JP2008123839A - Manufacturing method of alkaline battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide the manufacturing method of an alkaline battery capable of enhancing electrolyte leakage resistance characteristics. <P>SOLUTION: The manufacturing method of an alkaline battery is equipped with a process for storing a negative electrode side half cell having a negative electrode 16, a negative electrode cup 13 and an electrolyte in inert gas atmosphere, and a process for combining the negative electrode side half cell after storage with a positive electrode side half cell having a positive electrode 14, a positive electrode can 11, a separator 15, a gasket 12, and an electrolyte and then crimping the opening short edge of the positive electrode can 11. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for manufacturing an alkaline battery, and more particularly to a flat-type mercury-free alkaline battery such as a coin-type alkaline battery or a button-type alkaline battery.

  Coin-type or button-type flat alkaline batteries are used in small electronic devices such as electronic watches and portable electronic computers. Conventionally, an alkaline battery as shown in FIG. 4 has been proposed as such an alkaline battery.

  As shown in FIG. 4, the alkaline battery includes a positive electrode 104 having silver oxide as a main positive electrode active material, a positive electrode can 101 in which the positive electrode 104 is disposed, a separator 105 mounted on the positive electrode 104, A ring-shaped gasket 102 placed on the separator 105, a negative electrode cup 103 that seals the opening of the positive electrode can 101, and a negative electrode 106 disposed in the negative electrode cup 103.

  Conventionally, an alkaline battery has been manufactured by the following steps. First, a positive electrode 104 containing silver oxide as a main positive electrode active material is disposed in the positive electrode can 101, and a separator 105 and a gasket 102 are disposed on the positive electrode 104, and an electrolysis mainly composed of an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution is provided thereon. Inject liquid. Thereby, the positive electrode side half cell which has the positive electrode 104, the positive electrode can 101, the separator 105, the gasket 102, and electrolyte solution is obtained.

  The negative electrode cup 103 containing a granular zinc alloy as a main negative electrode active material is filled in the negative electrode cup 103, and an electrolyte mainly composed of a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution is injected into the negative electrode 106. Thereby, the negative electrode side half battery which has the negative electrode 106, the negative electrode cup 103, and electrolyte solution is obtained.

  The positive half-cell and the negative half-cell are combined, and finally the opening end edge of the positive electrode can 101 is crimped inward to be sealed and held. The alkaline battery is manufactured through the above steps.

  In the alkaline battery produced by the above process, the occurrence of liquid leakage is a greater problem than before. The leakage is largely caused by the generation of hydrogen gas inside the battery. Hydrogen gas is usually generated from the surface of the granular zinc alloy and the inner surface of the negative electrode cup 103.

  Conventionally, in order to suppress the generation of hydrogen gas, a method of adding mercury having a high hydrogen overvoltage has been employed. When the surface of the granular zinc alloy is amalgamated with mercury, generation of hydrogen gas from the surface of the granular zinc alloy can be suppressed. Further, by covering the inner surface of the negative electrode cup 103 with mercury, generation of hydrogen gas from the inner surface of the negative electrode cup 103 can be suppressed.

  By the way, in recent years, researches on environmental problems have been actively conducted in various fields, and many studies have been made on alkaline batteries in order to avoid the use of mercury that directly affects the environment.

  For example, as a method for suppressing the generation of hydrogen gas from a granular zinc alloy in an alkaline electrolyte, a method of adding a metal having a high hydrogen overvoltage as an alloy to granular zinc is disclosed. In order to effectively suppress the generation of hydrogen gas from the inside of the negative electrode cup, for example, one or more of tin (Sn), indium (In), and bismuth (Bi), which are metals having a high hydrogen overvoltage, are used. There has been proposed a method of depositing a coating layer made of an alloy on the inner surface of the negative electrode cup (see Patent Document 1). For example, a method of adding a so-called inhibitor that suppresses hydrogen generation to an alkaline electrolyte has been proposed (see Patent Document 2).

