JP2000294231A - Organic electrolyte battery - Google Patents

Abstract

(57) [Summary] To improve the discharge characteristics at low temperature of an organic electrolyte battery without lowering the discharge characteristics at room temperature. A spiral electrode formed by winding a sheet-shaped positive plate (4) made of a positive electrode active substance, a conductive agent and a binder, and a sheet-shaped negative plate (6) made of an alkali metal or an alloy thereof through a separator (12). An organic electrolyte battery comprising Group 3 and having an organic electrolyte solution in which lithium is dissolved, wherein the positive electrode active material has a specific surface area of 60 to 95 m ² / g and an average particle size of 30 to 40 μm. To
By using a chemical manganese dioxide having a specific surface area of 23 to 30 m ² / g after heat treatment at a temperature of 380 to 470 ° C., the discharge characteristics at a low temperature are improved while the discharge characteristics at a low temperature are improved. Can be prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an organic electrolyte battery,
In particular, the present invention relates to a lithium battery, and more particularly, to an organic electrolyte battery in which a positive electrode material is improved to improve its low-temperature discharge characteristics.

[0002]

2. Description of the Related Art An organic electrolyte battery, particularly a lithium battery, having a positive electrode using manganese dioxide as an active substance and a negative electrode using an alkali metal or an alloy thereof as an active substance has a high energy density. It has been put to practical use as a power source for many electronic devices. This organic electrolyte battery is currently used for applications such as cameras, but as multi-functionality of electronic devices such as cameras progresses, batteries as power sources also have well-balanced discharge characteristics over a wide temperature range, especially There is a demand for higher discharge characteristics at low temperatures.

In such a background, a conductive agent mixed with manganese dioxide of the positive electrode, a low-viscosity electrolytic solution and a high-conductivity electrolytic solution, etc. have been studied. However, even in these improvements, the low-temperature discharge characteristics were not particularly satisfactory. In addition, Patent No. 2,522,
As shown in the '328 invention, attempts have been made to improve low-temperature discharge characteristics and heavy-load discharge characteristics by using manganese dioxide having a high specific surface area.

[0004]

However, when the specific surface area of manganese dioxide is increased, the amount of active substance in the positive electrode body is reduced, and the discharge characteristics at room temperature are deteriorated. In addition, when manganese dioxide having a high specific surface area is used as the positive electrode active material, the electrode reaction can be activated, but the reactivity with the electrolytic solution is high, and there is a problem that the characteristic deterioration during long-term storage is increased.

In addition, chemical manganese dioxide, which is a positive electrode active substance, is neutralized with NaOH in the production process, so that a large amount of Na was present in manganese. Precipitated in the material, causing characteristic deterioration.

The present invention has been made in view of these problems, and has as its object to improve low-temperature discharge characteristics in an organic electrolyte battery, and to further improve long-term storage properties. Is what you do.

[0007]

In order to achieve the above object, the present invention provides a sheet-like positive electrode plate comprising a positive electrode active substance, a conductive agent and a binder, and a sheet-like negative electrode plate comprising an alkali metal or an alloy thereof. Has a spiral electrode group wound with a separator interposed therebetween and has an organic electrolyte solution in which a lithium salt is dissolved. In the organic electrolyte battery, the specific surface area is 60 to 95 m ² / g, Chemical manganese dioxide having a particle size of 30 to 40 µm
Heat treatment in the range of 470 ° C. and specific surface area after heat treatment of 23
It is characterized by using a chemical manganese dioxide of up to 30 m ² / g.

In the above, heat treatment is performed at a temperature in the range of 390 to 470 ° C., and the specific surface area after the heat treatment is 23 to 30 m ² /
g of chemical manganese dioxide may be used.
Heat treatment in the range of 80 to 430 ° C., and chemical manganese dioxide having a specific surface area of 25 to 30 m ² / g after the heat treatment may be used.

In an organic electrolyte battery, by using manganese dioxide having a large specific surface area as a positive electrode active substance, a positive electrode mixture can be activated and discharge characteristics at a low temperature can be improved. However, on the other hand, when manganese dioxide having a large specific surface area is used, the packing density in the positive electrode production stage decreases, so that the amount of manganese dioxide, which is a positive electrode active substance, decreases, and the discharge characteristics at room temperature tend to decrease. In the present invention, by performing a heat treatment on the above-mentioned chemical manganese dioxide under a certain condition under a certain condition, the discharge characteristic at a low temperature can be improved while preventing a decrease in the discharge characteristic at a normal temperature. In addition, in the case of electrolytic manganese dioxide, it is not impossible to obtain the specific surface area to achieve the above-mentioned purpose due to the production problem, but there are many technical and production efficiency problems. Not.

