JP2522029B2 - Method for manufacturing end plate electrode in liquid circulation type laminated battery - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to a method for manufacturing an end plate electrode in a liquid circulation type laminated battery.

B. Summary of the Invention The present invention is a method for manufacturing an end plate electrode used in a liquid circulation type battery, in which one end surface of the end plate electrode main body is provided with a bonding resin body that is easily bonded to a frame body. Since it is held by the frame body, the joint strength between the end plate electrode body and the frame body is improved, the sealing property between the body and the frame body is also improved, and the durability is improved. It was made possible.

C. Conventional Technology Recently, the development of a battery power storage system has been promoted, and as a part thereof, an electrolyte circulating zinc-bromine laminated secondary battery as illustrated in FIG. 4 has been developed.

As shown in the structural principle diagram of FIG. 4, this means that the battery main body 1 is made up of a separator 2 made of an ion exchange membrane or a porous membrane.
It is divided into an anode chamber 3 and a cathode chamber 4. Liquid supply pipes 5 and 6 and liquid return pipes 7 and 8 for circulating the electrolytic solution are respectively provided in these bipolar chambers.
The respective electrolytic solution tanks 9 and 10 for the anode and the cathode connected by the above are provided. The electrolytic solutions of zinc bromide (ZnBr ₂ ) for the anode and the cathode are configured to be circulated to the electrode chambers 3 and 4 by the liquid feed pumps 13 and 14, respectively.

 In addition, 11 is an anode, 12 is a cathode, and 15 is a valve.

In the battery configured as above, when charging,
The electrolyte circulates in the direction of the arrow in the figure, and Zn ⁺⁺ + 2e at the cathode 12.
^- → Zn, the anode 11 2Br ^- → resulting reaction Br ² + 2e, an anode 11
The bromine produced in 1. becomes a molecule, mixes in the electrolytic solution, partially dissolves, and most of it becomes a complex compound by the complexing agent in the anolyte, and it precipitates and accumulates in the electrolytic solution tank 10 on the anode chamber side. It When discharging, each electrode should be
In 11 and 12, a reaction opposite to the above reaction formula occurs, and the precipitate (Zn, Br ₂ ) is consumed (oxidized, reduced) on each electrode 11 and 12, and electric energy is released.

The zinc-bromine battery using the above-described configuration principle,
A stacking system having a so-called vertical cell stacking structure in which a large number of electrode plates are installed vertically (substantially in the vertical direction) as elements and a stacked battery as shown in FIG. The entire vertical stack is composed of a pair of tightening end plates 16 and 16 that are pressed from both ends so as to be sandwiched with bolts and nuts, and laminated end plates 17 and 17 that are pressing members disposed inside each of them. Between them, for example, 30 cells are stacked to form a vertical shape.
That is, the stack is composed of a carbon plastic end plate electrode 18 having a collecting mesh 19, a separator plate 21 over the packing 20 and then a spacer mesh 22 for holding a predetermined interval, and a carbon plastic The flat plate intermediate electrodes 23 are stacked in this order, and then the packing 20 is stacked, and finally the other end plate electrode 18 made of carbon plastic is stacked so that a total of 30 cells are stacked vertically.

The positive electrode manifold 21 and the negative electrode manifold 25, which are the liquid flow holes, are formed in the vertically stacked stack as described above.

Further, as shown in FIG. 5, each separator plate 21 is formed by integrally molding a frame plate 21a around a separator 2 made of a microporous membrane by injection molding of plastic. Each has a micro channel 26 in a front and back symmetrical shape. The micro-channels 26 shown by solid lines in the drawing are the positive electrode manifolds 24 on diagonal lines, respectively.
The electrolyte introduced from above is evenly spread and flowed over the entire surface of the separator 2, or the electrolyte is recovered from this. The microchannel 26 shown by a broken line in the drawing is for introducing and collecting the electrolytic solution from the negative electrode manifold 25.

In this way, the unit battery illustrated in FIG. 4 is configured between the electrodes arranged on both side surfaces of each separator plate 21.

In such a battery, it is necessary to fill the inside of each of the anode chamber 3 and the cathode chamber 4 of the stack with the electrolytic solution and then circulate the electrolytic solution when the battery is used for operation.

First, regarding the filling of the vertical stack with the electrolytic solution, the electrolytic solution is injected into each of the anode chamber 3 and the cathode chamber 4 from the lower manifold, and the air is expelled from the upper manifold to remove the air from each chamber. It is desirable that the electrolyte be filled with the electrolyte.

If you inject the electrolyte from the upper manifold,
The electrolytic solution is discharged from the lower manifold instead of the air, and the air may remain in the room.

D. Problems to be Solved by the Invention In the laminated battery configured as shown in FIG. 5, the end plate electrode 18 has an end plate electrode body 18a and a frame body for holding the electrode body 18a as shown in FIG. Formed from 18b. Electrode body
The end plate electrode 18 is integrally formed by injection molding using a material composed of a homogeneous kneaded material of polyethylene / carbon black / graphite 18a and a material of a homogeneous kneaded material of polyethylene and glass fiber for the frame 18b. .