JP 2003-272636 A JP 2002-373651 A

  However, in the method of using a metal having a high hydrogen overvoltage as an alloy for granular zinc as described in Patent Document 1 or the method of adding an inhibitor to an alkaline electrolyte as described in Patent Document 2, Hydrogen gas generated from the surface of the zinc alloy and the inner surface of the negative electrode cup 103 could not be completely suppressed, and sufficiently satisfactory leakage resistance characteristics could not be obtained as compared with the method using mercury.

  Accordingly, an object of the present invention is to provide a method for producing an alkaline battery capable of improving leakage resistance.

  As a result of diligent research, the inventors of the present application have shown that gas generation from the inner surface of the negative electrode cup occurs in the presence of an alkaline aqueous solution such as sodium hydroxide or aqueous potassium hydroxide solution and zinc, and the inner surface of the negative electrode cup is , Copper (Cu), tin (Sn), indium (In), bismuth (Bi) or the like, but after filling the negative electrode cup with the negative electrode and electrolyte, after a few minutes, the inner surface of the negative electrode cup becomes zinc. From the surface of the negative electrode cup plated with zinc, it was found that gas was hardly generated.

  That is, a large amount of hydrogen gas is generated until the inner surface of the negative electrode cup is plated with zinc, specifically, within 1 minute immediately after the negative electrode cup is filled with the negative electrode and the electrolyte. I found out.

  Conventionally, after combining a negative electrode-side half cell filled with a negative electrode and an electrolyte in a negative electrode cup and a positive electrode half cell having a positive electrode can, a positive electrode, a separator, a gasket, and an electrolyte, the positive electrode can can be obtained within less than 1 minute. The inner peripheral surface of the opening edge of each was crimped inward to keep it sealed. This is to prevent the electrolytic solution mainly composed of sodium hydroxide or potassium hydroxide aqueous solution from being converted to sodium carbonate or potassium carbonate by carbon dioxide in the atmosphere.

  However, when the negative electrode cup is filled with the negative electrode and the electrolyte and sealed within less than 1 minute, or when the negative electrode side half battery and the positive electrode side half battery are combined and sealed within less than 1 minute, a large amount of hydrogen gas is generated. Since it is in the process of being generated, hydrogen gas is stored inside the battery, and if even a small amount of hydrogen gas is generated thereafter, liquid leakage tends to occur.

That is, in order to solve the above-described problem, the first invention
Storing the negative electrode-side half-cell having the negative electrode, the negative electrode cup, and the electrolyte in an inert gas atmosphere;
A step of crimping the short edge of the positive electrode can by combining the negative electrode side half battery with the positive electrode, positive electrode can, separator, gasket, and positive electrode side half battery having an electrolyte solution after storage. It is a manufacturing method of an alkaline battery.

The second invention is
A negative electrode-side half-cell having a negative electrode, a negative electrode cup and an electrolyte;
A positive electrode, a positive electrode can, a separator, a gasket, and a positive electrode-side half-cell having an electrolyte solution, and after storing in an inert gas atmosphere,
And a step of crimping while decompressing the opening edge of the positive electrode can after storage.

  In the first invention, after the negative electrode-side half battery is stored in an inert gas atmosphere so that the electrolyte does not touch the atmosphere and the generation of hydrogen gas is reduced, the negative electrode-side half battery and the positive electrode-side half battery And the opening short edge of the positive electrode can is crimped and sealed, so that the occurrence of liquid leakage can be suppressed.

  In the second invention, after the negative electrode-side half battery and the positive electrode-side half battery are combined and stored in an inert gas atmosphere so that the electrolyte does not touch the atmosphere, the generation of hydrogen gas is reduced. Since the opening edge of the positive electrode can is crimped and sealed while reducing the pressure, the occurrence of liquid leakage can be suppressed.

  According to the present invention, the leakage resistance characteristics of the alkaline battery can be improved.

  Embodiments of the present invention will be described below with reference to the drawings.

  First, an example of the configuration of an alkaline battery manufactured using the manufacturing method of the present invention will be described with reference to FIG. This alkaline battery is, for example, a coin-type or button-type alkaline battery.

