CA2303226C - Process for producing spinel type lithium manganate - Google Patents
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- CA2303226C CA2303226C CA002303226A CA2303226A CA2303226C CA 2303226 C CA2303226 C CA 2303226C CA 002303226 A CA002303226 A CA 002303226A CA 2303226 A CA2303226 A CA 2303226A CA 2303226 C CA2303226 C CA 2303226C
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Complex oxides containing manganese and at least one other metal element
- C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
- H01M50/109—Primary casings; Jackets or wrappings characterised by their shape or physical structure of button or coin shape
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
A process of producing spinet-type lithium manganate which is characterized by comprising pulverizing electrodeposited manganese dioxide, neutralizing the powder with sodium hydroxide or sodium carbonate to a pH of 2 or higher, mixing the electrolytic manganese dioxide with a lithium raw material, and firing the mixture.</SDOA B>
Description
PROCESS OF PRODUCING SPINEL-TYPE LITHIUM MANGANATE
Technical Field The present invention relates to a process of producing spinet-type lithium manganate. More particularly it relates to a process for producing spinet-type lithium manganate which, when used as a cathode material of a nonaqueous secondary battery, suppresses dissolution of manganese therefrom thereby securing improved high-temperature characteristics of the battery such as high-temperature storage properties and high-temperature cycle characteristics. .
Background Art 1 o With the recent rapid development of portable and wireless electronic equipment such as personal computers and telephones, the demand for secondary batteries as a driving power source has been increasing. In particular nonaqueous secondary batteries are expected for their smallest size and high energy density. Cathode active materials for nonaqueous secondary batteries meeting the demand include lithium cobaltate (LiCoOa), lithium nickelate (LiNiOz), lithium manganate (LiMnz04), etc. Having an electrode potential of 4 V or higher with respect to lithium, these complex oxides are capable of providing batteries having a high energy density.
Of the above-described complex oxides, LiCoOz and L~liOz have a theoretical capacity of about 280 mAh/g, while LiMnzO4 has a theoretical capacity as low as 148 mAh/g 2 o but is deemed suited for use in electric vehicles and the like because of an abundant and inexpensive supply of manganese oxide as a raw material and freedom from such thermal instability in charging as observed with LiNiOz.
However, lithium manganate (LiMnzOa) is disadvantageous in that manganese dissolves out in high temperature to reduce the high-temperature battery performance, such 2 5 as high-temperature storage properties and high-temperature cycle characteristics.
Disclosure of the Invention Accordingly, an aspect of the present invention is to provide a process for producing spinet-type lithium manganate which, when used as a cathode material of a nonaqueous secondary battery, suppresses dissolution of manganese therefrom thereby securing improved high-temperature characteristics of the battery such as high-temperature storage properties and high-temperature cycle characteristics and to provide a nonaqueous secondary battery using the cathode material.
s Japanese Patent Laid-Open No. 139861/90 teaches that addition of a given amount of sodium to spinet-type lithium manganate brings about improvement on the room temperature cycle life. The publication describes a process comprising adding a sodium raw material to a manganese raw material and a lithium raw material and firing the mixture.
Being inexpensive and abundant, electrolytic manganese dioxide is suitable as a manganese 1 o raw material for spinet-type lithium manganate. After electrolysis, electrolytic manganese dioxide is usually neutralized with ammonia for use in manganese dry batteries and with soda for use in alkali manganese batteries. It is known that soda-neutralized electrolytic manganese dioxide contains a small amount of residual sodium. The amount of the residual sodium depends on the neutralization conditions.
15 Having noted the neutralization conditions of electrolytic manganese dioxide, the present inventors have found that spinet-type lithium manganate obtained under specific neutralization conditions accomplishes the above object.
The present invention has been completed based on the above finding and provides a process of producing spinet-type lithium manganate which is characterized by comprising 2 o pulverizing electrodeposited manganese dioxide, neutralizing the powder with sodium hydroxide or sodium carbonate to a pH of 2 or higher, mixing the resulting electrolytic manganese dioxide with a lithium raw material, and firing the mixture.
Brief Description of the Drawings Fig. 1 is a cross sectional view of a coin type nonaqueous secondary battery prepared 2s in Examples and Comparative Examples.
Best Mode for Carrying out the Invention The present invention will now be described in detail.
In the present invention, electrolytic manganese dioxide is used as a raw manganese material of spinel-type lithium manganate.
The electrolytic manganese dioxide used in the invention is obtained by the following method. For example, electrolysis of a manganese sulfate solution having a prescribed concentration is conducted while heating at a constant current density by using a carbon s plate as a cathode and a titanium plate as an anode to electrodeposit manganese dioxide on the anode. The elecfrodeposited manganese dioxide is peeled off the anode and pulverized to a prescribed particle size, preferably an average particle diameter of 5 to 30 pm.
Since the cathode of a nonaqueous secondary battery has a film form of about 100 um in thickness, too large particles cause cracks and the like and are difficult to make 1 o into a film of uniform thickness. Spinel-type lithium manganate synthesized from electrolytic manganese dioxide having an average particle size of 5 to 30 pm provides a cathode material fit for film formation without requiring an additional pulverization operation. It is assumed that the thus obtained finely particulate electrolytic manganese dioxide, upon being neutralized with sodium, allows sodium to be uniformly distributed z s therethrough.
