧‧ Seal 412‧‧‧Second opening 414‧‧‧Third opening 418,648‧‧‧Distribution runner 420‧ ‧‧Fourth opening 422‧‧‧Fifth opening 424‧‧‧Sixth opening 426‧‧‧First middle rectangular opening 428‧‧‧First electrolyte discharge manifold 430‧‧‧First electrolyte supply manifold 500、500-1‧‧‧Charging positive plate module 501, 502‧‧‧Second through opening 503a, 503b‧‧‧Protruding part 504‧‧‧Charging positive plate 505, 507‧‧‧ Groove 506‧‧ ‧Second isolation membrane 508‧‧‧Oxygen evolution reaction catalyst 510‧‧‧Charging positive collector plate 600,600-1‧‧‧Middle shell 602‧‧‧Second middle rectangular opening 604‧‧‧Second electrolysis Liquid discharge manifold 606‧‧‧Second electrolyte supply manifold 630‧‧‧Third electrolyte channel module 630c‧‧‧Seventh opening 630d‧‧ Eighth opening 630e‧‧‧Ninth opening 640‧‧ ‧Fourth electrolyte channel module 640c‧‧‧Tenth opening 640d‧‧‧Eleventh opening 640e‧ ‧‧Twelfth opening 700, 700A‧‧‧Negative plate 700c‧‧‧Middle rectangular opening 700d, 700e‧‧‧Flange 700-1‧‧‧Negative plate module 701‧‧‧Porous metal material 702,707‧ ‧‧Charging negative current collector plate 703, 705‧‧‧ Clip 704, 706‧‧‧Discharging negative current collector plate 800‧‧‧Rear housing 802‧‧‧The third electrolyte discharge manifold 804‧‧‧The third Electrolyte supply manifold 900‧‧‧Charging electrode module 910‧‧‧Charging electrode 920‧‧‧Third isolation membrane G‧‧‧Ambient air

1A is a perspective view of an assembly structure of a metal-air flow secondary battery according to an embodiment of the present invention. Fig. 1B is a back perspective view of the structure of Fig. 1A. 2A is a three-dimensional schematic diagram of a metal-air flow secondary battery according to another embodiment of the present invention. 2B is an exploded view of the front assembly structure of the metal-air flow secondary battery shown in FIG. 2A. 2C is an exploded view of the assembled structure on the back of the metal-air flow secondary battery of FIG. 2B. 3A is a schematic diagram of the charging reaction mechanism of the metal-air flow secondary battery of FIG. 2B. 3B is a schematic diagram of the working mechanism of the discharge reaction of the metal-air flow secondary battery of FIG. 2B. FIG. 4A is a simplified diagram of the working mechanism of the charging reaction shown in FIG. 3A. FIG. 4B is a simplified diagram of the working mechanism of the discharge reaction shown in FIG. 3B. 5 is a perspective view of an assembled structure of a metal liquid flow air secondary battery according to another embodiment of the present invention. Fig. 6A is a perspective schematic view of a metal-air flow secondary battery according to another embodiment of the present invention. 6B is an exploded view of the front assembly structure of the metal-air flow secondary battery shown in FIG. 6A. 6C is an exploded view of the assembled structure on the back of the metal-air flow secondary battery of FIG. 6B. FIG. 7A is a schematic diagram of the charging reaction mechanism of the metal-air flow secondary battery of FIG. 6B. FIG. 7B is a schematic diagram of the working mechanism of the discharge reaction of the metal-air flow secondary battery of FIG. 6B. FIG. 8A is a simplified diagram of the working mechanism of the charging reaction shown in FIG. 7A. FIG. 8B is a simplified diagram of the working mechanism of the discharge reaction shown in FIG. 7B. Fig. 9 shows the relationship between voltage and time of a metal-air flow secondary battery according to another embodiment of the present invention.

