JPH09306510A - Nonaqueous battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To keep initial performance for a long time, in a primary nonaqueous battery, which is housed in the battery can, and in which the opening part of the battery can is sealed. SOLUTION: At least one kind carbonate, selected from the carbonate of K, Na, Ca, Mg, or Al is made to exist inside a battery can 2 (e.g. the center space part of a power generation element). The contained quantity of the carbonate is preferably 1-20wt.% of a positive electrode active material. This can prevent the deterioration of the positive electrode active material or a nonaqueous electrolyte due to the mixing of moisture, because the carbonate can absorb the moisture despite the moisture is mixed into the inside of the battery can 2.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a primary or secondary non-aqueous battery.

[0002]

2. Description of the Related Art In non-aqueous batteries, the performance of non-aqueous batteries is deteriorated because the positive electrode active material and the non-aqueous electrolyte are deteriorated when water is mixed into the battery can, resulting in a decrease in battery capacity and deterioration in storability. Will fall.

Therefore, conventionally, it has been attempted to prevent the mixing of water by maintaining the non-aqueous battery manufacturing process in a dry atmosphere or improving the sealing property of the battery can.

[0004]

However, there is a limit to the atmosphere adjustment of the space where the manufacturing line is installed, and it is difficult to achieve a sufficiently satisfactory dry atmosphere, so that water is mixed during the manufacturing process. There is a risk. Also,
Since the improvement of the sealing property of the battery can is naturally limited, it is impossible to completely prevent the mixing of water, and there is a disadvantage that the performance may be deteriorated in a storage test for a long period of time.

Further, when the non-aqueous battery is a rechargeable secondary battery, a method of incorporating a pressure-sensitive current cutoff mechanism utilizing an increase in internal pressure due to overcharging is widely adopted as a countermeasure for the overcharge. However, depending on the condition of overcharge, the rise of the internal pressure delays, so the operation of the pressure-sensitive current cutoff mechanism is delayed, and in the worst case, it may not be possible to avoid ignition or rupture of the non-aqueous battery, and further improvement is required. Was wanted.

In view of the above circumstances, the first object of the present invention is to provide a primary non-aqueous battery capable of maintaining the initial performance for a long period of time, and to maintain the initial performance for a long period of time. In addition, a second object is to provide a secondary non-aqueous battery capable of reliably avoiding ignition or burst during overcharge.

[0007]

That is, according to the present invention, a power generating element (3) in which a positive electrode sheet (5) and a negative electrode sheet (6) are arranged so as to face each other with a separator (7) in between and wound, is a battery. In the primary non-aqueous battery (1) housed in the can (2) and having the opening of the battery can sealed, K, N
At least one kind of carbonate selected from carbonates of a, Ca, Mg or Al is made to exist inside the battery can.

Further, according to the present invention, the power generating element (3) in which the positive electrode sheet (5) and the negative electrode sheet (6) are arranged so as to face each other via the separator (7) and wound, is placed in the battery can (2). In the primary non-aqueous battery (1) which is housed and the opening of this battery can is sealed, K, Na, Ca, Mg or Al
At least one kind of carbonate selected from among the above-mentioned carbonates is used as an empty space in the battery can (for example, the central space portion of the power generation element, the upper side, the lower side, the outer periphery or the inside of the sealing body).
Configured to exist.

Further, according to the present invention, the power generating element (3) in which the positive electrode sheet (5) and the negative electrode sheet (6) are arranged so as to face each other via the separator (7) and wound, is placed in the battery can (2). In the primary non-aqueous battery (1) which is housed and the opening of this battery can is sealed, K, Na, Ca, Mg or Al
At least one kind of carbonate selected from the above-mentioned carbonates is present in the positive electrode sheet.

Further, the present invention is constituted such that the content of the above-mentioned carbonate is 1 to 20% by weight of the positive electrode active material.

Here, the content of the carbonate is 1 of the positive electrode active material.
The reason for limiting the content to 20% by weight is that when the content is less than 1% by weight of the positive electrode active material, a significant difference is not exhibited as compared with the case where no carbonate is contained, and conversely this content is This is because if the amount of the positive electrode active material exceeds 20% by weight, the battery capacity will decrease.

