JP2002308627A - Method of manufacturing spinel type lithium manganate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress the elution of Mn in charging, to improve the high temperature property of a battery, such as high temperature preservation properties or high temperature cycle property and to improve current load factor. SOLUTION: The spinel type lithium manganate is manufactured by pulverizing electrodeposited manganese dioxide, neutralizing the resultant manganese dioxide with sodium hydroxide or sodium carbonate to adjust its pH to >=2, mixing the electrodeposited manganese dioxide having >=50 m<2> /g specific surface area and a lithium raw material with a compound containing at least one or more elements selected from magnesium, aluminum, nickel, cobalt, iron, copper, zinc, calcium, silicon, phosphorus, titanium, chromium, sodium, potassium, vanadium and boron so as to replace 0.05-12.5 mol% manganse with the elements of the compound and firing the mixture. A non-aqueous electrolyte secondary battery uses the spinel type lithium manganate as a positive electrode material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing spinel-type lithium manganate. The present invention relates to a method for producing a spinel-type lithium manganate that suppresses and improves the high-temperature characteristics of a battery such as high-temperature storage characteristics and high-temperature cycle characteristics.

[0002]

2. Description of the Related Art In recent years, portable personal computers and telephones have become portable.
With the rapid progress of cordless technology, the demand for secondary batteries as power sources for their drive is increasing. Among them, non-aqueous electrolyte secondary batteries are particularly expected because they have the smallest size and high energy density. As a positive electrode material of a nonaqueous electrolyte secondary battery satisfying the above demand, lithium cobaltate (L
iCoO ₂ ), lithium nickelate (LiNiO ₂ ),
And lithium manganate (LiMn ₂ O ₄ ). Since these composite oxides have a voltage of 4 V or more with respect to lithium, a battery having a high energy density can be obtained.

[0003] Among the above composite oxides, LiCoO ₂ , L
INiO ₂ whereas the theoretical capacity of about 280 mAh / g, but LiMn ₂ O ₄ is as small as 148 mAh / g, and that manganese oxide as a raw material is abundant and inexpensive, during charging, such as LiNiO ₂ Is considered to be suitable for EV applications because of its lack of thermal instability.

However, since lithium manganate (LiMn ₂ O ₄ ) elutes Mn at a high temperature, there is a problem that the battery characteristics at a high temperature such as a high-temperature storage property and a high-temperature cycle characteristic are inferior.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a positive electrode material for a non-aqueous electrolyte secondary battery, which suppresses the amount of Mn elution during charging, and has a high temperature storage property and high temperature cycle characteristics. Another object of the present invention is to provide a method for producing a spinel-type lithium manganate having improved battery characteristics, a cathode material comprising the lithium manganate, and a non-aqueous electrolyte secondary battery using the cathode material.

[0006]

Various manganese compounds have been studied as a manganese raw material for spinel-type lithium manganate. Since electrolytic manganese dioxide is inexpensive and abundant, it is suitable as a manganese raw material for spinel-type lithium manganate. As a positive electrode active material of a lithium primary battery, a material obtained by firing electrolytic manganese dioxide having a high specific surface area at a specific temperature is used. The specific surface area of this electrolytic manganese dioxide depends on the electrolytic conditions. Soda neutralization is applied to alkaline manganese batteries. It is known that a small amount of sodium remains in soda-neutralized electrolytic manganese dioxide, and the amount of sodium depends on neutralization conditions. The present inventors perform a neutralization treatment on electrolytic manganese dioxide, which is a manganese raw material, under specific conditions, assume that the specific surface area is equal to or greater than a certain value, and replace a part of manganese with a specific element,
It has been found that the above object can be achieved.

Accordingly, the present invention provides a method for producing
After grinding the gun, add sodium hydroxide or sodium carbonate
And the pH is adjusted to 2 or more, and the specific surface area is
50m ²/ G or more electrolytic manganese dioxide and lithium
Raw materials and magnesium, aluminum, nickel, Kovar
G, iron, copper, zinc, calcium, silicon, phosphorus, titanium
, Chromium, sodium, potassium, vanadium, borane
Compound containing at least one element selected from elements
And the compound is 0.05 to 12.5 mol% of manganese.
Characterized by mixing and firing to replace
The method for producing spinel lithium manganate
You.

[0008] Further, there is provided the method for producing spinel-type lithium manganate described above, wherein the firing temperature is 750 ° C or more.

A positive electrode material for a non-aqueous electrolyte secondary battery comprising a spinel-type lithium manganate obtained by the above-described production method.

A non-aqueous electrolyte secondary battery comprises a positive electrode using the above-described positive electrode material, a negative electrode capable of inserting and extracting lithium, and a non-aqueous electrolyte.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a method for producing spinel-type lithium manganate according to an embodiment of the present invention will be described in detail. In the present invention, electrolytic manganese dioxide is used as a manganese raw material for spinel-type lithium manganate.
The electrolytic manganese dioxide in the present invention is obtained by the following method. A manganese sulfate solution having a predetermined concentration is used as an electrolytic solution, a carbon plate is used as a cathode, and a titanium plate is used as an anode. While heating, electrolysis is performed at a constant current density to deposit manganese dioxide on the anode. Next, the deposited manganese dioxide is peeled off from the anode and ground to a predetermined particle size. The electrolytic manganese dioxide pulverized to the predetermined particle size is washed with water and dried after neutralization with sodium. As the sodium neutralization, specifically, it is neutralized with sodium hydroxide or sodium carbonate. The order of pulverization and neutralization is not particularly limited, and pulverization may be performed after neutralization.