After soda neutralization, the electrolytic manganese dioxide ground to a prescribed particle size is washed with water and dried. Specifically, soda neutralization is effected with sodium hydroxide or sodium carbonate. The order of pulverization and neutralization is not particularly restricted. That is, pulverization may be preceded by neutralization.
2 o The pH of the neutralized electrolytic manganese dioxide is 2 or higher, preferably from 2 to 5.5, still preferably from 2 to 4. The higher the pH, the less the amount of manganese dissolved in high temperature, but the less the initial discharge capacity. At a pH lower than 2, the effect is insufficient.
In the present invention, the resulting electrolytic manganese dioxide is mixed with a 2 s lithium raw material and fired to give spinel-type lithium manganate.
Lithium salts include lithium carbonate (Li2C03), lithium nitrate (LiN03), and lithium hydroxide (LiOH). The molar ratio of Li in the lithium raw material to Mn in the electrolytic manganese dioxide, Li/Mn, is preferably 0.50 to 0.60.
Technical Field The present invention relates to a process of producing spinet-type lithium manganate. More particularly it relates to a process for producing spinet-type lithium manganate which, when used as a cathode material of a nonaqueous secondary battery, suppresses dissolution of manganese therefrom thereby securing improved high-temperature characteristics of the battery such as high-temperature storage properties and high-temperature cycle characteristics. .
Background Art 1 o With the recent rapid development of portable and wireless electronic equipment such as personal computers and telephones, the demand for secondary batteries as a driving power source has been increasing. In particular nonaqueous secondary batteries are expected for their smallest size and high energy density. Cathode active materials for nonaqueous secondary batteries meeting the demand include lithium cobaltate (LiCoOa), lithium nickelate (LiNiOz), lithium manganate (LiMnz04), etc. Having an electrode potential of 4 V or higher with respect to lithium, these complex oxides are capable of providing batteries having a high energy density.
Of the above-described complex oxides, LiCoOz and L~liOz have a theoretical capacity of about 280 mAh/g, while LiMnzO4 has a theoretical capacity as low as 148 mAh/g 2 o but is deemed suited for use in electric vehicles and the like because of an abundant and inexpensive supply of manganese oxide as a raw material and freedom from such thermal instability in charging as observed with LiNiOz.
However, lithium manganate (LiMnzOa) is disadvantageous in that manganese dissolves out in high temperature to reduce the high-temperature battery performance, such 2 5 as high-temperature storage properties and high-temperature cycle characteristics.
Disclosure of the Invention Accordingly, an aspect of the present invention is to provide a process for producing spinet-type lithium manganate which, when used as a cathode material of a nonaqueous secondary battery, suppresses dissolution of manganese therefrom thereby securing improved high-temperature characteristics of the battery such as high-temperature storage properties and high-temperature cycle characteristics and to provide a nonaqueous secondary battery using the cathode material.
s Japanese Patent Laid-Open No. 139861/90 teaches that addition of a given amount of sodium to spinet-type lithium manganate brings about improvement on the room temperature cycle life. The publication describes a process comprising adding a sodium raw material to a manganese raw material and a lithium raw material and firing the mixture.
Being inexpensive and abundant, electrolytic manganese dioxide is suitable as a manganese 1 o raw material for spinet-type lithium manganate. After electrolysis, electrolytic manganese dioxide is usually neutralized with ammonia for use in manganese dry batteries and with soda for use in alkali manganese batteries. It is known that soda-neutralized electrolytic manganese dioxide contains a small amount of residual sodium. The amount of the residual sodium depends on the neutralization conditions.
15 Having noted the neutralization conditions of electrolytic manganese dioxide, the present inventors have found that spinet-type lithium manganate obtained under specific neutralization conditions accomplishes the above object.
The present invention has been completed based on the above finding and provides a process of producing spinet-type lithium manganate which is characterized by comprising 2 o pulverizing electrodeposited manganese dioxide, neutralizing the powder with sodium hydroxide or sodium carbonate to a pH of 2 or higher, mixing the resulting electrolytic manganese dioxide with a lithium raw material, and firing the mixture.
Brief Description of the Drawings Fig. 1 is a cross sectional view of a coin type nonaqueous secondary battery prepared 2s in Examples and Comparative Examples.
Best Mode for Carrying out the Invention The present invention will now be described in detail.
In the present invention, electrolytic manganese dioxide is used as a raw manganese material of spinel-type lithium manganate.
The electrolytic manganese dioxide used in the invention is obtained by the following method. For example, electrolysis of a manganese sulfate solution having a prescribed concentration is conducted while heating at a constant current density by using a carbon s plate as a cathode and a titanium plate as an anode to electrodeposit manganese dioxide on the anode. The elecfrodeposited manganese dioxide is peeled off the anode and pulverized to a prescribed particle size, preferably an average particle diameter of 5 to 30 pm.
Since the cathode of a nonaqueous secondary battery has a film form of about 100 um in thickness, too large particles cause cracks and the like and are difficult to make 1 o into a film of uniform thickness. Spinel-type lithium manganate synthesized from electrolytic manganese dioxide having an average particle size of 5 to 30 pm provides a cathode material fit for film formation without requiring an additional pulverization operation. It is assumed that the thus obtained finely particulate electrolytic manganese dioxide, upon being neutralized with sodium, allows sodium to be uniformly distributed z s therethrough.