Although the use of manganese dioxide having a high specific surface area can activate the electrode reaction, it has high reactivity with the electrolytic solution, and the characteristic deterioration during long-term storage becomes large. This is because the organic electrolyte solution in the battery is decomposed by manganese dioxide, and by using an organic electrolyte containing fluorine as the lithium salt, the reaction can be suppressed and the characteristic deterioration during long-term storage can be prevented. Therefore, in the present invention, it is preferable to use an organic electrolyte containing fluorine as the lithium salt dissolved in the electrolytic solution.

[0011] Further, even when Na is present in a large amount in manganese dioxide, the characteristic deterioration during long-term storage is increased. This is thought to be because Na contained in the manganese dioxide undergoes a substitution reaction with lithium contained in the supporting electrolyte to form a film on the surface of the negative electrode active material and cause characteristic deterioration. However, by adjusting the Na content to about 600 ppm or less, it is possible to prevent characteristic deterioration during long-term storage.

[0012]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described with reference to FIG. FIG. 1 is a cross-sectional view showing a main configuration of an organic electrolyte battery CR123A according to one embodiment of the present invention. (Example 1) As the positive electrode active substance, the specific surface area is 60 to 9
5 m ² / g, a chemical manganese dioxide having an average particle diameter of 30 to 40 .mu.m, and a heat treatment at a temperature four hundred and twenty to four hundred forty ° C., a specific surface area was used to prepare a 28 m ² / g. The chemical manganese dioxide used here was obtained by roasting manganese dioxide ore, adding HNO ₃ to the ore, and converting it into manganese nitrate.
After being purified, (NH ₄ ) ₂ CO ₃ was added to form manganese carbonate, and NH ₄ NO ₃ was added thereto, followed by heating and oxidation to obtain manganese carbonate.

5 parts by weight of graphite powder as a conductive agent was added to 90 parts by weight of the above-prepared specific surface area of 28 m ² / g,
Polytetrafluoroethylene (PTF) as binder
E) 5 parts by weight of the aqueous dispersion (as a solid content) is kneaded to prepare a positive electrode mixture, and the positive electrode mixture is applied to a stainless steel expanded metal, dried and rolled to obtain a predetermined shape. And dried again to obtain a sheet-shaped positive electrode plate 4.

Further, a lithium aluminum alloy foil as a negative electrode active material is cut into a predetermined size to form a sheet-shaped negative electrode plate 6, and a part of a negative electrode current collector plate 7 made of an L-shaped nickel-plated steel plate is partly formed. Was crimped.

Next, the sheet-shaped positive electrode plate 4 and the sheet-shaped negative electrode plate 6 were spirally wound through a separator 12 made of a polypropylene microporous film to form an electrode group 3. An end portion of the negative electrode current collector plate 7 projecting from a lower surface in a direction perpendicular to a winding center axis of the electrode group 3 is connected to a resin insulating plate 8 (arranged in parallel with an end surface of the electrode group 3). The electrode group 3 was bent inward. This electrode group 3
Is inserted into the outer can 1 also serving as a negative electrode terminal, with the end face on the negative electrode current collector side as the head, and the inner bottom surface of the outer can 1 and the end of the negative electrode current collector plate 7 are denoted by 9 in FIG. Resistance welding.

After the electrode group 3 is housed in the outer can 1 as described above, lithium trifluorometasulfonate (LiCF ₃ SO ₃₎ is mixed in a mixed solvent of propylene carbonate and 1,2-dimethoxyethane at a mixing ratio of 3: 7. ) Is 0.5mo
A predetermined amount of the 1 / l dissolved organic electrolyte was injected, and the sealing body 2 and the positive electrode terminal 11 were fixed by caulking at the open end of the outer can 1.
The organic electrolyte battery CR123A was assembled. A positive electrode lead 5 projecting from the upper surface of the electrode group 3 is resistance-welded to the bottom surface of the sealing body 2.

Example 2 The same structure as in Example 1 except that the above-mentioned chemical manganese dioxide was subjected to a heat treatment at a temperature of 390 to 410 ° C. to have a specific surface area of 30 m ² / g as a positive electrode active substance. The organic electrolyte battery of Example 1 was prepared, and the battery was used as Example 2.