The pH of the neutralized electrolytic manganese dioxide is 2
As mentioned above, it is preferably 2 to 5.5. The higher the pH,
Although the amount of Mn elution at a high temperature is reduced, the initial discharge capacity is reduced. If the pH is less than 2, the effect is insufficient. The specific surface area of the neutralized electrolytic manganese dioxide is 50 m ^2.
/ G or more. When the specific surface area is 50 m ² / g or less, the reactivity with the lithium raw material is deteriorated, and a uniform product cannot be obtained. In addition, the specific surface area is 5
With electrolytic manganese dioxide of 0 m ² / g or more, uniform spinel-type lithium manganate can be obtained, but the specific surface area also increases, so the reaction area with the electrolytic solution also increases, and Mn
The elution volume is not reduced. Thus, by neutralizing sodium, the remaining sodium reacts in a state of being uniformly dispersed when calcined, thereby reducing the amount of Mn eluted.

In the present invention, this electrolytic manganese dioxide is recycled.
Titanium raw materials and magnesium, aluminum, nickel,
Cobalt, iron, copper, zinc, calcium, silicon, metal
, Titanium, chromium, sodium, potassium, vanadium
Containing at least one element selected from the group consisting of
And calcination to form a spinel-type manganese oxide.
Get Umm. As a lithium raw material, lithium carbonate (L
i_TwoCO_Three), Lithium nitrate (LiNO ₃), Lithium hydroxide
(LiOH). Electrolytic manganese dioxide
And the Li / Mn molar ratio of the lithium source is 0.50 to 0.6.
0 is preferred.

Compounds containing an element that partially replaces manganese include magnesium, aluminum, nickel,
Cobalt, iron, copper, zinc, calcium, silicon, phosphorus, titanium, chromium, sodium, potassium, vanadium, boron oxides, hydroxides or carbonates. The substitution amount is 0.05 to 12.5 mol% of manganese.
It is. If the substitution amount exceeds 12.5% of manganese, the amount of manganese eluted at high temperatures is reduced, but the initial capacity is reduced. On the other hand, if the substitution amount is less than 0.05 mol% of manganese, the improvement in battery characteristics at high temperatures is not sufficient.

These electrolytic manganese dioxide and lithium raw materials are preferably ground before or after mixing the raw materials in order to obtain a larger reaction area. The weighed and mixed raw materials may be used as they are or may be granulated. The granulation method may be wet or dry, and may be extrusion granulation, tumbling granulation, flow granulation, mixing granulation, spray drying granulation, pressure molding granulation, or flake granulation using a roll or the like. .

The raw material thus obtained is put into a firing furnace and fired at 600 to 1000 ° C. to obtain a spinel type lithium manganate. A temperature of about 600 ° C. is sufficient to obtain a single-phase spinel-type lithium manganate, but a firing temperature of 750 ° C. or higher, preferably 850 ° C. or higher is necessary because a low firing temperature does not promote grain growth. Becomes Examples of the firing furnace used here include a rotary kiln and a stationary furnace. The firing time is 1 hour or more, preferably 5 to 20 hours.

In this way, a spinel-type lithium manganate produced by using a compound containing a certain amount of sodium and containing an element that partially replaces manganese is obtained. The content of sodium is preferably 0.07 to 2.5% by weight. This spinel-type lithium manganate is used as a positive electrode material of a non-aqueous electrolyte secondary battery.

In the non-aqueous electrolyte secondary battery of the present invention, the positive electrode material, a conductive material such as carbon black, and a binder such as Teflon (registered trademark) are mixed to form a positive electrode mixture, and the negative electrode is formed. As the non-aqueous electrolyte, a lithium salt such as lithium hexafluorophosphate (LiPF ₆ ) is dissolved in a mixed solvent such as ethylene carbonate-dimethyl carbonate. However, there is no particular limitation.

The non-aqueous electrolyte secondary battery of the present invention can suppress the elution of manganese in a charged state, so that battery characteristics at high temperatures such as high-temperature storage and high-temperature cycle characteristics can be improved. Hereinafter, the present invention will be specifically described based on examples and the like, but the present invention is not particularly limited thereto.

[0020]

EXAMPLE 1 A manganese sulfate aqueous solution having a sulfuric acid concentration of 10 g / l and a manganese concentration of 55 g / l was prepared as a manganese electrolytic solution. The temperature of the electrolytic solution was heated to 90 ° C., and electrolysis was performed at a current density of 90 A / m ² using a carbon plate as a cathode and a titanium plate as an anode. Next, the manganese dioxide electrodeposited on the anode was peeled off and crushed into chips of 7 mm or less, and the chips were further crushed to an average particle size of about 20 μm.

10 kg of this manganese dioxide was washed with 20 liters of water, and after washing water was discharged, 20 liters of water was added again. Here, 140 g of sodium hydroxide was dissolved, neutralized for 24 hours while stirring, washed with water, filtered,
It was dried (50 ° C., 12 hours). Table 1 shows the pH, sodium content and specific surface area of the obtained powder measured according to JIS K14677-1984.

Lithium carbonate was mixed with 950 g of manganese dioxide having an average particle diameter of about 20 μm, 41.7 g of aluminum hydroxide (substituted for 5 mol% of manganese), and a Li / (Mn + substituted element) molar ratio of 0.54. Then, the resultant was fired in a box furnace at 850 ° C. for 20 hours to obtain spinel-type lithium manganate. Table 1 shows the substitution elements of the spinel-type lithium manganate and the substitution amounts of manganese.

A positive electrode mixture is prepared by mixing 80 parts by weight of the thus obtained spinel type lithium manganate, 15 parts by weight of carbon black as a conductive agent and 5 parts by weight of polytetrafluoroethylene as a binder. did.