After soda neutralization, the electrolytic manganese dioxide ground to a prescribed particle size is washed with water and dried. Specifically, soda neutralization is effected with sodium hydroxide or sodium carbonate. The order of pulverization and neutralization is not particularly restricted. That is, pulverization may be preceded by neutralization.
2 o The pH of the neutralized electrolytic manganese dioxide is 2 or higher, preferably from 2 to 5.5, still preferably from 2 to 4. The higher the pH, the less the amount of manganese dissolved in high temperature, but the less the initial discharge capacity. At a pH lower than 2, the effect is insufficient.
In the present invention, the resulting electrolytic manganese dioxide is mixed with a 2 s lithium raw material and fired to give spinel-type lithium manganate.
Lithium salts include lithium carbonate (Li2C03), lithium nitrate (LiN03), and lithium hydroxide (LiOH). The molar ratio of Li in the lithium raw material to Mn in the electrolytic manganese dioxide, Li/Mn, is preferably 0.50 to 0.60.
For obtaining a larger reactive cross-sectional area, it is preferred that the electrolytic manganese dioxide and the lithium raw material be ground before or after being mixed.
The weighed and mixed materials can be used either as such or after being granulated.
Granulation can be carried out in either a wet system or a dry system. Methods of s granulation include piston granulation; tumbling granulation, fluidized bed granulation, mixing granulation, spray drying, pressure forming granulation, and flaking granulation using a roll, etc.
The resulting raw material is put in firing furnace and fired at 600 to 1000°C to obtain spinet-type lithium manganate. . While a firing temperature of about 600°C would be io enough fox obtaining spinet-type lithium manganate of single phase, grain gowth does not proceed at a low firing temperature. Therefore, a firing temperature of 750°C or higher, preferably 850°C or higher is required. The firing furnaces which can be used include a rotary kiln and a stationary furnace. The firing time is 1 hour or longer, preferably 5 to 20 hours.
Zs In this manner, spinet-type lithium manganate containing a given amount of sodium can be obtained. A preferred sodium content is 0.05 to 1.0% by weight. The sodium-containing spinet-type lithium manganate is useful as a cathode material of a nona.queous secondary battery.
In the nonaqueous secondary battery of the present invention, the above-described 2 o cathode material is mixed with a conductive material, such as carbon black, and a binder, TM
such as Teflon binder, to prepare a cathode material mixture. For an anode, lithium or a material capable of intercalating and disintercalating lithium, such as carbon, is used.
Nonaqueous electrolytes which can be used are not particularly limited and include a lithium salt, e.g., lithium hexafluorophosphate (LiPFs), dissolved in a mixed solvent, such as 2s ethylene carbonate/dimethyl carbonate.
Since manganese can be suppressed from dissolving in a charged state, the nonaqueous secondary battery according to the present invention exhibits improved high-temperature battery characteristics such as high-temperature storage properties and high-temperature cycle characteristics.
The present invention will now be illustrated in greater detail with reference to Examples, but it should be understood that the invention is not limited thereto.
An aqueous manganese sulfate solution having a sulfuric acid concentration of 50 g/1 s and a manganese concentration of 40 g/1 was prepared as an electrolytic solution. The electrolytic solution was heated to 95°C, and electrolysis was performed at a current density of 60 A/m2 using a carbon plate as a cathode and a titanium plate as an anode.
Manganese dioxide thus electrodeposited was peeled and crushed into chips under the size of 7 mm, which were pulverized to an average particle size of about 20 ~,m.
l o Ten kilograms of the manganese dioxide was washed with 201 of water. After discharging the washing, 201 of water was added to the manganese dioxide, and 3 5 g of sodium hydroxide was dissolved therein, followed by stirnng for 24 hours to carry out neutralization. The particles were washed with water, filtered, and dried (50°C x 30 mins.).
The pH as measured in accordance with JIS K1467-1984 and the sodium content of the 1 s resulting powder are shown in Table 1.
One kilogram of the thus obtained manganese dioxide having an average particle size of about 20 ~,m was mixed with lithium carbonate at an Li/Mn molar ratio of 0.54, and the mixture was fired in a box type kiln at 800°C for 20 hours.
Eighty parts by weight of the resulting spinel-type lithium manganate, 15 parts by 2 o weight of carbon black, and 5 parts by weight of polytetrafluoroethylene (binder) were mixed to prepare a cathode material mixture.
A coin type nonaqueous secondary battery shown in Fig. 1 was assembled by using the resulting cathode material mixture. A cathode case 1 made of organic electrolytic solution-resistant stainless steel has a current collector 3 of the same stainless steel spot 2 s welded on the inner side thereof. A cathode made of the cathode material mixture is press bonded on the upper side of the current collector 3. A porous polypropylene resin separator 6 impregnated with an electrolytic solution is placed on the upper side of the cathode 5. A sealing member 2 having an anode 4 made of metallic lithium bonded to the lower side thereof is fit into the opening of the cathode case 1 via a polypropylene gasket 7 thereby to seal the battery. The sealing member 2 combines the function as an anode terminal and is made of stainless steel similarly to the cathode case 1. The battery had a diameter of 20 mm and a height of 1.6 mm. The electrolytic solution used consisted of an equal volume mixture of ethylene carbonate and 1,3-dimethoxyethane having dissolved therein 1 mol/1 of lithium hexaffuorophosphate as a solute.
