JP2000082504A - Air cell and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly reliable air cell with excellent mechanical strength and leakage resistance and a large discharge capacity and its manufacturing method. SOLUTION: An air cell 1 includes a cylindrical cell can 2 having a bottom face and a hollow cylindrical air electrode 3 stored in the cell can 2. One end of the air electrode 3 is held and sealed in a first metal sealing material 19 having a folded back portion formed by folding a metal plate back and the other end of the air cell 3 is held and sealed in a second sealing material 14 having a folded back portion formed by folding a metal plate back and a block plate and the opening end thereof is blocked by the block plate. The air electrode 3 is stored in the cylindrical cell can 2 having the bottom face, with the side blocked by the second metal sealing material 14 being located on the bottom face side of the cell can 2, and at least the second metal sealing material 14 is fixed to the cell can 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cylindrical air battery and a method for manufacturing the same.

[0002]

2. Description of the Related Art With the spread of portable electronic devices in recent years, the demand for batteries as portable power sources is only increasing. In particular, the emergence of lighter, stronger, and longer-life batteries, that is, high energy density batteries, is expected. On the other hand, a high capacity alkaline manganese battery has recently been developed to respond to such a demand, but it cannot be said that sufficient electric capacity has yet been obtained.

[0003] Furthermore, recently, there has been a great deal of interest in the effective use of resources and the global environment, and it is necessary to respond to the demand to reduce the burden on the environment. Fuel cells, air cells, and the like using oxygen as a positive electrode active material are known as promising cell systems that meet these conditions. In these battery systems, since the positive electrode active material is oxygen,
Compared with other battery systems, they are not only less burden on the environment but also excellent in terms of electrical capacity that can be taken out.

An air battery is a battery that does not fill the battery with a positive electrode active material and uses oxygen in the air as the positive electrode active material. A special porous electrode (hereinafter referred to as an air electrode) for reacting oxygen in the air is used as a positive electrode of the air battery. The thickness of this air electrode is extremely thin as compared with a general alkaline battery positive electrode.
The capacity for the negative electrode is much larger than other battery systems.
For this reason, the air battery is a high energy density battery having about twice the energy density of other alkaline batteries. That is, an air battery is an ideal primary battery as a portable power supply.

[0005] In addition, button-type and coin-type air batteries have been put to practical use as power supplies for hearing aids, pagers, and the like. However, applications of these small-sized batteries are limited, and it is desired to commercialize a cylindrical air battery that can be used for a wider range of applications.

Here, an example of a configuration of a conventional cylindrical air battery is shown in FIG.

The air electrode 51 used in the air battery 50 has a hollow cylindrical shape and includes a catalyst layer 52 having an oxygen reducing ability, a metal current collector 53, and a gas permeable film 54. A gasket 55, a positive electrode terminal plate 56, and a gasket 57 are respectively arranged at predetermined positions at a closed end of the air electrode 51 on the positive electrode terminal side, and the metal current collector 53 and the positive electrode terminal plate 56 of the air electrode 51 Are electrically connected via a lead wire 58. Then, the gas permeable membrane 54
An air diffusion material 59 is provided on the outside of the
A bottomed cylindrical separator 60 made of a nonwoven fabric or the like is mounted inside 2 with its bottom portion facing the positive electrode terminal.
Then, inside the separator 60, a gelled negative electrode mixture 6 composed of granular zinc, an aqueous solution of potassium hydroxide, a gelling agent and the like.
1 is arranged.

A gasket 62 is arranged at a predetermined position at the opening end of the air electrode 51 on the side of the negative electrode terminal. Further, after a negative electrode terminal plate 63 is disposed, a cylindrical outer can 65 having an air hole 64 is removed. Covering and narrowing 66 by drawing
Is formed, and by bending the opening of the outer can 65 inward, the components inside the battery are sealed, thereby forming a cylindrical air battery.

The current collection of the negative electrode is performed by electrically connecting the negative electrode current collector pin 67 inserted in the negative electrode mixture 61 to the negative electrode terminal plate 63. The air hole 64 of the air battery 50 is closed by a seal 68 when not in use.

[0010]

An air battery is a battery using oxygen as a positive electrode active material, zinc as a negative electrode active material, and a strong alkaline aqueous solution as an electrolyte. Therefore, the battery must have sufficient reliability to prevent leakage of the electrolyte.

