JP2002319409A - Lead acid storage battery anode current collector and lead acid storage battery using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lead acid storage battery anode current collector that is capable of maintaining a high-rate capacity for a long period and a lead acid storage battery using the same. SOLUTION: This is a current collector for a lead acid storage battery anode that has a surface layer of a non-Sb system lead alloy made of a different composition from the base metal on at least a part of the surface of the non-Sb system lead alloy base metal. The surface layer contains one or more of a metal selected from alkaline metal or alkaline earth metal.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a negative electrode current collector for a lead storage battery and a lead storage battery using the same.

[0002]

2. Description of the Related Art A negative electrode of a lead storage battery is made of a so-called non-S, such as Pb-Ca alloy, Pb-Sn alloy, pure Pb, or the like.
A b-based lead alloy lattice has been used. Those using a non-Sb-based lead alloy lattice do not require water refilling and have excellent maintenance performance.

[0003]

The lead storage battery has a problem that the high-rate capacity at a low temperature is reduced as the charge / discharge cycle progresses. This is because the negative electrode active material shrinks and the surface area decreases as the charge / discharge cycle progresses.

[0004] In order to suppress such a problem, it has been proposed to add an inorganic additive such as a Ba compound to the negative electrode active material. However, since these inorganic additives are aggregated or released, There is a problem that the effect is small and lacks sustainability.

An object of the present invention is to provide a negative electrode current collector for a lead storage battery, which can suppress the shrinkage of the negative electrode active material and decrease in the surface area and maintain a high rate capacity for a long period of time, and a lead storage battery using the same. That is.

[0006]

According to a first aspect of the present invention, there is provided a current collector for a lead-acid battery, wherein at least a part of the surface of the non-Sb-based lead alloy substrate is provided with a substrate. Is a negative electrode current collector for a lead storage battery having a surface layer of a non-Sb-based alloy having a different composition, wherein the surface layer contains one or more metals selected from alkali metals and alkaline earth metals. .

According to a second aspect of the present invention, there is provided the negative electrode current collector for a lead storage battery according to the first aspect, wherein the surface layer contains 0.1 to 5.0 wt% Ba. .

According to a third aspect of the present invention, in the negative electrode current collector for a lead storage battery, in the first aspect, the surface layer contains 0.2 to 5.0 wt% Ca. .

According to a fourth aspect of the present invention, in the negative electrode current collector for a lead storage battery according to the first, second or third aspect, the thickness of the surface layer is 30% or less of the thickness of the substrate. It is characterized by the following.

According to a fifth aspect of the invention, there is provided a negative electrode current collector for a lead storage battery according to the first, second, third or fourth aspect, wherein the base material and the surface layer are integrated by rolling. There is a feature.

According to a sixth aspect of the present invention, there is provided a negative electrode current collector for a lead-acid battery according to the first, second, third, fourth or fifth aspect, wherein the current collector is expanded or stamped. Alternatively, it is characterized in that it has a sheet shape. According to the lead storage battery of the invention described in claim 7,
A negative electrode current collector according to 2, 3, 4, 5, or 6 is used.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to a non-Sb-based lead alloy having a negative electrode current collector having a non-Sb-based lead alloy having a composition different from that of the substrate.
A negative electrode current collector for a lead storage battery having a surface layer of a b-based alloy, wherein the surface layer contains at least one kind of an alkali metal or an alkaline earth metal.

In the case of a negative electrode current collector formed only of a non-Sb lead alloy containing an alkali metal or an alkaline earth metal,
Due to the nature of the alloy, disadvantages such as brittleness and corrosiveness are increased, and the life performance is adversely affected. The strength and corrosion resistance of the body are ensured, and the provision of a non-Sb alloy surface layer containing at least one alkali metal or alkaline earth metal suppresses the contraction of the negative electrode active material and the decrease in specific surface area for a long time. be able to.

The content of the alkali metal or alkaline earth metal is preferably, for example, in the range of 0.1 to 5.0 wt% for Ba and 0.2 to 5.0 wt% for Ca.