  As shown in FIG. 1, the alkaline battery includes a positive electrode 14, a positive electrode can 11 in which the positive electrode 14 is disposed, a separator 15 placed on the positive electrode 14, and a ring placed on the separator 15. And the negative electrode cup 13 which seals the opening of the positive electrode can 11, and the negative electrode 16 disposed in the negative electrode cup 13.

  The positive electrode can 11 has a structure in which nickel plating is applied to a stainless steel plate. The positive electrode can 11 also serves as a positive electrode terminal. In the positive electrode can 11, a positive electrode 14 molded in a pellet shape is disposed. The positive electrode 14 is made of, for example, silver oxide as a main positive electrode active material, and is molded into a coin shape or a button shape.

  A separator 15 is disposed on the positive electrode 14. The separator 15 has, for example, a three-layer structure of a nonwoven fabric, cellophane, and a film obtained by graft polymerization of polyethylene. For example, a ring-shaped gasket 12 made of nylon is disposed on the inner peripheral surface of the opening edge of the positive electrode can 11.

  The negative electrode cup 13 is produced, for example, by molding a three-layer clad material made of nickel (Ni), stainless steel, and copper (Cu) into a cup shape. A tin coating layer, an indium coating layer, or a bismuth coating layer may be formed on the surface of copper (Cu) by plating, vapor deposition, or sputtering.

  The negative electrode cup 13 is filled with a negative electrode 16 having a granular zinc alloy as a main negative electrode active material. As the granular zinc alloy, for example, it is desirable to use an alloy of bismuth (Bi), indium (In), aluminum (Al) and zinc (Zn). Specifically, for example, bismuth (Bi) and zinc (Zn), bismuth (Bi) and indium (In) and zinc (Zn), or bismuth (Bi), indium (In), aluminum (Al) and zinc ( Zinc alloy powder composed of Zn) can be used.

  The negative electrode cup 13 is inserted into the opening edge of the positive electrode can 11 so as to accommodate the negative electrode 16. The negative electrode cup 13 is clamped and held tightly by the inner peripheral surface of the opening edge of the positive electrode can 11 via the gasket 12.

  Next explained is a method for manufacturing an alkaline battery according to the first embodiment of the invention. The alkaline battery manufacturing method according to the first embodiment of the present invention includes a negative electrode side half battery which is stored in an inert gas atmosphere and then combined with the negative electrode side half battery and the positive electrode side half battery, and the positive electrode can open short edge. It is characterized by crimping. Here, as shown in FIG. 2, the positive-side half-cell is a positive electrode can 11, a positive electrode 14 disposed on the positive electrode can 11, a separator 15 and a gasket 12 disposed on the positive electrode 14, and a positive electrode. It has what has the electrolyte solution inject | poured in the can 11. FIG. Further, as shown in FIG. 3, the negative electrode-side half battery refers to a battery having a negative electrode cup 13, a negative electrode 16 disposed in the negative electrode cup 13, and an electrolyte. Hereinafter, a method for manufacturing an alkaline battery according to the first embodiment of the present invention will be described in detail.

  First, the positive electrode 14 is disposed on the positive electrode can 11, the separator 15 is disposed on the positive electrode 14, and the ring-shaped gasket 12 is disposed on the separator 15. Next, for example, an electrolytic solution mainly containing a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution is injected. Thus, the positive half-cell 17 is produced.

  The negative electrode cup 13 is filled with a negative electrode 16 having a thickener and a granular zinc alloy which is a main negative electrode active material. Next, an electrolyte mainly composed of sodium hydroxide or potassium hydroxide solution is injected. In this way, the negative electrode half battery 18 is produced.

  Here, when the negative electrode-side half battery 18 is manufactured, after filling the negative electrode 16 having a thickener and a granular zinc alloy which is a main negative electrode active material, a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution is mainly used. However, for example, the negative electrode cup 13 may be filled with a mixture of zinc, a thickener, and an electrolyte and molded into a pellet.

