JPS6095857A - Nonaqueous electrolyte battery - Google Patents

Abstract

PURPOSE:To enable the shape of a molded positive mixture to be maintained in a higher degree so as to improve the yield of a nonaqueous electrolyte battery by decreasing its internal resistance during initial discharge without causing any decrease of the discharge capacity by mixing a specified amount of graphite used as a conductive agent into lead bismuthate used as a positive active material. CONSTITUTION:A nonaqueous electrolyte battery is constituted using a negative electrode 20 containing an alkali metal as a negative active material and a positive electrode 16 containing lead bismuthate as a positive active material. The positive electrode 16 contains graphite as a conductive agent. The proportion of the weight of graphite to the total weight of the positive electrode 16 (graphite/Bi2Pb2O5 + graphite X 100) is adjusted to within the range or 0.05-2%. By the means mentioned above, it is possible to decrease the internal resistance of the battery during its initial discharge, and the shape retention of the molded positive mixture is improved. As a result, crakcs or fissures hardly develop in the molded positive mixture during the assembly of the battery, thereby improving the yield of the battery.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention □ relates to a 'Jl aqueous electrolyte battery, and more particularly to a non-aqueous electrolyte battery in which the positive electrode active material is lead bismuthate. □ For example, use an alkali metal such as lithium as an i-electrode active material v1 and 7-
In recent years, a high-energy cell battery using a non-aqueous electrolyte has attracted attention as a small-sized, high-energy melon battery.

As a type of this type of non-aqueous electrolytic M battery, bismuth acid "t"
:1 ('B i 2 pH 20 g) as a positive electrode active material is known. In this battery, metallic lead and metallic bismuth are produced in lead bismuthate, which is a positive electrode active material, by a positive electrode reaction accompanying discharge. The metal lead and metal bismuth are electrically conductive, and when they are generated in the positive electrode active material, the electrical conductivity between the active material particles increases. This is the cause of the flatness of the discharge voltage of this battery and the good utilization rate of lead bismuthate.

However, in the above battery, at the beginning of the discharge at 111 J, metal lead of M, which is equivalent to 1 minute to increase the conductivity of the electrode side to (Jl), is not generated. In the 11th period, there was a problem that 4 internal resistance was relatively high.

For this reason, a3 Lj is particularly high in the early stage of discharge. Pulse/+9
゛There is a dissatisfaction with the cap that the closing circuit 1i- during market time is relatively low, and the challenge for these 4,000) 1 torpedo solution batteries is to improve this characteristic and further improve the discharge performance.゜Tekote゛Conventionally, the positive electrode active material: ``Cold powder metal lead was added to the lead hissunate in advance in a warm environment, and the discharge was started for the first time. Improving the discharge characteristics of J3L in IJ
Measures have been taken.

However, using metallic lead as a conductive agent and mixing it with 'C' means that the ■ of lead bismuthate, which is a J active material, decreases. In this respect, it is difficult to say that metallic lead is a good conductive agent, and if a considerable amount of metallic lead of ω is mixed into lead acetate, the initial discharge performance of the battery can be improved. I couldn't stand it. Therefore, the discharge capacity tr1 of 11°C -I due to the decrease in -C and lead bismuthate was extremely significant. In addition, the strength of the positive electrode molding mixture, which is formed by combining lead bismuthate with metallic lead, is relatively low, and during the battery drawing process, there are cracks and chips in the electrode molding mixture. Drops are likely to occur, which causes a decrease in yield.

What is the general trend?11 Signs of harmful metals
! Inserting lead, which has a strong chemical resistance, into a battery completely changes the product image of that battery. Furthermore, handling metallic lead, for example, in powder form, during the manufacturing process of batteries has many undesirable factors, such as the fact that the manufacturing equipment is heavily contaminated.

This invention was made in view of the conventional problems mentioned above, and its purpose is to improve initial discharge performance with minimal suspension in non-aqueous electrolytic M batteries that use lead carbon bismuthate as the positive electrode active material. When a conductive agent with an effect of 1! is mixed into the positive electrode active material, the discharge initial JIIJ is accompanied by a decrease in discharge capacity of 0.1.
The purpose of this invention is to reduce the internal resistance of a3tJ, improve the shape retention strength of the iE electrode forming mixture, and improve the yield of batteries.