100‧‧‧Battery unit

200‧‧‧Discharge positive plate module

202‧‧‧Discharge positive plate

202a, 300a, 402a‧‧‧front

202b, 300b, 402b‧‧‧Back

204‧‧‧First through opening

206a, 206b‧‧‧Protrusion

214‧‧‧Discharge positive collector plate

300‧‧‧Air Electrode Module

302‧‧‧Air electrode

400‧‧‧Front shell

400a‧‧‧First side

400b‧‧‧Second side

402‧‧‧First electrolyte channel module

404‧‧‧Second Electrolyte Channel Module

406‧‧‧First opening

408, 432, 608, 612, 806‧‧‧ groove

410, 416, 434, 610, 614, 808‧‧‧ seal

412‧‧‧Second opening

414‧‧‧The third opening

420‧‧‧Fourth opening

422‧‧‧Fifth opening

424‧‧‧The sixth opening

426‧‧‧The first middle rectangular opening

428‧‧‧First electrolyte discharge manifold

430‧‧‧First electrolyte supply manifold

500‧‧‧Charging positive plate module

502‧‧‧Second through opening

504‧‧‧Charging positive plate

506‧‧‧Second Isolation Film

508‧‧‧Oxygen evolution reaction catalyst

510‧‧‧Charging positive collector plate

600‧‧‧Medium shell

602‧‧‧The second middle rectangular opening

604‧‧‧Second electrolyte discharge manifold

606‧‧‧Second electrolyte supply manifold

700‧‧‧Negative plate

702‧‧‧Charging negative collector plate

704‧‧‧Discharge negative collector plate

800‧‧‧Back shell

802‧‧‧The third electrolyte discharge manifold

804‧‧‧The third electrolyte supply manifold

G‧‧‧Ambient air

Claims (23)

A metal-air flow secondary battery includes: a front housing, which is composed of a first electrolyte channel module and a second electrolyte channel module, and has a first accommodating space for accommodating a Electrolyte; a discharge positive plate module, located on a first side of the front housing, including a discharge positive plate with a plurality of first through openings, wherein the first electrolyte channel module is located between the discharge positive plate Between the module and the second electrolyte channel module; an air electrode module located between the discharge positive plate module and the front housing, including an oxygen reduction reaction catalyst, in contact with the electrolyte; The rear case is located on a second side of the front case; a negative plate is located between the rear case and the front case and is in contact with the electrolyte; a charging positive plate module is located on the front case Between the positive electrode plate and the negative electrode plate, it includes a positive electrode plate having a second through opening and an oxygen evolution reaction catalyst; and a middle casing located between the positive electrode plate module and the negative electrode plate and has a Two accommodating spaces for accommodating the electrolyte, wherein the front housing further includes a groove located in the first electrolyte channel module for accommodating the air electrode module and the discharge positive plate module. For the metal-air flow secondary battery described in item 1 of the scope of patent application, the discharge positive plate further includes a plurality of protrusions, which are arranged on a surface away from the air electrode module to form a plurality of air conductors. The drainage channels are respectively communicated with the first through openings. The metal-air flow secondary battery described in item 1 of the scope of patent application, wherein the air electrode module includes an air electrode facing the discharge positive plate module; and a first isolation film disposed on the air Between the electrode and the front housing, and the oxygen reduction reaction catalyst faces the first isolation membrane. The metal-air flow secondary battery according to the first item of the patent application, wherein the first electrolyte channel module includes a first opening, a second opening and a third opening located above and below the first opening. The opening and the second electrolyte channel module of the front housing include a fourth opening and a first opening respectively corresponding to the first opening, the second opening and the third opening of the first electrolyte channel module. Five openings and a sixth opening, and the front housing further includes: a first middle rectangular opening formed by the first opening and the fourth opening to form the first accommodating space; and a first electrolysis The liquid supply manifold and the first electrolyte discharge manifold are respectively adjacent to the first middle rectangular opening, wherein the first electrolyte supply manifold is composed of the third opening and the sixth opening, and the first electrolytic solution The liquid discharge manifold is composed of the second opening and the fifth opening; and a plurality of distribution channels are located on the back of the first electrolyte channel module and communicate with the first middle rectangular opening and the first electrolyte The supply manifold connects the first middle rectangular opening and the first electrolyte discharge manifold to transport the electrolyte in the first electrolyte supply manifold to the first accommodating space, and transfer the first electrolyte The electrolyte in the accommodating space is output from the first electrolyte discharge manifold. The metal-air flow secondary battery according to claim 4, wherein the middle casing includes: a second middle rectangular opening to form the second accommodating space; and a second electrolyte supply manifold And a second electrolyte discharge manifold, respectively adjacent to the second middle rectangular opening; wherein, the first electrolyte supply manifold and the second electrolyte supply manifold are corresponding and connected, the first The positions of the electrolyte discharge manifold and the second electrolyte discharge manifold correspond to and communicate with each other. The metal-air flow secondary battery according to item 5 of the scope of patent application, wherein the middle casing further includes a groove surrounding the outer edge of the second middle rectangular opening and communicating with the second accommodating space to accommodate The charging positive plate module. The metal-air flow secondary battery according to item 4 of the scope of patent application, wherein the rear housing includes a third electrolyte discharge manifold and a third electrolyte supply manifold, and the first electrolyte supply manifold The position of the third electrolyte supply manifold is corresponding and connected, and the position of the first electrolyte discharge manifold and the third electrolyte discharge manifold are corresponding and connected. According to the metal-air flow secondary battery described in item 1 of the scope of patent application, the charging positive plate module further includes a second isolation film, which is arranged on the side of the charging positive plate away from the front housing. In the metal-air flow secondary battery described in item 1 of the scope of patent application, the rear housing further includes a groove for accommodating the negative electrode plate. A metal-air flow secondary battery, including: A large number of battery cells, each of which includes the metal-air flow secondary battery as described in items 1 to 9 of the scope of the patent application, and the rear housing of one of the two adjacent battery cells and the other The discharge positive plate module contacts. A metal-air flow secondary battery includes: a front housing, which is composed of a first electrolyte channel module and a second electrolyte channel module, and has a first accommodating space for accommodating a Electrolyte; a discharge positive plate module, located on a first side of the front housing, including a discharge positive plate with a plurality of first through openings, wherein the first electrolyte channel module is located between the discharge positive plate Between the module and the second electrolyte channel module; an air electrode module located between the discharge positive plate module and the front housing, including an oxygen reduction reaction catalyst, in contact with the electrolyte; The middle casing is located on a second side of the front casing and has a second accommodating space for containing the electrolyte; a negative plate module is located on a first side of the middle casing and the front casing There is a third accommodating space for accommodating the deposition of the electrolyte and the generated metal; a charging positive plate module, located on a second side of the middle casing, including a charging device with a second through opening Positive plate; and a charging electrode module, located between the charging positive plate module and the middle shell, with an oxygen evolution reaction catalyst in contact with the electrolyte. The metal-air flow secondary battery described in item 11 of the scope of patent application, wherein the discharge positive plate further includes a plurality of protruding parts arranged on a surface away from the air electrode module to form a plurality of air conductors Drainage channels, respectively A through opening communicates. The metal-air flow secondary battery according to item 11 of the scope of patent application, wherein the air electrode module includes: an air electrode facing the discharge positive plate module; and a first isolation film disposed on the air Between the electrode and the front housing, and the oxygen reduction reaction catalyst faces the first isolation membrane. The metal-air flow secondary battery according to claim 11, wherein the first electrolyte channel module includes a first opening, a second opening and a third opening located above and below the first opening. The opening and the second electrolyte channel module of the front housing include a fourth opening and a first opening respectively corresponding to the first opening, the second opening and the third opening of the first electrolyte channel module. Five openings and a sixth opening, and the front housing further includes: a first middle rectangular opening formed by the first opening and the fourth opening to form the first accommodating space; and a first electrolysis The liquid supply manifold and the first electrolyte discharge manifold are respectively adjacent to the first middle rectangular opening, wherein the first electrolyte supply manifold is composed of the third opening and the sixth opening, and the first electrolytic solution The liquid discharge manifold is composed of the second opening and the fifth opening; and a plurality of distribution channels are located on the back of the first electrolyte channel module and communicate with the first middle rectangular opening and the first electrolyte Supply manifold and connect the first middle rectangular opening and the first electrolyte discharge manifold to supply the first electrolyte to the manifold The electrolyte in the channel is transported to the first accommodating space, and the electrolyte in the first accommodating space is output from the first electrolyte discharge manifold. The metal-air flow secondary battery according to claim 11, wherein the front housing further includes a groove located in the first electrolyte channel module for accommodating the air electrode module and the discharge Positive plate module. The metal-air flow secondary battery according to item 14 of the scope of patent application, wherein the middle casing includes: a second middle rectangular opening to form the second accommodating space; and a second electrolyte supply manifold And a second electrolyte discharge manifold, respectively adjacent to the second middle rectangular opening; wherein, the first electrolyte supply manifold and the second electrolyte supply manifold are corresponding and connected, the first The positions of the electrolyte discharge manifold and the second electrolyte discharge manifold correspond to and communicate with each other. According to the metal-air flow secondary battery described in item 16 of the scope of the patent application, the middle casing further includes a groove surrounding the second middle rectangular opening and communicating with the second accommodating space to accommodate the Negative plate module. According to the metal-air flow secondary battery described in item 11 of the scope of patent application, the discharge positive plate module further includes a separator disposed on the side of the discharge positive plate away from the front housing. The metal-air flow secondary battery described in item 11 of the scope of patent application, wherein the negative plate module includes a porous metal material. The metal-air flow secondary battery described in item 11 of the scope of patent application, wherein the charging positive plate further includes a plurality of protruding parts arranged on a surface away from the charging electrode module to form a plurality of oxygen conductors The drainage channels are respectively communicated with the second through openings. The metal-air flow secondary battery according to item 11 of the scope of patent application, wherein the charging electrode module further includes a charging electrode and a third isolation film, and the charging electrode module has a module facing the charging positive plate The charging electrode is arranged on the opposite side of the charging electrode module, and the third isolation film is arranged on the front side of the charging electrode module. A metal-air flow secondary battery includes: a front housing, which is composed of a first electrolyte channel module and a second electrolyte channel module, and has a first accommodating space for accommodating a Electrolyte; a discharge positive plate module, located on a first side of the front housing, including a discharge positive plate with a plurality of first through openings, wherein the first electrolyte channel module is located between the discharge positive plate Between the module and the second electrolyte channel module; an air electrode module located between the discharge positive plate module and the front housing, including an oxygen reduction reaction catalyst, in contact with the electrolyte; The rear case is located on a second side of the front case; a negative plate is located between the rear case and the front case and is in contact with the electrolyte; a charging positive plate module is located on the front case Between the positive electrode plate and the negative electrode plate, a charging positive plate having a second through opening, an oxygen evolution reaction catalyst, and a second isolating film are included. The second isolating film is arranged on the charging positive plate away from the front housing. One Side; and a middle shell, located between the charging positive plate module and the negative plate, with a second accommodating space to accommodate the electrolyte. A metal-air flow secondary battery includes: a front housing, which is composed of a first electrolyte channel module and a second electrolyte channel module, and has a first accommodating space for accommodating a Electrolyte; a discharge positive plate module, located on a first side of the front housing, including a discharge positive plate with a plurality of first through openings, wherein the first electrolyte channel module is located between the discharge positive plate Between the module and the second electrolyte channel module; an air electrode module located between the discharge positive plate module and the front housing, including an oxygen reduction reaction catalyst, in contact with the electrolyte; The rear case is located on a second side of the front case; a negative plate is located between the rear case and the front case and is in contact with the electrolyte; a charging positive plate module is located on the front case Between the positive electrode plate and the negative electrode plate, it includes a positive electrode plate having a second through opening and an oxygen evolution reaction catalyst; and a middle shell, located between the positive electrode plate module and the negative electrode plate, with a first Two accommodating spaces for accommodating the electrolyte, wherein the rear housing further includes a groove for accommodating the negative plate.

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