The resulting battery was subjected to a charge and discharge test. The charge and discharge test was carried out at 20°C and at a current density of 0.5 mA/cm2 within a voltage range of from 3 V to 4.3 V. The battery was charged to 4.3 V and, after storing at l0 80°C for 3 days, the discharge capacity of the battery was confirmed. Further, the storage characteristics of the battery were confirmed in terms of discharge capacity retention after the storage, with the discharge capacity before the storage being taken as 100. The initial discharge capacity and the capacity retention against high-temperature storage thus obtained are shown in Table 1.
Spinet-type lithium manganate was synthesized in the same manner as in Example 1, except that the amount of sodium hydroxide added to neutralize the electrolytic manganese dioxide was changed to 53 g. The pH and Na content after the neutralization are shown in Table 1. A coin type nonaqueous secondary battery was assembled using the resulting 2 o spinet-type lithium manganate as a cathode material, and the initial discharge capacity and the capacity retention against high-temperature storage were measured in the same manner as in Example 1. The results obtained are shown in Table 1.
Spinet-type lithium manganate was synthesized in the same manner as in Example 1, 2 5 except that the amount of sodium hydroxide added to neutralize the electrolytic manganese dioxide was changed to 80 g. The pH and Na content after the neutralization are shown in Table 1. A coin type nonaqueous secondary battery was assembled using the resulting spinet-type lithium manganate as a cathode material, and the initial discharge capacity and the capacity retention against high-temperature storage were measured in the same manner s o as in Example 1. The results obtained are shown in Table 1.
Spinet-type lithium manganate was synthesized in the same manner as in Example 1, except that the amount of sodium hydroxide added to neutralize the electrolytic manganese dioxide was changed to 120 g. The pH and Na content after the neutralization are shown s in Table 1. A coin type nonaqueous secondary battery was assembled using the resulting spinet-type lithium manganate as a cathode material, and the initial discharge capacity and the capacity retention against high-temperature storage were measured in the same manner as in Example 1. The results obtained are shown in Table 1.
to Spinet-type lithium manganate was synthesized in the same manner as in Example 1, except that the amount of sodium hydroxide added to neutralize the electrolytic manganese dioxide was changed to 160 g. The pH and Na content after the neutralization are shown in Table 1. A coin type nonaqueous secondary battery was assembled using the resulting spinet-type lithium manganate as a cathode material, and the initial discharge capacity and 1 s the capacity retention against high-temperature storage were measured in the same manner as in Example 1. The results obtained are shown in Table 1.
Spinet-type lithium manganate was synthesized in the same manner as in Example l, except that the firing temperature was changed to 900°C. The pH and Na content after the 2 o neutralization are shown in Table 1. A coin type nonaqueous secondary battery was assembled using the resulting spinet-type lithium manganate as a cathode material, and the initial discharge capacity and the capacity retention against high-temperature storage were measured in the same manner as in Example 1. The results obtained are shown in Table 1.
2s Spinet-type lithium manganate was synthesized in the same manner as in Example 1, except that the firing temperature was changed to 700°C. The pH and Na content after the neutralization are shown in Table 1. A coin type nonaqueous secondary battery was assembled using the resulting spinet-type lithium manganate as a cathode material, and the initial discharge capacity and the capacity retention against high-temperature storage were s o measured in the same manner as in Example 1. The results obtained are shown in Table 1.
COMP~R_A_TIVE EKA_M_PLE 1 Spinel-type lithium manganate was synthesized in the same manner as in Example l, except that the neutralization of the electrolytic manganese dioxide was not conducted (i.e., the amount of sodium hydroxide added was 0 g). The pH and Na content after the s neutralization are shown in Table 1. A coin type nonaqueous secondary battery was assembled using the resulting spinel-type lithium manganate as a cathode material, and the initial discharge capacity and the capacity retention against high-temperature storage were measured in the same manner as in Example 1. The results obtained are shown in Table 1.
pH {JIS)Na Initial DischargeHigh-temp. Storage (wt%) Ca aci (mAh/ Ca aci Retention (%) 1 2.5 0.13 122 75 2 3.5 0.20 118 79 3 4.5 0.45 114 82 Example 4 5Ø 0.54 113 85 5 6.0 0.65 107 86 6 3.5 0.20 116 88 7 3.5 0.20 119 70 Com ara. 1.6 0.04 123 64 Exam le Spinel-type lithium manganate was synthesized in the same manner as in Example 1, except that the electrolytic manganese dioxide was pulverized to an average particle size of S p.m. In the same manner as in Example 1, a coin type nonaqueous secondary battery was s assembled using the resulting spinel-type lithium manganate as a cathode material. The charge and discharge test was carried out at current densities of 0.5 mA/cm2 and 1.0 mA/cm2. The ratio of the discharge capacity at the current density of 1.0 mA/cm2 to that at the current density of 0.5 mA/cm2, taken as 100, was obtained as a current load ratio.
The current load ratio is shown in Table 2.
1 o F~g!VIPLE 9 The coin type nonaqueous secondary battery prepared in Example 1 was evaluated in the same manner as in Example 8. The current load ratio is shown in Table 2.
Spinet-type lithium manganate was synthesized in the same manner as in Example l, except that the electrolytic manganese dioxide was pulverized to an average particle size of 30 p,m. A coin type nonaqueous secondary battery was assembled using the resulting spinet-type lithium manganate as a cathode material in the same manner as in Example 1, and evaluated in the same manner as in Example 8. The current load ratio is shown in Table 2.