Further, according to the present invention, a positive electrode sheet (5) and a negative electrode sheet (6) are arranged so as to face each other with a separator (7) in between, and a power generating element (3) is wound into a battery can (2).
In a secondary non-aqueous battery (1A) that is housed inside, the opening of the battery can is sealed, and a pressure-sensitive current interruption mechanism that operates according to an increase in internal pressure is provided, K, Na, Ca, Mg or At least one kind of carbonate selected from Al carbonates is made to exist inside the battery can.

It should be noted that the numbers in parentheses are for convenience of representing corresponding elements in the drawings, and therefore the present invention is not limited to the description in the drawings. The same applies to the column of “Claims”.

[0014]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a cross-sectional view showing a primary non-aqueous battery in which a carbonate is charged in the central space of a power generating element, FIG. 2 is a cross-sectional view showing a primary non-aqueous battery in which a carbonate is charged above the power generating element, and FIG. 5 is a cross-sectional view showing a primary non-aqueous battery in which carbonate is injected below the power generating element, FIG. 4 is a cross-sectional view showing a primary non-aqueous battery in which carbonate is injected around the periphery of the power generating element, FIG.
Is a cross-sectional view showing a primary non-aqueous battery in which a carbonate is put inside the sealing body, FIG. 6 is a graph showing the effect of addition of carbonate on the battery capacity, and FIG. 7 is a graph showing a pressure-sensitive current interruption mechanism. It is sectional drawing which shows the following non-aqueous batteries.

First, the case where the present invention is applied to a primary non-aqueous battery will be described.

As shown in FIG. 1, this primary non-aqueous battery 1 has a cylindrical battery can 2 in which a power generating element 3 is housed. The power generating element 3 is formed by arranging and winding a positive electrode sheet 5 and a negative electrode sheet 6 so as to face each other with a separator 7 in between.
A pressing plate 13 and a bottom plate 15 are provided above and below, respectively. Further, a negative electrode lead plate 12 is provided so as to electrically connect the bottom portion of the battery can 2 and the negative electrode sheet 6. on the other hand,
A positive electrode terminal plate 10 is fitted in the opening of the battery can 2 via an insulating gasket 9, and a positive electrode lead plate 11 is provided so as to electrically connect the positive electrode terminal plate 10 and the positive electrode sheet 5. .

By the way, in the central space of the power generating element 3,
Carbonate of K, Na, Ca, Mg or Al (ie K ₂
At least one selected from CO ₃ , Na ₂ CO ₃ , CaCO ₃ , MgCO ₃ or Al ₂ (CO ₃ ) ₃ )
A variety of carbonates have been added. In FIG. 1, the portion with a mesh pattern indicates the position of introducing the carbonate.

Since the primary non-aqueous battery 1 has the above-mentioned structure, when water is mixed in the battery can 2 during or after its manufacture, the carbonate absorbs the water. Therefore, it is possible to prevent the deterioration of the positive electrode active material and the non-aqueous electrolyte due to the mixing of water, and the reduction of the battery capacity and the deterioration of the storability are not caused. Therefore, the initial performance of the primary non-aqueous battery 1 can be maintained for a long period of time.

In the above-mentioned embodiment, the case where the carbonate is put into the central space of the power generating element 3 has been described, but the position where the carbonate is put is not limited to this, and other places inside the battery can 2 are described. It is also possible to use the empty space to add carbonate. For example, as shown in FIG. 2, carbonate may be added to the upper side of the power generation element 3, or carbonate may be added to the lower side of the power generation element 3 as shown in FIG. Also,
As shown in FIG. 4, carbonate may be charged into the outer periphery of the power generation element 3, and as shown in FIG. 5, carbonate is charged into the inside of the sealing body 19 composed of the positive electrode terminal plate 10 and the support plate 17. It doesn't matter. In addition, in FIGS. 2-5, the part with a mesh pattern shows the injection | pouring position of carbonate. Further, it is possible to allow carbonate to be present in the positive electrode sheet 5 of the power generation element 3.

In order to investigate how the addition of the above-mentioned carbonate affects the battery capacity, when the content of the carbonate is changed within the range of 0 to 25% by weight of the positive electrode active material. We investigated how the battery capacity changes. As a result, as shown in FIG. 6, when the content of carbonate exceeds 20% by weight of the positive electrode active material, the battery capacity starts to decrease,
It can be seen that the battery capacity is hardly reduced when the content is 20% by weight or less. This is because the particle size of the positive electrode active material is about 10 microns, whereas the particle size of the carbonate is about several microns, and when the content is up to about 20% by weight, the carbonate is contained in the positive electrode sheet 5. It is considered that this is because the amount of the positive electrode active material present per unit area of the positive electrode sheet 5 does not change due to the shape of entering the voids.

