JPH06302340A - Zinc-bromine battery and installation structure thereof - Google Patents

Abstract

PURPOSE:To enhance conveying performance in manufacturing and absorb expansion/contraction of constituting members by connecting respective bolts with a single connecting plate, and mounting the connecting plate with a pair of fastening end plates on members freely movable rectilinearly. CONSTITUTION:In a sub-module, cells C1-C3 laminated in series are adapted as one unit and current collecting electrodes 7, fastening end plates 8 and laminated end plates 9 for pressing positioned inside of the end plates 8 are arranged. Respective bolts 22 positioned outside of disk springs 23 are connected to each other by means of a single connecting plate 25, and the connecting plate 25 with a pair of fastening end plates 8 are mounted on members 26a, 26b, 26c freery movable rectilinearly. Since the fastening end plates 8 as well as the connecting plate 25 are freely movable laterally in the arrow A direction, expansion/contraction of constituting members can be absorbed by the members 26a-26c. Also, since the members 26a-26c are linear bearings, conveying performance in manufacturing can be enhanced and moving operation can be simplified.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolyte circulating type laminated secondary battery, and more particularly to a zinc-bromine battery for storing electric power and its installation structure.

[0002]

2. Description of the Related Art A zinc-bromine battery is a secondary battery that uses bromine as a positive electrode active material and zinc as a negative electrode active material.
It is used to store electricity at night when electricity demand is low and to release it in the daytime.

Bromine generated on the positive electrode side at the time of charging reacts with the bromine complexing agent added to the electrolytic solution to be returned to the positive electrode side storage tank as an oil-like precipitate, and at the time of discharging, it is pumped to the unit cell. It is sent in and returned. The component of the electrolytic solution is ZnBr
₂ aqueous solution, a salt such as NH ₄ Cl for reducing resistance, Pb, Sn, quaternary ammonium salts for preventing dendrite on the negative electrode zinc side and promoting uniform electrodeposition, and a bromine complexing agent Is. A separator is inserted between the positive electrode and the negative electrode to prevent self-discharge caused by the bromine generated in the positive electrode diffusing into the negative electrode and reacting with zinc.

In this zinc-bromine battery, the electrodes are mainly of a bipolar type, a battery body in which a plurality of unit cells (unit cells) are electrically stacked in series, an electrolytic solution storage tank, and an electrolytic solution between them. It is composed of a pump and a piping system for circulating the liquid.

FIG. 5 is an exploded perspective view showing an example of a battery body constituting the zinc-bromine battery, in which an insulating frame 1b is arranged on the outer periphery of an electrode portion 1a of a bipolar plate-shaped intermediate electrode 1 having a rectangular flat plate shape. Similarly, a rectangular flat plate-shaped separator plate 2
The frame 2a is formed on the outer periphery of the separator 3.
The separator plate 2 and, if necessary, the packing 4 and the spacer mesh 5 are stacked on the intermediate electrode 1 to form a single cell, and a plurality of the single cells are stacked to form a battery body.

A collector electrode 7 having a collector mesh 6 and a pair of tightening end plates 8 are provided at both ends of the stacked battery bodies.
A pressing laminated end plate 9 located inside thereof is arranged. Then, a bolt for tightening, which will be described later, is passed between both the tightening end plates 8 and 8 to tighten the bolt,
A battery main body is integrally laminated and fixed.

In each unit cell of the battery body constructed as described above, each intermediate electrode 1 and the frame body 2a of the separator plate 2 are provided.
Positive electrode manifold 10 formed in two corners above and below
Then, the electrolytic solution flows in and out from the negative electrode manifold 11 through the channels 12 and the microchannels 13 provided in the frame body 2a of the separator plate 2, respectively.

The above zinc-bromine battery has been confirmed to have a battery efficiency of about 80% and a total energy efficiency of about 70% in a 50 KW class battery.