Using this positive electrode mixture, a coin-type nonaqueous electrolyte secondary battery shown in FIG. 1 was produced. That is, the current collector 3 also made of stainless steel is spot-welded inside the positive electrode case 1 made of stainless steel having resistance to organic electrolyte.
On the upper surface of the current collector 3, a positive electrode 5 made of the above positive electrode mixture is pressed. On the upper surface of the positive electrode 5, a separator 6 made of microporous polypropylene resin impregnated with an electrolytic solution is arranged. At the opening of the positive electrode case 1, a sealing plate 2 to which a negative electrode 4 made of metallic lithium is joined is disposed below a gasket 7 made of polypropylene, whereby the battery is sealed. The sealing plate 2 also serves as a negative electrode terminal,
It is made of the same stainless steel as the positive electrode case 1. The diameter of the battery is 20 mm, and the total height of the battery is 1.6 mm. As the electrolytic solution, a solution obtained by mixing ethylene carbonate and 1,3-dimethoxyethane in an equal volume was used as a solvent, and a solution in which lithium hexafluorophosphate was dissolved at 1 mol / liter as a solute was used.

The battery obtained in this manner was subjected to a charge / discharge test. The charge / discharge test is performed at 20 ° C.
The current density was 0.5 mA / cm ² , and the voltage was in the range of 4.3 V to 3.0 V. The batteries were charged at 4.3 V and stored in an environment of 80 ° C. for 3 days, and the storage characteristics of the batteries were checked using the discharge capacity of these batteries as the capacity retention ratio. Table 1 shows the measurement results of the initial discharge capacity and the high-temperature storage capacity retention rate.

[0026]

[Table 1]

Example 2 A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that the amount of sodium hydroxide added during neutralization of electrolytic manganese dioxide was changed to 75 g. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. In addition, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using this spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. Show.

Example 3 A spinel-type lithium manganate was synthesized in the same manner as in Example 1, except that the amount of sodium hydroxide added during neutralization of electrolytic manganese dioxide was changed to 280 g. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. In addition, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using this spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. Show.

Example 4 A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that the sintering temperature was 900 ° C. PH after neutralization of used electrolytic manganese dioxide, sodium content,
Table 1 shows the specific surface area, the substitution element of the obtained spinel-type lithium manganate, and the substitution amount of manganese. Further, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using this spinel-type lithium manganate as a positive electrode material,
The initial discharge capacity and the high-temperature storage capacity retention rate were measured, and the results are shown in Table 1.

Example 5 A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that the firing temperature was 750 ° C. PH after neutralization of used electrolytic manganese dioxide, sodium content,
Table 1 shows the specific surface area, the substitution element of the obtained spinel-type lithium manganate, and the substitution amount of manganese. Further, a coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using this spinel-type lithium manganate as a positive electrode material,
The initial discharge capacity and the high-temperature storage capacity retention rate were measured, and the results are shown in Table 1.

Example 6 995 g of electrolytic manganese dioxide and 4.17 g of aluminum hydroxide (substituted by 0.5 mol% of manganese) prepared in Example 1 were adjusted to have a Li / (Mn + substituted element) molar ratio of 0.54. , And spinel-type lithium manganate was synthesized in the same manner as in Example 1. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 1 shows the results.

Example 7 875 g of electrolytic manganese dioxide prepared in Example 1, 104.25 g of aluminum hydroxide (substituting 12.5 mol% of manganese) and a Li / (Mn + substituted element) molar ratio of 0.5 were used.
Example 1 except that lithium carbonate was mixed so as to obtain No. 4.
In the same manner as described above, spinel-type lithium manganate was synthesized. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. Shown in

Example 8 995 g of electrolytic manganese dioxide prepared in Example 1, 2.16 g of magnesium oxide (substituting 0.5 mol% of manganese) and the Li / (Mn + substituted element) molar ratio were set to 0.54. A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 1 shows the results.

Example 9 950 g of electrolytic manganese dioxide prepared in Example 1 and 21.6 g of magnesium oxide (substituting 5 mol% of manganese)
And spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of Li / (Mn + substituent element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Further, the spinel-type lithium manganate was used as a cathode material in Example 1
In the same manner as in the above, a coin-type nonaqueous electrolyte secondary battery was produced, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured.

Example 10 900 g of electrolytic manganese dioxide and 43.2 g of magnesium oxide (substituted for 10 mol% of manganese) prepared in Example 1 were mixed with lithium carbonate so that the molar ratio of Li / (Mn + substituted element) was 0.54. Was synthesized in the same manner as in Example 1 except that was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 1 shows the results.

Example 11 995 g of electrolytic manganese dioxide and 4.96 g of nickel hydroxide (substituted by 0.5 mol% of manganese) prepared in Example 1 were adjusted to have a Li / (Mn + substituted element) molar ratio of 0.54. , And spinel-type lithium manganate was synthesized in the same manner as in Example 1. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 1 shows the results.

Example 12 950 g of electrolytic manganese dioxide and 49.6 g of nickel hydroxide (substituted for 5 mol% of manganese) prepared in Example 1 were carbonated so that the molar ratio of Li / (Mn + substituted element) was 0.54. A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. Shown in

Example 13 900 g of electrolytic manganese dioxide prepared in Example 1 and 99.2 g of nickel hydroxide (replace 10 mol% of manganese)
And spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of Li / (Mn + substituent element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Further, the spinel-type lithium manganate was used as a cathode material in Example 1
In the same manner as in the above, a coin-type nonaqueous electrolyte secondary battery was produced, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. The results are shown in Table 1.