Next, the case where the present invention is applied to a secondary non-aqueous battery will be described.

As shown in FIG. 7, this secondary non-aqueous battery 1A has a cylindrical battery can 2 in which a power generating element 3 is housed. The power generating element 3 is formed by winding a positive electrode sheet 5 and a negative electrode sheet 6 so as to face each other with a separator 7 in between, and a bottom plate 15 is provided below the power generating element 3. Further, a negative electrode lead plate 12 is provided so as to electrically connect the bottom portion of the battery can 2 and the negative electrode sheet 6. On the other hand, a sealing body 19 is fitted in the opening of the battery can 2 via an insulating gasket 9, and the sealing body 19 is a positive electrode cup with a positive terminal plate 10 and a pressure sensitive plate 20 stacked on each other. It is sandwiched by 21. Further, a fixing plate 22 is welded to the central concave portion 20a of the pressure sensitive plate 20 below the gasket 9 with a predetermined strength,
The positive electrode lead plate 11 is provided so as to electrically connect the fixed plate 22 and the positive electrode sheet 5.

By the way, in the positive electrode sheet 5 of the power generation element 3, a carbonate of K, Na, Ca, Mg or Al (that is,
At least one carbonate selected from K ₂ CO ₃ , Na ₂ CO ₃ , CaCO ₃ , MgCO ₃ or Al ₂ (CO ₃ ) ₃ ) is added.

Since the secondary non-aqueous battery 1A has the above-described structure, when the water is mixed in the battery can 2 during or after its production, the secondary non-aqueous battery 1A has the same structure as described above. Since the carbonate absorbs this water, it is possible to prevent the deterioration of the positive electrode active material and the non-aqueous electrolyte due to the mixing of water, which may lead to a decrease in battery capacity and a deterioration in storage stability. There is no such thing. Therefore, the initial performance of the secondary non-aqueous battery 1A can be maintained for a long period of time.

In addition, when the secondary non-aqueous battery 1A is charged and the battery is overcharged due to a failure of the charger,
The internal pressure of the non-aqueous battery 1A increases. Then, the pressure sensitive plate 20
Is pushed up and deformed into a spherical shape, and its central recess 20a
Is separated from the fixed plate 22 to cut off the current, and further charging is blocked. At this time, the battery voltage rises with charging, but when it reaches a certain value, the carbonate decomposes to generate gas, so the rise in internal pressure is accelerated accordingly.
The pressure-sensitive current cutoff mechanism operates quickly. Therefore, the secondary non-aqueous battery 1A can be surely prevented from igniting or exploding, which is excellent in safety.

In the above embodiment, the central recess 20a of the pressure sensitive plate 20 is separated from the fixed plate 22 due to the rise of the internal pressure during overcharging, and the secondary non-sensitivity mechanism is provided to shut off the current. Although the water-based battery 1A has been described, any one may be adopted as long as it is a pressure-sensitive current interruption mechanism that operates according to an increase in internal pressure.

[0027]

Embodiments of the present invention will be described below. <Example 1> a cathode active material (LiCoO ₂₎ and a conductive agent (graphite) and binder (PVDF) and a 90: 5 were mixed in a weight ratio of 5, which corresponds to 40% of the total weight thereof n -Methyl-2-pyrrolidinone was added and thoroughly mixed to obtain a positive electrode slurry. This positive electrode slurry was applied to an aluminum current collector by the doctor blade method,
After drying with hot air at 100 ° C., rolling was performed to prepare a positive electrode sheet.

On the other hand, the negative electrode active material (carbon) and the binder (PVDF) were mixed in a weight ratio of 90:10, and n-methyl-2-pyrrolidinone corresponding to 70% of the total weight thereof was added. The mixture was thoroughly mixed to obtain a negative electrode slurry.
The negative electrode slurry was applied to a copper current collector, dried with hot air at 100 ° C., and then rolled to prepare a negative electrode sheet.

Next, after attaching a positive electrode lead plate and a negative electrode lead plate to the positive electrode sheet and the negative electrode sheet, respectively,
It was placed so as to face each other with a polypropylene separator interposed therebetween and wound, to obtain a power generating element.

