JP2513624Y2 - Zinc-bromine secondary battery - Google Patents

Description

[Detailed Description of the Invention] A. Industrial Application Field of the Invention The present invention relates to a piping system for connecting a battery main body having a battery reaction chamber to an electrolytic solution storage tank, and a switching valve for flowing the electrolytic solution through the flow path. The present invention relates to a zinc-bromine secondary battery that can be circulated in a changeable manner.

B. Outline of the Invention The present invention relates to a zinc-bromine secondary battery in which a battery body and an electrolytic solution storage tank are connected by an electrolytic solution circulation passage having a switching valve. At least 5
By constructing a cylinder having one flow hole and at least four valve bodies that move integrally inside the cylinder, the valve body can be operated to move the electrolyte solution from the upper part to the lower part of the positive electrode chamber, or from the lower part to the upper part. It is designed to change the circulation route.

C. Conventional Technology Recently, the development of a battery power storage system has been promoted, and a zinc-bromine battery, which is a laminated secondary battery, has been developed as a part of it.

As shown in FIGS. 3 to 6, this zinc-bromine battery includes a battery main body 1 composed of a battery reaction chamber having a positive electrode and a negative electrode, electrolytic solution storage tanks 2a and 2b, an internal battery main body 1 and an electrolytic solution. It is configured with a piping system for circulating an electrolytic solution between the storage tanks 2a and 2b.

The battery reaction chamber of the battery body 1 includes a pair of positive electrode plates 3
The space between the negative electrode plate 4 and the negative electrode plate 4 is partitioned by a separator 5 to form a positive electrode chamber 6 and a negative electrode chamber 7. In many cases, the battery main body 1 having such a battery reaction chamber is formed as a laminated body (so-called stack) in which electrodes are bipolar type and a plurality of single cells are electrically stacked in series.

Between the negative electrode chamber 7 of the battery main body 1 and the negative electrode electrolytic solution storage tank 2b, a negative electrode electrolytic solution circulation passage including a liquid sending pipe 8 having a pump 10 and a drain pipe 9 is formed, and the pump 10 is driven. The electrolytic solution is circulated so as to flow from the bottom to the top of the negative electrode chamber 7. Further, a four-way valve 11 is arranged between the positive electrode chamber 6 and the upper and lower liquid supply / drain pipes 12 and 13, and a delivery pipe having a pump 16 between the four-way valve 11 and the positive electrode electrolyte storage tank 2a. The positive electrode electrolyte circulation passage is formed by connecting 14 and the discharge pipe 15.

During normal operation, the four-way valve 11 is switched to the position shown by the solid line in FIG. 3 so that the electrolyte in the positive electrode electrolyte storage tank 2a is driven by the pump 16 and the delivery pipes 14b, 14 are discharged during charging. At times, through the delivery pipes 14a, 14, through the four-way valve 11, through the upper liquid sending and draining pipe 12, flow from the upper part to the lower part of the positive electrode chamber 6, through the lower liquid sending and draining pipe 13, and through the four-way valve 11. , Through the discharge pipe 15 to circulate back to the positive electrode electrolyte storage tank 2a.

In this way, flowing the electrolytic solution from the top to the bottom of the positive electrode chamber 6 is
For the following reasons. That is, since the specific gravity of the bromine complex compound contained in the electrolytic solution is heavy, when the electrolytic solution is caused to flow from the lower side to the upper side, the bromine complex compound does not sufficiently reach the upper portion of the positive electrode electrolytic solution chamber 6, resulting in a sufficient battery capacity. This is because no reaction occurs.

Further, at the time of starting the battery, the air in the positive electrode chamber 6 is evacuated, so that the liquid is introduced from the lower portion to fill the inside.

That is, the electrolytic solution in the positive electrode electrolytic solution storage tank 2a is pumped.
16 is driven to send out toward the four-way valve 11 through the sending pipe 14.

At this time, the four-way valve 11 is switched to the position shown by the broken line in FIG. 3 so that the electrolytic solution is sent to the lower liquid sending and discharging pipe 13, whereby the electrolytic solution is made to flow upward from below the positive electrode chamber 6. .

Then, the electrolyte solution filled so as to expel the air in the positive electrode chamber 6 is sent from the upper sending and discharging liquid pipe 12 through the discharge pipe 15 through the four-way valve 11 to the positive electrode electrolytic solution storage tank 2a. Circulate.

After the air removal from the positive electrode chamber is completed at the time of starting as described above, the four-way valve 11 is switched to the position shown by the solid line to shift to the normal operation state described above.

Further, as described above, the four-way valve 11 used to change the flow path of the positive electrode electrolyte has the structure illustrated in FIGS. 4 to 6.