FIG. 6 is a schematic diagram for explaining the operating principle of the zinc-bromine battery, in which 14 is a positive electrode side storage tank, and the positive electrode electrolyte solution 15 and bromine are contained in the positive electrode side storage tank 14. Complex compound 16 is stored. Reference numeral 17 denotes a negative electrode side storage tank in which the negative electrode electrolytic solution 18 is stored. The positive electrode electrolyte solution 15 is supplied to the positive electrode side pump 19
Driven by the four-way valve 20, flows from the positive electrode manifold 10 of the battery main body into the single cell through the four-way valve 20 and flows back to the positive electrode side storage tank 14, while the negative electrode electrolyte solution 18 flows into the negative electrode. As the side pump 21 is driven, the side pump 21 flows through the unit cell separated from the negative electrode manifold 11 of the battery body to the separator 3 and returns to the negative electrode side storage tank 17.

FIG. 7 shows a module structure of a battery main body in which the above-mentioned components are assembled. One sub-module has 30 cells C ₁ or C ₂ , C ₃ stacked in series as one unit. In the illustrated example, the sub-module is based on a total of 3 units, that is, 90 cells.
Incidentally, 22 and 22 are bolts for tightening inserted between both tightening end plates 8 and 8, and 23 and 23 are disc springs. The disc spring 23 is arranged in order to prevent cracking of the constituent members due to the tightening force of the bolts 22 and to prevent breakage due to expansion and contraction due to changes in the outside air temperature and heat generated during charging and discharging. There is.

FIG. 8 is a side view showing an example in which the battery main body is arranged horizontally, and 24 in the figure is a hole for a manifold. That is, in order to maintain good characteristics of the zinc-bromine battery, it is necessary to expel air that is inevitably mixed in the electrolytic solution during the circulation of the electrolytic solution to the outside of the battery as soon as possible. The battery main body adopts the horizontal type shown in FIG. 8 as a basic installation structure.

By adopting this horizontal type, the negative electrode electrolytic solution 18 always flows from the lower part to the upper part as shown by the arrow in FIG. 6, and accordingly, the air in the electrolytic solution becomes easy to escape. still,
Since the positive electrode electrolyte solution 15 needs to uniformly supply the complex generated by charging into the battery, it is flowed from the upper part to the lower part under normal conditions and is discharged from the lower part to the upper part at regular intervals for a few minutes to discharge air. There is.

The normal zinc-bromine battery manufacturing process is carried out in the order of "lamination → tightening adjustment → hot water circulation → cooling → tightening force adjustment → air seal test". The unit itself tends to shrink due to the creep of the components during cooling, and it is easy for the air to escape even when circulating hot water, and it is necessary to drain water before the seal test, so the battery body should be horizontal. desirable.

In manufacturing the module of the battery main body, after stacking the above-mentioned constituent materials mainly composed of plastics, a press of about 20 tons and a hot water circulating step are repeated a plurality of times, and a bolt 22 is used for tightening. After that, a method of performing a seal test using air is implemented. The number of days required for all processes is about 8 days / vehicle.

[0015]

However, in the case of such a conventional zinc-bromine battery, the battery body is deformed irregularly due to the frictional force when the battery body is installed horizontally on the ground directly. As a result, the surface pressure on each component becomes non-uniform, which promotes the occurrence of fatigue fracture, and there is a problem that the battery characteristics vary due to the creep of each material during manufacturing.

That is, when manufacturing and installing a zinc-bromine battery, if the battery body is placed horizontally and placed directly on the ground, a large frictional force is applied to the battery body due to the weight of the battery body, and as shown in FIG. As schematically shown, the battery body may move irregularly only in the upper part with respect to the ground plane 30. This movement has the effect of suppressing variations in the starting material during the hot water circulation, but since the surface pressure on the constituent materials in the battery body becomes non-uniform, the above effect is canceled out and the surface during battery operation is canceled. There is a problem that the fatigue fracture of each component is promoted as the pressure rises.

