JP2003068308A - Lead battery and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lead battery in which the property of the battery in use is improved when left overcharged without sacrificing the charging and discharging property of the battery. SOLUTION: Globular or massive particles containing 2% by mass or more of Sn is retained fast on the surface of the lattice body.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a lead storage battery and a method for manufacturing the same.

[0002]

2. Description of the Related Art Lead-acid batteries generally contain lead powder obtained by oxidizing a part of lead, water and sulfuric acid as main components, and monofilaments such as resin, carbon fine powder, and organic additives as necessary. Add
A paste is made by kneading, and this paste is applied to a continuous porous body such as a cast lattice or an expanded lattice, and an active material paper-like body is abutted as necessary to form the electrode plate shape,
A paste type electrode plate that is aged and dried to form an electrode plate is often used. This electrode plate is mainly composed of a separator made of a glass mat or a separator / electrolyte holder to form an electrode plate group, which is incorporated in a battery case and then dilute sulfuric acid is added for chemical charge or chemical conversion. The function of the lead storage battery is given by being incorporated in the battery case after charging.

[0003]

In recent years, lead-acid batteries for starting engines for automobiles have been different in use method and design concept of vehicles, and it has become difficult to cope with lead-acid batteries adapted for conventional vehicles. Due to the wide variety of vehicle users,
Even if the test method that has been supposed to be used up to now is cleared, problems will occur in actual use. Specifically, conventional lead-acid batteries for vehicles have been considered for strong use in deep charge / discharge tests, which are resistant to overcharge. In recent years, due to maintenance-free vehicles and cost reduction,
There has been an increase in the usage of lead-acid batteries that are used after being left for a long time when they have become insufficiently charged. It has been clarified that in such a method of use, the properties of the lattice / active material interface change during standing and the engine starting performance deteriorates. That is, it was found that a charging / discharging cycle including incomplete charging was performed during vehicle running, and this resulted in a large decrease in characteristics during standing.

An object of the present invention is to provide a lead-acid battery and a method of manufacturing the same which can improve the over-discharge leaving characteristic during use of the battery without sacrificing the charge / discharge characteristics of the battery.

[0005]

In the lead-acid battery according to the present invention, spherical or lump-shaped particles containing Sn in an amount of 2 mass% or more are invaded on the surface of the grid.

In a lead storage battery using such a grid,
Adhesion at the lattice / active material interface is improved, and a lead-acid battery with excellent overdischarge leaving characteristics can be obtained. Further, when particles are digged into the surface of the lattice, a work-hardened layer is formed on the surface of the lattice, and the mechanical strength of the lattice can be improved.

In this case, the particles preferably contain 2% by mass or more of Sb. By doing so, it is possible to obtain a lead storage battery having better discharge leaving characteristics and further improve the mechanical strength of the lattice.

Further, it is preferable that the lattice is made of an expanded lattice. According to the present invention, the expanded lattice body is resistant to overcharge but is inferior in overdischarge leaving property according to the present invention.

Further, the lattice body contains 0.3 to 1% by mass of Sb.
It is preferable that it is prepared by a continuous casting method including the above.
When the lattice body is formed by the continuous casting method as described above, the lattice body can be formed without causing solidification cracking even if Sb is small. In addition, 2 mass% of Sn on the surface of this lattice
Since the spherical or lumpy particles including the above will bite,
The overdischarge leaving characteristic can be improved.

Next, in the method for manufacturing a lead storage battery of the present invention,
Spherical or lumpy particles containing Sn in an amount of 2% by mass or more are sprayed onto the surface of the lattice to invade them.

When the spherical or lumpy particles containing Sn in an amount of 2% by mass or more are sprayed by sandblasting or the like, the particles can easily penetrate into the surface of the lattice.

Further, it is preferable that the particles contain 2% by mass or more of Sb. By doing so, it is possible to obtain a lead storage battery having better discharge leaving characteristics and further improve the mechanical strength of the lattice.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, each example of the embodiments will be shown in order to describe the present invention more specifically, but the present invention is not limited thereto.

(Embodiment 1) Pb-0.09 mass% C
a-1.0% by mass Sn cast lattice (w108 x
h115 × t1.5 mm) with 70 g of paste,
A positive electrode plate was obtained. PbSn powder manufactured by Nippon Atomize was separated by sieving into the same lattice, and the average particle size was 50
Particles of Pb-Sn alloy adjusted to have a size of μm are prepared, and the particles are sprayed with compressed air from a nozzle of 20 mmφ at a pressure of 20 Mpa for 30 seconds to dig into the surface of the grid body, and 70 g of the paste is filled in the grid body. Then, a positive electrode plate was obtained. The 12V25Ah battery shown in Table 1 was prepared by combining these four positive electrode plates and four negative electrode plates to form an electrode plate group.