Example 3 The same structure as in Example 1 except that the above-mentioned chemical manganese dioxide was subjected to a heat treatment at a temperature of 450 to 470 ° C. to have a specific surface area of 23 m ² / g as a positive electrode active substance. Example 3 was prepared.

Comparative Example 1 The same structure as in Example 1 except that the above-mentioned chemical manganese dioxide was subjected to heat treatment at a temperature of 360 to 380 ° C. to have a specific surface area of 34 m ² / g as a positive electrode active substance. The organic electrolyte battery of Comparative Example 1 was prepared.

Comparative Example 2 The same structure as in Example 1 except that the above-mentioned chemical manganese dioxide was subjected to heat treatment at a temperature of 470 to 490 ° C. to have a specific surface area of 19 m ² / g as a positive electrode active substance. The organic electrolyte battery of Comparative Example 2 was prepared.

Comparative Example 3 The same structure as in Example 1 was used except that electrolytic manganese dioxide was heated at a temperature of 350 to 430 ° C. to have a specific surface area of 17 m ² / g as a positive electrode active substance. An organic electrolyte battery was prepared, and Comparative Example 3 was used. This is a conventional example.

(Evaluation) For each battery prepared above,
The low-temperature discharge characteristics and continuous discharge characteristics were evaluated, and the results are shown in Table 1.

1) The low-temperature discharge characteristics were as follows: 20 batteries were subjected to 1200 mA intermittent discharge (discharge in which a constant current of 1200 mA was passed for 3 seconds and paused for 7 seconds) in an atmosphere at a temperature of -20.degree. The electric capacity up to 5 V was obtained, expressed as a ratio (%) when the value of Comparative Example 3 was set to 100, and the average value was shown in Table 1.

2) The continuous discharge characteristics were as follows: 20 batteries were subjected to 100Ω continuous discharge in an atmosphere at a temperature of 20 ° C.
The electric capacity up to the end voltage of 2.0 V was obtained, expressed as a ratio (%) when the value of Comparative Example 3 was set to 100, and the average value was shown in Table 1.

[0025]

[Table 1]

As can be seen from Table 1, by increasing the specific surface area of the chemical manganese dioxide, the positive electrode mixture was activated, and the discharge characteristics at -20 ° C. were improved in accordance with the specific surface area, and the specific surface area was 23 m ^2. / G (Example 3), an improvement in properties exceeding 30% can be seen, and the specific surface area 34
With m ² / g (Comparative Example 1), characteristics exceeding 80% could be obtained. However, on the other hand, as for the discharge characteristics at 20 ° C., the specific surface area of 34 m ² / g (Comparative Example 1) was the lowest. This is because, when the specific surface area of the chemical manganese dioxide increases, the density at the time of manufacturing the positive electrode plate decreases, the mass as the positive electrode active material decreases, and the discharge capacity decreases. At a specific surface area of 19 m ² / g (Comparative Example 2), the discharge characteristics at −20 ° C. were improved only by 6%, and the effect of the chemical manganese dioxide was not obtained.
In the discharge characteristics at 0 ° C., the reduction rate is 1%, which is the highest value.

From the above results, the specific surface area is 60 to 95 m.
² / g, a chemical manganese dioxide having an average particle size of 30 to 40 μm is heat-treated at a temperature in the range of 390 to 470 ° C., and the specific surface area after the heat treatment is set to 23 to 30 m ² / g. The discharge characteristics at −20 ° C. can be improved without significantly lowering the discharge characteristics at 20 ° C. The specific surface area of the chemical manganese dioxide after heat treatment is 2
If it is 3 m ² / g or less, no effect can be obtained in the discharge characteristics at −20 ° C., and if the specific surface area of the chemical manganese dioxide after heat treatment is 30 m ² / g or more, 20
Deterioration of discharge characteristics at ℃ occurs.

Example 4 Chemical manganese dioxide having a specific surface area of 65 to 85 m ² / g and an average particle diameter of 30 to 40 μm as a positive electrode active substance was heated at a temperature range of 400 to 410 ° C. to have a specific surface area of 28 m ^2. / G was used. The manganese dioxide used here was obtained by roasting a manganese dioxide ore, adding HNO ₃ to the manganese nitrate, adding NH ₄ NO ₃ to the manganese nitrate, and heating and oxidizing the chemical manganese dioxide with ammonia. Neutralized.
The Na content after neutralization was 419 ppm.

