JP5081384B2 - Manufacturing method of zinc alloy powder for battery, zinc alloy powder for battery, and alkaline battery - Google Patents

Description

The present invention relates to a method for producing a zinc alloy powder for a battery, a zinc alloy powder for a battery, and an alkaline battery, and particularly relates to an effective method applied to a sealed alkaline dry battery.

  In batteries such as alkaline batteries, zinc or zinc alloy powder is mainly used as a negative electrode material. Zinc has been favorably used as a negative electrode material for batteries because of its high hydrogen overvoltage and relatively low price. However, there is a problem that hydrogen gas is likely to be generated when the battery is used only with zinc. If this gas generation cannot be suppressed, the internal pressure of the battery will increase and cause leakage.

  In order to suppress gas generation, zinc halide obtained by amalgamating zinc with mercury has been used in the past. However, since the use of mercury causes environmental problems, negative electrode materials that do not contain mercury are currently used.

  As the negative electrode material not containing mercury, for example, zinc alloy powder to which indium, bismuth, aluminum or the like is added is used (see Patent Documents 1 and 2). This zinc alloy powder is said to have the effect of suppressing gas generation and the effect of improving pulse discharge without using mercury.

The zinc alloy for batteries is pulverized by a gas atomization method. In the gas atomization method, molten metal can be directly pulverized regardless of machining. A zinc alloy powder produced by the gas atomization method is used as a negative electrode material for a battery (see Patent Documents 2 and 3).
JP 2003-17077 A JP 2004-253276 A JP-A-2005-93130

  In recent years, portable electronic devices with large current consumption, such as digital cameras, have become widespread. Along with this, there is an increasing demand for improvement in discharge performance, particularly large current discharge characteristics and electric capacity of alkaline batteries used in the equipment. In this case, it is necessary to improve the discharge performance without impairing the leakage resistance.

  Use of zinc alloy powder as the negative electrode material is effective in suppressing gas generation and preventing leakage. The high current discharge characteristics can be improved by reducing the particle size of the zinc alloy powder. This is considered to be because by reducing the particle size of the zinc alloy powder, the surface area related to the reactivity increases and the reactivity as the negative electrode active material increases. However, as the reactivity increases, the generation of hydrogen gas increases and the leakage resistance deteriorates.

  In the zinc alloy powder for batteries, aluminum, indium, bismuth, and the like are known as alloy-added metals effective for controlling gas generation. Aluminum has the effect of smoothing the surface of the alloy powder fine particles by alloying with zinc, thereby reducing the surface area related to reactivity and suppressing gas generation. Indium has the effect of suppressing gas generation due to corrosion during storage as a battery by increasing the hydrogen overvoltage on the surface of the alloy powder. Bismuth, like indium, has the effect of suppressing gas generation before discharge, but tends to increase gas generation after discharge. As described above, in the zinc alloy powder for a battery, the particle size state, the kind of the additive metal, and the like are greatly involved in the battery characteristics and the leakage resistance.

  Here, the present inventor examined the electric capacity of a battery that has a high current discharge characteristic and a high demand for performance improvement in the zinc alloy powder for a battery. It has been found.

  In order to improve the electric capacity of the battery, an increase in the amount of the active material, particularly the zinc alloy powder as the negative electrode material, is the most reliable and effective. However, in an alkaline dry battery with a standardized outer size, there is a certain limitation on the filling volume of the negative electrode material, and it is difficult to increase the amount.

  In view of this, the present inventor examined increasing the apparent density of the zinc alloy powder in order to substantially increase the filling amount of the negative electrode material in a situation where the filling volume of the negative electrode material is restricted. According to the inventor's research focusing on this apparent density, the apparent density of the zinc alloy powder is related to the particle size state of the powder, and it is found that the apparent density can be increased if the particle size distribution is concentrated in a narrow range. did.

  On the other hand, the zinc alloy powder produced by the conventional gas atomization method has a wide particle size distribution range and large particle size variation. In order to increase the apparent density of the zinc alloy powder, it is necessary to perform particle size selection by sieving. In this case, in order to significantly increase the apparent density, it is necessary to finely screen the powder so that the particle size distribution of the powder is concentrated within a narrow range.

  However, when trying to finely select the particle size by sieving, the number of processes increases and the process becomes complicated, and the amount of powder outside the selection increases, resulting in a decrease in yield. It turned out to cause problems.

The present invention solves the problems as described above, and its purpose is to make it possible to significantly improve battery performance, particularly electric capacity, without reducing productivity and without impairing battery leakage resistance. The present invention provides a zinc alloy powder for a battery, a zinc alloy powder for a battery, and an alkaline battery.

 Other objects and configurations of the present invention will become apparent from the description of the present specification and the accompanying drawings.

  The solution provided by the present invention is as follows.

