JPH0131665B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to a framed electrode used in an electrolyte circulation type battery such as a metal (for example, Zn)-halogen (for example, Br) battery.

B: Summary of the Invention The present invention provides a framed electrode in which a conductive plastic electrode plate is surrounded by an insulating frame member to form a battery reaction chamber on the electrode plate surface. This is an electrode with a frame that is integrated by sandwiching a material between the electrode plate and the insulating frame member so as to be in contact with the surface of the electrode plate.

C. Prior Art FIG. 1 is an explanatory diagram of the principle of an electrolyte circulation type battery. This battery has electrodes 1 and 3 arranged on both sides with a separator 5 in between to form a unit cell. In addition, in FIG. 1, electrode 1 is a negative electrode, and electrode 3 is a positive electrode. Then, the negative electrode liquid is supplied from the negative electrode liquid storage tank 6 to the battery reaction chamber (negative electrode chamber) 2 between the electrode 1 (negative electrode) and the separator 5 and circulated.
The positive electrode solution is supplied from a positive electrode storage tank 7 to a battery reaction chamber (positive electrode chamber) 4 between the positive electrode (positive electrode) and the separator 5 and is circulated therein. Note that 9a and 9b are pumps for liquid circulation, and 10a and 10b are valves.

FIG. 2 is an exploded perspective view of the case where a required electrolyte circulation type battery is constructed by stacking a large number of unit cells each consisting of an electrode and a separator as shown in FIG.

In this figure, 11 is an aluminum clamping end plate, 12 is a resin clamping end plate, 13 is a buckle, 1
4 is an electrode end plate, and 15 is a terminal made of wire mesh or the like.

Then, the battery is constructed by stacking electrodes 1 and separators 5 alternately, and clamping end plates are placed on both sides in the stacking direction.
1 are arranged and the whole is tightened with bolts 16 and nuts 17.

This type of electrode 1 is integrally equipped with an insulating frame member around the electrode plate, and is arranged at the center in the thickness direction of the insulating frame member so as to form battery reaction chambers (positive electrode chamber, negative electrode chamber) on both sides of the electrode plate. An electrode plate is provided in the section to form a so-called frame electrode.

Further, this insulating frame member is provided with a manifold 18 through which an electrolytic solution flows, and a flow path 20 that communicates between this manifold 18 and the battery reaction chamber.
This flow path 20 is formed by a channel 19a and a microchannel 19b.

Incidentally, since the insulating frame member of the electrode is required to have insulation properties and chemical resistance, this frame is formed of polyolefin-based synthetic resin (for example, polyethylene).

On the other hand, the electrode plate is made of a conductive resin (for example, carbon plastic) having a base polymer of polyolefin resin (for example, polyethylene).

This kind of integration of the electrode plate and the insulating frame member is
This is done by placing frame members shaped like a picture frame on both sides of a rectangular electrode plate, overlapping them, charging them into a mold, and molding them under heat and pressure inside the mold using the heat breath method. .

On the other hand, the electrolytic solution (for example, positive electrode solution) is applied to the clamping end plate 1
1. The manifold 18 that passes through the insulating frame of the electrode 1 and the frame of the separator 5 in the stacking direction is passed through the channel 19a of the flow path 20 provided on one side of the frame of each electrode 1. The current is guided into the chamber (positive electrode chamber), further rectified by the microchannel 19b on one side of the insulating frame, and flows along the front surface of the electrode plate.

The electrolytic solution that has flowed along the electrode plate in the battery reaction chamber of each electrode is transferred to other electrodes via flow paths (microchannels and channels, not shown) formed on the other side of the insulating frame of the electrode. It is guided to the manifold and refluxed to the positive electrode electrolyte tank (see reference numeral 7 in FIG. 1).

Note that the negative electrode liquid flows to the battery reaction chamber formed on the other side of the electrode plate of each electrode through a flow route different from that of the positive electrode liquid, but the flow path configuration is different from that of the positive electrode. Since this is the same as in the case of liquid, its explanation will be omitted.

D: Problem to be Solved by the Invention Now, in the conventional framed electrode configured as described above, the insulating frame member integrally molded with the electrode plate has a coefficient of linear expansion nearly twice that of the electrode plate. Because of the large size, there was a problem that some warpage inevitably remained after integral molding.

FIG. 3 is an explanatory diagram showing constituent members of a framed electrode attempted to solve such problems. This framed electrode has a molded filler (for example, talc, glass wool, etc.) 30 having the same shape as the insulating frame member between insulating frame members 21 and 22 that are integrally molded with a conductive plastic electrode plate (for example, carbon plastic) 1. By sandwiching them and pressurizing them simultaneously to integrally mold them, a filler-containing layer is integrally formed within the frame. As a result, the coefficient of linear expansion of the insulating frames 2a and 2b can be adjusted to that of the electrode plate 1.
The coefficient of linear expansion is made close to that of 1, to eliminate warpage after molding.

However, in such a configuration, although the warping of the molded product is eliminated, a new problem arises in that the surface flatness of the molded product frame is significantly impaired, and post-processing such as annealing is required after molding. There was a drawback.