Example 14 995 g of electrolytic manganese dioxide prepared in Example 1, 4.97 g of cobalt hydroxide (substituting 0.5 mol% of manganese), and the molar ratio of Li / (Mn + substituted element) was 0.54. , And spinel-type lithium manganate was synthesized in the same manner as in Example 1. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 1 shows the results.

Example 15 950 g of electrolytic manganese dioxide and 49.7 g of cobalt hydroxide (substituted for 5 mol% of manganese) prepared in Example 1 were carbonated so that the Li / (Mn + substituted element) molar ratio was 0.54. A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. Shown in

Example 16 875 g of electrolytic manganese dioxide prepared in Example 1 and 124.25 g of cobalt hydroxide (12.5 mol% of manganese)
Was replaced with lithium carbonate so that the molar ratio of Li / (Mn + substituted element) was 0.54, and spinel-type lithium manganate was synthesized in the same manner as in Example 1. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. Shown in

Example 17 995 g of electrolytic manganese dioxide prepared in Example 1, 2.16 g of diiron trioxide (substituting 0.5 mol% of manganese), and the molar ratio of Li / (Mn + substituted element) was 0.54. A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed as described above. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. Shown in

Example 18 950 g of electrolytic manganese dioxide prepared in Example 1 and 21.6 g of diiron trioxide (substituting 5 mol% of manganese) with Li
/ (Mn + substituted element) A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so as to have a molar ratio of 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. Shown in

Example 19 875 g of electrolytic manganese dioxide prepared in Example 1 and 54 g of diiron trioxide (substituting 12.5 mol% of manganese) with L
A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of i / (Mn + substituted element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. Shown in

Example 20 997.5 g of the electrolytic manganese dioxide prepared in Example 1,
Spinel-type manganese in the same manner as in Example 1 except that 2.13 g of copper monoxide (substituting 0.25 mol% of manganese) and lithium carbonate were mixed so that the molar ratio of Li / (Mn + substituting element) was 0.54. Synthesis of lithium oxide was performed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 1 shows the results.

Example 21 950 g of electrolytic manganese dioxide prepared in Example 1, 42.6 g of copper monoxide (substituting 5 mol% of manganese) with Li /
A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of (Mn + substituted element) was 0.54. PH after neutralization of the used electrolytic manganese dioxide, sodium content, specific surface area,
Table 1 shows the substitution elements of the obtained spinel-type lithium manganate and the substitution amounts of manganese. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured.
Shown in

Example 22 900 g of electrolytic manganese dioxide prepared in Example 1, 85.2 g of copper monoxide (substituting 10 mol% of manganese) with Li
/ (Mn + substituted element) A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so as to have a molar ratio of 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. Shown in

Example 23 997.5 g of the electrolytic manganese dioxide prepared in Example 1
Spinel-type manganic acid as in Example 1 except that 2.18 g of zinc oxide (substituting 0.25 mol% of manganese) and lithium carbonate were mixed so that the molar ratio of Li / (Mn + substituting element) was 0.54. Synthesis of lithium was performed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 1 shows the results.

Example 24 950 g of electrolytic manganese dioxide prepared in Example 1, 43.5 g of zinc oxide (substituting 5 mol% of manganese) with Li /
A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of (Mn + substituted element) was 0.54. PH after neutralization of the used electrolytic manganese dioxide, sodium content, specific surface area,
Table 1 shows the substitution elements of the obtained spinel-type lithium manganate and the substitution amounts of manganese. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured.
Shown in

Example 25 900 g of electrolytic manganese dioxide prepared in Example 1, 87 g of zinc oxide (substituted by 10 mol% of manganese) and Li /
A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of (Mn + substituted element) was 0.54. PH after neutralization of the used electrolytic manganese dioxide, sodium content, specific surface area,
Table 1 shows the substitution elements of the obtained spinel-type lithium manganate and the substitution amounts of manganese. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured.
Shown in

Example 26 997.5 g of the electrolytic manganese dioxide prepared in Example 1,
1.98 g of calcium hydroxide (substituting 0.25 mol% of manganese) and a molar ratio of Li / (Mn + substituting element) of 0.54
A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed such that
Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. Shown in

Example 27 950 g of electrolytic manganese dioxide prepared in Example 1 and 39.6 g of calcium hydroxide (substituting 5 mol% of manganese)
And spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of Li / (Mn + substituent element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Further, the spinel-type lithium manganate was used as a cathode material in Example 1
In the same manner as in the above, a coin-type nonaqueous electrolyte secondary battery was produced, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. The results are shown in Table 1.

Example 28 900 g of electrolytic manganese dioxide and 79.2 g of calcium hydroxide (substituted for 10 mol% of manganese) prepared in Example 1 were carbonated so that the molar ratio of Li / (Mn + substituted element) was 0.54. A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 1 shows the results.

Example 29 997.5 g of the electrolytic manganese dioxide prepared in Example 1
Spinel-type manganic acid in the same manner as in Example 1 except that 1.53 g of silicon dioxide (substituting 0.25 mol% of manganese) and lithium carbonate were mixed so that the molar ratio of Li / (Mn + substituent element) was 0.54. Synthesis of lithium was performed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 1 shows the results.