5 parts by weight of graphite powder as a conductive agent, 5 parts by weight of an aqueous dispersion of polytetrafluoroethylene (PTFE) as a binder, and 90 parts by weight of chemical manganese dioxide prepared to the above specific surface area of 28 m ² / g (solids content) ) To prepare a positive electrode mixture, apply this positive electrode mixture to expanded metal made of stainless steel, dry, roll, cut into a predetermined shape, and dry again to form a sheet-shaped positive electrode. Plate 4 was obtained.

Further, a lithium aluminum alloy foil as a negative electrode active material is cut into a predetermined size to form a sheet-shaped negative electrode plate 6,
A part of the negative electrode current collector plate 7 made of a nickel-plated steel plate was pressure-bonded to a part thereof.

Next, the sheet-shaped positive electrode plate 4 and the sheet-shaped negative electrode plate 6 were spirally wound through a separator 12 made of a polypropylene microporous film to form an electrode group 3. An end of the negative electrode current collector 7 protruding from the lower surface in a direction perpendicular to the winding center axis of the electrode group 3 is connected to the electrode group 3 via a resin insulating plate 8 arranged in parallel with the end face of the electrode group 3. Was bent inward. This electrode group 3 is provided with the outer can 1 serving also as a negative electrode terminal, with the end face on the negative electrode current collector side as the head.
Then, the inner bottom surface of the outer can 1 and the end of the negative electrode current collector plate 7 were subjected to resistance welding at a portion 9 in FIG.

After the electrode group 3 is housed in the outer can 1 as described above, lithium trifluorometasulfonate (LiCF ₃ SO ₃ ) is added as a supporting electrolyte in a mixed solvent of propylene carbonate and 1,2-dimethoxyethane. .5m
ol / l dissolved organic electrolyte is injected in a predetermined amount, and the positive electrode lead 5 protruding from the upper surface in the direction perpendicular to the winding center axis of the electrode group 3, the sealing body 2, and the sealing part which is resistance-welded at the bottom part of the sealing body 2. The body 2 was fixed by caulking at the open end of the outer can 1, and an organic electrolyte battery CR123A was assembled.

Example 5 An organic material having the same structure as in Example 4 except that the above-mentioned chemical manganese dioxide was heat-treated at a temperature of 380 to 390 ° C. to have a specific surface area of 30 m ² / g as a positive electrode active substance. An electrolyte battery was manufactured, and Example 5 was used.

Example 6 An organic material having the same structure as that of Example 4 except that the above-mentioned chemical manganese dioxide was heat-treated at a temperature of 420 to 430 ° C. to have a specific surface area of 25 m ² / g as a positive electrode active substance. An electrolyte battery was manufactured, and Example 6 was made.

(Comparative Example 4) An organic material having the same structure as in Example 4 except that the above-mentioned chemical manganese dioxide was heat-treated at a temperature of 360 to 370 ° C to have a specific surface area of 34 m ² / g as a positive electrode active substance. An electrolyte battery was manufactured, and Comparative Example 4 was made.

Comparative Example 5 An organic material having the same structure as in Example 4 except that the above-mentioned chemical manganese dioxide was heat-treated at a temperature of 440 to 450 ° C. to have a specific surface area of 23 m ² / g as a positive electrode active substance. An electrolyte battery was manufactured, and Comparative Example 5 was obtained.

Comparative Example 6 An organic material having the same structure as in Example 4 except that the above-mentioned chemical manganese dioxide was heat-treated at a temperature of 350 to 430 ° C. to have a specific surface area of 17 m ² / g as a positive electrode active substance. An electrolyte battery was prepared, and Comparative Example 6 was obtained. This is a conventional example.

After each of the above 100 batteries were manufactured, (1) low-temperature discharge characteristics and (2) continuous discharge characteristics were evaluated, and the results are shown in Table 2. (1) The low-temperature discharge characteristics are as follows.
1200 mA intermittent discharge (1200 m
A constant current of A was passed for 3 seconds, and the battery was discharged for 7 seconds), and the discharge capacity up to a final voltage of 1.5 V was determined.
Is expressed as a ratio (%) when the value of is set to 100, and the average value is shown in Table 2.

(2) The continuous discharge characteristics were as follows. For 20 batteries, a continuous discharge of 100Ω was performed in an atmosphere at a temperature of 20 ° C., and the electric capacity up to a final voltage of 2.0 V was obtained.
Is expressed as a ratio (%) when the value of is set to 100, and the average value is shown in Table 2.