However, the air electrode of the conventional configuration described above has a low mechanical strength of the three materials constituting the electrode and is extremely weak against external stress. It was buried in a gasket, and a tight sealing state could not be obtained only by constriction processing of the outer can and compression of the gasket part by bending sealing. In particular, there is a disadvantage that the electrolyte inside the battery easily leaks from the air hole through the inside of the battery can from the open end of the battery can of the air electrode. Therefore,
As the battery discharge progresses and the volume of the negative electrode mixture expands,
In some cases, the internal pressure of the battery increased and the electrolyte leaked from the fixing portion of the positive electrode. In addition, the electrolyte existing inside the battery is insufficient due to the leakage of the electrolyte, and the discharge duration of the battery is reduced. Here, the reason why the internal pressure of the battery increases due to the progress of the discharge is that zinc as the negative electrode active material changes into zinc oxide with the discharge reaction of the battery, and the volume of the solid component in the negative electrode expands.

Further, the current collection of the positive electrode using the lead wire
Since the connection of the lead wires is technically difficult, and the contact resistance of the connection portion varies widely, the discharge characteristics are not constant and defects are likely to occur.

With respect to the problem of the cylindrical air battery described above,
As shown in US Pat. 5,518,834, etc., a part of the member for sealing the open end of the cylindrical positive electrode was made of metal, or as shown in JP-A-59-99656, the electrode end was buried. Improvements such as disposing a metal reinforcing material from the outside of the gasket have been attempted. However, these improvements have not yet achieved sufficient reliability.

The present invention has been proposed in view of the above-mentioned conventional circumstances, and has excellent mechanical strength and liquid leakage resistance.
An object of the present invention is to provide a highly reliable air battery having a large discharge capacity and a method for manufacturing the same.

[0015]

An air battery according to the present invention has a cylindrical battery can having a bottom portion, and a hollow cylindrical air electrode housed inside the battery can. One end of the air electrode is sandwiched and sealed by a first metal sealing material having a folded portion formed by folding the metal plate, and the other end of the air electrode is formed by folding the metal plate and a closing plate. The air electrode is inserted into and sealed with a second metal sealing material having an opening end closed by the closing plate and a cylindrical battery can having a bottom surface. The battery can is housed such that the side closed by the metal sealing material is the bottom side of the battery can, and at least the second metal sealing material is fixed to the battery can.

In the air battery according to the present invention as described above, both ends of the air electrode are sealed with the first and second metal sealing materials, and one opening end of the air electrode is closed with the closing plate. Therefore, the mechanical strength of the air electrode is improved. In this air battery, since at least the second metal sealing material is fixed to the battery can, conduction is improved and internal resistance is reduced.

In the method for manufacturing an air battery according to the present invention, one end of the hollow cylindrical air electrode is sealed by sandwiching it with a first metal sealing material having a folded portion formed by folding a metal plate. The other end of the air electrode is sandwiched and sealed with a second metal sealing material having a folded portion formed by folding a metal plate and a closing plate, and the open end is closed by the closing plate, and the bottom portion is closed. The air electrode is housed inside a cylindrical battery can having the side closed by the second metal sealing material is the bottom side of the battery can, and at least the second metal sealing is performed. The material is fixed to the battery can.

In the method for manufacturing an air battery according to the present invention as described above, both ends of the air electrode are sealed with the first and second metal sealing materials, and one opening end of the air electrode is closed with a closing plate. Since the air electrode is closed, the mechanical strength of the air electrode is improved. In this method for manufacturing an air battery, at least the second metal sealing material is fixed to the battery can, so that conduction is improved and the internal resistance is reduced.

[0019]

Embodiments of the present invention will be described below.

<First Embodiment> FIG. 1 is a longitudinal sectional view showing one structural example of an air battery according to the present invention. The air battery 1 includes a battery can 2, an air electrode 3, and an air diffusion material 4.
, A separator 5, a negative electrode mixture 6, a gasket 7,
A negative electrode current collecting pin 8 and a negative electrode terminal plate 9 are provided.

As shown in FIG. 2, the air electrode 3 is a hollow cylindrical metal current collector 10, a catalyst layer 11 applied on the metal current collector 10, and pressed on the catalyst layer 11. And a gas permeable membrane 12. Further, both ends of the opening of the air electrode 3 are sealed and reinforced by a first metal sealing material 13 and a second metal sealing material 14.

As the metal current collector 10, a conductive metal net, expanded metal, punching metal, or the like is used. Examples of the material of the metal current collector 10 include nickel, stainless steel, and stainless steel plated with nickel.

The catalyst layer 11 contains various metal oxides having an oxygen reducing ability as a catalyst, and a catalyst layer mixture obtained by mixing the catalyst with carbon black, a dispersion, and the like is placed on the metal current collector 10. It is painted. Examples of the metal oxide having the oxygen reducing ability include a manganese oxide. As the dispersion, for example, an aqueous dispersion of polytetrafluoroethylene (hereinafter referred to as PTFE) or the like is used.