Spinet-type lithium manganate was synthesized in the same manner as in Example 1, 1 o except that the electrolytic manganese dioxide was pulverized to an average particle size of 3 5 Vim. A coin type nonaqueous secondary battery was assembled using the resulting spinet-type lithium manganate as a cathode material in the same manner as in Example 1, and evaluated in the same manner as in Example 8. The current load ratio is shown in Table 2.
Average Current Load Particle Ratio Size ( m) (%) Example Industrial Applicability As described above, use of spinet-type lithium manganate obtained by the process of the present invention in a nonaqueous secondary battery as a cathode material makes it possible to suppress dissolution of manganese during charging thereby to improve the battery characteristics, such as high-temperature storage properties and high-temperature cycle characteristics, and a current load ratio.
The weighed and mixed materials can be used either as such or after being granulated.
Granulation can be carried out in either a wet system or a dry system. Methods of s granulation include piston granulation; tumbling granulation, fluidized bed granulation, mixing granulation, spray drying, pressure forming granulation, and flaking granulation using a roll, etc.
The resulting raw material is put in firing furnace and fired at 600 to 1000°C to obtain spinet-type lithium manganate. . While a firing temperature of about 600°C would be io enough fox obtaining spinet-type lithium manganate of single phase, grain gowth does not proceed at a low firing temperature. Therefore, a firing temperature of 750°C or higher, preferably 850°C or higher is required. The firing furnaces which can be used include a rotary kiln and a stationary furnace. The firing time is 1 hour or longer, preferably 5 to 20 hours.
Zs In this manner, spinet-type lithium manganate containing a given amount of sodium can be obtained. A preferred sodium content is 0.05 to 1.0% by weight. The sodium-containing spinet-type lithium manganate is useful as a cathode material of a nona.queous secondary battery.
In the nonaqueous secondary battery of the present invention, the above-described 2 o cathode material is mixed with a conductive material, such as carbon black, and a binder, TM
such as Teflon binder, to prepare a cathode material mixture. For an anode, lithium or a material capable of intercalating and disintercalating lithium, such as carbon, is used.
Nonaqueous electrolytes which can be used are not particularly limited and include a lithium salt, e.g., lithium hexafluorophosphate (LiPFs), dissolved in a mixed solvent, such as 2s ethylene carbonate/dimethyl carbonate.
Since manganese can be suppressed from dissolving in a charged state, the nonaqueous secondary battery according to the present invention exhibits improved high-temperature battery characteristics such as high-temperature storage properties and high-temperature cycle characteristics.
The present invention will now be illustrated in greater detail with reference to Examples, but it should be understood that the invention is not limited thereto.
An aqueous manganese sulfate solution having a sulfuric acid concentration of 50 g/1 s and a manganese concentration of 40 g/1 was prepared as an electrolytic solution. The electrolytic solution was heated to 95°C, and electrolysis was performed at a current density of 60 A/m2 using a carbon plate as a cathode and a titanium plate as an anode.
Manganese dioxide thus electrodeposited was peeled and crushed into chips under the size of 7 mm, which were pulverized to an average particle size of about 20 ~,m.
l o Ten kilograms of the manganese dioxide was washed with 201 of water. After discharging the washing, 201 of water was added to the manganese dioxide, and 3 5 g of sodium hydroxide was dissolved therein, followed by stirnng for 24 hours to carry out neutralization. The particles were washed with water, filtered, and dried (50°C x 30 mins.).
The pH as measured in accordance with JIS K1467-1984 and the sodium content of the 1 s resulting powder are shown in Table 1.
One kilogram of the thus obtained manganese dioxide having an average particle size of about 20 ~,m was mixed with lithium carbonate at an Li/Mn molar ratio of 0.54, and the mixture was fired in a box type kiln at 800°C for 20 hours.
Eighty parts by weight of the resulting spinel-type lithium manganate, 15 parts by 2 o weight of carbon black, and 5 parts by weight of polytetrafluoroethylene (binder) were mixed to prepare a cathode material mixture.
A coin type nonaqueous secondary battery shown in Fig. 1 was assembled by using the resulting cathode material mixture. A cathode case 1 made of organic electrolytic solution-resistant stainless steel has a current collector 3 of the same stainless steel spot 2 s welded on the inner side thereof. A cathode made of the cathode material mixture is press bonded on the upper side of the current collector 3. A porous polypropylene resin separator 6 impregnated with an electrolytic solution is placed on the upper side of the cathode 5. A sealing member 2 having an anode 4 made of metallic lithium bonded to the lower side thereof is fit into the opening of the cathode case 1 via a polypropylene gasket 7 thereby to seal the battery. The sealing member 2 combines the function as an anode terminal and is made of stainless steel similarly to the cathode case 1. The battery had a diameter of 20 mm and a height of 1.6 mm. The electrolytic solution used consisted of an equal volume mixture of ethylene carbonate and 1,3-dimethoxyethane having dissolved therein 1 mol/1 of lithium hexaffuorophosphate as a solute.
The resulting battery was subjected to a charge and discharge test. The charge and discharge test was carried out at 20°C and at a current density of 0.5 mA/cm2 within a voltage range of from 3 V to 4.3 V. The battery was charged to 4.3 V and, after storing at l0 80°C for 3 days, the discharge capacity of the battery was confirmed. Further, the storage characteristics of the battery were confirmed in terms of discharge capacity retention after the storage, with the discharge capacity before the storage being taken as 100. The initial discharge capacity and the capacity retention against high-temperature storage thus obtained are shown in Table 1.
