JP2007035447A - Sealed primary cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sealed primary cell capable of suppressing damages to an equipment or the like due to leakage to a minimum by early finding it simply and surely, when there is leakage in one equipped with an anti-leak structure suffers due to inappropriate preservation or usage. <P>SOLUTION: The sealed primary cell provided with an anti-leak structure is so structured to generate odor in accompaniment to leakage. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a sealed primary battery having a leak-proof structure, and is effective when applied to, for example, a manganese primary battery, an alkaline primary battery, a lithium primary battery, and the like.

  Sealed primary batteries such as R-type manganese batteries, LR-type alkaline batteries, and CR-type lithium batteries have a leak-proof structure for preventing electrolyte leakage. However, even if it has a leak-proof structure, it may leak if stored or used improperly.

  In the case of misuse such as short-circuiting or charging, there is a risk that the battery internal pressure abnormally rises due to gas generation in the battery and the battery bursts. Along with this rupture, a large amount of electrolyte is instantaneously released. Battery rupture is particularly a concern in high energy density primary batteries such as alkaline batteries.

  As a measure for preventing battery rupture, a safety valve function is provided. This safety valve function is such that when the internal pressure of the battery rises abnormally, it breaks locally to form a gas venting path, and the local breakage point is selectively applied to a part of the sealing gasket, for example. It is formed by providing the thin part which is easy to fracture | rupture.

  Primary battery electrolytes include zinc chloride aqueous solution (manganese dry battery), high-concentration alkaline aqueous solution (alkaline dry battery), and organic solvent (lithium primary battery). ) Or short circuit or leakage of the electric circuit. In addition, the sealed primary battery is used by being incorporated in various battery-utilizing devices. If liquid leakage occurs in this device built-in state, it may cause failure or damage of the device.

For this reason, in sealed primary batteries, improving leakage resistance performance has been the most important technical problem from the past along with discharge performance, and technical development for that purpose continues (for example, Patent Document 1). . As a result, the liquid leakage resistance of the sealed primary battery gradually increases, and it has become possible to guarantee high reliability only when storage and use are performed appropriately.
JP-A-5-109411

  The sealed primary battery exhibits high leakage resistance when it is properly stored and used, and it is extremely difficult to avoid leakage when it is inappropriate. In addition, even if it is possible to demand high leakage resistance even for inappropriate storage and use, it is impossible to realize it on an industrial basis where mass production and cost reduction must be considered. It is.

  Inappropriate use of sealed primary batteries is especially the case where a dry cell is left in the device and forgotten. The left dry battery eventually becomes out of capacity due to current consumption or self-discharge in the device. This out-of-capacity state is a kind of overdischarge state, and liquid leakage tends to occur. In this state, the device becomes inoperable, and naturally does not function even if there is a battery remaining amount warning circuit or the like. Then, due to leakage (electrolytic solution) from the out-of-capacity battery, metal parts such as terminals are corroded (rust is generated), causing failure or damage of the device.

  Even when the battery is not built in the device, if a used dry battery is left in a drawer, for example, there is a problem in that surrounding articles are corroded or soiled due to leakage from the battery. Therefore, it is necessary to detect and appropriately dispose of the dry battery in which leakage occurs.

  In addition, when stocking a large number of dry batteries (sealed primary batteries), it cannot be said that there is a possibility that a defective liquid leaks into the stock due to some mistake. In this case as well, it is desired to detect the presence or absence of the leaked defective product as early as possible. This is because a defective liquid leaks the surrounding battery and becomes a defective product. However, it is very difficult to identify defective products from a large number.

  As described above, in sealed primary batteries, it is also important to improve leakage resistance. However, leakage batteries that are caused by improper storage or use can be detected as early as possible, whether or not they are leaked. It is even more important in preventing such damage. However, in the conventional technology, the discovery of the leaking battery is difficult and lagging.

  The present invention has been made in view of the background as described above, and its purpose is to easily determine whether or not there is a leak when a sealed primary battery having a leak-proof structure leaks due to improper storage or use. It is another object of the present invention to provide a sealed primary battery that can be surely detected at an early stage and minimize damage to equipment due to leakage.

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

The present invention provides the following solutions.
(1) A sealed primary battery having a leak-proof structure, wherein when a leak occurs, an odor is generated along with the leak.

  (2) In the above means (1), an odorous substance is added or applied to at least one of an electrolytic solution, a positive electrode active material, a negative electrode active material, a separator, a battery case, and a sealing body, and the odorous substance is non-coated. A sealed primary battery, which is confined so as not to leak out of the battery at the time of leakage.