  Next, the negative half-cell 18 is stored in an inert gas atmosphere. Examples of a method for storing the negative electrode-side half battery 18 in an inert gas atmosphere include, for example, a method for storing the negative electrode-side half battery 18 in an inert gas-sealed sealed container, or spraying an inert gas on the negative electrode-side half battery 18. The method is preferred.

  For example, nitrogen gas or argon gas can be used as the inert gas. Storage in an inert gas atmosphere means that when stored in the air, the electrolytic solution touches carbon dioxide in the air, resulting in the formation of carbonate crystals, which cause the negative-side half cell 18 and the positive-side half This is because the sealing performance when the battery 17 is combined is impaired.

  As a time which preserve | saves the negative electrode side half-cell 18 in inert gas atmosphere, 1 minute or more is preferable, for example, and 1 minute or more and 24 hours or less are more preferable. This is because when the time is longer than 1 minute, the generation of hydrogen gas is further reduced, and thus the liquid leakage resistance can be further improved. This is because storage for more than 24 hours is not preferable because it impairs battery productivity.

  Next, the negative-side half battery 18 and the positive-side half battery 17 are combined and finally sealed by crimping the opening edge of the positive electrode can 11 inward. Thus, an alkaline battery is obtained.

  In the first embodiment, after the negative half-cell 18 is stored in an inert gas atmosphere, the negative half-cell 18 and the positive half-cell 17 are combined, and the short opening edge of the positive electrode can 11 is crimped. Sealing can improve leakage resistance.

  That is, after the negative half-cell 18 is stored in an inert gas atmosphere so that the electrolyte does not touch the atmosphere and the generation of hydrogen gas is reduced, the negative half-cell 18 and the positive half-cell 17 , And the opening short edge of the positive electrode can 11 is crimped and sealed, so that the occurrence of liquid leakage can be suppressed.

  Next explained is a method for manufacturing an alkaline battery according to the second embodiment of the invention. In the alkaline battery manufacturing method according to the second embodiment of the present invention, the negative electrode side half battery 18 and the positive electrode side half battery 17 are combined and stored in an inert gas atmosphere, and then the opening edge of the positive electrode can 11 is decompressed. It is characterized by crimping. The method for manufacturing an alkaline battery according to the second embodiment of the present invention will be described in detail below.

  The manufacturing process of the positive-side half-cell 17 and the negative-side half-cell 18 is the same as that of the first embodiment, and a detailed description thereof will be omitted.

  In 2nd Embodiment, after combining the produced positive electrode side half cell 17 and the negative electrode side half cell 18, this is preserve | saved in inert gas atmosphere. For example, nitrogen gas or argon gas can be used as the inert gas. The storage in an inert gas atmosphere is that when stored in the air, the electrolyte solution touches carbon dioxide in the air and crystals of carbonate are produced, and these crystals cause the negative-side half-cell 18 and the positive-side half-cell 17. This is because the sealing performance when combined with is impaired.

  As a method of storing in an inert gas atmosphere, for example, a method of storing in an inert gas-sealed sealed container or a method of spraying an inert gas is preferable as in the first embodiment.

  As time to preserve | save in inert gas atmosphere, 1 minute or more is preferable, for example, and 1 minute or more and 24 hours or less are more preferable. This is because when the time is longer than 1 minute, the generation of hydrogen gas is further reduced, and thus the liquid leakage resistance can be further improved. This is because storage for more than 24 hours is not preferable because it impairs battery productivity.

  Next, the positive electrode can 11 is sealed by crimping while reducing the inner peripheral surface of the opening edge of the positive electrode can 11 to, for example, 50 mmHg or less. Thus, an alkaline battery is obtained.

  In the second embodiment, after the negative electrode-side half battery 18 and the positive electrode-side half battery 17 are combined and stored in an inert gas atmosphere, the opening edge of the positive electrode can 11 is crimped while being decompressed, The liquid leakage resistance can be improved.

  That is, after the negative electrode-side half battery 18 and the positive electrode-side half battery 17 are combined and stored in an inert gas atmosphere so that the electrolyte does not come into contact with the atmosphere, the generation of hydrogen gas is reduced, and then the positive electrode Since the opening edge of the can 11 is crimped and sealed while reducing the pressure, the occurrence of liquid leakage can be suppressed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to an Example.