Example 30 950 g of electrolytic manganese dioxide prepared in Example 1, 30.6 g of silicon dioxide (substituted for 5 mol% of manganese) and L
A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of i / (Mn + substituted element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. In addition, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. Shown in

Example 31 900 g of electrolytic manganese dioxide and 61.2 g of silicon dioxide (substituted for 10 mol% of manganese) prepared in Example 1 were mixed with lithium carbonate so that the molar ratio of Li / (Mn + substituted element) was 0.54. Was synthesized in the same manner as in Example 1 except that was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. Shown in

Example 32 997.5 g of the electrolytic manganese dioxide prepared in Example 1
Spinel-type manganic acid in the same manner as in Example 1 except that 2.13 g of titanium dioxide (substituting 0.25 mol% of manganese) and lithium carbonate were mixed so that the molar ratio of Li / (Mn + substituting element) was 0.54. Synthesis of lithium was performed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 1 shows the results.

Example 33 950 g of electrolytic manganese dioxide and 42.7 g of titanium dioxide (substituted for 5 mol% of manganese) prepared in Example 1 were replaced by L
A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of i / (Mn + substituted element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. Shown in

Example 34 Lithium carbonate was prepared in the same manner as in Example 1 except that 900 g of electrolytic manganese dioxide, 85.4 g of titanium dioxide (substituted for 10 mol% of manganese) and Li / (Mn + substituted element) molar ratio were 0.54. Was synthesized in the same manner as in Example 1 except that was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. Shown in

Example 35 995 g of electrolytic manganese dioxide prepared in Example 1, 4.06 g of dichromium trioxide (substituting 0.5 mol% of manganese), and the molar ratio of Li / (Mn + substituted element) was 0.54. A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed as described above. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 1 shows the results.

Example 36 The electrolytic manganese dioxide prepared in Example 1 was 950 g, dichromium trioxide 40.6 g (substituted 5 mol% of manganese) and the molar ratio of Li / (Mn + substituted element) was 0.54. A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. Shown in

Example 37 875 g of electrolytic manganese dioxide prepared in Example 1, 101.5 g of dichromium trioxide (substituting 12.5 mol% of manganese), and a molar ratio of Li / (Mn + substituted element) of 0.54 were obtained. A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed as described above. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 1 shows the results.

Example 38 997.5 g of the electrolytic manganese dioxide prepared in Example 1
Spinel-type manganese in the same manner as in Example 1 except that 1.83 g of diphosphorus pentoxide (substituting 0.25 mol% of manganese) and lithium carbonate were mixed so that the molar ratio of Li / (Mn + substituent element) was 0.54. Synthesis of lithium oxide was performed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 1 shows the results.

Example 39 950 g of the electrolytic manganese dioxide prepared in Example 1 and 36.6 g of diphosphorus pentoxide (substituting 5 mol% of manganese) with L
A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of i / (Mn + substituted element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. Shown in

EXAMPLE 40 900 g of electrolytic manganese dioxide prepared in Example 1, 73.2 g of diphosphorus pentoxide (substituting 10 mol% of manganese), and carbonic acid were added so that the molar ratio of Li / (Mn + substituted element) was 0.54. A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. Shown in

Example 41 997.5 g of the electrolytic manganese dioxide prepared in Example 1
1.33 g of sodium carbonate (0.25 mol% of manganese
Was replaced with lithium carbonate so that the molar ratio of Li / (Mn + substituted element) was 0.54, and spinel-type lithium manganate was synthesized in the same manner as in Example 1. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. Shown in

Example 42 990 g of electrolytic manganese dioxide prepared in Example 1, 5.3 g of sodium carbonate (substituting 1 mol% of manganese) and L
A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of i / (Mn + substituted element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. Shown in

Example 43 950 g of electrolytic manganese dioxide prepared in Example 1, 26.5 g of sodium carbonate (substituting 5 mol% of manganese), and lithium carbonate so that the molar ratio of Li / (Mn + substituted element) was 0.54. Was synthesized in the same manner as in Example 1 except that was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. Shown in

Example 44 997.5 g of the electrolytic manganese dioxide prepared in Example 1
Spinel-type manganic acid in the same manner as in Example 1 except that 1.73 g of potassium carbonate (substituting 0.25 mol% of manganese) and lithium carbonate were mixed so that the molar ratio of Li / (Mn + substituent element) was 0.54. Synthesis of lithium was performed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 1 shows the results.

Example 45 990 g of electrolytic manganese dioxide prepared in Example 1 and 6.92 g of potassium carbonate (substituting 1 mol% of manganese) with L
A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of i / (Mn + substituted element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. Shown in

Example 46 950 g of electrolytic manganese dioxide prepared in Example 1 and 34.6 g of potassium carbonate (substituted by 5 mol% of manganese) were replaced by L
A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of i / (Mn + substituted element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. Shown in

Example 47 995 g of electrolytic manganese dioxide prepared in Example 1, 4.86 g of divanadium pentoxide (substituting 0.5 mol% of manganese), and the molar ratio of Li / (Mn + substituted element) was 0.54. A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed as described above. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 2 shows the results.

[0073]

[Table 2]

Example 48 The electrolytic manganese dioxide prepared in Example 1 and 950 g of divanadium pentoxide (substituted by 5 mol% of manganese) with Li / (Mn + substituted element) at a molar ratio of 0.54 were prepared. A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 2 shows the results.

Example 49 875 g of electrolytic manganese dioxide prepared in Example 1 and 121.5 g of divanadium pentoxide (substituting 12.5 mol% of manganese) with a molar ratio of Li / (Mn + substituted element) of 0.54
A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed such that
Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. In addition, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention were measured. Shown in

Example 50 997.5 g of the electrolytic manganese dioxide prepared in Example 1 was used.
Spinel-type manganese in the same manner as in Example 1 except that 0.97 g of boron trioxide (substituting 0.25 mol% of manganese) and lithium carbonate were mixed so that the molar ratio of Li / (Mn + substituting element) was 0.54. Synthesis of lithium oxide was performed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 2 shows the results.