That is, a rotor 18, which is a plate-shaped valve body, is rotatably arranged in a circular valve chamber main body 17 that intersects four pipe flow paths, and a rotary main shaft 19 integrated with the rotor 18 is coupled to a coupling 20.
It is connected to an actuator 21 of an electric motor via the drive motor, and drives the actuator 21 to execute the valve position switching operation of the rotor 18 via the rotating main shaft 19.

Further, in order to prevent electrolyte leakage from the four-way valve 11, an annular groove is formed in a part of the rotary main shaft 19 as shown in FIG. 6, and in consideration of chemical resistance and friction, fluorine O A ring 22 is attached to seal a space between the valve chamber body 17 and the inner wall of the housing.

D. Problems to be Solved by the Invention In the conventional electrolytic solution circulating zinc-bromine battery as described above, the flow path of the electrolytic solution to the positive electrode chamber of the battery main body is changed at the time of starting and normal operation. To do this, a four-way valve is required, but if this four-way valve is used for a long time,
The sealing O-ring may be worn, causing the electrolyte to leak out and wet the surrounding area, causing problems such as ground drop due to electric leakage and corrosion of surrounding equipment.

In view of the above points, the present invention aims to provide a zinc-bromine secondary battery, which is equipped with a switching valve device for switching the piping flow path of a zinc-bromine battery, which does not cause electrolyte leakage. And

E. Means for Solving the Problems In the zinc-bromine secondary battery of the present invention, the negative electrode chamber of the battery main body and the negative electrode electrolytic solution storage tank are connected by the negative electrode electrolytic solution circulation passage, and the positive electrode chamber and the positive electrode electrolytic solution are connected. In a zinc-bromine secondary battery in which a storage tank is connected through a positive electrode electrolyte circulation passage having a switching valve, the switching valve is formed by a cylinder and at least four valve bodies that move integrally in the cylinder. , A first, a second, a third, a fourth and a fifth through hole are sequentially arranged at a predetermined interval in the axial direction, and the second and the fourth through holes are provided in the positive electrolyte storage tank. The first and fifth communication holes are connected to the upper part (or the lower part) of the positive electrode chamber, the third communication hole is connected to the lower part (or the upper part) of the positive electrode chamber, and the four valve bodies are connected to each other. The first chamber, the second chamber, and the third chamber are partitioned and formed so that they can be moved by the switching operation means. Communicates the first and second communication holes, the second chamber communicates the third and fourth communication holes, the third chamber communicates with the fifth communication hole, and By the operation of 2, the first chamber becomes
The chamber is characterized in that the second and third communication holes are communicated with each other, and the third chamber is communicated with the fourth and fifth communication holes.

F. Action With the above-mentioned configuration, the series of valve bodies in the switching valve body are moved by operating the switching operation means, and the flow of the electrolytic solution circulating in the positive electrode chamber is changed from top to bottom. Or, it works to switch from the bottom to the top.

G. Example Hereinafter, an example of the switching valve device for a zinc-bromine secondary battery of the present invention will be described with reference to FIGS. 1 and 2.

In addition, in FIG. 1 and FIG.
The parts corresponding to those in FIG. 6 are not designated by the same reference numerals, and detailed description thereof will be omitted.

FIG. 1 is a schematic explanatory diagram showing the state of the battery of this embodiment during normal operation, where 1 is the battery main body, 2a is the positive electrode electrolyte storage tank, and 2b.
Is a negative electrode electrolyte storage tank.

Inside the battery body 1, a pair of positive electrode plate 3 and negative electrode plate 4 is partitioned by a separator 5 to form a positive electrode chamber 6 surrounded by the positive electrode plate 3 and the separator 5. A negative electrode chamber 7 surrounded by the negative electrode plate 4 and the separator 5 is formed.

The negative electrode chamber 7 and the negative electrode electrolyte storage tank 2b are connected to each other by a liquid supply pipe 8 having a pump 10 and a drain pipe 9 to form a negative electrode electrolyte circulation passage. Then, the pump 10 is driven to circulate the electrolytic solution so as to flow from the bottom to the top of the negative electrode chamber 7. A cathode electrolyte circulation passage having a switching valve body 23 is installed between the cathode chamber 6 and the cathode electrolyte storage tank 2a.

The switching valve body 23 is composed of a cylinder 24 and at least four valve bodies 31, 32, 33, 34 that move integrally in the cylinder 24. The cylinder 24 has first, second, third, fourth, and fifth through holes 44, 4 in the axial direction at a predetermined interval.
5,46,47,48 are arranged sequentially.

The four valve bodies 31, 32, 33, 34 are installed on one rod 35,
A first chamber 49 is defined between the valve elements 31 and 32, a second chamber 50 is defined between the valve elements 32 and 33, and a third chamber 51 is defined between the valve elements 33 and 34.