<Example 1>
As described below, an SR626SW battery having the structure shown in FIG. First, a three-layer clad material having a thickness of 0.2 mm was prepared by three layers of a nickel outer surface layer, a metal layer made of stainless steel (SUS304), and a current collector layer made of copper. Next, a tin coating layer was formed on the three-layer clad material using an electroless plating method.

  Next, the tin-plated clad material was punched and pressed to produce a negative electrode cup 13 having a U-shaped folded portion formed on the periphery.

A positive electrode mixture was obtained by mixing 15% by weight of manganese dioxide, 80% by weight of silver oxide, 4.5% by weight of graphite, and 0.5% by weight of polytetrafluoroethylene powder.

  Next, the positive electrode mixture was formed into a disk shape to form the positive electrode 14, which was inserted into the positive electrode can 11.

  Next, on the positive electrode 14, a separator 15 punched out into a circular shape of a three-layer structure of a non-woven fabric, cellophane, polyethylene grafted film was loaded, and a nylon ring-shaped gasket 12 was placed thereon, The separator 15 was dropped and impregnated with a 28% by weight aqueous sodium hydroxide solution as an alkaline electrolyte to obtain a positive electrode-side half battery 17 shown in FIG.

  On the other hand, a negative electrode 16 composed of a granular zinc alloy and a thickener was placed on the negative electrode cup 13.

  Next, this negative electrode 16 was dripped and impregnated with a 28 wt% sodium hydroxide aqueous solution as an alkaline electrolyte to obtain a negative electrode-side half battery 18 shown in FIG.

  Next, the negative half-cell 18 was stored in a nitrogen gas sealed container for 1 minute.

  Next, the negative electrode-side half cell 18 stored in a nitrogen gas atmosphere and the positive electrode-side half cell 17 were combined, and sealed by crimping the opening edge of the positive electrode can 11 inward. Thus, the alkaline battery of Example 1 was produced.

<Example 2>
An alkaline battery of Example 2 was manufactured in the same manner as Example 1 except that the negative electrode-side half battery 18 was stored in a nitrogen gas sealed container for 1 hour.

<Example 3>
An alkaline battery of Example 3 was manufactured in the same manner as in Example 1 except that the negative electrode-side half battery 18 was stored in a nitrogen gas sealed container for 24 hours.

<Example 4>
An alkaline battery of Example 4 was manufactured in the same manner as in Example 1 except that the negative electrode-side half battery 18 was stored in an argon gas sealed container for 1 minute.

<Example 5>
An alkaline battery of Example 5 was manufactured in the same manner as in Example 1 except that the negative electrode-side half battery 18 was stored in an argon gas sealed container for 1 hour.

<Example 6>
An alkaline battery of Example 6 was manufactured in the same manner as in Example 1 except that the negative electrode-side half battery 18 was stored in an argon gas sealed container for 24 hours.

<Example 7>
An alkaline battery of Example 7 was manufactured in the same manner as in Example 1 except that the negative electrode-side half battery 18 was stored in a nitrogen gas sealed container for 50 seconds.

<Comparative Example 1>
Comparative Example 1 was performed in the same manner as in Example 1 except that the step of storing the negative electrode-side half battery 18 in a nitrogen gas sealed container was omitted and the negative electrode-side half battery 18 and the positive electrode-side half battery 17 were immediately combined. An alkaline battery was manufactured.

<Comparative example 2>
An alkaline battery of Comparative Example 2 was produced in the same manner as in Example 1 except that the negative electrode-side half battery 18 was stored in the atmosphere for 1 hour.

  100 alkaline batteries of Examples 1 to 7 and 100 alkaline batteries of Comparative Examples 1 to 2 were prepared, stored in an oven at 60 ° C. and 90% relative humidity for 100 days, and the occurrence rate of liquid leakage was measured. did. The measurement results are shown in Table 1.