E: Means for Solving the Problems In the present invention, in order to achieve the above-mentioned object, an insulating frame member is provided between the rectangular conductive plastic electrode plate and the synthetic resin insulating frame member on the surface thereof. These three materials are integrated by sandwiching a glass wool material having a substantially similar frame shape so as to be in direct contact with the surface of the electrode plate.

In this case, preferably the thickness of the electrode plate and the thickness of the glass wool material are approximately equal, and the thickness of the insulating frame member superimposed on the glass wool material is 1.2 to 2.0, particularly Preferably, it is selected within the range of 1.6±0.1. It is also desirable to use an insulating frame member filled with a filler in advance, and furthermore, the width of each side of the glass wool material is preferably slightly narrower than the width of each corresponding side of the insulating frame member.

F: Function In the framed electrode of the present invention, since the glass wool material is in contact with the surface of the electrode plate and is sandwiched between the electrode plate and the insulating frame member and integrated, the glass wool material prevents thermal deformation of the insulating frame member. suppresses and prevents warping,
Since the resin of the insulating frame member is present in a sufficient thickness on the outer surface side of the insulating frame portion, the flatness of the surface of the insulating frame portion is also ensured satisfactorily.

G: Examples Examples of the present invention will be described below with reference to the drawings.

FIG. 4 is an exploded view of the structure of the framed electrode according to the present invention. In the figure, reference numeral 1 denotes a conductive plastic electrode plate, which is made of carbon plastic, for example. 21 is an insulating frame member for microchannel molding, and 22 is an intermediate insulating frame member, both of which are made of thermoplastic insulating resin. Note that these insulating frame members may be filled with filler such as talc in advance.

Reference numeral 40 denotes a glass wool material that is directly stacked on the electrode plate 1, and has a frame shape that is almost the same as the insulating frame members 21 and 22. That is, this glass wool material 40 has a punched part 41 formed in its center so that the electrode surface is exposed, and the width d ₄₀ of the peripheral frame part.
is configured to be equal to or narrower than the width _d22 of the corresponding portion of the insulating frame member 22. The thickness h ₄₀ of this glass wool material 40 and the insulating frame members 21 and 22
The ratio of the total thickness of (h ₂₁ + h ₂₂ ) to h ₄₀ / (h ₂₁ +
_h22 ) is desirably in the range of 1/1.2 to 1/2.0, and the optimum value was about 1/1.6±0.1.

These members are laminated symmetrically on both sides with the electrode plate 1 as the center as shown in FIG. It is integrally molded into a frame electrode. In the obtained framed electrode, warping of the molded product was completely eliminated, and the surface of the insulating frame had sufficient flatness.

In addition, in the above embodiment, the reason why it is preferable to select the thickness of the glass wool material 40 within the range described above with respect to the total thickness of the insulating frame members 21 and 22 is that the thickness of the glass wool material If it is too thin, the molded product will warp, and if it is too thick, it will cause unevenness on the surface of the insulating frame.Also, if the insulating frame is too thick, excess resin will flow out onto the effective electrode surface. This is because an insulating film may be formed, which may have the effect of narrowing the effective electrode area.

H: Effect of the invention As described above, according to the present invention, by integrally molding each member by laminating and pressurizing, there is no warpage.
Moreover, since a framed electrode of constant quality with good surface flatness of the insulating frame portion can be obtained, it can be used for assembling an electrolyte circulation type battery without the need for post-treatment such as annealing.

[Brief explanation of drawings]

Figure 1 is a diagram explaining the principle of electrolyte circulation type battery, Figure 2
The figure is an exploded perspective view of a conventional electrolyte circulation type stacked battery in which a large number of unit cells are laminated, Figure 3 is an explanatory diagram showing each component of a prototype framed electrode, and Figure 4 is a framed electrode according to the present invention. FIG. 2 is an explanatory diagram showing a superposed state of each component. DESCRIPTION OF SYMBOLS 1... Conductive plastic electrode plate, 21... Insulating frame member for microchannel molding, 22... Intermediate insulating frame member, 2a, 2b... Insulating frame, 40...
Glass wool material.

Claims (1)

[Scope of Claims] 1. An insulating frame member made of synthetic resin is provided around at least one surface of a rectangular conductive plastic electrode plate integrally with the electrode plate to constitute a framed electrode, and the framed electrode A framed electrode configured to form a battery reaction chamber surrounded by the electrode plate and the insulating frame member by overlapping the electrode plates and to allow the electrolyte to flow into and out of the battery reaction chamber via the insulating frame member. A glass wool material having a frame shape substantially similar to that of the insulating frame member is sandwiched and integrated between the electrode plate and the insulating frame member in direct contact with the surface of the electrode plate. An electrode with a frame. 2. The frame according to claim 1, wherein the thickness of the electrode plate and the thickness of the glass wool material are approximately equal, and the thickness of the insulating frame member is 1.2 to 2.0 times the thickness of the glass wool material. With electrode. 3. The framed electrode according to claim 1, wherein the insulating frame member is filled with a filler. 4. The framed electrode according to claim 1, wherein the width of each side of the frame-shaped glass wool material is narrower than the width of each corresponding side of the insulating frame member.