In order to deal with the above, as shown in FIG. 10, for example, there may be considered a means in which a support base 31 is integrally provided on the lower bolt 22 so that the battery main body does not come into direct contact with the ground. However, a large bending force is applied to the bolt 22 and the support base 31 due to the weight of the battery body, and the lower bolt 22 is likely to be deformed during operation, and the support base 31 is removed at each manufacturing step. Since it is necessary, there is a difficulty that a complicated operation is required.

The present invention has been made in view of the above points, and does not deform the battery body irregularly due to a frictional force when the battery body is installed as a horizontal type, and makes the surface pressure of each component uniform. It is an object of the present invention to obtain a zinc-bromine battery and its installation structure which can prevent fatigue damage and have improved transportability during manufacturing.

[0019]

In order to achieve the above object, the present invention provides a single cell by stacking a separator plate and an intermediate electrode, and stacking a plurality of the single cells to form a battery main body. An interposing disc spring arranged on the outer side of one of the clamping end plates by disposing a collecting electrode having a collecting mesh at both ends of the battery body, a laminated end plate for pressing and a pair of clamping end plates. A zinc-bromine battery, in which both clamp end plates are bolted together to be integrally laminated and fixed below, first, claim 1
According to the above, each bolt located outside the disc spring is connected using one connecting plate, and the connecting plate and the pair of tightening end plates are mounted on a member that moves freely in a straight line.
The zinc-bromine battery is configured to enhance the transportability of the battery main body during manufacturing and absorb expansion and contraction of each component.

According to a second aspect of the present invention, each bolt located outside the disc spring is connected by using one connecting plate, and at least the tightening end plate located in the vicinity of the disc spring is freely linear. (EN) Provided is a structure for installing a zinc-bromine battery which is mounted on a moving member and absorbs expansion and contraction of each constituent material during operation.

[0021]

According to the zinc-bromine battery of the present invention, the tightening end plate constituting the battery body and the connecting plate connecting the tightening bolts can be freely moved in the linear direction by the member that moves in a straight line. Since it can move, this member can absorb expansion and contraction of each component of the battery main body, and at the time of manufacturing, the battery main body can be moved by simply getting on and off the member that moves linearly. The operation of moving the battery body is extremely simplified, and the transportability is improved.

According to the installation structure of the battery main body of the second aspect, at least the tightening end plate located in the vicinity of the disc spring is mounted on the member which moves in a straight line, and the other parts are simply mounted. By arranging the member for adjusting the height, it becomes possible to absorb the expansion and contraction of each component during operation.

[0023]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of a zinc-bromine battery and its installation structure according to the present invention will be described in detail below with reference to the drawings, in which the same reference numerals are given to the same components as the conventional components.

FIG. 1 is a side view showing a basic embodiment of the present invention, in which one sub-module constituting a battery has 30 cells C ₁ or C ₂ , C ₃ stacked in series as one unit. In the illustrated example, the submodule is based on a total of 3 units, that is, 90 cells. A collector electrode 7 having a collector mesh, a pair of tightening end plates 8 and a pressing laminated end plate 9 located inside thereof are arranged at both ends of each sub-module.

Usually, the tightening end plate 8 is made of fiber reinforced plastic resin (FRP), and the laminated end plate 9 is made of vinyl chloride resin (PVC). Reference numeral 22 denotes a tightening bolt inserted between the tightening end plates 8 and 8, 23 denotes a disc spring, and a plurality of the above tightening bolts 22 are passed between both tightening end plates 8 and 8, By tightening the bolts 22 with the disc springs 23 interposed, a battery body integrally laminated and fixed is configured.

The disc spring 23 has a function of preventing cracks and the like from being generated in the constituent members due to stress concentrated at the interface when the two tightening end plates 8 are fastened with each other by using the bolts 22, and the outside temperature It has a function of preventing a change caused by expansion and contraction of the constituent material due to heat generation during charging / discharging, and has an effect of minimizing a load change exerted on the constituent material.