Next, the power generating element was inserted into the battery can, and potassium carbonate was charged into the central space of the power generating element (see FIG. 1). Finally, the opening of the battery can was sealed to remove the primary non-primary material. A water-based battery (diameter 18 mm, height 65 mm) was assembled.

Example 2 A primary non-aqueous battery (diameter 18 mm, height 65 mm) was assembled in the same manner as in Example 1 except that sodium carbonate was used instead of potassium carbonate.

Example 3 A primary non-aqueous battery (diameter 18 mm, height 65 mm) was assembled in the same manner as in Example 1 except that calcium carbonate was used instead of potassium carbonate.

Example 4 A primary non-aqueous battery (diameter 18 mm, height 65 mm) was assembled in the same manner as in Example 1 except that magnesium carbonate was used instead of potassium carbonate.

Example 5 A primary non-aqueous battery (diameter 18 mm, height 65 mm) was assembled in the same manner as in Example 1 except that aluminum carbonate was used instead of potassium carbonate.

<Example 6> A primary non-aqueous battery (similar to Example 1) except that potassium carbonate was charged to the upper side of the power generating element instead of being charged to the central space of the power generating element (see FIG. 2). (Diameter 18 mm, height 65 mm) was assembled.

<Example 7> A primary non-aqueous battery was used in the same manner as in Example 1 except that potassium carbonate was charged under the power generating element instead of in the central space of the power generating element (see FIG. 3). (Diameter 18 mm, height 65 mm) was assembled.

<Example 8> A primary non-aqueous battery (in the same manner as in Example 1) except that potassium carbonate was charged to the outer periphery of the power generating element (see FIG. 4) instead of being charged to the central space of the power generating element (see FIG. 4). (Diameter 18 mm, height 65 mm) was assembled.

<Example 9> A primary non-aqueous battery (in the same manner as in Example 1) except that potassium carbonate was put into the inside of the sealing body instead of being put into the central space of the power generating element (see FIG. 5). (Diameter 18 mm, height 65 mm) was assembled.

Example 10 A primary non-aqueous battery (diameter 18 mm, height 18 mm) was prepared in the same manner as in Example 1 except that potassium carbonate was present in the positive electrode sheet instead of being introduced into the central space of the power generating element. 65 mm) was assembled.

That is, the positive electrode active material (LiCoO ₂ ), potassium carbonate, conductive agent (graphite) and binder (PV
DF) was mixed at a weight ratio of 81: 9: 5: 5, and n-methyl-2-pyrrolidinone corresponding to 40% of the total weight thereof was added and sufficiently mixed to obtain a positive electrode slurry.
This positive electrode slurry was applied to an aluminum current collector by a doctor blade method, dried with hot air at 100 ° C., and then rolled to prepare a positive electrode sheet.

On the other hand, the negative electrode active material (carbon) and the binder (PVDF) were mixed at a weight ratio of 90:10, and n-methyl-2-pyrrolidinone corresponding to 70% of the total weight thereof was added. The mixture was thoroughly mixed to obtain a negative electrode slurry.
The negative electrode slurry was applied to a copper current collector, dried with hot air at 100 ° C., and then rolled to prepare a negative electrode sheet.

Next, after attaching a positive electrode lead plate and a negative electrode lead plate to the positive electrode sheet and the negative electrode sheet, respectively,
It was placed so as to face each other with a polypropylene separator interposed therebetween and wound, to obtain a power generating element.

Next, this power generating element was inserted into a battery can,
Finally, the opening of the battery can was sealed to assemble a primary non-aqueous battery (diameter 18 mm, height 65 mm).

Comparative Example 1 A primary non-aqueous battery (diameter 18 mm, height 65 mm) was assembled in the same manner as in Example 1 except that potassium carbonate was not added.

That is, the positive electrode active material (LiCoO ₂ ), the conductive agent (graphite), and the binder (PVDF) were mixed in 9 parts.
Mix in a weight ratio of 0: 5: 5 to a total weight of 40
% Of n-methyl-2-pyrrolidinone was added and thoroughly mixed to obtain a positive electrode slurry. This positive electrode slurry was applied to an aluminum current collector by a doctor blade method, dried with hot air at 100 ° C., and then rolled to prepare a positive electrode sheet.