Example 51 990 g of electrolytic manganese dioxide prepared in Example 1 and 3.86 g of boron trioxide (substituting 1 mol% of manganese) with L
A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of i / (Mn + substituted element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. Shown in

Example 52 950 g of the electrolytic manganese dioxide prepared in Example 1 and 19.3 g of boron trioxide (substituting 5 mol% of manganese) were replaced by L
A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of i / (Mn + substituted element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. In addition, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention were measured. Shown in

Comparative Example 1 A manganese sulfate aqueous solution having a sulfuric acid concentration of 50 g / l and a manganese concentration of 40 g / l was prepared as a manganese electrolytic solution. The temperature of the electrolytic solution was heated to 95 ° C., and electrolysis was performed at a current density of 60 A / m ² using a carbon plate as a cathode and a titanium plate as an anode. Except for this, the synthesis of spinel-type lithium manganate was performed in the same manner as in Example 1. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 2 shows the results.

Comparative Example 2 A spinel-type lithium manganate was synthesized in the same manner as in Comparative Example 1 except that the electrolytic manganese dioxide was not neutralized (the amount of sodium hydroxide added was 0 g). PH after neutralization of used electrolytic manganese dioxide, sodium content,
Table 1 shows the specific surface area, the substitution element of the obtained spinel-type lithium manganate, and the substitution amount of manganese. Further, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using this spinel-type lithium manganate as a positive electrode material,
The initial discharge capacity and high-temperature storage capacity retention were measured, and the results are shown in Table 2.

Comparative Example 3 A spinel-type lithium manganate was synthesized in the same manner as in Example 1, except that the electrolytic manganese dioxide was not neutralized (addition amount of sodium hydroxide was 0 g). PH after neutralization of used electrolytic manganese dioxide, sodium content,
Table 1 shows the specific surface area, the substitution element of the obtained spinel-type lithium manganate, and the substitution amount of manganese. Further, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using this spinel-type lithium manganate as a positive electrode material,
The initial discharge capacity and high-temperature storage capacity retention were measured, and the results are shown in Table 2.

COMPARATIVE EXAMPLE 4 850 g of electrolytic manganese dioxide prepared in Comparative Example 1, 125.1 g of aluminum hydroxide (substituting 15 mol% of manganese), and carbonic acid were added so that the molar ratio of Li / (Mn + substituted element) was 0.54. A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 2 shows the results.

Comparative Example 5 850 g of electrolytic manganese dioxide and 125.1 g of aluminum hydroxide (substituted for 15 mol% of manganese) prepared in Example 1 were carbonated so that the molar ratio of Li / (Mn + substituted element) was 0.54. A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 2 shows the results.

Comparative Example 6 850 g of electrolytic manganese dioxide and 64.8 g of magnesium oxide (substituted for 15 mol% of manganese) prepared in Example 1 were mixed with lithium carbonate so that the molar ratio of Li / (Mn + substituted element) was 0.54. Was synthesized in the same manner as in Example 1 except that was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 2 shows the results.

COMPARATIVE EXAMPLE 7 850 g of electrolytic manganese dioxide and 148.8 g of nickel hydroxide (substituted for 15 mol% of manganese) prepared in Example 1 were carbonated so that the Li / (Mn + substituted element) molar ratio was 0.54. A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 2 shows the results.

Comparative Example 8 850 g of electrolytic manganese dioxide and 149.1 g of cobalt hydroxide (substituted for 15 mol% of manganese) prepared in Example 1 were carbonated so that the molar ratio of Li / (Mn + substituted element) was 0.54. A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 2 shows the results.

Comparative Example 9 850 g of electrolytic manganese dioxide prepared in Example 1 and 64.8 g of diiron trioxide (substituting 15 mol% of manganese) were replaced by L
A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of i / (Mn + substituted element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. In addition, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention were measured. Shown in

Comparative Example 10 850 g of electrolytic manganese dioxide and 127.8 g of copper monoxide (substituted for 15 mol% of manganese) prepared in Example 1 were replaced by L
A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of i / (Mn + substituted element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. In addition, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention were measured. Shown in

Comparative Example 11 850 g of electrolytic manganese dioxide and 130.5 g of zinc oxide (substituted for 15 mol% of manganese) prepared in Example 1 were replaced with L
A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of i / (Mn + substituted element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. In addition, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention were measured. Shown in

Comparative Example 12 850 g of electrolytic manganese dioxide and 118.8 g of calcium hydroxide (substituted for 15 mol% of manganese) prepared in Example 1 were carbonated so that the Li / (Mn + substituted element) molar ratio was 0.54. A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 2 shows the results.

Comparative Example 13 Lithium carbonate was prepared in the same manner as in Example 1 except that 850 g of electrolytic manganese dioxide, 91.8 g of silicon dioxide (substituted 15 mol% of manganese) and Li / (Mn + substituted element) molar ratio were 0.54. Was synthesized in the same manner as in Example 1 except that was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. In addition, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention were measured. Shown in

Comparative Example 14 850 g of electrolytic manganese dioxide and 128.1 g of titanium dioxide prepared in Example 1 (substituting 15 mol% of manganese)
And spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of Li / (Mn + substituent element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Further, the spinel-type lithium manganate was used as a cathode material in Example 1
In the same manner as in the above, a coin-type nonaqueous electrolyte secondary battery was produced, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. The results are shown in Table 2.

Comparative Example 15 The electrolytic manganese dioxide prepared in Example 1, 850 g of dichromium trioxide and 121.8 g of dichromium trioxide (substituted by 15 mol% of manganese) were adjusted to have a Li / (Mn + substituted element) molar ratio of 0.54. A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 2 shows the results.