Spinet-type lithium manganate was synthesized in the same manner as in Example 1, except that the amount of sodium hydroxide added to neutralize the electrolytic manganese dioxide was changed to 53 g. The pH and Na content after the neutralization are shown in Table 1. A coin type nonaqueous secondary battery was assembled using the resulting 2 o spinet-type lithium manganate as a cathode material, and the initial discharge capacity and the capacity retention against high-temperature storage were measured in the same manner as in Example 1. The results obtained are shown in Table 1.
Spinet-type lithium manganate was synthesized in the same manner as in Example 1, 2 5 except that the amount of sodium hydroxide added to neutralize the electrolytic manganese dioxide was changed to 80 g. The pH and Na content after the neutralization are shown in Table 1. A coin type nonaqueous secondary battery was assembled using the resulting spinet-type lithium manganate as a cathode material, and the initial discharge capacity and the capacity retention against high-temperature storage were measured in the same manner s o as in Example 1. The results obtained are shown in Table 1.
Spinet-type lithium manganate was synthesized in the same manner as in Example 1, except that the amount of sodium hydroxide added to neutralize the electrolytic manganese dioxide was changed to 120 g. The pH and Na content after the neutralization are shown s in Table 1. A coin type nonaqueous secondary battery was assembled using the resulting spinet-type lithium manganate as a cathode material, and the initial discharge capacity and the capacity retention against high-temperature storage were measured in the same manner as in Example 1. The results obtained are shown in Table 1.
to Spinet-type lithium manganate was synthesized in the same manner as in Example 1, except that the amount of sodium hydroxide added to neutralize the electrolytic manganese dioxide was changed to 160 g. The pH and Na content after the neutralization are shown in Table 1. A coin type nonaqueous secondary battery was assembled using the resulting spinet-type lithium manganate as a cathode material, and the initial discharge capacity and 1 s the capacity retention against high-temperature storage were measured in the same manner as in Example 1. The results obtained are shown in Table 1.
Spinet-type lithium manganate was synthesized in the same manner as in Example l, except that the firing temperature was changed to 900°C. The pH and Na content after the 2 o neutralization are shown in Table 1. A coin type nonaqueous secondary battery was assembled using the resulting spinet-type lithium manganate as a cathode material, and the initial discharge capacity and the capacity retention against high-temperature storage were measured in the same manner as in Example 1. The results obtained are shown in Table 1.
2s Spinet-type lithium manganate was synthesized in the same manner as in Example 1, except that the firing temperature was changed to 700°C. The pH and Na content after the neutralization are shown in Table 1. A coin type nonaqueous secondary battery was assembled using the resulting spinet-type lithium manganate as a cathode material, and the initial discharge capacity and the capacity retention against high-temperature storage were s o measured in the same manner as in Example 1. The results obtained are shown in Table 1.
COMP~R_A_TIVE EKA_M_PLE 1 Spinel-type lithium manganate was synthesized in the same manner as in Example l, except that the neutralization of the electrolytic manganese dioxide was not conducted (i.e., the amount of sodium hydroxide added was 0 g). The pH and Na content after the s neutralization are shown in Table 1. A coin type nonaqueous secondary battery was assembled using the resulting spinel-type lithium manganate as a cathode material, and the initial discharge capacity and the capacity retention against high-temperature storage were measured in the same manner as in Example 1. The results obtained are shown in Table 1.
pH {JIS)Na Initial DischargeHigh-temp. Storage (wt%) Ca aci (mAh/ Ca aci Retention (%) 1 2.5 0.13 122 75 2 3.5 0.20 118 79 3 4.5 0.45 114 82 Example 4 5Ø 0.54 113 85 5 6.0 0.65 107 86 6 3.5 0.20 116 88 7 3.5 0.20 119 70 Com ara. 1.6 0.04 123 64 Exam le Spinel-type lithium manganate was synthesized in the same manner as in Example 1, except that the electrolytic manganese dioxide was pulverized to an average particle size of S p.m. In the same manner as in Example 1, a coin type nonaqueous secondary battery was s assembled using the resulting spinel-type lithium manganate as a cathode material. The charge and discharge test was carried out at current densities of 0.5 mA/cm2 and 1.0 mA/cm2. The ratio of the discharge capacity at the current density of 1.0 mA/cm2 to that at the current density of 0.5 mA/cm2, taken as 100, was obtained as a current load ratio.
The current load ratio is shown in Table 2.
1 o F~g!VIPLE 9 The coin type nonaqueous secondary battery prepared in Example 1 was evaluated in the same manner as in Example 8. The current load ratio is shown in Table 2.
Spinet-type lithium manganate was synthesized in the same manner as in Example l, except that the electrolytic manganese dioxide was pulverized to an average particle size of 30 p,m. A coin type nonaqueous secondary battery was assembled using the resulting spinet-type lithium manganate as a cathode material in the same manner as in Example 1, and evaluated in the same manner as in Example 8. The current load ratio is shown in Table 2.
Spinet-type lithium manganate was synthesized in the same manner as in Example 1, 1 o except that the electrolytic manganese dioxide was pulverized to an average particle size of 3 5 Vim. A coin type nonaqueous secondary battery was assembled using the resulting spinet-type lithium manganate as a cathode material in the same manner as in Example 1, and evaluated in the same manner as in Example 8. The current load ratio is shown in Table 2.