The gas permeable film 12 is a porous film having oxygen gas permeability and excellent water repellency. Such a gas permeable film 12 is made of a fluororesin. The fluororesin used for the gas permeable membrane 12 is not particularly limited as long as it has oxygen gas permeability and alkali resistance, and examples thereof include PTFE.

The first metal sealing material 13 has a folded portion 13a formed by folding a metal plate.
One end of the air electrode 3 is sealed and reinforced by sandwiching one open end of the air electrode 3 along the circumference of the air electrode 3a.

The second metal sealing member 14 is provided with a folded portion 14 a and a closing plate 14 for closing the open end of the air electrode 3.
and b are formed integrally. This folded portion 14a
The other end of the air electrode 3 is sandwiched along its circumference to seal and reinforce the other end of the air electrode 3. At this time, the closing plate 14b closes the open end of the air electrode 3. By closing the open end of the air electrode 3, the leakage resistance of the air battery 1 can be further improved.

Then, the first and second metal sealing members 13,
The 14 folded portions 13a and 14a are radially compressed together with the air electrode 3. Thereby, contact between the first and second metal sealing materials 13 and 14 and the metal current collector 10 is achieved, and the density of the catalyst layer 11 is further increased. Thereby, both ends of the cylindrical air electrode 3 are firmly fixed,
The mechanical strength of the air electrode 3 can be greatly improved, the liquid leakage resistance can be improved, and the variation in current collection can be reduced.

The first and second metal sealing materials 13 and 14
For example, nickel-plated steel, nickel-plated stainless steel, copper, brass and the like are used. When copper or brass is used for the first and second metal sealing materials 13 and 14, it is preferable to apply tin plating.

As shown in FIG. 1, the air battery 1 having the above-described air electrode 3 has the air electrode 3 in the battery can 2 having an air hole 15 on the side surface and also serving as a positive electrode terminal. The side closed by the second metal sealing member 14 having the closing plate 14 b is inserted so as to face the bottom surface of the battery can 2. A hollow bottomed cylindrical separator 5 is inserted inside the air electrode 3.
Is filled with a gelled negative electrode mixture 6.

Then, the opening of the battery can 2 is sealed by the negative electrode terminal plate 9 to which the gasket 7 and the nail-shaped negative electrode current collecting pins 8 are welded. Thereby, the air electrode 3 is strongly pressed against the inner wall of the battery can 2. Here, when the granular zinc in the negative electrode mixture 6 comes into contact with the metal sealing material, a local battery is formed at that portion, and the zinc causes self-discharge, thereby reducing the discharge capacity. Therefore, the gasket 7 is intended to prevent contact between the metal sealing material and the negative electrode mixture 6 in addition to sealing the battery.

Further, the constricted portion 16 formed at the portion of the battery can 2 facing the second metal sealing material 14 causes the second metal sealing material 14 to be strongly pressed against the constricted portion 16 and Current collection between the air electrode 2 and the air electrode 3 is secured. This allows
It is possible to suppress the internal resistance value of the battery and reduce the variation in the resistance value. In addition, the current collection of the negative electrode is ensured by the nail-shaped negative electrode current collector pin 8 welded to the negative electrode terminal plate 9 being pressed into a through hole formed in the center of the gasket 7 and reaching the negative electrode mixture 6. You.

An insulating tube 17 is mounted on the side of the battery can 2, and a seal 18 for sealing the air hole 15 is mounted on the side of the insulating tube 17. The seal 18 is peeled off before using the battery.

In such an air battery 1, both ends of the air electrode 3 are provided with the first metal sealing material 13 and the second metal sealing material 14.
, The mechanical strength of the air electrode 3 is greatly improved, and the liquid leakage resistance from the electrode end can be improved. Further, in the air battery 1, the first and second metal sealing materials 13 and 14 are radially compressed together with the air electrode 3, so that the metal current collector 10 and the first and second metal sealing materials are combined. The materials 13 and 14 are in strong contact with each other, and the variation in current collection of the air electrode 3 can be reduced.

Next, a method of manufacturing such an air battery 1 will be described.

First, a metal oxide having an oxygen reducing ability, carbon black, a dispersion and the like are mixed to prepare a paste-like catalyst layer mixture. Here, as the metal oxide having the oxygen reducing ability, for example, manganese oxide or the like is used. In addition, the dispersion has, for example, a solid content of 60%.
Of PTFE is used.

Next, the above catalyst layer mixture is applied on a metal current collector 10 made of a hollow cylindrical stainless steel net whose surface is nickel-plated and dried. Thereafter, a cylindrical catalyst layer 11 having a thickness of, for example, 1.0 mm is formed through a press roll process.

