JPS58117658A - Sealed lead-acid battery - Google Patents

Abstract

PURPOSE:To provide a sealed lead-acid battery having no fluid liquid by holding an electrolyte in an electrode plate and a separatory made of glass fiber. CONSTITUTION:A sealed lead-acid battery is formed with glass fiber having a fiber diameter of 10mum or less, and a positive grid of lead alloy such as Pb-Ca alloy not containing antimony, and sp.gr. 1.30-1.40 dilute sulfuric acid electrolyte having amount equivalent to 10cc or less per 1Ah capacity. Therefore, charge current receiving performance in charge after excess discharge is improved. Moreover, some acid or salt which does not detriorate performance of the lead-acid battery is added in an electrolyte to give buffer action of hydrogen ion to the electrolyte at excess discharge.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a sealed lead-acid battery without a flowing liquid, in which an electrolytic solution is retained in a separator and electrode plates mainly made of glass fiber.

Conventionally, sealed lead-acid batteries have been required to be smaller and lighter and can be used in any direction as electric drifters for portable pulls.
The amount of electrolyte is significantly reduced compared to ordinary lead-acid batteries, and there is almost no sulfuric acid that can freely flow. Therefore, in order to ensure the absolute amount of sulfuric acid, 180-
A relatively high concentration of sulfuric acid with a specific gravity of 140 has to be used. On the other hand, in order to optimize the reaction efficiency of the anode and anode active material, the balance between the amount of active material involved in the reaction and the absolute amount of sulfuric acid in the electrolyte should be adjusted so that the absolute amount of sulfuric acid is slightly larger. It is desirable to do so. When such a sealed lead-acid battery is stored in an over-discharged state for a long period of time, a chemical reaction occurs between the excess sulfuric acid amount and the active L+lJ near the lattice, resulting in highly conductive sulfuric acid. Lead is generated, and the sulfate ions in the electrolytic Kk are consumed thereby, and the electrolyte becomes medium r1. Due to the deterioration of the conductivity, the charging current acceptance performance deteriorates significantly after being stored for a long period of time.

This defense is based on the above-mentioned sealed vessel Vk battery Iζ,
am, using glass & miscellaneous with a diameter of 10μ or less, and 1 on the positive electrode grid.
．． 1 Uses a Pb alloy that does not contain antimony such as a Pb-Ca alloy, and uses Japanese sulfur @ electrolyte with a specific gravity of 180 to 140 in an amount equivalent to 10 cc or less per capacity IAh, and has a comfortable structure. Therefore, it is possible to improve the charging flow acceptance performance during recovery charging after being left to over discharge.

Furthermore, in the present invention, an acid and a salt that do not deteriorate the performance of the lead battery are added to the electrolytic solution to give fineness to the hydrogen ion concentration of the electrolytic solution during overdischarge. In addition, 0.08 to 020 g per cell, 7'Ah of boric acid,
and sodium tetraborate in mm in the electrolyte. Furthermore, Pb-Ca alloy or Pb
-Ca-Sn alloy is used, and in the case of i'b-Ca-Sn alloy, Ca-containing phosphor is 0.05 to 0.12w1:s, Sn
The content is 0.8-1. Owt is in full swing.

A practical history of the present invention is shown below. Two #IJ electrode plates filled with a paste made of lead oxide and dilute sulfuric acid in a lattice made of Pb-Ca-Sn alloy, and eight cathode plates filled with a paste made of lead oxide, dilute sulfuric acid, barium sulfate, etc. , combined using a mat-like separator mainly composed of glass fibers with a fiber diameter of 1Oμ or less, and injecting an electrolytic solution containing 10 g of boric acid, 10 g of sodium tetraborate, and 10 g of sodium sulfate per 1 g of dilute sulfuric acid, IO time rate volume ji with electrolyte specific gravity after charging set to 1.82 8. Here are the experimental results for OAh batteries.

Furthermore, if the NJAls mat-like separator made of glass fiber used as a separator has a diameter of 10 g or more, the holding power of the electrolyte will be poor, so the electrolyte will be unevenly distributed at the bottom of the electrode plate, which will deteriorate the electrical conductivity of the upper part of the electrode plate. After over-discharging, the charging performance becomes worse. Also, Pb-C
In a-Sn alloys, if Ca-containing violet is less than 0.06%, the mechanical strength is insufficient (on the 112 line, corrosion resistance is poor. On the other hand, if Sn-containing violet is less than O, S%, corrosion resistance is improved. It is less effective, and if it lasts for more than one year, it lacks mechanical strength and increases costs.

Figure 1 J! 10Q7'12V (II) constant resistance 24#
After discharging for one hour, the resistor was removed and the battery was left at room temperature for one month. This shows the change in pH of the electrolytic solution, and FIG. 2 shows the current acceptance during recovery charging after being left unused. In both figures, the figure below indicates the product of the present invention, and the line (to) indicates the conventional product. The example used for comparison was a conventional example in which 16 g of sodium sulfate per 1 g of sulfuric acid was added as an electrolyte to a battery similar to the example of the present invention, and the specific gravity of the electrolyte after charging was set to 1682.

In Figure 1, in the battery injected with the electrolyte of the present invention, the pH value of the electrolyte remains in the acidic range even after being left for one month after overdischarging, whereas in the conventional example, the pH value of the electrolyte changes to the neutral range. Compared to , it can be seen that the current is very easy to flow. 92
After discharging for 24#P with the constant resistance of 109/12V shown in the figure, leave it at room temperature for one month, and then turn the voltage to 14.7V, 700V.
This result is clearly seen in the change in charging current when recovery charging is performed at mA.

As described above, the present invention makes it possible to improve the charge acceptance performance of conventional lead-acid batteries, which was said to be poor after being left over-discharged, by adding an additive to the electrolyte, and is extremely effective from an engineering perspective. .

In addition, boric acid, sodium tetraneate,
Sodium sulfate has no effect if it is less than 6 g per electrolyte II, and becomes difficult to dissolve if it is more than 40 g.

[Brief explanation of the drawings] Figure 1 shows the relationship between the number of days of storage and the pH of the electrolyte, and Figure 2 shows the relationship between the number of days of storage and the pH of the electrolyte. It is a diagram showing the change over time of the electric current building conducted. Prisoner: Invention product, (B): Conventional product Agent Yoshihiro Morimoto

Claims (1)

[Scope of Claims] 1. A sealed lead-acid battery without a flowing liquid, in which the electrolyte is held in a separator and an electrode plate mainly made of glass fiber, and the separator contains glass fiber with a fine diameter of 10 tones or less. , the positive electrode grid is made of a lead alloy that does not contain antimony, such as a P b -Ca alloy, and an electrolytic solution with a specific gravity of 1.80 to 1.40 is used in an amount of 10 cc or less per capacity IAh. lead-acid battery. 2. 0.08~G per cell! 6g/Ah of boric acid,
and sodium tetraborate dissolved in the electrolyte. The sealed lead acid battery according to claim 1111. 8. The sealed lead-acid battery according to claim 1, characterized in that a Pb-Ca-Sn alloy is used as the lattice. 4. Ca content of Pb-Ca-Sn alloy is 0.0
5~0.1.2wt*, Sn-containing mackerel 0.8~1.0w
The sealed lead-acid battery according to claim 8, characterized in that the battery is T5&i.