The first flow hole 44 is connected to the liquid delivery pipe 26 that communicates with the upper portion of the positive electrode electrolyte chamber 6.

The third flow hole 46 is provided in the lower portion of the positive electrode chamber 6 to connect the liquid delivery pipe 25.
Connect with.

The fifth flow hole 48 is connected to the liquid delivery pipe 27 branched from the liquid delivery pipe 26.

The second flow hole 45 is connected to the discharge pipe 28 that communicates with the upper portion of the positive electrode electrolyte storage tank 2a.

The fourth flow hole 47 is connected to a delivery pipe 29 having a pump 16 which communicates with an intermediate portion of the positive electrode electrolyte storage tank 2a. Along with this, a delivery pipe 30 for bromine complex compound delivery mixing, which branches from the delivery pipe 29 and is connected to the lower portion of the positive electrode electrolyte storage tank 2a, is provided.
In this way, the positive electrode electrolyte circulation passage is formed.

The switching valve main body 23 makes these four valve bodies 31, 32, 33, 34 movable by switching operation means. By the first operation of the switching operation means, the first chamber 49 communicates the first and second communication holes 44 and 45, and the second chamber 50 communicates the third and fourth communication holes 46 and 47. , The third chamber 51 communicates with the fifth flow hole 48. In the second operation, the first chamber 49 is the first through hole 44, the second chamber 50 is the second and third through holes 45, 46, and the third chamber 51 is the fourth and fifth.
The communication holes 47 and 48 are connected to each other.

The switching valve body 23 has the third through-hole 46 formed in the positive electrode electrolyte chamber 6
It is connected to the liquid sending pipe 25 communicating with the lower part of.

The cylinder 24 of the switching valve body 23 piped in this way is
It is configured as a cylinder having a diameter equal to or larger than that of the pipes 25, 26, 27, 28, 29 connected thereto.

A switching operation means is attached to the switching valve body 23. That is, the upper and lower ends of the cylinder 24 are connected to one end of the liquid feed pipes 36, 37 for operation as switching operation means.

Further, the other ends of the liquid feed pipes 36, 37 for operation are bifurcated and connected to one ends of the supply pipe 42 and the liquid condensing pipe 43 via control valves 38, 39, 40, 41, respectively.

The other end of each supply pipe 42 is connected to the delivery pipe 29 in the vicinity of the pressurized liquid discharge side of the pump 16 so that the pressurized liquid can be taken in.

The other end of each liquid condensing pipe 43 is connected to the discharge pipe 28.

Next, the operation of the apparatus of the present embodiment configured as described above will be described.

First, to start the zinc-bromine battery, the battery body 1
The electrolyte must be filled so that no air remains in the empty positive and negative electrode chambers 6 and 7.

Therefore, on the negative electrode chamber 7 side, the pump 10 is driven to circulate the electrolytic solution in the negative electrode electrolytic solution storage tank 2b from below to above the negative electrode chamber 7 to completely exhaust the air.

On the positive electrode chamber 6 side, the control valve 38 is closed and the control valve 39 is opened as the first operation, so that the pressurized liquid sent from the pump 16 is supplied to the upper portion of the cylinder 24 of the switching valve body 23 and the valve body 31. Then, the four valve bodies 31, 32, 33, 34 are moved to the lower start corresponding position as shown in FIG. At this time, by closing the control valve 40 and opening the control valve 41, the electrolytic solution in the space between the valve body 34 and the lower portion of the cylinder 24 is discharged along with the movement of the valve body 34. It is something to put back in 28.

In this state, the electrolytic solution in the positive electrode electrolytic solution storage tank 2a passes through the delivery pipes 29, 30 and is pressurized by the pump 16, and the switching valve main body 23
In the cylinder 24 of the positive electrode electrolyte chamber 6 through the fourth flow hole 47, the second chamber 50 and the third flow hole 46, the liquid supply pipe 25.
It is shed from the bottom to the top.

Further, the liquid is circulated through the liquid supply pipe 26, the first flow hole 44, the first chamber 49, the discharge pipe 28 and the positive electrolyte storage tank 2a.

Next, the second operation for shifting from the starting state shown in FIG. 2 to the normal operating state is as follows.

That is, the control valve 38 is opened and the control valve 39 is closed. At the same time, the control valve 40 is opened and the control valve 41 is closed. Then, the electrolytic solution pressurized by the pump 16 is supplied into the space between the lower portion of the cylinder 24 and the valve body 34 through the supply pipe 42 and the liquid delivery pipe 36 for operation, and the four valve bodies 31 are provided. , 32, 33, 34 are moved to the upper position corresponding to the normal operation as shown in FIG. In addition,
At this time, the electrolytic solution between the upper part of the cylinder 24 and the valve body 31 is returned to the discharge pipe 28 through the operation liquid sending pipe 36 and the liquid condensing pipe 43.