Next, the metal current collector 10 on which the catalyst layer 11 has been formed is inserted into a cylindrical gas permeable film 12 having a water repellency and a thickness of, for example, 0.1 mm, and is subjected to a press roll process. By bringing the gas permeable film 12 and the metal current collector 10 into close contact with each other, the cylindrical air electrode 3 as shown in FIG. 2 is produced.

Next, a first metal sealing material 13 and a second metal sealing material 14 are attached along the circumference of both open ends of the air electrode 3 manufactured as described above. In order to attach the first and second metal sealing members 13 and 14 to the open ends of the air electrode 3, the folded portions 13a and 13 formed by folding the metal plate are used.
The open end of the air electrode 3 is sandwiched between the electrodes 4a. And
The folded portions 13a and 14a and the air electrode 3 are radially compressed along the circumference of the open end. As a result, the metal current collector 10 appearing at the open end of the air electrode 3 becomes the first and second metal current collectors.
Of the catalyst layer 1 and 14
1 and the gas permeable membrane 12 are both compressed in the radial direction and have a high density. One open end of the air electrode 3 is closed by a closing plate 14b of the second metal sealing material 14.

In order to compress the folded portion 13a and the air electrode 3 in the radial direction along the circumference of the open end, for example, as shown in FIG. 2, a method of reducing the outer diameter φA of the folded portion 13a, or And a method of increasing the inner diameter φB of the folded portion 13a. Further, these methods may be used in combination. The compression of the folded portion 14a and the air electrode 3 in the radial direction may be performed in the same manner as described above.

Then, the air battery 1 is manufactured using the air electrode 3 manufactured as described above.

First, an air diffusing material 4 made of a nonwoven fabric or the like is attached to the outside of the air electrode 3. Then, the air electrode 3 on which the air diffusion material 4 is mounted is inserted into the battery can 2 such that the side where the second metal sealing material 14 is disposed faces the bottom surface of the battery can 2. The battery can 2 also serves as an external positive electrode terminal of the air electrode 3, and has an air hole 15 formed on a side surface thereof.

Next, a portion of the battery can 2 facing the second metal sealing material 14 is drawn from the circumferential direction to form a constricted portion 16. As a result, the second metal sealing material 14 is strongly pressed against the constricted portion 16 and the battery can 2 and the air electrode 3 are pressed.
Power collection is secured.

Next, a hollow bottomed cylindrical separator 5 made of a nonwoven fabric such as a natural pulp material is provided inside the air electrode 3.
It is inserted so as to contact the air electrode 3. Further, the inside of the separator 5 is filled with a gelled negative electrode mixture 6 composed of granular zinc, an aqueous solution of potassium hydroxide, a gelling agent and the like.

Next, the gasket 7 is inserted into the opening of the battery can 2. Here, a nail-shaped negative electrode current collecting pin 8 penetrates through the center of the gasket 7 and is electrically connected to the negative electrode terminal plate 9. Here, the metal current collector 10 of the air electrode 3 is
Via the second metal sealing material 14, the battery can 2 is connected with a low contact resistance at the constricted portion 16 of the battery can 2 also serving as the positive electrode terminal. On the other hand, for the current collection of the negative electrode, the nail-shaped
, And is secured by reaching the negative electrode mixture 6 through the gasket 7.

Finally, the battery can 2 and the negative electrode terminal plate 9 are caulked and sealed by mechanically bending the opening of the battery can 2 inward. Then, the insulating tube 17 is attached to the outer surface of the battery can 2, and the air hole 15 is formed on the insulating tube 17.
The seal 18 for closing the seal is mounted. In this way,
As shown in FIG. 1, a cylindrical air battery 1 having an outer diameter of, for example, 14 mm and a height of, for example, 50 mm is manufactured.

In the air battery 1 according to the present embodiment,
As shown in FIG. 3, the first metal sealing material 13 of the battery can 2
It is preferable that a constricted portion 19 is formed also at a position facing the first metal sealing material, and the first metal sealing material 13 is fixed by the constricted portion 19. By fixing not only the second metal encapsulant 14 but also the first metal encapsulant 13 with the constricted portion 19 formed in the battery can 2, current collection between the battery can 2 and the air electrode 3 is performed. Is secured more. Thereby, the effect of suppressing the internal resistance of the air battery 1 and reducing the variation in current collection can be further improved.

At this time, it is preferable that a resin selected from asphalt-based, polyamide-based, and polyolefin-based is applied to the contact surface between the first metal sealing material 13 and the battery can 2. By applying a resin to the joint surface between the first metal sealing material 13 and the battery can 2, the interface between the battery can 2 and the first metal sealing material 13 can be firmly sealed.
Thereby, it is possible to prevent the electrolyte from leaking from the air hole 15 through the gap between the battery can 2 and the first metal sealing material 13, and it is possible to improve the leakage resistance of the air battery 1.