  (3) In the above means (1) or (2), an electrolytic solution comprising a potassium hydroxide aqueous solution, a positive electrode mixture using manganese dioxide and / or nickel oxyhydroxide as an active material, and zinc or a zinc alloy as an active material Odor substance is added or applied to at least one of negative electrode gel, non-work cloth separator, positive electrode can, and sealing gasket, and the odor substance is confined so that it does not leak outside the battery when it is not leaking. A sealed primary battery, characterized in that

  (4) In any one of the above means (1) to (3), as an odor substance, an aromatic compound, aromatic hydrocarbon, aliphatic hydrocarbon, terpene, ester, ketone, alcohol, aldehyde, ketone, lactone, oxide A sealed primary battery, wherein at least one organic compound selected from phenol, musk, or the like is added or applied thereto.

  (5) In any one of the above means (1) to (4), when the internal pressure of the battery is abnormally increased, a safety valve function is provided so that a gas venting path is formed by locally breaking. A sealed primary battery characterized in that an odorous substance in the battery is released to the outside by operation.

  (6) A sealed primary battery characterized in that, in the above means (5), an odorous substance is arranged in the middle of a gas vent path formed by operation of a safety valve function.

  When a sealed primary battery equipped with a leak-proof structure leaks due to improper storage or use, the presence or absence of the leak is detected easily and reliably at an early stage to minimize damage to the equipment due to the leak. It is possible to provide a sealed primary battery that makes it possible.

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

  FIG. 1 is a cross-sectional view showing a schematic configuration of an alkaline dry battery (LR6) according to an embodiment of the present invention. The dry battery shown in the figure is a sealed alkaline primary battery using an electrolytic solution made of a high-concentration potassium hydroxide aqueous solution, and is formed into a bottomed cylindrical metal battery can 11 and a ring (circular tube). A positive electrode mixture 21, a cylindrical separator 22, a negative electrode gel 23, a negative electrode current collector 31, a negative electrode terminal plate 32, a metal annular seat plate 33, a resin sealing gasket 35, and the like are used.

  The positive electrode can 11 is a battery case that serves as both a positive electrode current collector and a positive electrode terminal, and a convex positive electrode terminal portion 12 is integrally formed on the outer bottom by pressing. Further, a bead portion (constriction portion) 13 is formed at a position slightly lower than the opening portion, and a sealing body 30 described later is mounted on the bead portion 13.

  The positive electrode mixture 21 contains manganese dioxide, nickel oxyhydroxide, or manganese dioxide and nickel oxyhydroxide as active materials. The separator 22 is configured by using a liquid absorbing material such as unemployed cloth and a liquid-permeable sheet or film material, and is loaded inside the positive electrode mixture 21. The negative electrode gel 23 is obtained by gelling zinc or a zinc alloy, which is a negative electrode active material, and is filled inside the separator 22. The positive electrode mixture 21, the cylindrical separator 22, and the negative electrode gel 23 form the power generation element 20 in the presence of an alkaline electrolyte.

  The negative electrode current collector 31 has its base end (upper end) fixed to the inner center of the negative electrode terminal plate 32 by spot welding, and its front end is inserted into the negative electrode gel 23. The sealing gasket 35 closes the opening of the positive electrode can 11 and is interposed between the opening of the positive electrode can 11 and the peripheral portion of the negative electrode terminal plate 32 in a pressurized state, thereby hermetically sealing the inside of the positive electrode can 11. To do.

  The peripheral portion of the gasket 35 is clamped inwardly at the opening of the positive electrode can 11 so that the peripheral portion is sandwiched between the opening of the positive electrode can 11 and the peripheral portion of the negative electrode terminal plate 32 in a pressurized state. Is done. The negative electrode current collector 31, the negative electrode terminal plate 32, the annular seat plate 33, and the resin sealing gasket 35 are assembled into the sealing body 30 in advance and then loaded into the opening of the positive electrode can 11.

  The dry battery (sealed primary battery) has a safety valve function by a thin portion formed in a part of the sealing gasket 35. This safety valve function prevents the battery from bursting by forming a gas vent path by breaking the thin wall portion of the gasket 35 due to the battery internal pressure when the battery internal pressure abnormally increases.

  Further, in addition to the above configuration, when the electrolyte in the battery leaks to the outside due to the operation of the safety valve function, the odorous substance is also released to the outside along with the leakage of the dry battery (sealed primary battery). It is comprised so that. An odorous substance is a substance that makes the human body feel a significant odor or odor (a strange odor). This includes products other than cosmetic and edible fragrances that are subject to preference.

  The odor substance is discharged outside the battery only when leakage occurs to dissipate the odor, and is used in a state of being confined inside the battery so as not to dissipate the odor to the outside when the non-leakage is normal. For this purpose, an odor substance may be added or applied to at least one of the electrolytic solution, the positive electrode mixture 21, the negative electrode gel 23, the separator 22, the inside of the positive electrode can 11, and the inside of the sealing gasket 35 inside the battery. As a result, the odor substance leaks together with the electrolyte only when the liquid leaks, but is confined so as not to leak out of the battery when the liquid does not leak.