On the other hand, the negative electrode active material (carbon) and the binder (PVDF) were mixed in a weight ratio of 90:10, and n-methyl-2-pyrrolidinone corresponding to 70% of the total weight thereof was added. The mixture was thoroughly mixed to obtain a negative electrode slurry.
The negative electrode slurry was applied to a copper current collector, dried with hot air at 100 ° C., and then rolled to prepare a negative electrode sheet.

Next, after attaching a positive electrode lead plate and a negative electrode lead plate to the positive electrode sheet and the negative electrode sheet, respectively,
It was placed so as to face each other with a polypropylene separator interposed therebetween and wound, to obtain a power generating element.

Next, this power generating element was inserted into a battery can,
Finally, the opening of the battery can was sealed to assemble a primary non-aqueous battery (diameter 18 mm, height 65 mm).

<Storage Test> A storage test was conducted on the above-mentioned Examples 1 to 9 and Comparative Example 1 in the following procedure. First,
The capacity was confirmed by discharging for 10 cycles. afterwards,
The battery was charged to a predetermined voltage (4.2 V) and then stored in a thermostat at 60 ° C. for 3 months. Next, charge and discharge again,
The state of capacity deterioration was examined.

The results are shown in Tables 1 and 2. In Tables 1 and 2, the retention capacity ratio is {(capacity after storage) /
(Capacity before storage)} × 100%.

[0051]

[Table 1]

[0052]

[Table 2]

As is clear from Tables 1 and 2, the holding capacity ratio was 70.7% in Comparative Example 1 and 99.4-99.5% in Examples 1-9. The value was extremely high.

Further, it can be seen from Table 1 that the storage capacity ratio hardly changes even if the kind of carbonate is changed.

Further, it can be seen from Table 2 that the storage capacity ratio hardly changes even if the carbonate feeding position is changed.

Example 11 Positive electrode active material (LiCo
O ₂ ), potassium carbonate, a conductive agent (graphite), and a binder (PVDF) are mixed in a weight ratio of 81: 9: 5: 5, and n-methyl-corresponding to 40% of the total weight thereof is mixed.
2-Pyrrolidinone was added and thoroughly mixed to obtain a positive electrode slurry. This positive electrode slurry was applied to an aluminum current collector by a doctor blade method, dried with hot air at 100 ° C., and then rolled to prepare a positive electrode sheet.

On the other hand, the negative electrode active material (carbon) and the binder (PVDF) were mixed at a weight ratio of 90:10, and n-methyl-2-pyrrolidinone corresponding to 70% of the total weight thereof was added. The mixture was thoroughly mixed to obtain a negative electrode slurry.
The negative electrode slurry was applied to a copper current collector, dried with hot air at 100 ° C., and then rolled to prepare a negative electrode sheet.

Then, after attaching a positive electrode lead plate and a negative electrode lead plate to the positive electrode sheet and the negative electrode sheet, respectively,
It was placed so as to face each other with a polypropylene separator interposed therebetween and wound, to obtain a power generating element.

Next, this power generating element was inserted into a battery can,
Finally, a pressure-sensitive current interruption mechanism was provided to assemble a secondary non-aqueous battery (diameter 18 mm, height 65 mm).

Example 12 A secondary non-aqueous battery (diameter 18 mm, height 65 mm) was assembled in the same manner as in Example 11 except that sodium carbonate was used instead of potassium carbonate.

Example 13 A secondary non-aqueous battery (diameter 18 mm, height 65 mm) was assembled in the same manner as in Example 11 except that calcium carbonate was used instead of potassium carbonate.

Example 14 Secondary non-aqueous battery (diameter 18 mm, height 65 mm) was prepared in the same manner as in Example 11 except that magnesium carbonate was used instead of potassium carbonate.
Was assembled.

<Example 15> A secondary non-aqueous battery (diameter 18 mm, height 65 mm) was obtained in the same manner as in Example 11 except that aluminum carbonate was used instead of potassium carbonate.
Was assembled.

Comparative Example 2 A secondary non-aqueous battery (diameter 18 mm, height 65 mm) was assembled in the same manner as in Example 11 except that lithium carbonate was used instead of potassium carbonate.

Comparative Example 3 A secondary non-aqueous battery (diameter 18 mm, height 65 mm) was assembled in the same manner as in Example 11 except that potassium carbonate was not added.