In Table 1, Pb-0.09 mass% Ca
-Cast lattice made of 1.0 mass% Sn (w108 x h
The conventional lead-acid battery is a lead-acid battery using a grid body that does not spray particles onto a 115 × t1.5 mm). In addition, a lead storage battery using a grid body in which particles with an Sn content of 0 mass% were sprayed and bitten was used as Comparative Example 1 battery, and a grid body in which particles with an Sn content of 0.5 mass% was sprayed and bited. The lead-acid battery using Comparative Example 2 battery, the lead-acid battery using the grid body sprayed with particles having an Sn content of 1% by mass was used as Comparative Example 3 battery, and the Sn content of the particles is 2% by mass. The lead-acid battery using the grid body sprayed and bittened is the present invention product 1 battery, and the lead-acid battery using the grid body sprayed with the particles having the Sn content of 5 mass% and bited is the product 2 battery of the present invention. A lead-acid battery using a grid body in which particles having a Sn content of 10% by mass are sprayed and bite into the lead-acid battery of the present invention 3
It has a battery.

[0016]

[Table 1] According to this Table 1, it can be seen that the batteries of the present invention 1 to 3 have improved 5HR recovery capacity after overdischarge as compared with the conventional battery and the batteries of Comparative Examples 1 to 3.

(Embodiment 2) Pb-0.09 mass% C
a-1.0% by mass Sn cast lattice (w108 x
h115 × t1.5mm) Pb- (0-10% by mass)
A sphere of Sb having a diameter of 30 mm was prepared with a graphite mold, and the sphere was crushed with a cylindrical ball mill having an internal volume of 10 liters to prepare particles of Pb-2 mass% Sn-Sb alloy, and these particles were sieved. The particles were prepared by adjusting so that the average particle diameter was 50 μm. 20 of these particles
From the nozzle of mmφ, the lattice body was blown with compressed air adjusted to 20 Mpa for 30 seconds to dig into the surface of the lattice body, and 70 g of the paste was filled in the lattice body to obtain a positive electrode plate. A battery of 12V25Ah shown in Table 2 was prepared by combining these four positive electrode plates and four negative electrode plates with and without an electrode plate group.

In Table 2, Pb-0.09 mass% Ca
-Cast lattice made of 1.0 mass% Sn (w108 x h
115 × t1.5 mm), a lead storage battery using a grid body in which particles having an Sb content of 0 mass% was sprayed and bittened was used as Comparative Example 4 battery, and particles having an Sb content of 0.5 mass% were sprayed. A lead storage battery using a grid body that has been bitten into is a comparative example 5 battery, and a lead storage battery using a grid body that has been sprayed with particles having an Sb content of 1% by mass is a comparative example 6 battery, and the Sb content is Is a lead-acid battery using a grid body in which 2% by mass of particles are sprayed and bitten into the product 4 of the present invention,
A lead storage battery using a grid body in which particles having an Sb content of 5% by mass were sprayed and engulfed was defined as a battery 5 of the present invention, and a grid body in which particles having an Sb content of 10% by mass was sprayed and engulfed was used. The lead storage battery is the present invention product 6 battery.

[0019]

[Table 2] According to this Table 2, the batteries 4 to 6 of the present invention are comparative examples 4 to 6.
It can be seen that the 5HR recovery capacity after overdischarging is improved as compared with the 6 batteries.

(Embodiment 3) Pb-0.09 mass% C
a-1.0 mass% Sn cast latticed body or expanded latticed body of the same weight (w108 × h115 × t1.
5 mm) Pb-2 mass% -Sn- (0-10 mass%)
A spherical body of Sb having a diameter of 30 mm was prepared with a graphite mold, and this was crushed with a cylindrical ball mill having an internal volume of 10 liters to prepare particles of Pb-2 mass% Sn- (0-10 mass%) Sb alloy. The particles were prepared by sieving these particles so that the average particle size was 50 μm. The particles were blown onto the lattice body for 30 seconds together with compressed air adjusted to 20 Mpa from a nozzle of 20 mmφ so as to bite into the surface of the lattice body, and 70 g of paste was applied to the lattice body.
It filled and obtained the positive electrode plate. These four positive plates and negative plates 4
12V2 shown in Table 3 combined to form an electrode plate group
A 5 Ah battery was made.

In Table 3, Pb-0.09 mass% Ca
-Cast lattice made of 1.0 mass% Sn (w108 x h
115 × t1.5 mm), a lead storage battery using a grid body in which particles having an Sn content of 2 mass% and an Sb content of 0 mass% were sprayed and bittened into was a Comparative Example 7 battery, and the Sb content was A lead storage battery using a grid body in which 2% by mass and Sb content of 2% by mass were sprayed and bittened was defined as Comparative Example 8 battery, and Pb-0.09% by mass Ca-1.0% by mass.
A lead storage battery using a lattice body in which particles are not sprayed on an expanded lattice body made of Sn (hereinafter, referred to as Ex lattice body) was used as a battery of Comparative Example 9, and the Sn content was 2% by mass and S.
A lead storage battery using a grid body in which b content of 0 mass% was sprayed and bittened was referred to as the invention product 7 battery, and Sn content of 2 mass% and Sb content of 2 mass% was sprayed. The lead-acid battery using the grid body that has been bitten into is the product 8 battery of the present invention.

[0022]

[Table 3] According to this Table 3, the batteries 7 and 8 of the present invention are comparative examples 7 to 8.
It can be seen that the 5HR recovery capacity after overdischarging is improved as compared with the No. 9 battery.