(1) A method for producing a zinc alloy powder used for a negative electrode of an alkaline battery,
The zinc alloy powder is manufactured by only the centrifugal spray method without sieving using a mesh,
In the centrifugal spraying method, aluminum (Al), bismuth (Bi), and indium (In) are added in amounts of 0.001 wt% to 0.03 wt%, 0.001 wt% to 0.02 wt%, and 0.01 wt% to 0.00, respectively. The zinc alloy powder is milled so that it is contained in an amount of 07 wt% and a zinc alloy powder having a particle size of 75 μm or less is present at 10% to 20%.
The manufacturing method of the zinc alloy powder for batteries characterized by the above-mentioned.

(2) A zinc alloy powder for a battery that is powdered by the production method described in the above means (1) .
(3) An alkaline battery using zinc as a negative electrode active material, wherein the zinc alloy powder for a battery described in the above means (2) is used as the negative electrode zinc.

  It is possible to provide a zinc alloy powder for a battery and an alkaline battery that can significantly improve the battery performance, particularly the electric capacity, without reducing the productivity and without impairing the leakage resistance of the battery.

  Operations / effects other than those described above will be apparent from the description of the present specification and the accompanying drawings.

  FIG. 1 shows an embodiment of an LR type alkaline dry battery to which the technology of the present invention is applied. The battery shown in FIG. 1 is an alkaline primary battery, and a power generation element 20 including a positive electrode mixture 21, a separator 22, and a negative electrode mixture 23 is accommodated in a bottomed cylindrical metal positive electrode can 11 together with an alkaline electrolyte. ing.

  The positive electrode can 11 is a deep-drawn nickel-plated steel plate. The positive electrode can 11 serves as a positive electrode current collector and a positive electrode terminal, and a convex positive electrode terminal portion 12 is integrally formed at the bottom thereof.

  The opening of the positive electrode can 11 is sealed using a negative electrode terminal plate 32 and a resin gasket 35. A rod-shaped negative electrode current collector 31 is fixed inside the negative electrode terminal plate 32, and the current collector 31 is inserted into the gel-like negative electrode mixture 23.

  The positive electrode mixture 21 is formed by adding a conductive additive such as graphite to a positive electrode active material into a predetermined mixture shape. The positive electrode active material includes manganese dioxide (EMD) and / or oxywater. Nickel oxide is used. For the negative electrode mixture 23, gelled zinc using zinc alloy powder is used.

  The structural configuration of the battery is basically the same as the conventional one. The features of the battery of the present invention that are different from conventional ones are the powder state of the zinc alloy powder used in the negative electrode mixture 23 and the alloy composition thereof.

  That is, the zinc alloy powder is not a zinc alloy powder produced by a conventional gas atomizing method, but a powdered body formed by centrifugal spraying. Further, the powder bodies are aluminum (Al) 0.001 wt% to 0.03 wt%, bismuth (Bi) 0.001 wt% to 0.02 wt%, indium (In) 0.01 wt% to 0.07 wt%, respectively. It is added as an alloy component. Further, the powder body is formed so that at least a zinc alloy powder having a particle size of 250 μm or less is present at a frequency of 85% or more.

  Here, the present inventors have a large difference in characteristics between the battery zinc alloy powder produced by the gas atomization method and the battery zinc alloy powder formed by the centrifugal spray method, It has been found that when used as a negative electrode material for alkaline batteries under certain conditions, there is a great difference in battery performance.

  That is, the zinc alloy powder produced by the gas atomization method has a broad particle size distribution state and very large particle size variation as shown in the particle size distribution curve A of FIG. With such a zinc alloy powder in a particle size state, it is difficult to optimize the setting to achieve both suppression of gas generation and improvement of large current discharge characteristics. For this reason, in the zinc alloy powder manufactured by the gas atomization method, precise particle size selection by sieving is indispensable.

  On the other hand, the zinc alloy powder for batteries made by centrifugal spraying has a sharp particle size distribution state as shown in the particle size distribution curve B or C in FIG. 2 without performing particle size selection by sieving. Thus, the characteristic that the range of particle size variation is narrow is obtained.

  For this reason, the sieving step, which is indispensable in the gas atomization method, can be eliminated. Furthermore, it was confirmed that the zinc alloy powder for batteries powdered by the centrifugal spraying method can variably set the central particle size of the zinc alloy powder with good reproducibility by variably setting the powdering conditions such as spraying conditions. For example, a particle size distribution such as curve B and a particle size distribution such as curve C can be freely selected by changing the spraying conditions of the centrifugal spraying method. Thereby, while improving productivity, the optimization setting which balances the suppression of gas generation and the improvement of a large current discharge characteristic can be performed favorably.

  Further, it should be noted that the zinc alloy powder for a battery according to the present invention, which has been formed by the centrifugal spray method, is manufactured by a gas atomization method due to a small particle size variation of the powder. It has also been found that the apparent density is greater for the powder. This brings about an unexpected great effect of increasing the electric capacity by substantially increasing the filling amount of the negative electrode material in the alkaline dry battery whose outer size is standardized.

