JPH0436957A - Lead-acid storage battery - Google Patents

Abstract

PURPOSE:To provide excellent recovery characteristic after overdischarging even though charging is made at a regular voltage by using a pos. electrode plate whose grid is made of Pb-St series alloy in low St content, and using a neg. electrode plate whose grid is made of Pb-Ca series alloy and to whose active substance Ba is added. CONSTITUTION:Each pos. electrode plate has a grid made from Pb-St series alloy of St content below 4 wt.%, while each neg. electrode plate has a grid made of Pb-Ca series alloy, wherein the Ba content relative to the active substance is restricted under 3 wt.%. such pos. and neg. electrode plates are combined to constitute an electrode plate group, and therewith a lead acid storage battery is constructed. Decrease of the St content causes pulling-up of the charge potential of the pos. electrode plates, which increases further the necessity for charge recovery after overdischarging, but decreasing Ba in the neg. electrode active material causes a large flow of the charging current. Thereby the charge receipt characteristic is improved, and priority is established about the duation time even in the low-temp. rapid discharge characteristic, and a battery is accomplsihed which is equipped with excellent regular voltage charge recovery from the condtion left overdischarged.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an additive for an electrode plate group and a negative electrode active material of a lead-acid battery.

Conventional technology for paste-type electrode plates can be roughly divided into two methods: one is to use a lead-antimony alloy as a lattice by casting, and the other is to create a sheet from a lead-calcium alloy and then machine it into an expanded shape. There are two ways to use it: one method is to use it as a punched board, and the other is to use it as a punched board. Lead alloys containing antimony have good castability and increased lattice strength in manufacturing, and have excellent charge recovery properties after long-term over-discharge, but they tend to cause more self-discharge and the electrolyte during battery use. The problem was that there was a large decrease in

On the other hand, lead-calcium alloy lattices reduce the loss of electrolyte during battery use and eliminate the need for water replenishment, so there is a recent tendency for maintenance-free batteries using this to increase.

However, if a lead-calcium alloy lattice is used for the positive electrode, abnormal overdischarge may occur, or if left as is for a long period of time, a high resistance nonconducting film may form at the interface between the positive electrode lattice and the active material. As a result, charging acceptance performance deteriorates, and charging may not be possible depending on practical use conditions.

Therefore, the positive electrode plate reduces the antimony content of the lattice to 4
The weight should be lower than that, and the test should be 3 bases in terms of castability and strength.

Although some issues remain, we have used a lead lattice with a lower content than before to reduce self-discharge and suppress the loss of electrolyte during battery use. - A hybrid method in which each electrode plate is created using a calcium-based alloy lattice to increase the hydrogen overvoltage to cause gas decomposition of the electrolyte during charging, and then combine them to form a group of electrode plates. Batteries have come to be used for different purposes.

Problems to be Solved by the Invention However, the active material itself has not been particularly improved, and as the amount of antimony decreases, the oxygen overvoltage of the positive electrode increases, resulting in an increase in charging voltage, and when used while being charged at a constant voltage, the battery The charging current that should be sufficient to charge the battery is reduced, and the positive electrode active material is not completely charged, which tends to cause problems particularly in charge recovery after overdischarge.

The present invention uses a positive electrode plate using a lead-antimony alloy with a low antimony content as a lattice body, a lead-calcium alloy lattice body, and adds barium salt such as barium or barium sulfate to the active material. An object of the present invention is to provide a lead-acid battery that has excellent recovery properties from an overdischarge state even when charged at a constant voltage by using an electrode plate group consisting of a negative electrode plate and a negative electrode plate.

Means for Solving the Problems The present invention provides a positive electrode plate using a lead-antimony based alloy as a lattice body in which the antimony content is 4@weight or less, and a positive electrode plate in which the amount of barium relative to the active material is limited to 3 weight range or less. This is a lead-acid battery that uses an electrode plate group in combination with a negative electrode plate that uses a lead-calcium alloy lattice. Furthermore, this lead-acid battery is characterized in that barium sulfate is used as barium added to the negative electrode active material.

By configuring the battery in this way, it is possible to improve the flow of current during charging after over-discharging, that is, the charge acceptance, and to provide a lead-acid battery with excellent recovery properties.

Example 5, ／＼－－／ The present invention will be explained in detail below.

The negative electrode plate contains 0.0% calcium as a lead-calcium alloy.
08 Weight Section (hereinafter simply referred to as Section), a slab containing 0.6 c$ of tin and the remainder lead was cold rolled with a roll to a thickness of 0.8
A thin plate with a thickness of mm is prepared and expanded into a net shape to form a lattice body.

On the other hand, the amount of barium present in the active material is 06.

Barium sulfate with a particle size of 1μ or less is added to lead oxide together with lignin-based organic matter to give a concentration of 1%, 3%, and 5%, and the paste obtained by mixing with dilute sulfuric acid is filled into the grid body. . At this time, a sheet mainly made of pulp was pasted on one or both sides, and then aged and dried to create an unformed negative electrode plate.

The positive electrode plate is made of antimony 4 as a lead-antimony alloy.
A lattice body containing 0.2% arsenic and the balance lead was created by casting, and using this, it was created by a known method.

These electrode plates and separators were combined to create an electrode plate group in which the amount of positive electrode active material per cell was 50 C1 and the amount of negative electrode active material was 40 oy. Comparative tests were conducted using automobile batteries.

As a method for examining the charge recovery properties of these batteries after overdischarge, a 12V 10W light bulb was connected and the batteries were discharged at 40° C. for 20 days, and then left open for 16 days. As a result, the specific gravity of the electrolyte decreased to 101, resulting in an overdischarge state.

. These batteries at 15℃, maximum current 25, constant voltage 15
A low-temperature rapid discharge of 30 OA was performed in an atmosphere of -16° C. using the charging current at the 15th minute when charging at V and the state after 4 hours of charging. The results are shown in Figure 1 and the following table. The results show that when the barium content was 3 or less, a larger charging current flowed than when the barium content was 5, and the charge acceptance characteristics were good. At the same time, the temperature is -15℃ as shown in the table.

300 people's low-temperature rapid discharge characteristics also showed superiority in duration, and a battery with excellent constant-voltage charge recovery from over-discharging could be obtained.

In this way, in the present invention, reducing the amount of antimony increases the charging potential of the positive electrode plate, further increasing the need for charge recovery after overdischarge, but reducing barium in the negative electrode active material increases charge acceptance. The characteristics are positively influenced for the reasons mentioned above, and battery performance can be maintained.

Furthermore, for the 9-pole lattice, a calcium-based lead alloy sheet was expanded and used, but even if a punched plate was used, no difference in properties was observed.) Effects of the Invention This Invention is an electrode plate consisting of a positive electrode plate using a lead-antimony alloy with a low antimony content as a lattice body, and a negative electrode plate using a lead-calcium alloy lattice body and containing barium sulfate in the active material. By using a group, it is possible to provide a lead-acid battery that has excellent recovery properties from the state after overdischarge even when charged at a constant voltage.

[Brief explanation of drawings]

Figure 1 shows a test battery with a constant voltage of 1 at a maximum current of 26 A at 15°C.
It is a figure which shows the transition of the charging current at the 15th minute when charging at 5V.

Claims (2)

[Claims] (1) A positive electrode plate having a lead-antimony alloy lattice with an antimony content of 4% by weight or less, and barium added so that the amount of barium in the active material is 3% by weight or less,
and a negative electrode plate using a lead-calcium alloy lattice. (2) The lead-acid battery according to claim 1, wherein the barium added to the active material of the negative electrode is barium sulfate.