Since the end plate electrode 18 has an insert thickness that is about four times that of the intermediate electrode 23, it is assumed that the degree of melting of the resin between the electrode body 18a and the frame body 18b is as thin as that of the intermediate electrode 23. Bad when compared. As a result, there is almost no adhesion between the electrode body 18a and the joint surface between the frame body 18b, and the frame body 18b structurally merely supports the electrode body 18a. For this reason, as shown in FIG. 7, when the electrode body 18a is pulled downward, the electrode body 18a immediately comes out of the frame 18b.
In such an adhesive state, it is almost impossible to seal the liquid, and when operating as a battery, the electrode body
Liquid may leak from the joint surface between the frame 18a and the frame 18b.

As a result, there is a problem that the water pressure, withstand voltage, and seismic resistance are low due to long-term use as a battery, and the performance and reliability of the battery are significantly reduced.

An object of the present invention is to provide a method for manufacturing an end plate electrode in a liquid circulation type laminated battery in which a joint surface between an electrode body and a frame is firmly adhered to prevent liquid leakage or the like. .

E. Means for Solving the Problems The present invention provides a battery main body in which an end plate electrode having a positive electrode terminal and a separator between the end plate electrode having a negative electrode terminal and an intermediate electrode are provided in parallel, In a liquid circulation type battery in which an electrode liquid for a positive electrode and a negative electrode is circulated, a bonding resin body is provided in close contact with one surface of the electrode body of the end plate electrode, and the periphery of the bonding resin body and the electrode body is framed. It is integrally joined and molded by the body.

F. Working Since the joint resin body is formed on one surface of the electrode body by the compression molding machine, the joint resin body and the frame body are firmly adhered when integrally molded with the frame body. As a result, the sealing property between the frame body and the electrode body, the withstand voltage, and the earthquake resistance are improved.

G. Embodiment Hereinafter, an embodiment of the present invention will be described with reference to the drawings.

In FIG. 1, 31 is a frame body for the end plate electrodes.
Is formed from a homogeneous mixture of polyethylene and glass fibers. 32 is an electrode body of the end plate electrode, and this body 32 is formed from a homogeneously kneaded product of polyethylene / carbon black / graphite. Reference numeral 33 is a bonding resin body made of polyethylene and formed in close contact with one surface of the electrode body 32.

First, the electrode body 32 and the bonding resin body 33 are molded by a compression molding machine (heat press machine), and the bonding resin body 33 is brought into close contact with one surface of the electrode body 32. Next, the frame body 31, the electrode body 32 and the bonding resin body 33, which are in close contact with each other, are bonded and molded using an injection molding machine (not shown). When the frame body 31 and the electrode main body 32 are bonded in this manner, the frame body 31 and the bonding resin body 33 are melted and bonded, so that the bonding becomes strong.

Next, the results of a tensile test performed on the end plate electrode formed in the above-mentioned example and the end plate electrode shown in the conventional example will be shown.
In this test, a frame and an electrode body each having a shape as shown in FIGS. 2 and 3A and B were manufactured in total of 16 pieces, 8 pieces each, and a tensile test was conducted. It should be noted that FIG. 3A is according to the embodiment of the present invention, and FIG. 3B is according to the conventional example.

As a result of the above-mentioned test, the conventional example had a tensile strength of 20 kg to 30 kg, but the present invention also had a tensile strength of 80 kg to 90 kg. Further, when a water resistance test was conducted, the conventional example had a limit of up to 0.45 kg / cm ² , but the present invention improved the water resistance up to 2.35 kg / cm ² .

H. Effects of the Invention As described above, according to the present invention, the adhesive strength between the frame body and the electrode body can be remarkably improved, and along with this, the sealing property is also improved to improve the reliability and water resistance of the battery. There is an advantage that the property can be improved.

[Brief description of drawings]

FIG. 1 is an enlarged sectional view of an essential part showing an embodiment of the present invention,
FIG. 2 is a front view showing the shape of an end plate electrode sample used in a tensile test, and FIGS. 3A and 3B are sectional views showing the shapes of a sample according to the present invention similarly used in a tensile test and a sample according to a conventional example. FIG. 4 is a schematic configuration diagram showing the principle of a zinc-bromine battery, FIG. 5 is an exploded perspective view of a main part of a stack portion of the battery, FIG. 6 is a front view of an end plate electrode, and FIG. 7 is an end plate. It is a fragmentary sectional view of an electrode. 31 …… frame body, 32 …… electrode body, 33 …… bonding resin body.

Claims (1)

(57) [Claims] 1. An electrode solution for a positive electrode and a negative electrode is placed in a battery main body, which is arranged in parallel with a separator and an intermediate electrode interposed between an end plate electrode having a positive electrode terminal and an end plate electrode having a negative electrode terminal. In a method of manufacturing an end plate electrode in a liquid circulation type laminated battery that is circulated, after molding an electrode body and a bonding resin body by a compression molding machine, the bonding resin body is closely molded on one entire surface of the electrode body. After that, the frame body, and the contact-molded electrode body and the bonding resin body are integrally bonded and molded using an injection molding machine, and a method for manufacturing an end plate electrode in a liquid circulation type laminated battery.