Further, at this time, as shown in FIG. 4, it is preferable to dispose a resin sealing ring 20 between the first metal sealing material 13 and the battery can 2. First metal sealing material 1
By arranging the sealing ring 20 between 3 and the battery can 2,
The interface between the battery can 2 and the first metal sealing material 13 can be firmly sealed, and the liquid leakage resistance is further improved.

A resin selected from an asphalt-based, polyamide-based, or polyolefin-based resin is used for the contact surface between the sealing ring 20 and the first metal sealing material 13 and the contact surface between the sealing ring 20 and the battery can 2. By coating, the sealing is performed more reliably, and the reliability of the leak resistance of the air battery 1 can be improved.

It is preferable that the sealing ring 20 and the gasket 7 are integrated into one part. By integrating the sealing ring 20 and the gasket 7, the number of parts can be reduced, and the cost can be reduced and the productivity can be improved.

<Second Embodiment> FIG. 5 shows an example of the configuration of an air battery 30 according to the present embodiment.

The air battery 30 has a hollow cylindrical air electrode 31. The air electrode 31 includes a hollow cylindrical metal current collector 32, a catalyst layer 33 coated on the metal current collector 32, and a gas permeable membrane 3 pressed on the catalyst layer 33.
4, and both ends of the opening are metal sealing materials 3
Sealed and reinforced by 5,36. Since the air electrode 31 has substantially the same configuration as the air electrode 3 in the above-described first embodiment, a detailed description is omitted here.

The air battery 30 is connected to the battery can 37 via the air diffusion member 38 such that the side closed by the metal sealing member 36 having the closing plate faces the bottom surface of the battery can 37. 37. This battery can 37
It has an air hole 39 on the side and also serves as an external positive electrode terminal of the air battery 30.

A hollow bottomed cylindrical separator 40 is inserted inside the air electrode 31, and the inside of the separator 40 is filled with a gelled negative electrode mixture 41. The opening of the battery can 37 is
And a negative electrode terminal plate 44 to which the negative electrode current collecting pin 43 is welded. And on the side of the battery can 37,
An insulating tube 45 is mounted, and a seal 46 for sealing the air hole 39 is mounted. Here, the air battery 30 has substantially the same configuration as the air battery 1 in the above-described first embodiment, and a detailed description thereof will be omitted.

In the air battery 30 according to the present embodiment, the bottom surface of the battery can 37 and the metal sealing material disposed on the bottom surface side of the battery can 37 of the air electrode 31 inserted inside the battery can 37. 36 are connected by, for example, spot welding.

By welding the battery can 37 and the metal sealing material 36 located on the bottom side of the battery can 37, the conduction between the battery can 37 and the metal sealing material 36 is further improved. Therefore, the internal resistance of the air battery 30 can be reduced, the reliability in current collection can be increased, and the discharge characteristics can be improved.

In the air battery 30 according to the present embodiment, as shown in FIG.
It is preferable that a constricted portion 47 is formed at a position facing the metal sealing material 35 disposed on the opening end side of the first and the metal sealing material 35 is fixed by the constricted portion 47. The metal sealing material 35 disposed on the opening end side is replaced with a constricted portion 47 formed on the battery can 37.
Thus, current collection between the battery can 37 and the air electrode 31 is further ensured. Thereby, the internal resistance of the air battery 30 can be further reduced, the reliability in current collection can be further increased, and the discharge characteristics can be further improved.

At this time, it is preferable that a resin selected from an asphalt-based, polyamide-based, or polyolefin-based resin is applied to a contact surface between the metal sealing material 35 and the battery can 37. By applying resin to the joint surface between the metal sealing material 35 and the battery can 37, the interface between the battery can 37 and the metal sealing material can be firmly sealed. Thereby, it is possible to prevent the electrolyte from leaking from the air hole 38 through the gap between the battery can 37 and the metal sealing material.
0 can improve the liquid leakage resistance.

Further, at this time, it is preferable to dispose a resin sealing ring 48 between the metal sealing material 35 and the battery can 37 as shown in FIG. By disposing a sealing ring 48 between the metal sealing material 35 and the battery can 37, the battery can 3
The interface between 7 and the metal sealing material 35 can be firmly sealed, and the liquid leakage resistance is further improved.

A resin selected from asphalt, polyamide, and polyolefin is applied to the contact surface between the sealing ring 48 and the metal sealing material 35 and the contact surface between the sealing ring 48 and the battery can 37. As a result, the sealing is performed more reliably, and the reliability of the leak-resistant characteristics of the air battery 30 can be improved.