That is, the positive electrode active material (LiCoO ₂ ), the conductive agent (graphite), and the binder (PVDF) were mixed together.
Mix in a weight ratio of 0: 5: 5 to a total weight of 40
% Of n-methyl-2-pyrrolidinone was added and thoroughly mixed to obtain a positive electrode slurry. This positive electrode slurry was applied to an aluminum current collector by a doctor blade method, dried with hot air at 100 ° C., and then rolled to prepare a positive electrode sheet.

On the other hand, the negative electrode active material (carbon) and the binder (PVDF) were mixed in a weight ratio of 90:10, and n-methyl-2-pyrrolidinone corresponding to 70% of the total weight thereof was added. The mixture was thoroughly mixed to obtain a negative electrode slurry.
The negative electrode slurry was applied to a copper current collector, dried with hot air at 100 ° C., and then rolled to prepare a negative electrode sheet.

Then, after attaching a positive electrode lead plate and a negative electrode lead plate to the positive electrode sheet and the negative electrode sheet, respectively,
It was placed so as to face each other with a polypropylene separator interposed therebetween and wound, to obtain a power generating element.

Next, this power generating element was inserted into a battery can,
Finally, a pressure-sensitive current interruption mechanism was provided to assemble a secondary non-aqueous battery (diameter 18 mm, height 65 mm).

<Overcharge Test> The above-mentioned Examples 11 to 15 and Comparative Examples 2 and 3 were subjected to an overcharge test in the following procedure.

First, the battery charger is charged to a predetermined voltage (4.2V). After that, overcharge was started under the condition of 12V-4A, and the time from the start of overcharge to the operation of the pressure-sensitive current cutoff mechanism and the maximum temperature reached during the test were measured, and the number of ruptures / ignitions was examined.

The results are shown in Table 3.

[0073]

[Table 3]

As is clear from Table 3, the time from the start of overcharge to the operation of the pressure-sensitive current cutoff mechanism was 28 to 30 minutes in Comparative Examples 2 and 3, whereas in Example 11 to 15 It was shortened to 20-23 minutes. Further, the maximum temperature reached during the test was 80 to 200 ° C. in Comparative Examples 2 and 3, whereas it was decreased to 50 to 70 ° C. in Examples 11 to 15. Further, regarding the number of bursts / ignitions, in Comparative Examples 2 and 3, the number was 2 to 10 out of 50 (that is, 4 to 20%), whereas in Examples 11 to 15, the number of bursts and ignitions resulted. There was nothing.

[0075]

As described above, according to the present invention, the power generating element 3 in which the positive electrode sheet 5 and the negative electrode sheet 6 are arranged so as to face each other with the separator 7 in between and wound, is the battery can 2.
In the primary non-aqueous battery 1 that is housed inside and has the opening of the battery can 2 sealed, K, Na, Ca, Mg or Al
Since at least one kind of carbonate selected from the above-mentioned carbonates is made to exist inside the battery can 2, the moisture mixed in the battery can 2 depends on the carbonate in the battery can 2. Since it is absorbed, it is possible to prevent the deterioration of the positive electrode active material and the non-aqueous electrolyte due to the mixing of water, and it is possible to maintain the initial performance of the primary non-aqueous battery 1 for a long period of time.

According to the present invention, the power generating element 3 in which the positive electrode sheet 5 and the negative electrode sheet 6 are arranged so as to face each other with the separator 7 in between and wound, is housed in the battery can 2, and the battery can 2 is In the primary non-aqueous battery 1 with the opening sealed, at least one carbonate selected from the carbonates of K, Na, Ca, Mg or Al is made to exist in the empty space in the battery can 2. Since it was configured as
Since the water mixed in the battery can 2 is absorbed by the carbonate in the empty space, it is possible to prevent the deterioration of the positive electrode active material and the non-aqueous electrolyte due to the mixing of the water, and the primary non-aqueous battery 1 It is possible to maintain the initial performance for a long period of time.

Further, according to the present invention, the positive electrode sheet 5 and the negative electrode sheet 6 are arranged so as to face each other with the separator 7 interposed therebetween, and the wound power generating element 3 is housed in the battery can 2. In the primary non-aqueous battery 1 with the opening sealed, at least one carbonate selected from carbonates of K, Na, Ca, Mg or Al is present in the positive electrode sheet 5. Therefore, since the water content mixed in the battery can 2 is absorbed by the carbonate in the positive electrode sheet 5, the deterioration of the positive electrode active material and the non-aqueous electrolyte due to the water content can be prevented, and the primary non-aqueous electrolyte can be prevented. It is possible to maintain the initial performance of the water-based battery 1 for a long period of time.

