JPS60117549A - Manufacture of lead-acid battery - Google Patents

Abstract

PURPOSE:To increase charging ability in repeating use by dispersing electroconductive powder having liquid holding ability in active material, separating the mixture into the desired two layers, and forming it on the surface, facing a separator, of a plate. CONSTITUTION:A specified amount of electrolyte is impregnated in anode and cathode plate 4a and 4b, and a separator 5 so that no free electrolyte exists. Either one or both of the anode and cathode plates 4a and 4b is manufactured by fixing slurry-like active material in each or both of current collectors 2 and 3 comprising lead or lead alloy. Electroconductive powder having liquid holding ability is dispersed in active material, and this mixture is poured into containers 1a and 1b in which current collectors are fixed and separated into two layers of an active material layer and an electroconductive liquid holding layer by ultrasonic vibration to form the liquid holding layer on the surface, facing the separator, of the plate. Thereby, a change on standing is suppressed and charging ability in repeating use is increased sence electrolyte is held on the surface of the separator.

Description

[Detailed description of the invention] (a) Industrial application field The present invention is applicable to lead-acid batteries, especially lead-acid batteries with a so-called retainer, which have a limited amount of electrolyte so that there is no free electrolyte. This invention relates to an electrolyte holding means.

The same prior art The conventional glue-type lead-acid battery uses a separator made of a highly liquid-retaining material (for example, glass fiber) so that the electrolyte region injected into the battery case does not exist in a loose state. We are hiring.

However, if a lead-acid battery is left open for a long time with both terminals open, the chemical reaction inside the battery case will not proceed and the separator will absorb the electrolyte impregnated into the anode and cathode plates. At least one surface of the negative and anode plates in the tank becomes dry. Next time you use lead acid batteries.

There was a drawback that electrons could not move smoothly between the positive electrode plate and the negative electrode plate, resulting in a decrease in current conductivity.

In addition, the general lead battery 1 battery has a mechanism in which the cathode side active material absorbs the gas generated inside the battery case due to the reaction during charging, and in order to make this gas absorption reaction proceed smoothly, the electrolyte solution is used. The electrochemical capacity of the sulfuric acid injected as 3 - C is the active material forming the electrode plate (less than d. It is formed from C synthetic resin considering the sulfuric acid property.Generally, it is common to use HeBS resin (the acrylic component in the composition has high water vapor permeability), HeS resin, etc.

However, this type of synthetic resin has water vapor permeability due to its physical properties, and when the lead acid is stored at 1°C for a long period of time, it passes through the wall of the battery case and releases the moisture inside as water vapor, causing the battery to A phenomenon occurs in which the internal electrolyte 1alf rises. This phenomenon is more severe in batteries with a larger surface area per capacity, or in batteries where the thickness of the battery cannot be increased due to miniaturization.In particular, in small and thin batteries, the battery life may be shorter than normal due to concentration of 1L solution. It has the disadvantage that it is shorter than the lead-acid Kameike.

(/4 Purpose of the Invention The present invention has been made in view of the problems of the prior art as described above. When a lead-acid battery is left with both poles open, a large amount of electrolyte is deposited on the negative and anode plates and the surface. It holds the battery and improves the conductivity when using it alone.

The purpose is to completely prevent electrolyte leakage from the battery container.

4) The negative and anode plates and separators of the invention are impregnated with a limited amount of electrolyte so that no free electrolyte exists, and the above-mentioned 1'2
・At least one of the anode plates is made of lead or lead alloy 1
In a plate-like back-heavy body (nunullary-like active material?) formed by closely contacting M11.

A conductive powder having lfk retention properties is completely dispersed in the active material, and this mixture is poured into a tank equipped with the current collector on the inside, and the mixture is subjected to ultrasonic vibration. - Separate into two layers, t71ψ, 1 and conductor '11i property/1711→, and form a R's layer on the separator side surface of the electrode plate. 10j: L This is what makes 7th graders go to 1st grade.

(・Ya・) -Ryoni Rikikame Example (IF3) (ib) is a lead-acid battery exterior box according to an embodiment of the present invention, which is a two-piece tooth-shaped case molded with -C resin. be. +21.131 is a βj anode mounting body disposed at the opposite inner corner of the exterior boxes (1a) and (1b). (・da) (4b)
are the negative and positive electrode plates interposed in the 1- of 2L + 31, and the 1st and positive electrode plates (4a) (
In step 4b), a porous separator (5) is pressed and clamped onto the plate with an appropriate pressure. And hijki Yin/Yangga'1
Suitable for ffi plates (4a), (4b) and separators (5)11! :C2 electrolyte (C not stated) is impregnated and held in such a manner that substantially no free electrolyte is present in the outer case (1a) (1b).

The carved body is cast from lead-calcium alloy 11j.

By punching or expanded band processing [50X50
x 2ffl〃and 50 x 50 x 111m0
．． The C-qiJ member cut to outside dimensions is used as a positive electrode current collector, later named as a negative electrode current collector.

Next, a method of forming the iiJ negative/positive electrode plate will be explained. -Lead oxide (PbO powder)
100:2! o) Add H and knead to prepare an active material base. Conductive raw powder is added to the active material base made of this C [Carbon Bravuk, graphite].

8) Add at least water so that water:conductive powder-20=2 and disperse C to prepare a slurry of active material paste.