Similar effects can be obtained when two or more kinds of alkali metals or alkaline earth metals are combined.

As a method for providing a lead alloy layer having a composition different from that of the base material on the surface of the current collector, several known techniques such as pressure bonding, thermal spraying, immersion in a molten lead alloy, and electroplating can be applied. Further, a method in which a surface layer member is integrated on both surfaces or one surface of a substrate by rolling and rolling is also simple.

The material of the substrate is not particularly limited, but may be pure lead, a Pb-Ca alloy containing Ca, a Pb-Sn alloy containing Sn, or the like. Al, A
Lead alloys containing elements conventionally used to improve the properties of lead alloys, such as g, Se, Bi, etc., are also preferred.

Further, in addition to alkali metals or alkaline earth metals, Sn, Al, Ag, Se,
Elements such as Bi, which are conventionally added and used, may be added to improve the properties of the lead alloy.

If the thickness of the alloy surface layer is too large, problems such as a decrease in productivity and workability of the current collector may occur. Therefore, the thickness of the current collector base material is preferably 30% or less, more preferably 30% or less. It is desirable that the thickness be 10% or less.

The form of the current collector is not particularly limited, but is preferably an expanded lattice, a punched lattice, or a sheet from the viewpoint of productivity and workability.

[0021]

Embodiments of the present invention will be described below. (Example 1) A case where the present invention is applied to an expanded lattice will be described as an example of a current collector in which the above surface layer is provided on a lead alloy base material.

First, a base material of 10 mm thick Pb-
A Pb-Li alloy sheet having a thickness of 0.3 mm is superimposed on the surface (one side) of a continuous cast plate of 0.1 wt% Ca-0.5 wt% Sn alloy.
b-K, Pb-Mg, Pb-Ca, Pb-Sr, Pb-
A stack of Ba alloy sheets is prepared, and these are rolled by a rolling roller to a thickness of 1.0 m integrated.
m was prepared. As a result, a rolled sheet having a Pb-alkali metal or alkaline earth metal alloy surface layer having a thickness of 30 μm on one surface of the substrate was produced. This rolled sheet is shown in FIG. The amount of each element added to the lead alloy in the surface layer was 0.5 wt%.

Next, the produced rolled sheet was developed into a mesh by using a reciprocating expander to form a grid. In these lattices, lead powder and dilute sulfuric acid, ligninsulfonic acid, B
A paste prepared by kneading aSO ₄ and carbon was filled, aged, and dried to prepare a negative electrode plate.

A roll of five sheets of the negative electrode and a rolled sheet of Pb-0.07 wt% Ca-1.3 wt% Sn alloy having a thickness of 1.0 mm were expanded into a mesh using a reciprocating expander to form a lead powder. And a paste prepared by kneading the mixture with dilute sulfuric acid, filled, aged and dried, and six positive electrode plates were alternately laminated via a separator to form an electrode plate group.
These electrode groups were inserted into a battery case, and a predetermined amount of diluted sulfuric acid was injected to form a battery, thereby producing a 2V30Ah open-type lead-acid battery.
This battery is designed so that the amount of the positive electrode active material is much larger than that of the negative electrode active material, and the capacity is limited by the negative electrode plate.

These lead storage batteries were first subjected to a capacity test at -15 ° C. with a discharge current of 90 A (3 CA) to confirm the initial capacity. Then, at 40 ° C., discharge =
[10A (１ ／ CA) discharge × 4 minutes], charge = [10
A for 1000 cycles of a constant current charge (final voltage charge of 2.45 V) +2.45 V constant voltage charge × 10 minutes], and a discharge current of 90 A (3 C
The capacity test in A) was performed, and the change in capacity from before the cycle test was examined. For comparison, a grating having no surface layer on the substrate surface was similarly prepared and subjected to a test.