Further, according to the present invention, since the content of the above-mentioned carbonate is 1 to 20% by weight of the positive electrode active material, the above-mentioned effect can be remarkably achieved without lowering the battery capacity. Can be

Further, according to the present invention, the positive electrode sheet 5 and the negative electrode sheet 6 are arranged so as to face each other with the separator 7 in between, and the wound power generating element 3 is housed in the battery can 2 and the battery can 2 Secondary non-aqueous battery 1 having an opening sealed and further provided with a pressure-sensitive current interruption mechanism that operates according to an increase in internal pressure
In A, at least one kind of carbonate selected from carbonates of K, Na, Ca, Mg or Al is made to exist in the inside of the battery can 2, so that the inside of the battery can 2 is Since the mixed water is absorbed by the carbonate in the battery can 2, it is possible to prevent the deterioration of the positive electrode active material and the non-aqueous electrolyte due to the mixing of the water, and to improve the initial performance of the secondary non-aqueous battery 1A. The secondary non-aqueous battery 1A is ignited or ruptured because it can be maintained for a long period of time, and when overcharged, the carbonate decomposes to generate gas, the rise in internal pressure is accelerated, and the pressure-sensitive current cutoff mechanism operates quickly. It is possible to reliably avoid the, and it is excellent in safety.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a primary nonaqueous battery in which a carbonate is put in a central space portion of a power generation element.

FIG. 2 is a cross-sectional view showing a primary non-aqueous battery in which a carbonate is put on the upper side of a power generation element.

FIG. 3 is a cross-sectional view showing a primary non-aqueous battery in which a carbonate is put under the power generation element.

FIG. 4 is a cross-sectional view showing a primary non-aqueous battery in which a carbonate is put around the power generation element.

FIG. 5 is a cross-sectional view showing a primary non-aqueous battery in which a carbonate is put inside a sealing body.

FIG. 6 is a graph showing the effect of addition of carbonate on battery capacity.

FIG. 7 is a cross-sectional view showing a secondary nonaqueous battery having a pressure-sensitive current cutoff mechanism.

[Explanation of symbols] 1 ... Primary non-aqueous battery 1A ... Secondary non-aqueous battery 2 ... Battery can 3 ... Power generating element 5 ... Positive electrode sheet 6 ... Negative electrode sheet 7 ... Separator

Claims (5)

[Claims] 1. A power generation element (3) in which a positive electrode sheet (5) and a negative electrode sheet (6) are arranged so as to face each other with a separator (7) in between, and the wound power generating element (3) is housed in a battery can (2), In the primary non-aqueous battery (1) in which the opening of the battery can is sealed, at least one carbonate selected from carbonates of K, Na, Ca, Mg or Al is added to the inside of the battery can. A non-aqueous battery characterized by being present. 2. A power generating element (3) in which a positive electrode sheet (5) and a negative electrode sheet (6) are arranged so as to face each other with a separator (7) in between, and the wound power generating element (3) is housed in a battery can (2). In the primary non-aqueous battery (1) with the opening of the battery can sealed, at least one carbonate selected from carbonates of K, Na, Ca, Mg or Al is vacant in the battery can. A non-aqueous battery characterized by being placed in a space. 3. A power generating element (3) in which a positive electrode sheet (5) and a negative electrode sheet (6) are arranged so as to face each other with a separator (7) in between, and the wound power generating element (3) is housed in a battery can (2), In the primary non-aqueous battery (1) in which the opening of the battery can is sealed, at least one carbonate selected from carbonates of K, Na, Ca, Mg or Al is present in the positive electrode sheet. A non-aqueous battery characterized by being made. 4. The positive electrode active material having a carbonate content of 1 to 20.
The non-aqueous battery according to any one of claims 1 to 3, wherein the non-aqueous battery is wt%. 5. A power generating element (3) in which a positive electrode sheet (5) and a negative electrode sheet (6) are arranged so as to face each other with a separator (7) in between, and the wound power generating element (3) is housed in a battery can (2). In a secondary non-aqueous battery (1A) having a pressure-sensitive current interrupting mechanism that seals the opening of this battery can and operates in response to an increase in internal pressure, a carbonate of K, Na, Ca, Mg or Al A non-aqueous battery, wherein at least one kind of carbonate selected from the above is present inside the battery can.