  As shown in Table 1, the batteries of Examples 1 to 6 all exhibited a leak rate of 30% or less of the allowable level. In particular, Example 2, Example 3, Example 5 and Example 6 stored in nitrogen gas or argon gas for 1 hour or longer showed a leak rate of 20% or less, which was a good result. Further, in Example 7, the liquid leakage occurrence rate was considerably improved, but exceeded 30%. As a result, compared with the batteries of Examples 1 to 6, the liquid leakage resistance was slightly inferior.

  On the other hand, in the battery of Comparative Example 1, the leakage occurrence rate exceeded 50%. Furthermore, in Comparative Example 2, the leakage occurrence rate was very high at 100%. The reason for the very high leakage rate in Comparative Example 2 is that a sodium carbonate crystal is formed from a sodium hydroxide electrolyte and carbon dioxide in the air. This crystal causes the negative half-cell 18 to be connected to the positive half-cell 17. This is considered to be because the sealing performance when combined is impaired.

  Further, in Examples 1 to 7 and Comparative Examples 1 to 2, the storage in the nitrogen gas atmosphere was not performed for more than 24 hours, but this was compared with the storage for 1 hour and the storage for 24 hours. This is because there is no difference in the rate of occurrence of liquid leakage, and storage for more than 24 hours is undesirable because it impairs battery productivity.

  As described above, the step of storing the negative electrode 16, the negative electrode cup 13, and the negative electrode-side half battery 18 in the inert gas atmosphere, the negative electrode-side half battery 18, the positive electrode 14, the positive electrode can 11, the separator 15, and the gasket. 12 and the positive electrode-side half battery 17 having an electrolyte solution, and then the step of crimping the opening short edge of the positive electrode can 11 is manufactured to produce an alkaline battery, whereby the leakage resistance can be improved. all right.

  Moreover, as time to preserve | save in inert gas atmosphere, 1 minute or more was preferable and it turned out that 1 minute or more and 24 hours or less are more preferable.

<Example 8>
As described below, an SR626SW battery having the structure shown in FIG. First, a three-layer clad material having a thickness of 0.2 mm was prepared by three layers of a nickel outer surface layer, a metal layer made of stainless steel (SUS304), and a current collector layer made of copper. Next, a tin coating layer was formed on the three-layer clad material using an electroless plating method.

  Next, the tin-plated clad material was punched and pressed to produce a negative electrode cup 13 having a U-shaped folded portion formed on the periphery.

  A positive electrode mixture was obtained by mixing 15% by weight of manganese dioxide, 80% by weight of silver oxide, 4.5% by weight of graphite, and 0.5% by weight of polytetrafluoroethylene powder.

  Next, the positive electrode mixture was formed into a disk shape to form the positive electrode 14, which was inserted into the positive electrode can 11.

  Next, a separator 15 punched in a circular shape having a three-layer structure of a nonwoven fabric, cellophane, and polyethylene graft polymerized film is loaded on the positive electrode 14, and a nylon ring-shaped gasket 12 is disposed on the separator 15. The separator 15 was dropped and impregnated with a 28 wt% aqueous sodium hydroxide alkaline electrolyte solution to obtain a positive electrode half cell 17 as shown in FIG.

  On the other hand, a negative electrode 16 composed of a granular zinc alloy and a thickener was placed on the negative electrode cup 13.

  Next, this negative electrode 16 was dripped and impregnated with an alkaline electrolyte of a 28 wt% aqueous sodium hydroxide solution to obtain a negative electrode-side half battery 18 shown in FIG.

  The negative electrode-side half battery 18 and the positive electrode-side half battery 17 thus obtained were combined and stored in a nitrogen gas sealed container for 1 minute.

  And it sealed by crimping, reducing the opening edge of the positive electrode can 11 inward to 50 mmHg or less. Thus, an alkaline battery of Example 8 was produced.

<Example 9>
The negative electrode-side half battery 18 and the positive electrode-side half battery 17 were combined, stored in a nitrogen gas sealed container for 1 hour, and then crimped while decompressing to 50 mmHg or less, in the same manner as in Example 8, except that A battery was manufactured.