Average Current Load Particle Ratio Size ( m) (%) Example Industrial Applicability As described above, use of spinet-type lithium manganate obtained by the process of the present invention in a nonaqueous secondary battery as a cathode material makes it possible to suppress dissolution of manganese during charging thereby to improve the battery characteristics, such as high-temperature storage properties and high-temperature cycle characteristics, and a current load ratio.
Claims (10)
1. A process of producing lithium manganate having a spinel structure comprising the steps of:
pulverizing electrolytic manganese dioxide;
neutralizing the manganese dioxide powder with sodium hydroxide or sodium carbonate to a pH of from 2 to 5.5;
mixing the neutralized electrolytic manganese dioxide powder with a lithium raw material; and firing the mixture.
pulverizing electrolytic manganese dioxide;
neutralizing the manganese dioxide powder with sodium hydroxide or sodium carbonate to a pH of from 2 to 5.5;
mixing the neutralized electrolytic manganese dioxide powder with a lithium raw material; and firing the mixture.
2. The process of producing lithium manganate having a spinel structure as set forth in claim 1, wherein the pulverized manganese dioxide has an average particle size of 5 to 30 µm.
3. The process of producing lithium manganate having a spinel structure as set forth in claim 1 wherein the firing is carried out at 750°C. or higher.
4. The process of producing lithium manganate having a spinel structure as set forth in claim 2, wherein the firing is carried out at 750°C. or higher.
5. A cathode material for a nonaqueous secondary battery comprising lithium manganate having a spinel structure and containing sodium in an amount of 0.05 to 1.0%
by weight obtained by the process of production set forth in claim 1.
by weight obtained by the process of production set forth in claim 1.
6. A nonaqueous secondary battery composed of a cathode using the cathode material set forth in claim 5, further including an anode capable of intercalating and disintercalating lithium, and a nonaqueous electrolytic solution.
7. A cathode material for a nonaqueous secondary battery comprising lithium manganate having a spinel structure and containing sodium in an amount of 0.05 to 1.0%
by weight obtained by the process of production set forth in claim 2.
by weight obtained by the process of production set forth in claim 2.
8. A cathode material for a nonaqueous secondary battery comprising lithium manganate having a spinel structure and containing sodium in an amount of 0.05 to 1.0%
by weight obtained by the process of production set forth in claim 3.
by weight obtained by the process of production set forth in claim 3.
9. A nonaqueous secondary battery composed of a cathode using the cathode material set forth in claim 7, further including an anode capable of intercalating and disintercalating lithium, and a nonaqueous electrolytic solution.
10. A nonaqueous secondary battery composed of a cathode using the cathode material set forth in claim 8, an anode capable of intercalating and disintercalating lithium, and a nonaqueous electrolytic solution.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10/217369 | 1998-07-31 | ||
| JP21736998A JP4185191B2 (en) | 1998-07-31 | 1998-07-31 | Method for producing spinel type lithium manganate |
| PCT/JP1999/003062 WO2000006496A1 (en) | 1998-07-31 | 1999-06-08 | Process for producing spinel type lithium manganate |
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| Publication Number | Publication Date |
|---|---|
| CA2303226A1 CA2303226A1 (en) | 2000-02-10 |
| CA2303226C true CA2303226C (en) | 2006-02-21 |
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| Application Number | Title | Priority Date | Filing Date |
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| CA002303226A Expired - Lifetime CA2303226C (en) | 1998-07-31 | 1999-06-08 | Process for producing spinel type lithium manganate |
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| Country | Link |
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| US (1) | US6383683B1 (en) |
| EP (1) | EP1043275B8 (en) |
| JP (1) | JP4185191B2 (en) |
| KR (1) | KR100435415B1 (en) |
| CN (1) | CN1151072C (en) |
| AU (1) | AU748398B2 (en) |
| CA (1) | CA2303226C (en) |
| DE (1) | DE69939892D1 (en) |
| WO (1) | WO2000006496A1 (en) |
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| US6576215B1 (en) * | 1999-04-08 | 2003-06-10 | Mitsui Mining & Smelting Co., Ltd. | Method for preparing lithium manganate having spinel structure |
| JP4274630B2 (en) * | 1999-05-21 | 2009-06-10 | 三井金属鉱業株式会社 | Method for producing spinel type lithium manganate |
| JP2001236957A (en) | 2000-02-25 | 2001-08-31 | Mitsui Mining & Smelting Co Ltd | Manganese dioxide for lithium primary battery and method for producing the same |
| JP4806755B2 (en) * | 2001-04-10 | 2011-11-02 | 三井金属鉱業株式会社 | Method for producing spinel type lithium manganate |
| US6872626B1 (en) | 2003-11-21 | 2005-03-29 | Taiwan Semiconductor Manufacturing Company, Ltd. | Method of forming a source/drain and a transistor employing the same |