[0040]

[Table 2]

As can be seen from Table 2, by increasing the specific surface area of the chemical manganese dioxide, the positive electrode mixture was activated,
The discharge characteristics at −20 ° C. are improved in accordance with the specific surface area, and the characteristics are improved more than 60% from the specific surface area of 25 m ² / g (Example 6), and the specific surface area is 34 m ² / g.
In (Comparative Example 4), characteristics exceeding 70% could be obtained. However, on the other hand, as for the discharge characteristics at 20 ° C., the characteristic with the specific surface area of 34 m ² / g (Comparative Example 4) was the lowest. This is because, when the specific surface area of the chemical manganese dioxide increases, the density at the time of manufacturing the positive electrode plate decreases, the mass as the positive electrode active material decreases, and the discharge capacity decreases. With a specific surface area of 23 m ² / g (Comparative Example 5),
The discharge characteristics at −20 ° C. have a 46% improvement rate and the effect of the discharge characteristics is the least, but the discharge characteristics at 20 ° C. have a decrease rate of 1%.
% And the result that the decrease in the discharge capacity is the least.

As described above, the specific surface area obtained by chemical synthesis is 65 to 85 m ² / g, and the average particle size is 30 to 40 μm.
m, the heat treatment temperature of manganese dioxide is in the range of 380 to 430 ° C. and the specific surface area is 25 to 30 m ² / g.
-20 ° C without significantly lowering the discharge characteristics at 0 ° C
Discharge characteristics can be improved. When the specific surface area of the chemical manganese dioxide is 25 m ² / g or less, −
A sufficient effect cannot be obtained in the discharge characteristics at 20 ° C., and when the specific surface area of the chemical manganese dioxide is 30 m ² / g or more, the discharge characteristics are reduced at 20 ° C.

<Experiment for Examining the Effect of Using a Compound Containing Fluorine in a Lithium Salt as a Supporting Electrolyte> (Example 1) 0.5 mol / LiPF ₆ as a supporting electrolyte
An organic electrolyte battery having the same configuration as in Example 1 was prepared except that 1 was used.

(Example 2) An organic electrolyte battery having the same structure as that of Example 1 was prepared except that 0.5 mol / l of LiBF ₄ was used as a supporting electrolyte.

Example 3 An organic electrolyte battery having the same structure as that of Example 4 was prepared except that lithium perchlorate (LiClO ₄ ) was used at 0.5 mol / l as an electrolyte.

The battery thus manufactured and the battery of Example 4 were stored in an atmosphere at a temperature of 60 ° C. for 60 days (60 ° C.,
(Accelerated test assuming normal temperature for one year in 20 days), and continuous discharge characteristics were evaluated at intervals of 20 days. Table 3 shows the results.

(1) The continuous discharge characteristics were as follows: 20 batteries were subjected to 100Ω continuous discharge in an atmosphere at a temperature of 20 ° C., and the electric capacity up to a cut-off voltage of 2.0 V was determined. The average value is shown in Table 3.

[0048]

[Table 3]

As described above, the electrolyte is LiCF ₃ S
The characteristic deterioration of each example using O ₃ , LiPF ₆ , and LiBF ₄ (lithium salt containing fluorine) was within 10% even after 60 days at 60 ° C., and the characteristic deterioration was less than that of Example 3 using LiClO _4. It was excellent.

In the embodiments, LiCF ₃ SO ₃ , LiPF ₆ , and LiBF ₄ are used as the lithium salt containing fluorine. However, LiCeF ₄ , Li ₂ C ₂ F ₄ (S
O ₃ ) ₂ , Li ₂ C ₄ F ₆ (SO ₃ ) ₂ , LiN (SO
₂ CF ₃ ) ₂ , LiC (SO ₂ CF ₃ ) ₃ , LiN (S
Similar results can be obtained by using O ₂ C ₂ F ₅ ) ₂ and LiC (SO ₂ C ₂ F ₅ ) ₃ .

<Experiment for Examining the Effect of Neutralizing Positive Electrode Active Substance with Ammonia> (Example 4) As a positive electrode active substance, ammonia neutralized Na
An organic electrolyte battery having the same configuration as that of Example 4 was produced except that chemical manganese dioxide having a content of 589 ppm was used.

(Example 5) An organic electrolyte battery having the same structure as that of Example 4 was produced except that a chemical manganese dioxide having a Na content of 371 ppm after ammonia neutralization was used as a positive electrode active substance.

(Example 6) An organic electrolyte battery having the same structure as that of Example 4 was produced except that a chemical manganese dioxide neutralized with sodium hydroxide and having a Na content of 1403 ppm was used as a positive electrode active substance.