<Example 10>
The negative electrode-side half battery 18 and the positive electrode-side half battery 17 were combined, stored in a nitrogen gas sealed container for 24 hours, and then crimped while decompressing to 50 mmHg or less, in the same manner as in Example 8, except that A battery was manufactured.

<Example 11>
The negative electrode-side half battery 18 and the positive electrode-side half battery 17 were combined, stored in an argon gas sealed container for 1 minute, and then crimped while decompressing to 50 mmHg or less, in the same manner as in Example 8, except that An alkaline battery was manufactured.

<Example 12>
The negative electrode-side half battery 18 and the positive electrode-side half battery 17 were combined, stored in an argon gas sealed container for 1 hour, and then crimped while being decompressed to 50 mmHg or less. An alkaline battery was manufactured.

<Example 13>
The alkali of Example 13 was used in the same manner as in Example 8 except that the negative half battery 18 and the positive half battery 17 were combined, stored in an argon gas sealed container for 24 hours, and then crimped while decompressing to 50 mmHg or less. A battery was manufactured.

<Example 14>
The alkali of Example 14 was used in the same manner as in Example 8 except that the negative half battery 18 and the positive half battery 17 were combined, stored in a nitrogen gas sealed container for 50 seconds, and then crimped while decompressing to 50 mmHg or less. A battery was manufactured.

<Comparative Example 3>
The negative electrode side half-cell 18 and the positive electrode side half-cell 17 are combined, and the step of holding in the nitrogen gas sealed container is omitted, and a comparative example is performed in the same manner as in Example 8 except that crimping is immediately performed while reducing the pressure to 50 mmHg or less. 3 alkaline batteries were produced.

<Comparative Example 4>
The alkaline battery of Comparative Example 4 was the same as Example 8 except that the negative half battery 18 and the positive half battery 17 were combined, stored in the atmosphere for 1 hour, and then crimped while decompressing to 50 mmHg or less. Manufactured.

  100 alkaline batteries of Example 8 to Example 14 and 100 alkaline batteries of Comparative Examples 3 to 4 were prepared, stored in an oven at 60 ° C. and 90% relative humidity for 100 days, and the occurrence rate of liquid leakage was measured. did. The measurement results are shown in Table 2.

  As shown in Table 2, all of the alkaline batteries of Examples 8 to 13 exhibited a leakage occurrence rate of 30% or less of an allowable level. In particular, in Examples 9, 10, 12, and 13 stored in nitrogen gas or argon gas for 1 hour or longer, the leakage rate was 20% or less. In Example 14, although the leakage occurrence rate was considerably improved, it exceeded 30%, resulting in slightly poor leakage resistance as compared with the batteries of Examples 8 to 13.

  On the other hand, in the battery of Comparative Example 3, the leakage occurrence rate exceeded 40%. In Comparative Example 4, the leakage occurrence rate was as high as 88%. The reason for the high leak rate in Comparative Example 4 is that a sodium carbonate crystal is formed from a sodium hydroxide electrolyte and carbon dioxide in the air, and when this crystal is combined with the negative half-cell and the positive half-cell, This is considered to be because the sealing performance of the was impaired.

  Further, in Examples 8 to 14 and Comparative Examples 3 to 4, storage in a nitrogen gas atmosphere was not performed for more than 24 hours, but this was compared with storage for 1 hour and storage for 24 hours. This is because there is no difference in the occurrence rate of liquid leakage and storage over 24 hours is not preferable because it impairs battery productivity.

  As described above, after the negative electrode 16, the negative electrode cup 13, and the negative electrode-side half battery 18 having the electrolyte solution are combined with the positive electrode 14, the positive electrode can 11, the separator 15, the gasket 12, and the positive electrode-side half cell 17 having the electrolyte solution. It has been found that leakage resistance can be improved by producing an alkaline battery by a production method having a step of storing in an inert gas atmosphere and a step of crimping while reducing the opening edge of the positive electrode can 11.

  Moreover, as time to preserve | save in inert gas atmosphere, 1 minute or more was preferable and it turned out that 1 minute or more and 24 hours or less are more preferable.