| US8003254B2 (en) | 2004-01-22 | 2011-08-23 | The Gillette Company | Battery cathodes |
| US20050164085A1 (en) * | 2004-01-22 | 2005-07-28 | Bofinger Todd E. | Cathode material for lithium battery |
| US8137842B2 (en) | 2004-01-22 | 2012-03-20 | The Gillette Company | Battery cathodes |
| CN100511777C (en) * | 2007-07-13 | 2009-07-08 | 张家港市国泰华荣化工新材料有限公司 | A making method of cathode material for lithium ion battery |
| CA2720600C (en) * | 2008-04-07 | 2017-09-12 | Jay Whitacre | Sodium ion based aqueous electrolyte electrochemical secondary energy storage device |
| US8333950B2 (en) * | 2009-08-27 | 2012-12-18 | Honeywell International Inc. | Process for the preparation of lithium metal oxides involving fluidized bed techniques |
| WO2012148569A2 (en) | 2011-03-01 | 2012-11-01 | Aquion Energy Inc. | Profile responsive electrode ensemble |
| US8298701B2 (en) | 2011-03-09 | 2012-10-30 | Aquion Energy Inc. | Aqueous electrolyte energy storage device |
| US8137830B2 (en) | 2011-07-19 | 2012-03-20 | Aquion Energy, Inc. | High voltage battery composed of anode limited electrochemical cells |
| US8945751B2 (en) | 2011-07-19 | 2015-02-03 | Aquion Energy, Inc. | High voltage battery composed of anode limited electrochemical cells |
| US8652672B2 (en) | 2012-03-15 | 2014-02-18 | Aquion Energy, Inc. | Large format electrochemical energy storage device housing and module |
| US8945756B2 (en) | 2012-12-12 | 2015-02-03 | Aquion Energy Inc. | Composite anode structure for aqueous electrolyte energy storage and device containing same |
| CN106299242A (en) * | 2016-08-16 | 2017-01-04 | 曹健 | A kind of porous spherical LiMn2o4preparation method |
| US10608236B2 (en) | 2017-08-15 | 2020-03-31 | Duracell U.S. Operations, Inc. | Battery cell with safety layer |
| US10637011B2 (en) * | 2017-08-15 | 2020-04-28 | Duracell U.S. Operations, Inc. | Battery cell with safety layer |
| CN108083342B (en) * | 2017-10-31 | 2019-08-13 | 湖南海利锂电科技股份有限公司 | Lithium-ion-power cell manganate cathode material for lithium and preparation method thereof |
| DOP2018000132A (en) * | 2018-05-24 | 2018-10-31 | Intec | STABILIZED POSITIVE ELECTRODE OF MANGANESE LITHIUM OXIDE FOR SECONDARY LITHIUM BATTERY AND THE METHOD FOR PRODUCTION. |
| EP4269359A4 (en) * | 2020-12-25 | 2024-11-27 | Tosoh Corporation | Spinel-type lithium manganese, method for producing same, and use of same |
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| JP3029889B2 (en) | 1991-07-15 | 2000-04-10 | 三井金属鉱業株式会社 | Manganese dioxide for lithium secondary battery and method for producing the same |
| JP3293866B2 (en) | 1991-12-18 | 2002-06-17 | 日立マクセル株式会社 | Lithium manganese composite oxide for positive electrode active material of lithium secondary battery, method for producing the same, and lithium secondary battery using the same |
| US5425932A (en) * | 1993-05-19 | 1995-06-20 | Bell Communications Research, Inc. | Method for synthesis of high capacity Lix Mn2 O4 secondary battery electrode compounds |
| JPH0963583A (en) | 1995-08-30 | 1997-03-07 | Toshiba Battery Co Ltd | Lithium secondary battery |
| JP3558751B2 (en) * | 1995-09-05 | 2004-08-25 | 東芝電池株式会社 | Non-aqueous solvent secondary battery |
| US6103422A (en) * | 1995-12-26 | 2000-08-15 | Kao Corporation | Cathode active material and nonaqueous secondary battery containing the same |
| JP3590178B2 (en) | 1996-01-08 | 2004-11-17 | 三井金属鉱業株式会社 | Electrolytic manganese dioxide, method for producing the same, and manganese dry battery |
| US6159636A (en) * | 1996-04-08 | 2000-12-12 | The Gillette Company | Mixtures of lithium manganese oxide spinel as cathode active material |
| US5783328A (en) * | 1996-07-12 | 1998-07-21 | Duracell, Inc. | Method of treating lithium manganese oxide spinel |
| JP3929548B2 (en) | 1997-04-21 | 2007-06-13 | ソニー株式会社 | Method for producing non-aqueous electrolyte secondary battery |
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1998
- 1998-07-31 JP JP21736998A patent/JP4185191B2/en not_active Expired - Lifetime
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1999
- 1999-06-08 KR KR10-2000-7003457A patent/KR100435415B1/en not_active Expired - Fee Related
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- 1999-06-08 DE DE69939892T patent/DE69939892D1/en not_active Expired - Lifetime
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| Publication number | Publication date |
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| CN1273564A (en) | 2000-11-15 |
| KR20010024357A (en) | 2001-03-26 |
| DE69939892D1 (en) | 2008-12-24 |
| CA2303226A1 (en) | 2000-02-10 |
| EP1043275B8 (en) | 2009-02-25 |
| EP1043275A1 (en) | 2000-10-11 |
| AU748398B2 (en) | 2002-06-06 |
| EP1043275A4 (en) | 2006-02-01 |
| US6383683B1 (en) | 2002-05-07 |
| WO2000006496A1 (en) | 2000-02-10 |
| JP2000048817A (en) | 2000-02-18 |
| AU4060799A (en) | 2000-02-21 |
| EP1043275B1 (en) | 2008-11-12 |
| JP4185191B2 (en) | 2008-11-26 |
| CN1151072C (en) | 2004-05-26 |
| KR100435415B1 (en) | 2004-06-10 |
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