Comparative Example 16 850 g of electrolytic manganese dioxide prepared in Example 1 and 109.8 g of diphosphorus pentoxide (substituted 15 mol% of manganese)
And spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of Li / (Mn + substituent element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Further, the spinel-type lithium manganate was used as a cathode material in Example 1
In the same manner as in the above, a coin-type nonaqueous electrolyte secondary battery was produced, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. The results are shown in Table 2.

Comparative Example 17 850 g of electrolytic manganese dioxide prepared in Example 1 and 79.5 g of sodium carbonate (replace 15 mol% of manganese)
And spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of Li / (Mn + substituent element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Further, the spinel-type lithium manganate was used as a cathode material in Example 1
In the same manner as in the above, a coin-type nonaqueous electrolyte secondary battery was produced, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. The results are shown in Table 2.

Comparative Example 18 850 g of electrolytic manganese dioxide prepared in Example 1 and 103.8 g of potassium carbonate (replace 15 mol% of manganese)
And spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of Li / (Mn + substituent element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Further, the spinel-type lithium manganate was used as a cathode material in Example 1
In the same manner as in the above, a coin-type nonaqueous electrolyte secondary battery was produced, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. The results are shown in Table 2.

Comparative Example 19 The electrolytic manganese dioxide prepared in Example 1 and 850 g of divanadium pentoxide (substituted by 15 mol% of manganese) were replaced by Li / (Mn + substituted element) in a molar ratio of 0.54. A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 2 shows the results.

Comparative Example 20 Carbon dioxide was prepared so as to obtain 850 g of electrolytic manganese dioxide, 57.9 g of boron trioxide (substituting 15 mol% of manganese) prepared in Example 1, and a Li / (Mn + substituted element) molar ratio of 0.54. A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. In addition, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention were measured. Shown in

Comparative Example 21 950 g of electrolytic manganese dioxide and 41.7 g of aluminum hydroxide (substituted for 5 mol% of manganese) prepared in Comparative Example 1 were carbonated so that the molar ratio of Li / (Mn + substituted element) was 0.54. A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured.
Table 2 shows the results.

Comparative Example 22 950 g of electrolytic manganese dioxide and 21.6 g of magnesium oxide prepared in Comparative Example 1 (substituting 5 mol% of manganese)
And spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of Li / (Mn + substituent element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Further, the spinel-type lithium manganate was used as a cathode material in Example 1
In the same manner as in the above, a coin-type nonaqueous electrolyte secondary battery was produced, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. The results are shown in Table 2.

Comparative Example 23 950 g of electrolytic manganese dioxide and 49.6 g of nickel hydroxide (substituted for 5 mol% of manganese) prepared in Comparative Example 1 were carbonated so that the molar ratio of Li / (Mn + substituted element) was 0.54. A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. In addition, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention were measured. Shown in

Comparative Example 24 950 g of electrolytic manganese dioxide and 49.7 g of cobalt hydroxide (substituted for 5 mol% of manganese) prepared in Comparative Example 1 were carbonated so that the molar ratio of Li / (Mn + substituted element) was 0.54. A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. In addition, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention were measured. Shown in

Comparative Example 25 950 g of electrolytic manganese dioxide and 21.6 g of diiron trioxide (substituted by 5 mol% of manganese) prepared in Comparative Example 1 were replaced with Li
/ (Mn + substituted element) A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so as to have a molar ratio of 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. In addition, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention were measured. Shown in

Comparative Example 26 950 g of electrolytic manganese dioxide prepared in Comparative Example 1, 42.6 g of copper monoxide (substituted for 5 mol% of manganese) and Li /
A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of (Mn + substituted element) was 0.54. PH after neutralization of the used electrolytic manganese dioxide, sodium content, specific surface area,
Table 1 shows the substitution elements of the obtained spinel-type lithium manganate and the substitution amounts of manganese. In addition, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention were measured.
Shown in

Comparative Example 27 950 g of electrolytic manganese dioxide prepared in Comparative Example 1, 43.5 g of zinc oxide (substituted for 5 mol% of manganese) and Li /
A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of (Mn + substituted element) was 0.54. PH after neutralization of the used electrolytic manganese dioxide, sodium content, specific surface area,
Table 1 shows the substitution elements of the obtained spinel-type lithium manganate and the substitution amounts of manganese. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured.
Shown in

Comparative Example 28 950 g of electrolytic manganese dioxide prepared in Comparative Example 1 and 39.6 g of calcium hydroxide (substituting 5 mol% of manganese)
And spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of Li / (Mn + substituent element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Further, the spinel-type lithium manganate was used as a cathode material in Example 1
In the same manner as in the above, a coin-type nonaqueous electrolyte secondary battery was produced, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. The results are shown in Table 2.