  The present invention is not limited to the above-described embodiments of the present invention, and various modifications and applications are possible without departing from the spirit of the present invention. For example, in the examples, an alkaline battery using a sodium hydroxide aqueous solution as the electrolytic solution has been described, but the same effect can be expected with potassium hydroxide. The present invention is not limited to the above-described embodiments and examples, and various other configurations can be adopted without departing from the gist of the present invention.

It is sectional drawing which shows an example of the alkaline battery manufactured with the manufacturing method of the alkaline battery by one Embodiment of this invention. It is sectional drawing which shows the positive electrode side half battery which comprises an alkaline battery. It is sectional drawing which shows the negative electrode side half battery which comprises an alkaline battery. It is sectional drawing which shows an example of the conventional alkaline battery.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 ... Positive electrode can 12 ... Gasket 13 ... Negative electrode cup 14 ... Positive electrode 15 ... Separator 16 ... Negative electrode 17 ... Positive electrode side half cell 18 ... Negative electrode side half cell 101. ..Positive electrode can 102 ... Gasket 103 ... Negative electrode cup 104 ... Positive electrode 105 ... Separator 106 ... Negative electrode

Claims (16)

Storing the negative electrode-side half-cell having the negative electrode, the negative electrode cup and the electrolyte in an inert gas atmosphere;
Combining the negative half-cell and the positive half, having a positive electrode, a positive electrode can, a separator, a gasket, and an electrolyte, and crimping the short edge of the positive electrode can after the storage. A method for producing an alkaline battery. The method for producing an alkaline battery according to claim 1, wherein the positive electrode is a positive electrode active material mainly composed of silver oxide, and the negative electrode is a negative electrode active material mainly composed of a granular zinc alloy. The method for producing an alkaline battery according to claim 1, wherein the electrolytic solution contains an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution. 2. The alkaline battery manufacturing method according to claim 1, wherein the inert gas is nitrogen gas or argon gas. The method for producing an alkaline battery according to claim 1, wherein the negative half-cell is stored in the inert gas atmosphere for 1 minute or longer. The method for producing an alkaline battery according to claim 1, wherein the negative half-cell is stored in the inert gas atmosphere for 1 minute to 24 hours. 2. The method for producing an alkaline battery according to claim 1, wherein the negative half-cell is produced by adding the electrolytic solution after putting the granular zinc alloy and the thickener in the negative electrode cup. 2. The alkali according to claim 1, wherein the negative half-cell is prepared in a step of mixing a granular zinc alloy, a thickener, and the electrolytic solution into a pellet shape and putting the pellet in the negative electrode cup. Battery manufacturing method. A negative electrode-side half-cell having a negative electrode, a negative electrode cup and an electrolyte;
A positive electrode, a positive electrode can, a separator, a gasket, and a positive electrode-side half-cell having an electrolyte solution, and then storing in an inert gas atmosphere;
And a step of crimping the open end edge of the positive electrode can while decompressing after the storage. The method for producing an alkaline battery according to claim 9, wherein the positive electrode is a positive electrode active material mainly composed of silver oxide, and the negative electrode is a negative electrode active material mainly composed of a granular zinc alloy. The method for producing an alkaline battery according to claim 9, wherein the electrolytic solution contains an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution. The method for producing an alkaline battery according to claim 9, wherein the inert gas is nitrogen gas or argon gas. 10. The method for producing an alkaline battery according to claim 9, wherein the negative half-cell is stored in the inert gas atmosphere for 1 minute or longer. 10. The method for producing an alkaline battery according to claim 9, wherein the negative half-cell is stored in the inert gas atmosphere for 1 minute to 24 hours. 10. The method for producing an alkaline battery according to claim 9, wherein the negative half-cell is produced in a step of adding the electrolytic solution after putting a granular zinc alloy and a thickener in the negative electrode cup. 10. The alkali according to claim 9, wherein the negative half-cell is produced in a step of mixing a granular zinc alloy, a thickener, and the electrolytic solution into a pellet shape and putting the pellet in the negative electrode cup. Battery manufacturing method.

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