It is preferable that the sealing ring 48 and the gasket 42 are integrated into one part. By integrating the sealing ring 48 and the gasket 42, the number of parts can be reduced, and cost reduction and productivity improvement can be achieved.

[0062]

EXAMPLE 1 A cylindrical air electrode as shown in FIG. 2 was prepared, and a cylindrical air battery as shown in FIG. 1 was prepared using this air electrode.

First, a metal oxide having an oxygen reducing ability, carbon black, and a dispersion were mixed to prepare a paste-like catalyst layer mixture. Here, manganese oxide was used as the metal oxide having the oxygen reduction ability. In addition, an aqueous dispersion of PTFE having a solid content of 60% was used as the dispersion.

Next, the above catalyst layer mixture was applied onto a metal current collector made of a hollow cylindrical stainless steel net with a nickel plating on the surface, and dried. Thereafter, a cylindrical catalyst layer having a thickness of 1.0 mm was formed through a press roll process.

Next, the metal current collector on which the catalyst layer is formed is
A cylindrical air electrode was manufactured by inserting the gas-permeable membrane into a cylindrical gas-permeable membrane having a water repellency and having a thickness of 0.1 mm and bringing the gas-permeable membrane into close contact with the catalyst layer using a press roll process.

Next, a first metal sealing material and a second metal sealing material were attached along the circumference of both open ends of the air electrode manufactured as described above. In order to attach the first and second metal sealing materials to both opening ends of the air electrode, the opening end of the air electrode is sandwiched between the folded portions formed by folding the metal plate, and the metal sealing material and the air are inserted. The electrode was radially compressed along the circumference of the open end.

Then, an air battery was manufactured using the air electrode manufactured as described above.

First, an air diffusion material made of a nonwoven fabric or the like was attached to the outside of the air electrode. Then, the air electrode to which the air diffusion material was attached was inserted into the battery can such that the side closed by the second metal sealing material having the closing plate was opposed to the bottom surface of the battery can. This battery can also serves as an external positive electrode terminal of the air electrode, and has an air hole formed on a side surface thereof.

Next, a portion of the battery can facing the metal sealing material disposed on the closed end side of the air electrode was drawn from the circumferential direction to form a constricted portion. Thereby, the metal sealing material is strongly pressed against the constricted portion, and current collection between the battery can and the air electrode is secured.

Next, a hollow bottomed cylindrical separator made of a nonwoven fabric of natural pulp material was inserted inside the air electrode so as to be in contact with the air electrode. Further, the inside of the separator was filled with a gelled negative electrode mixture composed of granular zinc, an aqueous solution of potassium hydroxide, and a gelling agent.

Next, the gasket was inserted into the opening of the battery can. Here, a nail-shaped negative electrode current collector pin penetrates through the center of the gasket, and is electrically connected to the negative electrode terminal plate. Here, the metal current collector of the air electrode is connected with a low contact resistance at a narrow portion of the battery can also serving as a positive electrode terminal via a metal sealing material. On the other hand, the current collection of the negative electrode is ensured by inserting a nail-shaped negative electrode current collector pin into the center of the gasket and penetrating the gasket to reach the negative electrode mixture.

Finally, the battery can and the negative electrode terminal plate were caulked and sealed by mechanically bending the opening of the battery can inward. Thus, the outer diameter is 14 mm and the height is 5
A 0 mm cylindrical air battery was produced.

<Embodiment 2> As shown in FIG. 3, a constricted portion is formed at a position of the battery can facing the metal sealing material arranged on the open end side of the air electrode, and the metal sealing material is formed. A cylindrical air battery was produced in the same manner as in Example 1, except that was fixed at the constricted portion. At this time, asphalt was applied to the contact surface between the metal sealing material disposed on the opening end side of the air electrode and the battery can.

<Embodiment 3> As shown in FIG. 4, a resin sealing ring is arranged between a metal sealing material disposed on the opening end side of the air electrode and the battery can, and A cylindrical air battery was manufactured in the same manner as in Example 1 except that a constricted portion was formed at a position facing the metal sealing material, and the metal sealing material was fixed at the constricted portion. At this time,
Asphalt was applied to the contact surface between the sealing ring and the metal sealing material and the contact surface between the sealing ring and the battery can.

Example 4 An air electrode was produced in the same manner as in Example 1, and metal sealing materials were provided at both ends.

Then, an air diffusion material made of a nonwoven fabric or the like was attached to the outside of the air electrode. Then, the air electrode to which the air diffusion material was attached was inserted into the battery can such that the side closed by the metal sealing material having the closing plate faced the bottom surface of the battery can. Then, without forming a constricted portion in the battery can, spot welding is performed on the bottom surface of the battery can and the metal sealing material disposed on the bottom surface side of the battery can, of the air electrode inserted inside the battery can. And the metal sealing material was fixed to the battery can. Except for this, a cylindrical air battery as shown in FIG. 5 was produced in the same manner as in Example 1.