In this embodiment, the bolts 22 located outside the disc spring 23 are connected by using one connecting plate 25, and the connecting plate 25 and the pair of tightening end plates 8 are freely connected. Members that move linearly, such as linear bearings 26a, 26
It is characterized by being mounted on b and 26c. The mounting of the battery main body on the three linear bearings 26a, 26b, 26c described above is mainly performed at the time of manufacturing the battery main body.

Therefore, according to this embodiment, the linear bearings 26a, 26b and 26c allow the tightening end plate 8 and the connecting plate 25 constituting the battery main body to freely move in the left-right direction in the drawing as shown by the arrow A. It is characterized by movement.
With the linear bearings 26a, 26b, 26c,
The operational characteristics of this embodiment are that the expansion and contraction of each component can be absorbed and the transportability of the battery main body at the time of manufacturing is improved. Especially at the time of manufacturing, the battery main body is used for the linear bearings 26a, 2 by using a crane or the like.
Since the battery main body can be moved only by getting on and off the 6b and 26c, the characteristic that the moving operation is extremely simplified is obtained.

Next, the structure of the battery body when it is installed will be described. In the example of FIG. 1, three linear bearings 26
Although an example using a, 26b, and 26c is shown, it is not always necessary to use three linear bearings when the battery main body is installed, and at least a portion close to the disc spring 23 in FIG. One tightening end plate 8 is mounted on the linear bearing 26b, and the other linear bearing 26
For the parts corresponding to a and 26c, a member for adjusting the height may simply be arranged.

One such linear bearing 26b
By using only the linear bearing 26b, it is possible to absorb the expansion and contraction of each component during operation by the linear bearing 26b.

The present embodiment will be described below based on the evaluation of characteristics. That is, in the test of the sealing property in the manufacturing process of the battery main body, after stacking the constituent materials mainly composed of the above plastics, the press of about 20 tons and the hot water circulating process are repeated a plurality of times, and the bolts 22 are used for tightening. After that, a method of performing a seal test using air is implemented. When a predetermined amount of the air is introduced, the battery body is deformed corresponding to the electrode structure, and the tension of each bolt 22 is changed.
2 and 3 show the results of comparison of the state between the vertical type in the free state and the horizontal type mounted on the linear bearing.

FIG. 2 shows the results of measuring the tensions of the bolts 22 and 22 using a strain gauge when the battery body is a vertical type in a free state, and FIG. 3 is a horizontal type in which the battery body is placed on a linear bearing. The same tension measurement result in the case of is shown. The tensions of the bolts 22 and 22 before the air is introduced are all the same. The numbers in Fig. 3 are bolts 2.
It shows the ratio when the average tension value of all 2, 22 is set to 1.

According to FIGS. 2 and 3, it has been found that substantially the same state as in the case where the battery main body is vertical type is realized also in the horizontal type on the linear bearing.

FIG. 4 shows a plate during cooling in each step of "stacking → tightening adjustment → hot water circulation (first time) → cooling → tightening adjustment → hot water circulation (second time) → cooling" when manufacturing the battery body. Amount of change corresponding to each position of the springs 23, 23 (m
It is the graph which plotted m). The graph (a) shows the change amount at the time of cooling after the hot water circulation (first time), and the graph (b) shows the change amount at the time of cooling after the hot water circulation (second time). The above-mentioned tightening adjustment means that the tensions of all the bolts 22 are made the same in each process, and the overall tension is always constant.

The positions of the disc springs 23.23 are, as shown in the figure, the side portions (1-5), the upper portion (6-9), and the side portions (1
0-14) and the lower part (15-18). Disc spring 23.
The change amount (mm) of 23 was measured with reference to the time of tightening adjustment with the bolt 22.

It can be seen from FIG. 4 that each disc spring 23.23 has substantially the same thermal expansion and contraction at the top and bottom, so that even if the battery body is arranged horizontally on the linear bearing. It turned out that there was no problem.