In order to achieve the above object, the present invention uses alkali metal as a negative electrode active material, and uses lead dismutate as a positive electrode active material! (V) using a positive electrode with a non-aqueous electrolyte.

An example of this defense is shown in the drawings (explained in detail).

This defense (t captured in the form of J battery) (゛ is 41
However, for example, the button type UL water city M liquid battery has +1
The four structures are shown in Figure 1. According to the same figure, a positive electrode 16, a lever lever 18, and a negative electrode 20 are laminated in a battery case consisting of a positive 441rlj 10, an El 444 terminal 12d3, and a seal 1 gasket 22 made of Suanresu Steel. A photovoltaic element is loaded in a sealed manner.

The negative electrode 20 uses the metal substrate 11 as an active material.

The positive (1.6) contains lead bismuthate as an active material. The lever 18 is made of a porous film such as polypropylene, which is coated with a non-aqueous electrolyte.

This will be explained in detail in Section 16 of '4i1i'. □ Positive 11
fli 1■6 is a molding mixture in which the active material CI/)' lead bismuthate is mixed with C graphite as a conductive agent. There is graphite of -C as a conductive 'ffl. This is a very low C content compared to the 4-i content of conventional metal 641 as a conductive agent. Contain once: It is common to have C
3. In other words, the conductivity of graphite is much better than that of lead metal, and its effect as a conductive agent is fully demonstrated. , it is possible to reduce the internal resistance at the initial stage of discharge without substantially changing the fQ of the mass M14) as a positive electrode active material.

In addition, the molding strength of a mixture of lead bismuthate and black 1)) is compared to that of the metal 14) iIl porcelain mixture. Ka improvement J
Ru. As a result, Δη cracks and chips in the J5 molding mixture occur during the battery assembly process.
Battery, Q) 3b', '4t rises lfj].

Figure 2 contains the graphite mentioned above.
! i ('C indicates the 1st series of I. One contains graphite.'
This is the relationship between the internal resistance at the initial stage of the discharge (, -,, d3), and the other is the relationship between the graphite-containing!t' and the discharge 111. I bl,\111
) is the relative value of the battery that does not include ↑I 00 (), the index (+Q (indicated).

It is clear from Figure 2 that the first 1 of the city!
! III internal resistance 1; L + [E electrode active material (・Arjisu 7 sulfuric acid 11);
Hanging Crab) 1 piece of IJ r human saku low 1, Ruru, If the graphite content is reduced to 0.05%, the effect of lowering the 811 resistance within the ivJ period is 1,1 heavy weight. become. Even if the graphite content is increased to 0.05% or more, the positive electrode internal resistance reduction effect does not change.

Further, the discharge time of the battery decreases as the graphite content increases, because as the black 1-1 content increases, the m of lead bismuthate, which is the upper electrode active material, decreases accordingly.

However, if the graphite content is 2% or less, the decrease in discharge time is only a slight amount C', which causes almost no problem.

If the graphite content exceeds 2%, the rate of decrease in discharge time will decrease rapidly and the discharge sound tn will decrease significantly. In addition, when multi-chambered graphite is added to the grain, the molding density is high < 4
i: It was confirmed that the diffusion of the electrolytic solution was inhibited, and as a result, the discharge capacity was reduced.

The above J, sea urchin, bismuth acid ≦ a) is used as a conductive agent in the positive electrode 1G, which takes the active substance v1, and the content of graphite containing c +t is 0.0! :) -・2% n It is possible to sufficiently avoid a decrease in resistance, and the strength as a molding mixture is also improved.

As explained in detail above, according to the present invention, it is possible to further improve the internal resistance characteristics and discharge performance of a non-aqueous electrolyte battery using bismuth lead as the electrode active material,
This increases the usefulness of this type of battery.

[Brief explanation of drawings]

FIG. 1 is a four-sectional view showing an example of the structure of a non-aqueous electrolyte battery to which the present invention is applied, and FIG. 2 is a graph for explaining the present invention in detail. 10...Positive electrode can 12...Negative electrode r1
6...Correct (tentative) 18...Leverator 2
0...Negative electrode 22...,)5+ 1-
'] Gasket Q: f i+'l Applicant Hata"
Irokanosuke

Claims (1)

[Claims] (1) A non-aqueous electrolyte battery using a negative electrode made of an alkaline metal as the negative electrode active material and a positive electrode made of lead dosumathate as the positive electrode active material.