FIG. 2 shows a list of batteries subjected to the test and the test results. The capacity after the cycle test is 10
It is shown as a percentage with respect to 0%. Compared with the conventional battery (A) prepared using a grid made of a rolled sheet having no surface layer on the base material, a grid made of a sheet having a surface layer containing an alkali metal or an alkaline earth metal on the surface according to the present invention is provided. It was found that the batteries (B to H) produced using the above had a larger remaining capacity after cycling and a greater capacity retention effect. Further, when the surface area of the negative electrode active material after the cycle was measured, the negative electrode active material having a surface layer was suppressed from decreasing in surface area.

Although the reason for this is not clearly understood, the alkali metal and alkaline earth metal added to the surface layer gradually elute during use of the battery, and precipitate as very fine crystals, or the negative electrode has good dispersibility. It is considered that the effect is maintained because it is taken into the active material.

In this embodiment, the case where one kind of alkali metal or alkaline earth metal is added is shown, but the same effect can be obtained when two or more kinds of these are combined.

(Example 2) An open-type lead-acid battery of 2V-30Ah was manufactured using an expanded grid manufactured in the same manner as in Example 1 except that the content of barium and calcium in the surface layer was changed. Under the same conditions as in Example 1, a capacity test and a cycle life test were performed. The relationship between the amount of barium and calcium added and the capacity after 1000 cycles is shown in FIGS.

As can be seen from the results, the Pb-Ba alloy has a content of 0.1 to 5.0 wt%, and the Pb-Ca alloy has a content of 0.1 to 5.0 wt%.
It was found that the effect of maintaining the high rate capacity was large at 2 to 5.0 wt% or more.

[0031]

As described above, the negative electrode current collector for a lead storage battery according to the present invention has a non-Sb-based lead alloy different from the base material on at least a part of the surface of the non-Sb-based lead alloy base material. A negative electrode current collector for a lead storage battery having a surface layer, wherein the surface layer is selected from an alkali metal and an alkaline earth metal.
It is characterized by containing the above metals. Further, the surface layer contains 0.1 to 5.0 wt% of Ba, or the surface layer contains 0.2 to 5.0 wt% of Ca. The thickness of the surface layer is 30% or less of the thickness of the base material, the base material and the surface layer are integrated by rolling, and the negative electrode current collector is expanded or stamped. And the like. Furthermore, it is a lead storage battery using these negative electrode current collectors.

From the above, it is possible to provide a negative electrode current collector and a lead storage battery which can suppress the contraction and the decrease in the surface area of the negative electrode active material and maintain the high rate capacity for a long period of time.

[Brief description of the drawings]

FIG. 1 is a perspective view showing an example of a rolled sheet for producing a current collector according to the present invention.

FIG. 2 is a diagram showing test results.

FIG. 3 is a diagram showing the relationship between the Ba content of the surface layer and the remaining capacity.

FIG. 4 is a diagram showing the relationship between the Ca content of the surface layer and the remaining capacity.

[Explanation of symbols]

 1 surface layer 2 substrate

Claims (7)

[Claims] 1. A negative electrode current collector for a lead storage battery having a non-Sb-based lead alloy surface layer having a composition different from that of the base material on at least a part of the surface of the non-Sb-based lead alloy base material. A negative electrode current collector for a lead-acid battery, wherein the layer contains one or more metals selected from alkali metals and alkaline earth metals. 2. The method according to claim 1, wherein said surface layer has a Ba content of 0.1 to 5.0 wt%.
The negative electrode current collector for a lead storage battery according to claim 1, comprising: 3. The method according to claim 1, wherein the surface layer has a Ca content of 0.2 to 5.0 wt%.
The negative electrode current collector for a lead storage battery according to claim 1, comprising: 4. The negative electrode current collector for a lead storage battery according to claim 1, wherein the thickness of the surface layer is 30% or less of the thickness of the base material. 5. The negative electrode current collector for a lead storage battery according to claim 1, wherein the base material and the surface layer are integrated by rolling. 6. The negative electrode current collector for a lead storage battery according to claim 1, wherein the negative electrode current collector is expanded or stamped. 7. A lead-acid battery using the negative electrode current collector according to claim 1, 2, 3, 4, 5, or 6.