(Embodiment 4) Pb-0.8 mass% Sb
-Pb-2 on a cast grid body of 1.0 mass% Sn or a cast grid body (w108 x h115 x t1.5 mm) of the same weight as a book mold type (hereinafter referred to as BM type).
A spherical body having a diameter of 30 mm and made of mass% Sn- (0 mass%, 2 mass%) Sb was made with a graphite mold, and this was used as an internal volume 1
Pb-2 mass% Sn- (0 mass%, 2 mass%) Sb alloy particles were prepared by crushing with a 0 liter cylindrical ball mill, and the particles were adjusted by sieving so that the average particle diameter was 50 μm. Particles of Pb-2 mass% Sn-Sb alloy were created. This was sprayed from a nozzle of 20 mmφ at a pressure of 20 Mpa to the lattice for 30 seconds to dig into the surface of the lattice, and the lattice was filled with 70 g of paste to obtain a positive electrode plate. The 12V25Ah battery shown in Table 4 was prepared by combining these four positive electrode plates and four negative electrode plates to form an electrode plate group.

In Table 4, Pb-0.8 mass% Sb-
BM type cast lattice body (w108) made of 1.0 mass% Sn
Xh115 × t1.5 mm), a lead storage battery using a grid body that does not spray particles was used as Comparative Example 10 battery, and particles having a Sn content of 2 mass% and an Sb content of 0 mass% were sprayed and made to bite. Comparative example 1 of a lead-acid battery using a grid
A lead storage battery using a grid body in which 1 battery is used and a particle having an Sb content of 2 mass% and an Sb content of 2 mass% is sprayed and eroded is used as a comparative example 12 battery, and Pb-0.09 mass% Ca -To a continuously cast lattice made of 1.0 mass% Sn,
Comparative example 1 of a lead-acid battery using a grid that does not spray particles
3 batteries, a lead storage battery using a grid body in which Sn content is 2% by mass and Sb content is 0% by mass and eroded and set as the battery 9 of the present invention, and Sn content is 2% by mass. In addition, the lead storage battery using the grid body in which the particles having the Sb content of 2 mass% are sprayed and bite into is the product 10 battery of the present invention.

[0025]

[Table 4] According to Table 4, the batteries 9 and 10 of the present invention are the same as Comparative Example 1
It can be seen that the 5HR recovery capacity after overdischarge is improved as compared with the 0 to 13 batteries.

[0026]

In the lead-acid battery according to the present invention, since spherical or lump-shaped particles containing Sn in an amount of 2% by mass or more are invaded on the surface of the lattice, the adhesion of the lattice / active material interface is improved, It is possible to obtain a lead-acid battery having good overdischarge leaving characteristics. Moreover, since the particles are dig into the surface of the lattice, a work-hardened layer is formed on the surface of the lattice, and the mechanical strength of the lattice can be improved.

When the particles contain Sb in an amount of 2% by mass or more, it is possible to obtain a lead storage battery having better discharge leaving characteristics and further improve the mechanical strength of the lattice.

Further, when the lattice body is made of the expanded lattice body in the present invention, the expanded lattice body is resistant to overcharge but is inferior in over-discharge leaving property, which can be improved by the present invention. it can.

Further, the lattice body contains 0.3 to 1% by mass of Sb.
If it is produced by the continuous casting method including Sb, it is possible to form a lattice without causing solidification cracking or the like even if Sb is small. In addition, spherical or massive S is formed on the surface of this lattice.
Particles containing 2% by mass or more of n bite into it, so that the over-discharge leaving property can be improved.

Next, in the method for manufacturing a lead storage battery of the present invention,
Since spherical or lumpy particles containing Sn in an amount of 2% by mass or more are sprayed onto the surface of the lattice to bite into them, the particles can be easily eroded into the surface of the lattice by sandblasting or the like.

If the particles contain 2% by mass or more of Sb,
It is possible to obtain a lead storage battery having better discharge leaving characteristics and further improve the mechanical strength of the lattice.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kazuya Sasaki             2-8-7 Nihonbashihonmachi, Chuo-ku, Tokyo             Inside Shin-Kobe Electric Machinery Co., Ltd. F term (reference) 5H017 AA01 BB00 BB08 CC05 DD05                       EE02 HH01

Claims (6)

[Claims] 1. A lead storage battery in which spherical or lump-shaped particles containing Sn in an amount of 2% by mass or more are digged into the surface of a lattice. 2. The lead acid battery according to claim 1, wherein the particles contain 2% by mass or more of Sb. 3. The lead storage battery according to claim 1, wherein the grid is made of an expanded grid. 4. The lattice body contains 0.3 to 1% by mass of Sb.
The lead storage battery according to any one of claims 1 to 3, wherein the lead storage battery is made by a continuous casting method. 5. A method of manufacturing a lead storage battery, wherein spherical or lumpy particles containing Sn in an amount of 2% by mass or more are sprayed onto the surface of a lattice to bite into the surface. 6. The method for manufacturing a lead storage battery according to claim 5, wherein the particles contain 2% by mass or more of Sb.