Example 7 An organic electrolyte battery having the same structure as that of Example 4 was produced except that a chemical manganese dioxide neutralized with sodium hydroxide and having a Na content of 751 ppm was used as a positive electrode active substance.

The battery thus manufactured and the battery of Example 4 were stored in an atmosphere at a temperature of 60 ° C. for 60 days (60 ° C.,
An accelerated test assuming normal temperature for one year in 20 days) was performed to evaluate continuous discharge characteristics. Table 4 shows the results.

(1) The continuous discharge characteristics were as follows: 20 cells were continuously discharged at 20 ° C. in an atmosphere of 20 ° C., and the electric capacity up to a final voltage of 2.0 V was determined. The average value is shown in Table 4 below.

[0057]

[Table 4]

As described above, in each of the examples using sodium hydroxide as the neutralizing agent, a voltage drop at the time of discharge which is considered to be caused by the film formed on the surface of the negative electrode active material occurred.
Although the discharge characteristics deteriorated by 10% or more, the discharge characteristics deteriorated after storage in each case using ammonia within 10%, and excellent discharge characteristics were obtained.

The method for producing the chemical manganese dioxide as the positive electrode active substance can be obtained by the following method in addition to the method shown in this embodiment. For example, manganese dioxide ore is roasted to Mn ₂ O _3, and H ₂ SO
₄ and refined as manganese sulfate, and this manganese sulfate was roasted to Mn ₂ O ₃ and H ₂ SO ₄ was added to obtain manganese dioxide.

The manganese dioxide was treated in the same manner as in the above embodiment, and the organic electrolyte battery CR123A was similarly treated.
Was assembled and evaluated. As a result, excellent evaluation was obtained in the same manner as in the above example.

[0061]

As described above, according to the present invention,
In an organic electrolyte battery, the discharge characteristics at a low temperature can be improved without lowering the discharge characteristics at a normal temperature, and an organic electrolyte battery applicable over a wide temperature range can be provided.

[Brief description of the drawings]

FIG. 1 is a vertical sectional view of an organic electrolyte battery according to one embodiment of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Outer can, 2 ... Sealing body, 3 ... Electrode group, 4 ... Sheet positive electrode plate, 5 ... Positive electrode lead, 6 ... Sheet negative electrode plate, 7 ... Negative current collector plate, 8 ... Insulating plate, 9 ... Resistance welding Part 10, negative electrode terminal, 11 positive electrode terminal, 12 separator, 13 positive electrode current collector plate, 14 positive electrode active material, 15 negative electrode active material.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Koji Fujita, Inventor 3-4-1-10 Minamishinagawa, Shinagawa-ku, Tokyo Inside Toshiba Battery Corporation (72) Inventor Junichi Shimizu 3-4-1 Minamishinagawa, Shinagawa-ku, Tokyo No. Toshiba Battery Corporation F term (reference) 5H003 AA01 BA01 BB02 BB04 BD01 BD02 BD05 BD06 5H015 AA02 CC01 EE05 EE06 5H024 AA03 AA12 CC02 FF11 FF19

Claims (5)

[Claims] 1. A spiral electrode group formed by winding a sheet-shaped positive plate made of a positive electrode active substance, a conductive agent and a binder, and a sheet-shaped negative plate made of an alkali metal or an alloy thereof through a separator. In an organic electrolyte battery having an organic electrolyte solution in which a lithium salt is dissolved, a chemical manganese dioxide having a specific surface area of 60 to 95 m ² / g and an average particle diameter of 30 to 40 μm is used as a positive electrode active substance at a temperature of 380.
To 470 ° C, and the specific surface area after the heat treatment is 2
An organic electrolyte battery using a chemical manganese dioxide having a concentration of 3 to 30 m ² / g. 2. The organic electrolyte battery according to claim 1, wherein heat treatment is performed at a temperature in the range of 390 to 470 ° C., and chemical manganese dioxide having a specific surface area after the heat treatment of 23 to 30 m ² / g is used. 3. The organic electrolyte battery according to claim 1, wherein heat treatment is performed at a temperature in the range of 380 to 430 ° C., and chemical manganese dioxide whose specific surface area after the heat treatment is 25 to 30 m ² / g is used. 4. The organic electrolyte battery according to claim 1, wherein the lithium salt is a compound containing fluorine. 5. The organic electrolyte battery according to claim 1, wherein the sodium content of the chemical manganese dioxide is 600 ppm or less.