When added, sedimentation due to the difference in ratio between the active material and the conductive powder occurs.
4. From the speed difference C2, the slurry is divided between the active control layer and the conductive powder.
, /1 and further dried.
Obtain an anode plate (4b) that holds the solution for 9 minutes.

The thickness dimension of this Yang et al. (Jy (4b) is 2.1111
It is about W.

On the other hand, the IXj other plate (4a) is made of active material paste '11' using resinate as a base, and is applied to the plate and dried.
Placed.

As above (2 U IIA-Anode Bipolar 4ji (11a
) (a b) 4 separators (5) are placed between a and the ratio M
Inject 1.30 sulfuric acid electrolyte. And the exterior surface μma
) (1b) is tightly sealed and subjected to chemical charging treatment to make it usable.

According to this manufacturing method, deviations in thickness and thickness of the active material are reduced. Figure 2 shows the dispersion state of the active material amount and thickness dimension (indicated by 0 in the figure) of the electrode plate according to the present invention and the active material amount and thickness dimension (indicated by X in the figure) of the electrode plate according to the conventional method. This is a comparison.

According to this figure, it is clear that in the electrode plate of the present invention, the prolide is relatively densely prolided and the spread is small, so that the variations in the active material layer and thickness dimensions are small.

This is a conventional living material Il! By measuring the thickness of the i′ layer, the electrode plates were manufactured under the assumption that the packing density was always uniform. According to the present invention, this difference can be compensated for.

In particular, it is easier to control the active material layer of the electrode plate.

In addition, a battery of the present invention (M) and a comparative battery FBI using an active material without conductive powder were prepared, and the change in discharge efficiency with respect to the standing period when left in a discharged state was determined. Results 4 are shown in Fig. 6. It is clear that the battery 1Al of the present invention is extremely superior to the conventional battery iBl.

't/Jl manufactured by the method of the present invention has a higher concentration of active material αI14 on the current collector in a wet state than a battery manufactured by the conventional method in which the number of poles is separately manufactured and placed on the current collector. Because the current collectors are placed and then dried, the close contact between the current collectors and the living stalks is extremely good.

To apply chemical metallization in this state, C2, oxidation 1? , the contributing current (P at the contact point between the second current collector and 1 m of active material
b0z generation is promoted and the current collector and the active material layer are more strongly integrated 11, and a uniform dense state is formed over the entire surface of the collector and the active material vj1.

On the other hand, in the conventional method, since the contact surface between the current collector and the active material layer is in local contact, PB caused by chemical formation such as -L transport
oz is generated only at the contact portion, and the concentricity between the current collector and the active material layer is still localized, and therefore there is a problem in that the battery characteristics tend to vary, especially when left unused at a high rate. In other words, when conventional batteries are left in a discharged state, sulfuric acid traces (8042
) Grape of the electrolyte occurs at a slow rate due to the boundary blood between the turtle body and the active material layer.
will be generated. and long-term Q) left unattended 62 P
The inactivation of b3O4 progresses and the effect of constant voltage charging t% after being left for a long period of time decreases.

-The current invention's arrangement/l port is as described above (σ) and the current collector and active material)
The dense layer nature of the armor interface is extremely good, and since it is further integrated into the whole during formation, the PbSO4 formation due to liquid creep is also caused by the current collector and the plagiarism * + m field during storage.
A stable state can be maintained, which is not the case with l.

Therefore, the charging characteristics after being left for a long period of time are also good and stable.

(f) Effects of the Invention As explained above, the present invention is made of oak with a carbon limit so that no free electrolyte exists in the negative and anode plates and the separator.
A slurry-like active material is closely fixed to a flat current collector made of lead or lead alloy, which is impregnated with an electrolytic solution and which is at least one of the negative and anode electrodes 41i. A conductive powder having a liquid-retaining property was dispersed in the mixture, and the mixture was poured into a battery case C2 equipped with the TEPCO body on the inner surface.

The mixture described in 11iI is separated into an active material layer and a conductive liquid retaining layer by ultrasonic vibration, and a liquid retaining layer is formed on the separator side surface 12 of the electrode plate, and is easy to manufacture. The active material m can be precisely controlled, the manufacturing process is extremely simplified, and at the same time it is effective in suppressing changes over time while left in a discharge state, and the electrolyte is retained on the separator side surface of the electrode plate. Therefore, it suppresses the deterioration of current conductivity after being left for a long period of time and contributes to improving the discharge efficiency, so it has extremely great industrial value.

[Brief explanation of the drawing]

FIG. 1 is an exploded perspective view of a lead Wz'+ cell according to the present invention, FIG. 2 is a correlation diagram between the active material l of the electrode plate and its thickness, and FIG. 3 is a diagram showing the characteristics of discharge efficiency over time. (4a)...Cathode plate-(4b)...Anode plate, (5)
... Separator f21 (31... Current collector - (1
a) (1 stop b)...Exterior surface (battery case). Figure 1 Figure 3 Abandoned self-reflection (bow)

Claims (1)

[Scope of Claims] A flat aggregate made of lead or a lead alloy (formed by closely fixing a Nissura-like active material) The mixture was injected into a battery container equipped with the TEPCO body C2 on the inner surface, and the 1411 mixture was separated into two layers, an active material layer and a conductive liquid-retaining layer, by ultrasonic vibration 62, and the liquid-retaining layer was separated. A method for producing a lead-acid battery, characterized in that it is formed on the surface of the separator + lil + of the fi plate. Features a patented lead-acid 'Kameike' manufacturing method.