Comparative Example 29 950 g of electrolytic manganese dioxide prepared in Comparative Example 1, 30.6 g of silicon dioxide (substituted for 5 mol% of manganese) and L
A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of i / (Mn + substituted element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. In addition, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention were measured. Shown in

Comparative Example 30 950 g of electrolytic manganese dioxide and 42.7 g of titanium dioxide (substituted for 5 mol% of manganese) prepared in Comparative Example 1 were mixed with L
A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of i / (Mn + substituted element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. In addition, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention were measured. Shown in

Comparative Example 31 The 950 g of electrolytic manganese dioxide, 40.6 g of dichromium trioxide (substituted for 5 mol% of manganese) prepared in Comparative Example 1, and the molar ratio of Li / (Mn + substituted element) were 0.54. A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. In addition, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention were measured. Shown in

Comparative Example 32 950 g of the electrolytic manganese dioxide prepared in Comparative Example 1, 36.6 g of diphosphorus pentoxide (substituting 5 mol% of manganese) and L
A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of i / (Mn + substituted element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the electrolytic manganese dioxide used. Also, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention rate were measured. Shown in

Comparative Example 33 950 g of electrolytic manganese dioxide prepared in Comparative Example 1, 26.5 g of sodium carbonate (substituting 5 mol% of manganese), and lithium carbonate in a Li / (Mn + substituted element) molar ratio of 0.54. Was synthesized in the same manner as in Example 1 except that was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. In addition, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention were measured. Shown in

Comparative Example 34 950 g of electrolytic manganese dioxide prepared in Comparative Example 1, 34.6 g of potassium carbonate (substituting 5 mol% of manganese) and L
A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of i / (Mn + substituted element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. In addition, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention were measured. Shown in

Comparative Example 35 The electrolytic manganese dioxide prepared in Comparative Example 1 was 950 g, divanadium pentoxide 48.6 g (substituting 5 mol% of manganese) and the Li / (Mn + substituted element) molar ratio was 0.54. A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. Also,
Using this spinel-type lithium manganate as a positive electrode material, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and the initial discharge capacity and high-temperature storage capacity retention were measured.
Table 2 shows the results.

Comparative Example 36 950 g of electrolytic manganese dioxide and 19.3 g of boron trioxide (substituted for 5 mol% of manganese) prepared in Comparative Example 1 were mixed with L
A spinel-type lithium manganate was synthesized in the same manner as in Example 1 except that lithium carbonate was mixed so that the molar ratio of i / (Mn + substituted element) was 0.54. Table 1 shows the pH, the sodium content, the specific surface area, the substitution element of the obtained spinel-type lithium manganate and the substitution amount of manganese after neutralization of the used electrolytic manganese dioxide. In addition, a coin-type nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 using the spinel-type lithium manganate as a positive electrode material, and the initial discharge capacity and the high-temperature storage capacity retention were measured. Shown in

Example 53 A spinel-type lithium manganate was synthesized in the same manner as in Example 1, except that the average particle size at the time of pulverizing the electrolytic manganese dioxide was 5 μm. Using this spinel-type lithium manganate as a positive electrode material, a coin-type non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 1, and two types of current densities of 0.5 mA / c were used.
It was evaluated in m ² and 1.0mA / cm ^2, 0.5mA / cm
The discharge capacity at a current density of ² was assumed to be 100, and 1.0 mA / c
The discharge capacity ratio at m ² was represented as a current load ratio. Table 3
Shows the current load factor.

[0116]

[Table 3]

Example 54 The same evaluation as in Example 53 was performed on the coin-type non-aqueous electrolyte secondary battery manufactured in Example 1. Table 3 shows the current load ratio.

Example 55 A spinel-type lithium manganate was synthesized in the same manner as in Example 1, except that the average particle size of the electrolytic manganese dioxide during pulverization was 30 μm. A coin-type non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1 using this spinel-type lithium manganate as a positive electrode material, and was evaluated in the same manner as in Example 53. Table 3 shows the current load ratio.

Example 56 A spinel-type lithium manganate was synthesized in the same manner as in Example 1, except that the average particle size of the electrolytic manganese dioxide during pulverization was 35 μm. A coin-type non-aqueous electrolyte secondary battery was manufactured in the same manner as in Example 1 using this spinel-type lithium manganate as a positive electrode material, and was evaluated in the same manner as in Example 53. Table 3 shows the current load ratio.

[0120]

As described above, by using the spinel-type lithium manganate obtained by the production method of the present invention as a positive electrode material for a non-aqueous electrolyte secondary battery, the amount of Mn elution during charging can be suppressed, Battery characteristics at high temperatures such as high-temperature storage characteristics and high-temperature cycle characteristics can be improved, and the current load factor can be improved.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a non-aqueous electrolyte secondary battery used in the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Positive electrode case 2 Sealing plate 3 Current collector 4 Metal negative electrode 5 Positive electrode 6 Separator 7 Gasket

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4G048 AA04 AA05 AB01 AB05 AC06 AD04 AD06 AE05 5H029 AJ04 AJ05 AK03 AL06 AL12 BJ03 CJ02 CJ08 CJ14 EJ01 EJ04 EJ12 HJ02 HJ07 HJ10 HJ14 5H050 AA07 CB07A10 CB GA05 GA10 GA15 HA02 HA07 HA10 HA14

Claims (4)

[Claims] A manganese dioxide deposited by electrolysis is ground, neutralized with sodium hydroxide or sodium carbonate,
Manganese dioxide having a specific surface area of 50 m ² / g or more, a lithium raw material, magnesium, aluminum, nickel, cobalt, iron, copper, zinc, calcium, silicon, phosphorus, titanium, chromium, sodium, A compound containing at least one element selected from potassium, vanadium, and boron is mixed and fired so that the compound replaces 0.05 to 12.5 mol% of manganese with the element. For producing a spinel-type lithium manganate. 2. The method for producing spinel-type lithium manganate according to claim 1, wherein the firing is performed at a temperature of 750 ° C. or higher. 3. A positive electrode material for a non-aqueous electrolyte secondary battery, comprising the spinel-type lithium manganate obtained by the production method according to claim 1. 4. A non-aqueous electrolyte secondary battery comprising a positive electrode using the positive electrode material according to claim 3, a negative electrode capable of inserting and extracting lithium, and a non-aqueous electrolyte.