[0037]

As described in detail above, according to the zinc-bromine battery and the installation structure thereof according to the present invention, the tightening end plate constituting the battery main body is free to move in the linear direction by the member that moves linearly freely. Since this member can move to the above position, it is possible to absorb expansion and contraction of each component of the battery body by this member. And when the battery body is installed horizontally, the surface pressure on each component becomes uniform, and the fatigue fracture of each component can be prevented, so that the occurrence of cracks or strains in the component is prevented. It is possible to extend the product life.

In particular, at the time of manufacture, since the battery body can be moved only by getting on and off the member which moves linearly, the operation of moving the battery body can be extremely simplified and the transportability can be improved. And the creep amount of each material during manufacturing becomes uniform, there is no variation in battery characteristics, abnormal stress does not occur in the components even during operation after installation, and a large bending force is applied to the bolt due to the weight of the battery body. Is not added, the deformation of the bolt is prevented and the battery performance can be maintained at a high level.

[Brief description of drawings]

FIG. 1 is a front view showing an embodiment of a zinc-bromine battery and an installation structure thereof according to the present invention.

FIG. 2 is a schematic diagram showing the results of measuring the tension of each bolt when the battery body is a vertical type in a free state.

FIG. 3 is a schematic diagram showing the results of measuring the tension of each bolt when the battery body is horizontal.

FIG. 4 is a graph showing the amount of change of a disc spring during cooling in this embodiment.

FIG. 5 is an exploded perspective view showing the configuration of a zinc-bromine battery body.

FIG. 6 is a schematic diagram showing the operating principle of a zinc-bromine battery.

FIG. 7 is a schematic diagram showing a module structure of a battery main body in which each component is assembled.

8 is a left side view of FIG. 7.

FIG. 9 is a schematic view showing a state in which the battery main body is horizontal and is directly placed on the ground.

FIG. 10 is a front view showing an example of a conventional zinc-bromine battery installation structure.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Intermediate electrode 2 ... Separator plate 3 ... Separator 8 ... Clamping end plate 9 ... Laminated end plate 10 ... Positive electrode manifold 11 ... Negative electrode manifold 12 ... Channel 13 ... Microchannel 14 ... Positive electrode side storage tank 17 ... Negative side storage tank 19 ... Positive side pump 21 ... Negative side pump 22 ... Bolt 23 ... Disc spring 25 ... Connection plate 26a, 26b, 26c ... Linear bearing

Claims (3)

[Claims] 1. A separator cell and an intermediate electrode are stacked to form a single cell, and a plurality of the single cells are stacked to form a battery main body, and a current collecting electrode having a current collecting mesh at both ends of the battery main body. , Laminated end plates for pressing and a pair of tightening end plates are arranged, and bolts are tightened between both tightening end plates with the interposition of a disc spring arranged outside one of the tightening end plates. In the zinc-bromine battery, the bolts located outside the disc spring are connected using a single connecting plate, and the connecting plate and the pair of tightening end plates are freely connected. By mounting on a member that moves in a straight line, the transportability of the battery main body during manufacturing is improved, and the expansion and
A zinc-bromine battery characterized by absorbing shrinkage. 2. A separator plate and an intermediate electrode are stacked to form a single cell, and a plurality of the single cells are laminated to form a battery main body, and a current collecting electrode having a current collecting mesh at both ends of the battery main body. , Laminated end plates for pressing and a pair of tightening end plates are arranged, and bolts are tightened between both tightening end plates with the interposition of a disc spring arranged outside one of the tightening end plates. In the installation structure of the zinc-bromine battery that is laminated and fixed to, the bolts located outside the disc spring are connected by using one connecting plate, and the tightening is provided at least at a portion close to the disc spring. An installation structure of a zinc-bromine battery, characterized in that the end plate is mounted on a member that moves freely in a straight line so as to absorb expansion and contraction of each constituent material during operation. 3. The zinc-bromine battery and its installation structure according to claim 1, wherein the member which moves linearly freely is a linear bearing.