<Embodiment 5> As shown in FIG. 6, a constricted portion is formed at a position of the battery can facing the metal sealing material disposed on the opening end side of the air electrode, and the metal sealing material is formed. A cylindrical air battery was produced in the same manner as in Example 4, except that the battery was fixed at the constricted portion. At this time, asphalt was applied to the contact surface between the metal sealing material disposed on the opening end side of the air electrode and the battery can.

<Embodiment 6> As shown in FIG. 7, a resin sealing ring is arranged between a metal sealing material disposed on the open end side of the air electrode and the metal can and a battery can. A cylindrical air battery was manufactured in the same manner as in Example 4, except that a constricted portion was formed at a position facing the metal sealing material, and the metal sealing material was fixed at the constricted portion. At this time,
Asphalt was applied to the contact surface between the sealing ring and the metal sealing material and the contact surface between the sealing ring and the battery can.

<Comparative Example> According to the method described in the above-mentioned prior art, as shown in FIG.
mm was manufactured. The composition of the catalyst layer of the air electrode and the negative electrode mixture, the material of each member, and the like were the same as those in Example 1.

Among the air cells manufactured as described above, the air cells of Examples 1, 4 and Comparative Examples were subjected to discharge characteristic evaluation tests, and the air cells of Examples 1 to 6 and Comparative Examples were tested. The battery was subjected to an evaluation test for leak resistance.

In the discharge characteristic test, the battery was discharged under a load of 10Ω, and the discharge capacity until the battery voltage fell below 0.9 V was measured. Further, as for the liquid leakage resistance, 30 samples were prepared for each battery, and each battery was discharged at a load of 10Ω. Then, 100 hours and 500 hours after the battery voltage dropped below 0.9 V, the number of batteries for which liquid leakage was confirmed was examined.

Test results of the discharge characteristics of the air cells of Examples 1, 4 and Comparative Examples, and Examples 1 to 6
Table 1 shows the test results of the leakage resistance characteristics of the air batteries of Comparative Examples.

[0083]

[Table 1]

From Table 1, it can be seen that the air batteries of Examples 1 and 4 in which the metal sealing materials were disposed at both ends of the air electrode,
After 00 hours, no liquid leakage was observed. However, in the air cell of the comparative example in which the metal sealing material was not disposed at both ends of the air electrode, liquid leakage was observed in 19 out of 30 samples. Was. Also, 500 hours after the discharge, the air batteries of Examples 1 and 4 showed leakage in 8 samples each, whereas the air batteries of Comparative Example leaked in all 30 samples. Was confirmed. Therefore, it was found that by sealing both ends of the air electrode with the metal sealing material, the leak resistance of the air battery was improved.

The air batteries of the first and fourth embodiments are:
A higher discharge capacity than the air battery of the comparative example was obtained. In particular, in the air battery of Example 4 in which the metal sealing material was welded to the battery can, a higher discharge capacity was obtained than in the air battery of Example 1 in which the air electrode was fixed at the constricted portion formed in the battery can, and a good discharge capacity was obtained. It turned out that continuity was secured.

The air battery of Example 2 in which the metal sealing material on the opening end side was also fixed by the constricted portion formed in the battery can had better leakage resistance than the air battery of Example 1. . Furthermore, in the air battery of Example 3 in which the sealing ring was arranged between the metal sealing material on the opening end side and the battery can, no leakage was observed even after 500 hours from the discharge, and further excellent leakage resistance characteristics Was obtained.

Further, in the air battery of Example 5 in which the metal sealing material at the opening end side was fixed by the constricted portion formed in the battery can, more excellent leakage resistance was obtained than in the air battery of Example 4. Was. Further, in the air battery of Example 6, in which a sealing ring was disposed between the metal sealing material on the opening end side and the battery can, 50 days after discharge.
No liquid leakage was observed even after 0 hour, indicating that more excellent liquid leakage resistance was obtained.

[0088]

In the air battery according to the present invention, both ends of the air electrode are sealed with a metal sealing material, and at least one of the metal sealing materials is fixed to the battery can. The characteristics, discharge characteristics and discharge capacity become excellent.

In the method for manufacturing an air battery according to the present invention, both ends of the air electrode are sealed with a metal sealing material, and at least one of the metal sealing materials is fixed to the battery can. An air battery having excellent liquid characteristics and excellent discharge characteristics and discharge capacity can be realized.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing one configuration example of an air battery according to the present invention.

FIG. 2 is a sectional view showing a configuration of an air electrode used in the air battery of FIG.