In this state, the electrolytic solution in the positive electrode electrolytic solution storage tank 2a passes through the delivery pipes 29, 30 and is pressurized by the pump 16, passes through the fourth through hole 47, the third chamber 51, and the fifth through hole 48. Flows from the top to the bottom in the positive electrode chamber 6 through the liquid feed pipe 27 and the liquid feed pipe 26. After this, the electrolytic solution circulates through the liquid supply pipe 25, the third flow hole 46, the second chamber 50, the second flow hole 45, and the positive electrolyte storage tank 2a.

In this way, the positive electrode electrolyte flows in the positive electrode electrolyte chamber 6 from the top to the bottom, so that the bromine complex compound having a large specific gravity is generated.
It is evenly distributed in the room underneath it, and a good response can be expected.

H. Effect of the Invention As described in detail above, the zinc-bromine secondary battery of the invention is
The valve body in the cylinder of the switching valve body provided in the positive electrode electrolyte circulation passage is moved and operated by the switching operation means to switch the vertical flow of the electrolytic solution circulating in the positive electrode chamber.

With this configuration, since the switching valve body does not have the rotor bearing portion for rotating the valve as in the conventional case, there is no liquid leakage due to wear of the bearing portion, and the sealed portion of the battery as a whole is piped. Since it is only the connection part, the reliability in preventing electrolyte leakage is improved, and it is possible to sufficiently prevent ground loss due to leakage of electrolyte caused by electrolyte leakage, corrosion of surrounding equipment, etc. and improve safety. The effect is that you can do it.

[Brief description of drawings]

FIG. 1 is an explanatory view of the overall schematic configuration of a zinc-bromine secondary battery according to an embodiment of the present invention at the time of normal operation, FIG. 2 is an overall schematic configuration illustration at the time of its start, and FIG. FIG. 4 is a cross-sectional side view of the four-way valve device portion, FIG. 5 is a cross-sectional front view of the four-way valve device portion, and FIG. 6 is a seal portion thereof. It is an expanded sectional view. 1 ... Battery main body, 2a ... Positive electrode electrolyte storage tank, 2b ... Negative electrolyte storage tank, 6 ... Positive electrode chamber, 7 ... Negative electrode chamber, 23 ... Switching valve body, 24 ... Cylinder, 25 ... … Liquid feed pipe, 26 …… Liquid feed pipe, 27 …… Liquid feed pipe, 28 …… Discharge pipe, 29 …… Delivery pipe, 30
...... Sending tube. 31,32,33,34 …… Valve body, 35 …… Steel body, 36,37
...... Operating liquid feed pipe, 38,39,40,41 ...... Control valve, 42 ...... Supply pipe, 43 ...... Condensation pipe, 44 ...... First through hole, 45 ...... Second through hole , 46 ... third through hole, 47 ... fourth through hole, 48 ... fifth through hole, 49 ... first chamber, 50 ... second chamber, 51 ... third
Room.

Claims (1)

(57) [Scope of utility model registration request] 1. A negative electrode electrolyte circulation passage in which the inside of a battery reaction chamber is partitioned by a separator to provide a positive electrode chamber and a negative electrode chamber, and the upper and lower parts of the negative electrode chamber communicate with a negative electrode electrolyte storage tank via a pump. And the upper and lower parts of the positive electrode chamber are connected to the positive electrode electrolyte storage tank via a switching valve and a pump, and by switching the switching valve, the electrolytic solution in the positive electrode storage tank is moved to the upper part of the positive electrode chamber. In a zinc-bromine secondary battery having a positive electrode electrolyte circulation passage for flowing from the bottom to the bottom or from the bottom to the top, the switching valve is formed by a cylinder and at least four valve bodies that move integrally in the cylinder. First, second, third, fourth and fifth through holes are sequentially arranged in this cylinder at predetermined intervals in the axial direction, and the second and fourth through holes are formed in the positive electrode electrolyzer. The first and fifth flow holes are connected to a liquid storage tank and the positive electrode is connected to the positive electrode. The upper part (or the lower part) of the chamber and the third flow hole communicate with the lower part (or the upper part) of the positive electrode chamber, and the four valve bodies define the first chamber, the second chamber and the third chamber. The first chamber communicates the first and second flow holes and the second chamber communicates the third and fourth flow holes by the first operation. , The third chamber is made to communicate with the fifth communication hole, and the first chamber has the first communication hole and the second chamber has the second and third communication holes in the second operation. The zinc-bromine secondary battery is characterized in that the third chamber communicates with the fourth and fifth flow holes.