  Further, in a battery having a safety valve function that is locally broken to form a gas venting path when the battery internal pressure rises abnormally, the odor substance in the battery is released to the outside by the operation of the safety valve function. It is good to add or apply to. In this case, the odor substance may be disposed in the middle of the gas vent path formed by the operation of the safety valve function, and does not necessarily need to be inside the gasket 35.

  As the odorous substance, an aromatic compound, aromatic hydrocarbon, aliphatic hydrocarbon, terpene, ester, ketone, alcohol, aldehyde, ketone, lactone, oxide, phenol, musk and the like can be used. One kind of odor substance may be used, but a plurality of kinds may be used as necessary. Although these are organic compounds, the odorous substances of these organic compounds have little influence on the power generation reaction in the battery, and thus are suitable for use in the present invention.

  As the odor quality, a fragrance used for cosmetics or food, or a toilet odor, which emits an odor (odor) different from the odor (or odor) felt daily is desirable. On the other hand, for example, an odor added to city gas is well known as a warning odor, so it can be said that it is suitable for the use of the present invention.

  The sealed primary battery configured as described above is used in case of leakage due to improper storage or use, such as forgetting it while it is built in the device or leaving it in a drawer. Since the odor is diffused from the battery along with the leakage, the occurrence of the leakage can be detected at an early stage.

  Also, even if a leaked defective product is mixed into a large number of stocks due to a mistake, the presence or absence of defective products can be easily and reliably determined by the odor emitted from the leaked defective product. Can do. As described above, since it is possible to easily and surely detect the presence or absence of liquid leakage at an early stage, it is possible to minimize damage to equipment or the like due to liquid leakage.

[Example 1]
The LR6 (AA) alkaline battery to which a small amount of fragrance was added was leaked under the following conditions (1) to (4), and the presence or absence of each odor was verified.
(1) 60 ° C./90% R.D. H. Save with. (2) 150 mA continuous charging. (3) Short-circuit in a state where only one is connected in reverse with four connected in series. (4) After discharging at 10Ω for 48 hours, stored at 60 ° C.
When leakage was generated under the above conditions (1) to (4), as shown in Table 1, it was possible to confirm the generation of odor associated with leakage even when leakage was performed under any conditions. . In addition, it was confirmed that none of the batteries had an odor when no liquid leaked.

  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 present invention can be suitably applied to a manganese primary battery and a lithium primary battery.

  When a sealed primary battery equipped with a leak-proof structure leaks due to improper storage or use, the presence or absence of the leak is detected easily and reliably at an early stage to minimize damage to the equipment due to the leak. It is possible to provide a sealed primary battery that makes it possible.

It is sectional drawing which shows schematic structure of the alkaline dry battery (LR6) which makes one Embodiment of this invention.

Explanation of symbols

11 Battery can (battery case)
12 Positive terminal portion 13 Bead portion (constriction)
DESCRIPTION OF SYMBOLS 20 Electric power generation element 21 Positive electrode mixture 22 Separator 23 Negative electrode gel 30 Sealing body 31 Negative electrode current collector 32 Negative electrode terminal board 33 Toroidal seat board 35 Sealing gasket

Claims (6)

  A sealed primary battery having a leak-proof structure, wherein when a leak occurs, an odor is generated along with the leak.   The odor substance is added or applied to at least one of an electrolyte solution, a positive electrode active material, a negative electrode active material, a separator, a battery case, and a sealing body. A sealed primary battery characterized in that it is confined so as not to leak out.   3. An electrolyte solution comprising an aqueous potassium hydroxide solution, a positive electrode mixture using manganese dioxide and / or nickel oxyhydroxide as an active material, a negative electrode gel using zinc or a zinc alloy as an active material, unemployed cloth, etc. An odorous substance is added or applied to at least one of the separator, the positive electrode can, and the sealing gasket, and the odorous substance is confined so as not to leak out of the battery when not leaking. Sealed primary battery.   4. The odor substance according to claim 1, wherein the odor substance is selected from an aromatic compound, an aromatic hydrocarbon, an aliphatic hydrocarbon, a terpene, an ester, a ketone, an alcohol, an aldehyde, a ketone, a lactone, an oxide, a phenol, and a musk. A sealed primary battery characterized in that at least one organic compound is added or coated.   5. The odorous substance in the battery according to any one of claims 1 to 4, comprising a safety valve function that is locally broken to form a gas venting path when the battery internal pressure rises abnormally, and the safety valve function is activated. Sealed primary battery characterized in that is discharged to the outside. 6. The sealed primary battery according to claim 5, wherein an odorous substance is arranged in the middle of a degassing path formed by the operation of the safety valve function.

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