In addition, about the centrifugal spraying method, it can implement suitably using the centrifugal disc spraying apparatus currently disclosed by patent document 4, for example.
As for the above-mentioned zinc alloy powder, the present inventor has further studied in detail, and in order to improve both the leakage resistance performance of the battery and the battery performance, particularly the electric capacity, it is particularly effective to have the following constitutional conditions. It turned out to be.

  That is, the zinc alloy powder contains aluminum (Al) 0.001 wt% to 0.03 wt%, bismuth (Bi) 0.001 wt% to 0.02 wt%, and indium (In) 0.01 wt% to 0.07 wt%. It is particularly desirable to add it as an alloy component.

  The zinc alloy powder needs to contain at least 85% zinc alloy powder having a particle size of 250 μm or less (see curve B in FIG. 2). However, more desirably, a powder form in which a zinc alloy powder having a particle size of 75 μm or less is present in an amount of 10% to 20% is particularly effective in obtaining the above effect (see curve B in FIG. 2).

  The following are typical examples of the present invention.

  As shown in Table 1, various kinds of LR6 (AA) alkaline batteries having different particle size states and zinc alloy powders (or zinc powder) having different particle size states and elemental compositions and different compositions of added metals (elements) were tested ( No. 1 to No. 25), and the amount of gas in the battery after storage at 60 ° C. for 10 days was measured for each sample. In Table 1, when the amount of gas in the battery was 2 cc / 1 cell or more, X was indicated, and less than that was indicated by ◯.

  The discharge characteristic is a cycle discharge test assuming a digital camera. The number of cycles until the end voltage becomes 1.05 V after 10 cycles per hour of discharge at 1500 mW for 2 seconds and 650 mW for 28 seconds is shown. Counting was performed, and the number of cycles of 90 or less was indicated by x, 90-100 times by Δ, 100-110 times by ◯, and more than 110 times by ◎.

  The test results shown in Table 1 are typical examples (parts) of many test results conducted by the present inventor. From Table 1, the present invention shows that the alloy composition of the zinc alloy powder is aluminum. The range of (Al) 0.001 wt% to 0.03 wt%, bismuth (Bi) 0.001 wt% to 0.02 wt%, and indium (In) 0.01 wt% to 0.07 wt% is effective in suppressing gas generation. It is confirmed that

  Also, for example, sample no. When the zinc alloy powder having an alloy composition of 16 was tested for changes in discharge characteristics and gas characteristics when the particle size state of the zinc alloy powder was changed, the results shown in Table 2 were obtained.

  In Table 2, the discharge characteristics are cycle discharge tests assuming a digital camera as in Table 1, and the number of cycles is indicated by ×, Δ, ○, ◎. As for the gas characteristics, as in Table 1, the amount of gas in the battery was indicated by ○ and ×.

  The test results shown in Table 2 are also typical examples (parts) of many test results conducted by the present inventor. From Table 2, the test results have a particle size distribution such as the distribution curve B in FIG. In addition, the presence of 85% or more of zinc alloy powder having a particle size of 250 μm or less, particularly the presence of 10% to 20% of zinc alloy powder having a particle size of 75 μm or less, is particularly effective for improving discharge characteristics, particularly electric capacity. It is confirmed that

As mentioned above, although this invention was demonstrated based on the typical Example, this invention can have various aspects other than having mentioned above. For example, the negative electrode material of the present invention can be suitably used not only for alkaline primary batteries but also for alkaline secondary batteries.
JP 2000-26907 A

  It is possible to provide a zinc alloy powder for a battery and an alkaline battery that can significantly improve the battery performance, particularly the electric capacity, without reducing the productivity and without impairing the leakage resistance of the battery.

It is sectional drawing which shows one Embodiment of the alkaline dry battery to which the technique by this invention was applied. It is a graph which shows the particle size distribution state of zinc alloy powder.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 Positive electrode can 12 Positive electrode terminal part 20 Electric power generation element 21 Positive electrode mixture 22 Separator 23 Negative electrode mixture (Use zinc alloy powder)
31 Negative current collector 32 Negative electrode terminal plate 35 Gasket

Claims (3)

A method for producing a zinc alloy powder used in a negative electrode of an alkaline battery,
The zinc alloy powder is manufactured by only the centrifugal spray method without sieving using a mesh,
In the centrifugal spraying method, aluminum (Al), bismuth (Bi), and indium (In) are added in amounts of 0.001 wt% to 0.03 wt%, 0.001 wt% to 0.02 wt%, and 0.01 wt% to 0.00, respectively. The zinc alloy powder is milled so that it is contained in an amount of 07 wt% and a zinc alloy powder having a particle size of 75 μm or less is present at 10% to 20%.
The manufacturing method of the zinc alloy powder for batteries characterized by the above-mentioned. The zinc alloy powder for batteries powdered by the manufacturing method according to claim 1 . An alkaline battery using zinc as the negative electrode active material, wherein the zinc alloy powder for a battery according to claim 2 is used as the negative electrode zinc.

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