FIG. 3 is a sectional view showing another configuration example of the air battery according to the present invention.

FIG. 4 is a sectional view showing another configuration example of the air battery according to the present invention.

FIG. 5 is a sectional view showing another configuration example of the air battery according to the present invention.

FIG. 6 is a sectional view showing another configuration example of the air battery according to the present invention.

FIG. 7 is a cross-sectional view showing another configuration example of the air battery according to the present invention.

FIG. 8 is a cross-sectional view showing one configuration example of a conventional air battery.

[Explanation of symbols]

1 air battery, 2 battery can, 3 air electrode, 4
Air diffusion material, 5 separator, 6 negative electrode mixture, 7
Gasket, 8 negative electrode current collector pin, 9 negative electrode terminal plate, 10 metal current collector, 11 catalyst layer, 12 gas permeable film, 13 first metal sealing material, 14 second metal sealing material

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Ryosuke Takagi 6-35, Kita-Shinagawa, Shinagawa-ku, Tokyo Sony Corporation F-term (reference) 5H011 AA17 CC06 DD06 DD13 FF02 HH02 HH04 5H032 AA03 AS03 AS11 BB04 BB05 BB10 CC04 EE01 EE04

Claims (14)

[Claims] 1. A battery having a cylindrical battery can having a bottom surface, and a hollow cylindrical air electrode housed in the battery can. One end of the air electrode is formed by folding a metal plate. The other end of the air electrode is sandwiched and sealed with a first metal sealing material having a folded portion, and a second metal sealing having a folded portion formed by folding the metal plate and a closing plate The air electrode was closed with the second metal sealing material inside a cylindrical battery can having a bottom surface portion while being sandwiched and sealed with a material, and the opening end was closed with the closing plate. An air battery which is housed so that its side is the bottom side of the battery can, and at least the second metal sealing material is fixed to the battery can. 2. A constricted portion is formed along the circumference of the battery can, and the second metal sealing material is fixed to the battery can by the constricted portion. The air battery according to claim 1, wherein 3. The air battery according to claim 1, wherein the second metal sealing material is fixed to the battery can by welding to the battery can. 4. The battery can according to claim 1, wherein a constricted portion is formed along a circumference of the battery can, and the first metal sealing material is fixed to the battery can by the constricted portion. The air battery according to claim 1, wherein 5. A resin selected from asphalt-based, polyamide-based, and polyolefin-based is applied to a contact surface between the first metal sealing material and the battery can. Air battery. 6. A sealing ring is provided between the battery can and the first metal sealing material, and the battery can has a constriction formed along a circumference thereof. The air battery according to claim 1, wherein the first metal sealing material is fixed to the battery can by the constricted portion. 7. A resin selected from asphalt-based, polyamide-based, and polyolefin-based is applied to a contact surface between the battery can and the sealing ring and a contact surface between the first metal sealing material and the sealing ring. 7. The air battery according to claim 6, wherein the air battery is worn. 8. A method for manufacturing an air battery, comprising sealing one end of a hollow cylindrical air electrode by sandwiching the first end with a first metal sealing material having a folded portion formed by folding a metal plate; The other end of the electrode is sandwiched and sealed with a second metal sealing material having a folded portion formed by folding a metal plate and a closing plate, and an open end is closed by the closing plate, and a bottom portion is provided. Inside the cylindrical battery can, the air electrode is housed so that the side closed by the second metal sealing material is the bottom surface side of the battery can, and at least the second metal sealing material. Is fixed to the battery can. 9. The battery can according to claim 8, wherein a constricted portion is formed along the circumference of the battery can, and the second metal sealing material is fixed to the battery can by the constricted portion. Manufacturing method of air battery. 10. The method for manufacturing an air battery according to claim 8, wherein the second metal sealing material is fixed to the battery can by welding to the battery can. 11. The battery can according to claim 8, wherein a constricted portion is formed along the circumference of the battery can, and the first metal sealing material is fixed to the battery can by the constricted portion. Manufacturing method of air battery. 12. The air according to claim 11, wherein a resin selected from asphalt-based, polyamide-based, and polyolefin-based is applied to a contact surface between the first metal sealing material and the battery can. Battery manufacturing method. 13. A sealing ring is provided between the battery can and the first metal sealing material, and a constricted portion is formed along the circumference of the battery can to form the first metal sealing. 9. The method for manufacturing an air battery according to claim 8, wherein a stopper is fixed to the battery can by the constricted portion. 14. A resin selected from an asphalt-based, polyamide-based, and polyolefin-based resin is applied to a contact surface between the battery can and the sealing ring and a contact surface between the first metal sealing material and the sealing ring. The method for manufacturing an air battery according to claim 13, wherein: