US20030003370A1 - Lithium secondary battery - Google Patents

Lithium secondary battery Download PDF

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US20030003370A1
US20030003370A1 US09/928,406 US92840601A US2003003370A1 US 20030003370 A1 US20030003370 A1 US 20030003370A1 US 92840601 A US92840601 A US 92840601A US 2003003370 A1 US2003003370 A1 US 2003003370A1
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alkyl
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lithium secondary
battery
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Juichi Arai
Shuuko Yamauchi
Mitsuru Kobayashi
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Hitachi Ltd
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Hitachi Ltd
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Assigned to HITACHI, LTD. reassignment HITACHI, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ARAI, JUICHI, KOBAYASHI, MITSURU, YAMAUCHI, SHUUKO
Publication of US20030003370A1 publication Critical patent/US20030003370A1/en
Priority to US10/725,328 priority Critical patent/US7074523B2/en
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0034—Fluorinated solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making

Definitions

  • the present invention relates to a lithium secondary battery and, more particularly, to a lithium secondary battery having improved overcharge characteristics as well as an electrical appliance utilizing the lithium secondary battery.
  • a lithium ion battery is characterized by its anode and cathode active materials made of a substance capable of occluding and releasing lithium ions. In principle, it works without requiring electrodeposition of lithium metal. Its anode and cathode may be made of a variety of substances capable of occluding and releasing lithium ions. Their combination permits one to design the battery capacity and working voltage as desired.
  • the cathode is practically made of a carbonaceous material. It is expected to be made of a Group IVA element or an oxide thereof, a lithium-transition metal composite nitride, or an organic compound such as polyacetylene.
  • the anode is practically made of LiMn 2 O 4 or LiCoO 2 and will be made of LiNiO 2 , LiFeO 2 , or LiMnO 2 under developmental stage.
  • a lithium ion battery formed from the above-mentioned anode active material and a carbonaceous material for the cathode undergoes charging by the following mechanism.
  • the anode permits lithium to dissolve in an electrolytic solution composed of an organic solvent and a lithium salt (as en electrolyte) dissolved therein.
  • the cathode (which is separated from the anode by a fine porous separator) causes the carbonaceous material to occlude (by intercalation) lithium ions from the electrolytic solution. Discharging proceeds in the reverse process, thereby delivering electrons to the external circuit.
  • the above-mentioned lithium ion battery has a designed battery capacity which is determined by the amount of lithium in the anode or the capacity of the cathode occluding lithium ions, whichever smaller. Charging in excess of this battery capacity is referred to as overcharging. In the overcharging state, the anode releases more lithium than it should keep, causing the active material to disintegrate, and the cathode receives excess lithium ions, causing lithium metal to separate out (a phenomenon called dendrite). This results in the battery increasing in voltage and temperature. Thus, overcharging of lithium batteries poses a problem with battery safety.
  • the above-mentioned aromatic compound produces a good effect of inhibiting overcharging but has a disadvantage of deteriorating the cycle characteristics and storage characteristics of the battery.
  • the above-mentioned object is achieved by a lithium secondary battery which is characterized in that its nonaqueous electrolytic solution contains a compound which is oxidized at a voltage higher than the charge end voltage of the lithium secondary battery and a compound which inhibits reactions at voltages lower than said charge end voltage.
  • the lithium secondary battery of the present invention is characterized in that it has a charge capacity of C 1 when it (in discharged state) is charged with constant current until a voltage V 1 of 1.2V is reached and it has a charge capacity of C 2 when it is charged further (at a voltage higher than V 1 ) until it cannot be charged any longer, with the ratio (4) of C 1 /C 2 being lower than 0.7.
  • the lithium secondary battery of the present invention achieves its good performance owing to the electrolytic solution which contains a fluorinated solvent represented by the chemical formula (1) below and an aromatic compound represented by the chemical formula (2) as an overcharge inhibiting substance.
  • the fluorinated solvent represented by the chemical formula (1) which is to be incorporated into the electrolytic solution, is exemplified by the following.
  • Cyclic or chain esters such as ethylene carbonate, fluoropropylene carbonate, butylene carbonate, chloroethylene carbonate, fluoroethylene carbonate, difluoroethylene carbonate, trifluoromethylpropylene carbonate, vinylene carbonate, dimethylvinylene carbonate, dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, diphenyl carbonate, 1,3-propylene carbonate, and 2,2-dimethyl-1,3-propylene carbonate); cyclic or chain ethers (such as dimethoxy methane, 1,2-dimethoxyethane, diglyme, triglyme, 1,3-di-oxolane, tetrahydrofuran, and 2-methylterahydrofuran); ⁇ -butyrolactone, sulfolane, methyl propionate, ethyl propionate, ethylene sulfide, dimethylsulfoxide, ethylmethyls
  • the electrolytic solution of the lithium battery contains a lithium salt as the supporting electrolyte.
  • Examples of the supporting electrolyte include LiPF 6 , LiBF 4 , LiClO 4 , LiSO 3 CF 3 , LiN(SO 2 CF 3 ), LiN(SO 2 CF 2 CF 3 ), LiC(SO 2 CF 2 CF 3 ) 3 , LiC(SO 2 CF 3 ) 3 , LiI, LiCl, LiF, LiPF 5 (SO 2 CF 3 ), and LiPF 4 (SO 2 CF 3 ) 2 .
  • Examples of the overcharge inhibiting compound represented by the chemical formula 2 or 3 include the following.
  • phenyltrimethylsilane examples include phenyltrimethylsilane, benzyltrimethylsilane, diphehylmethylsilane, diphenyldimethoxysilane, diphenylsilane, 4-methoxyphenylmethylsilane, and triphenylsilane.
  • the cathode of the lithium secondary battery may be formed from lithium metal, lithium-aluminum alloy, natural or artificial graphite, amorphous carbon, a composite material of carbon with a substance (such as silicon, germanium, and aluminum) which can be alloyed with lithium, or silicon oxide or tin oxide or a composite material thereof with carbon.
  • a substance such as silicon, germanium, and aluminum
  • the anode of the lithium secondary battery may be formed from any of the following materials.
  • the separator of the lithium secondary battery may be formed from a fine porous film of polymeric material such as polyethylene, polypropylene, vinylene copolymer, and polybutylene.
  • the porous film may be used in the form of double-layered or triple-layered laminate.
  • FIG. 1 is a sectional view of the cylindrical lithium secondary battery in one embodiment of the present invention.
  • This comparative example is designed to evaluate the overcharging characteristics and storage characteristics.
  • a cylindrical lithium secondary battery constructed as shown in FIG. 1 was produced in the following manner.
  • a mixture was prepared from artificial graphite (mesophase microbeads) and PVDF as a binder in a ratio of 91:9 by weight.
  • the mixture was dissolved in N-methylpyrrolidone (NMP for short) as a solvent to give a paste.
  • NMP N-methylpyrrolidone
  • This paste was applied to both sides of copper foil as a cathode current collector 1 .
  • the coating was dried, pressed with heating, and vacuum-dried. In this way the cathode layer 2 was formed on both sides of the cathode current collector 1 .
  • the cathode For the anode active material, a mixture was prepared from lithium cobaltite, graphite as a conducting material, and PVDF as a binder in a ratio of 85:7:8 by weight. The mixture was dissolved in NMP as a solvent to give a paste. This paste was applied to both sides of aluminum foil as an anode current collector 3 . The coating was dried, pressed with heating, and vacuum-dried. In this way the anode layer 4 was formed on both sides of the anode current collector 3 . Thus there was obtained the anode. A cathode lead 5 and an anode lead 6 (both made of nickel foil) were attached by electric welding respectively to the uncoated parts of the cathode and anode.
  • the outermost separator was fixed with a tape.
  • the thus obtained electrode group was inserted into a battery can 10 of stainless steel, in such a way that the cathode lead 5 comes into contact with the bottom of the can, with a polypropylene insulator 8 interposed between them.
  • the cathode lead 5 was connected by electric welding to the battery can 10 so as to form the cathode circuit.
  • the anode lead 6 was connected by electric welding to the anode cap 12 , with an anode insulator 9 interposed between them.
  • a mixed solvent was prepared from ethylene carbonate (EC) and dimethyl carbonate (DMC) in a ratio of 1:2 by volume.
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • 1M mol/dm ⁇ 3
  • the composition of the electrolytic solution will be described as “1M LiPF 6 EC/DMC (1/2 by volume)” hereinafter.
  • the thus obtained electrolytic solution (about 4 ml) was poured into the battery can 10 through its opening.
  • the cathode can 10 was mechanically crimped with an anode cap 12 (with a gasket 11 ).
  • anode cap 12 with a gasket 11
  • the anode cap 12 is equipped with a safety device which is a pressure switch CID (Current Interrupt Device, which opens the circuit at about 100 kPa) consisting of heat-sensitive resistance element PTC (Positive Temperature Coefficient, resistance trip temperature at about 80° C.) and aluminum foil circuit.
  • a safety device which is a pressure switch CID (Current Interrupt Device, which opens the circuit at about 100 kPa) consisting of heat-sensitive resistance element PTC (Positive Temperature Coefficient, resistance trip temperature at about 80° C.) and aluminum foil circuit.
  • CID Current Interrupt Device
  • the thus obtained battery was charged at a constant current of 1 A and a constant voltage of 4.2 V, with the charge end current being 20 mA. Then the battery was discharged at a discharge current of 1 A, with the discharge end voltage being 3 V. In other words, V 1 was 4.2 V and the discharge voltage was 3 V. The charging-discharging cycle was repeated twice. Then the battery was charged until 4.2 V at a current of 1 A. The battery was charged further (for overcharging) at 1 A until charging was interrupted by the action of the safety device. It was found that the battery has a charging capacity C 1 of 1380 mAh when charged to 4.2 V and the battery has an overcharging capacity C 2 of 1300 mAh when overcharged until charging was interrupted by the safety device. It follows therefore that the safety effect ( ⁇ ) of the battery defined in the formula (4) below is 0.94.
  • Safety effect ( ⁇ ) (Overcharging effect C 2 )/(Initial discharge capacity C 1 ) (4)
  • the smaller value of safety effect means that the battery is safe with a remote possibility of overcharging.
  • the battery prepared in the same way as above was charged at 1 A up to 4.2 V and then discharged at room temperature under the same conditions as mentioned above. The battery was charged again under the same conditions. The charged battery was allowed to stand at 60° C. for 10 days. After cooling to room temperature, the battery was discharged at 1 A. The battery was charged and discharged again and the recovered capacity was measured. The capacity after storage is designated as S 2 .
  • the storage characteristic was evaluated according to the formula (5) below.
  • the battery in Comparative Example 1 has a storage characteristic of 93%. The larger is this value, the better is the storage characteristic of the battery.
  • a cobalt-based battery was produced in the same way as in Comparative Example 1 except that the electrolytic solution (1M LiPF 6 EC/DMC (1/2 by volume)) contains 0.1 M of anisole (An for short hereinafter) dissolved therein.
  • the resulting battery had an overcharging capacity of 1120 mAh and a safety effect ( ⁇ ) of 0.81. However, it had a storage characteristic of 72%, which is lower than that of the battery in Comparative Example 1.
  • An electrolytic solution was prepared from 1M LiPF 6 EC/DMC (1/2 by volume), 5 vol % of methyl perfluorobutyrate (HFE1 for short hereinafter) as a fluorinated solvent, and 0.1 M of An. This electrolytic solution was used to produce the same cobalt-based battery as in Comparative Example 1. The resulting battery had a charging capacity (up to 4.2 V) of 1395 mAh, but it had an overcharging capacity of 870 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.62.
  • An electrolytic solution was prepared from 1M LiPF 6 EC/DMC (1/2 by volume), 5 vol % of 2,2,3,3,3-tetrafluoropropyl difluoromethyl ether (HFE2 for short hereinafter) as a fluorinated solvent, and 0.1 M of An.
  • This electrolytic solution was used to produce the same cobalt-based battery as in Comparative Example 1.
  • the resulting battery had a charging capacity (up to 4.2 V) of 1410 mAh, but it had an overcharging capacity of 820 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.58 (which is better than that in Example 1).
  • An electrolytic solution was prepared from 1M LiPF 6 EC/DMC (1/2 by volume), 5 vol % of nanofluorobutyl methyl ether (HFE3 for short hereinafter) as a fluorinated solvent, and 0.1 M of An.
  • This electrolytic solution was used to produce the same cobalt-based battery as in Comparative Example 1.
  • the resulting battery had a charging capacity (up to 4.2 V) of 1390 mAh, but it had an overcharging capacity of 810 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.58.
  • the fluorinated solvent of ether structure produces the effect of inhibiting overcharging.
  • the battery in this example had a storage characteristic of 88%, which is higher by 2% than that in Example 1. This suggests that the nanofluorobutyl methyl ether greatly improves the storage characteristics.
  • a manganese-based battery was prepared in the same way as in Comparative Example 1 except that the anode active material was lithium manganate and the cathode active material was amorphous carbon (PIC from Kureha Chemical Industry Co., Ltd.), with the electrolytic solution remaining unchanged from 1M LiPF 6 EC/DMC (1/2 by volume).
  • the battery was found to have a charging capacity of 920 mAh and an overcharging capacity of 850 mAh at 4.2 V and above. Therefore, the safety effect ( ⁇ ) of the battery was 0.94, and the storage characteristic of the battery was 94%.
  • a manganese-based battery was prepared in the same way as in Comparative Example 3 except that the electrolytic solution was replaced by the one consisting of 1M LiPF 6 EC/DMC (1/2 by volume) and 0.1M of An dissolved therein.
  • the resulting battery was found to have a charging capacity of 910 mAh (up to 4.2 V) and an overcharging capacity of 720 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.79, which means that the battery has better safety than that in Comparative Example 3.
  • the storage characteristic of the battery was 67%, which is lower than that of the battery in Comparative Example 3.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/DMC (1/2 by volume), 0.1M of An, and 5 vol % of HFE1.
  • the resulting battery was found to have a charging capacity of 920 mAh (up to 4.2 V) and an overcharging capacity of 640 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.70, which means that the battery has better safety than that in Comparative Example 4.
  • the storage characteristic of the battery was 72%, which is better than that of the battery in Comparative Example 4. This result suggests that the fluorinated solvent prevents the overcharging inhibiting agent (An) from lowering the storage characteristics even in the case of manganese-based battery.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/DMC (1/2 by volume), 0.1M of An, and 5 vol % of HFE2.
  • the resulting battery was found to have a charging capacity of 930 mAh (up to 4.2 V) and an overcharging capacity of 590 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.63, which means that the battery has better safety than that in Example 4.
  • the storage characteristic of the battery was 81%, which is better than that of the battery in Example 4. This result suggests that the fluorinated solvent of ether structure prevents the overcharging inhibiting agent from lowering the storage characteristics even in the case of manganese-based battery.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/DMC (1/2 by volume), 0.1M of 4-biphenyl benzoate (Bph for short hereinafter), and 5 vol % of HFE2.
  • the resulting battery was found to have a charging capacity of 910 mAh (up to 4.2 V) and an overcharging capacity of 550 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.60, which means that the battery has better safety than that in Example 4.
  • the storage characteristic of the battery was 83%. This result suggests that the Bph does not greatly decrease the storage characteristics unlike the battery in Comparative Example 4.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/DMC (1/2 by volume), 0.1M of 1,2-dimethoxybenzene (VL for short hereinafter), and 5 vol % of HFE2.
  • the resulting battery was found to have a charging capacity of 910 mAh (up to 4.2 V) and an overcharging capacity of 580 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.64, which means that the battery has better safety than that in Example 4.
  • the storage characteristic of the battery was 81%. This result suggests that the VL does not greatly decrease the storage characteristics unlike the battery in Comparative Example 4.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/DMC (1/2 by volume), 0.1M of 4-fluoroanisole (FAn for short hereinafter), and 5 vol % of HFE2.
  • the resulting battery was found to have a charging capacity of 920 mAh (up to 4.2 V) and an overcharging capacity of 530 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.58, which means that the battery has better safety than that in Example 4.
  • the storage characteristic of the battery was 83%. This result suggests that the FAn does not greatly decrease the storage characteristics unlike the battery in Comparative Example 4.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/DMC (1/2 by volume), 0.1M of 2,5-diphenylanisole (DFAn for short hereinafter), and 5 vol % of HFE2.
  • the resulting battery was found to have a charging capacity of 910 mAh (up to 4.2 V) and an overcharging capacity of 510 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.56, which means that the battery has better safety than that in Example 4.
  • the storage characteristic of the battery was 81%. This result suggests that the DFAn does not greatly decrease the storage characteristics unlike the battery in Comparative Example 4.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/DMC (1/2 by volume), 0.1M of 4-biphenylacetate (BphA for short hereinafter), and 5 vol % of HFE2.
  • the resulting battery was found to have a charging capacity of 900 mAh (up to 4.2 V) and an overcharging capacity of 510 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.57, which means that the battery has better safety than that in Example 4.
  • the storage characteristic of the battery was 83%. This result suggests that the BphA does not greatly decrease the storage characteristics unlike the battery in Comparative Example 4.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/DMC (1/2 by volume), 0.1M of phenyl propionate (PhP for short hereinafter), and 5 vol % of HFE2.
  • the resulting battery was found to have a charging capacity of 900 mAh (up to 4.2 V) and an overcharging capacity of 520 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.58, which means that the battery has better safety than that in Example 4.
  • the storage characteristic of the battery was 82%. This result suggests that the PhP does not greatly decrease the storage characteristics unlike the battery in Comparative Example 4.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/DMC (1/2 by volume), 0.1M of ethoxybenzene (EtOB for short hereinafter), and 5 vol % of HFE2.
  • the resulting battery was found to have a charging capacity of 910 mAh (up to 4.2 V) and an overcharging capacity of 570 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.63, which means that the battery has better safety than that in Example 4.
  • the storage characteristic of the battery was 81%. This result suggests that the EtOB does not greatly decrease the storage characteristics unlike the battery in Comparative Example 4.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/DMC (1/2 by volume), 0.1M of 4-bromoanisole (BrAn for short hereinafter), and 5 vol % of HFE2.
  • the resulting battery was found to have a charging capacity of 920 mAh (up to 4.2 V) and an overcharging capacity of 560 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.61, which means that the battery has better safety than that in Example 4.
  • the storage characteristic of the battery was 81%. This result suggests that the BrAn does not greatly decrease the storage characteristics unlike the battery in Comparative Example 4.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/DMC (1/2 by volume), 0.1M of An, and 5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 920 mAh (up to 4.2 V) and an overcharging capacity of 560 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.61, which means that owing to HFE3 as a fluorinated solvent the battery has better safety than that in Examples 4 and 5 which employs HFE1 or HFE2 as a fluorinated solvent.
  • the storage characteristic of the battery was 85%. Thus the battery in this example is greatly improved over that in Example 4 or 5. This result suggests that an adequate selection of fluorinated solvents contributes to improvement in safety and storage properties.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/DMC (1/2 by volume), 0.1M of PhP, and 5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 900 mAh (up to 4.2 V) and an overcharging capacity of 520 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.58.
  • PhP as an overcharge inhibiting agent contributes more to the battery safety when used in combination with HFE3 as a fluorinated solvent than when used in combination with HFE2 as a fluorinate solvent, as in Example 12.
  • the storage characteristic of the battery in this example is 85%, which is much better than that in Example 11. Thus it was confirmed in this example that HFE3 produces its good effect even though the kind of the overcharge inhibiting agent is changed.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/DMC (1/2 by volume), 0.1M of EtOB, and 5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 910 mAh (up to 4.2 V) and an overcharging capacity of 570 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.63.
  • EtOB as an overcharge inhibiting agent contributes more to the battery safety when used in combination with HFE3 as a fluorinated solvent than when used in combination with HFE2 as a fluorinate solvent, as in Example 12.
  • the storage characteristic of the battery in this example is 86%, which is much better than that in Example 12. Thus it was confirmed in this example that HFE3 produces its good effect even though the kind of the overcharge inhibiting agent is changed.
  • DMC was replaced by ethyl methyl carbonate (EMC for short hereinafter).
  • EMC ethyl methyl carbonate
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/EMC (1/2 by volume), 0.1M of An, and 5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 920 mAh (up to 4.2 V) and an overcharging capacity of 560 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.60, which is equal to that of the battery in Example 14 which employs DMC as the solvent.
  • the storage characteristic of the battery was 85%, which is equal to that of the battery which employs DMC as the solvent. This result suggests that EMC is as effective as DMC in safety and storage characteristics.
  • DMC was replaced by diethyl carbonate (DEC for short hereinafter).
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/DEC (1/2 by volume), 0.1M of An, and 5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 900 mAh (up to 4.2 V) and an overcharging capacity of 520 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.58, which is equal to that of the battery in Example 17 which employs EMC as the solvent.
  • the storage characteristic of the battery was 84%, which is slightly inferior to that of the battery which employs DMC or EMC as the solvent but is superior to that of the battery in Example 5. This result suggests that the performance of the battery depends little on the solvent of the electrolytic solution.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 PC (propylene carbonate), 0.1M of An, and 0.5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 890 mAh (up to 4.2 V) and an overcharging capacity of 490 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.55.
  • PC used alone for the electrolytic solution produces a better result than 1M LiPF 6 EC/DMC (1/2 by volume) used in Example 14.
  • the storage characteristic of the battery was 86%, which is better than that of the battery in Example 14.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 GBL (?-butyrolactone), 0.1M of An, and 0.5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 870 mAh (up to 4.2 V) and an overcharging capacity of 490 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.55. This result suggests that the battery in this example which employs GBL alone for the electrolytic solution is superior to that in Example 14.
  • the storage characteristic of the battery was 88%, which is better than that of the battery in Example 14.
  • the lithium salt was replaced by LiBF 4 .
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiBF 4 PC, 0.1M of An, and 0.5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 890 mAh (up to 4.2 V) and an overcharging capacity of 480 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.54, which is better than that of the battery in Example 19.
  • the storage characteristic of the battery was 87%, which is better than that of the battery in Example 19. This result suggests that in the case of a solvent consisting of PC alone, the electrolytic solution containing LiBF 4 is superior to that containing LiPF 6 .
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiBF 4 GBL, 0.1M of An, and 0.5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 890 mAh (up to 4.2 V) and an overcharging capacity of 480 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.54, which is better than that of the battery in Example 19.
  • the storage characteristic of the battery was 87%, which is better than that of the battery in Example 19. This result suggests that in the case of a solvent consisting of PC alone, the electrolytic solution containing LiBF 4 is superior to that containing LiPF 6 .
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiBF 4 EC/GBL/PC (1/1/1 by volume), 0.1M of An, and 0.5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 910 mAh (up to 4.2 V) and an overcharging capacity of 480 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.53, which is better than that of the battery in Example 22.
  • the storage characteristic of the battery was 89%, which is better than that of the battery in Example 22. This result suggests that the three-component solvent for the electrolytic solution also improves the safety and storage characteristics.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 0.8M LiN(SO 2 CF 2 CF 3 ) (LiBETI for short hereinafter) and 0.2M LiBF 4 dissolved in BGL, 0.1M of An, and 0.5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 930 mAh (up to 4.2 V) and an overcharging capacity of 490 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.53, which is better than that of the battery in Example 23.
  • the storage characteristic of the battery was 87%.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 0.2M LiPF 6 and 0.8M LiBF 4 dissolved in BGL, 0.1M of An, and 0.5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 940 mAh (up to 4.2 V) and an overcharging capacity of 490 mAh. Therefore, the safety effect (4) of the battery was 0.52, which is better than that of the battery in Example 23.
  • the storage characteristic of the battery was 88%. This result suggests that a mixture of lithium salts tends to increase the charging capacity although its effect of improving the safety and storage characteristics remains almost unchanged.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/DMC (1/2 by volume), 0.1M of phenyltrimethylsilane (PS1 for short hereinafter), and 5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 900 mAh (up to 4.2 V) and an overcharging capacity of 450 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.50, which is best among all the batteries obtained in the foregoing Examples.
  • the storage characteristic of the battery was 91%, which is best among all the batteries obtained in the foregoing Examples. This result suggests that the silicon compound (with a silyl group) used as the overcharge inhibiting agent greatly improves the battery safety and storage characteristics.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/DMC (1/2 by volume), 0.1M of diphenylmethylsilane (PS2 for short hereinafter), and 5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 910 mAh (up to 4.2 V) and an overcharging capacity of 430 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.47, which is best among all the batteries obtained in the foregoing Examples.
  • the storage characteristic of the battery was 92%, which is best among all the batteries obtained in the foregoing Examples.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/DMC (1/2 by volume), 0.1M of diphenylsilane (PS3 for short hereinafter), and 5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 920 mAh (up to 4.2 V) and an overcharging capacity of 430 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.47, which is equal to that of the battery in Example 27.
  • the battery in this Example has an improved charge capacity.
  • the storage characteristic of the battery was 93%, which is best among all the batteries obtained in the foregoing Examples.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/DMC (1/2 by volume), 0.1M of diphenyldimethoxysilane (PS4 for short hereinafter), and 5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 920 mAh (up to 4.2 V) and an overcharging capacity of 420 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.46, which is best among all the batteries obtained in the foregoing Examples.
  • the storage characteristic of the battery was 93%, which is equal to that of the battery in Example 28.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/DMC (1/2 by volume), 0.1M of 4-methoxyphenyltrimethylsilane (PS5 for short hereinafter), and 5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 920 mAh (up to 4.2 V) and an overcharging capacity of 410 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.465, which is best among all the batteries obtained in the foregoing Examples.
  • the storage characteristic of the battery was 93%, which is equal to that of the batteries in Examples 28 and 29.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiBF 4 EC/DMC (1/2 by volume), 0.1M of PS5, and 5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 910 mAh (up to 4.2 V) and an overcharging capacity of 390 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.43, which is best among all the batteries obtained in the foregoing Examples.
  • the storage characteristic of the battery was 93%, which is equal to that of the batteries in Examples 28 to 30. The result remained unchanged even though the lithium salt was replaced by LiBF 4 .
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 0.8M LiPF 6 0.2M LiBETI EC/DMC (1/2 by volume), 0.1 M of PS5, and 5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 920 mAh (up to 4.2 V) and an overcharging capacity of 410 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.45, which is equal to that of the battery employing a compound having a silyl group.
  • the storage characteristic of the battery was 94%, which is equal to that of the battery in Comparative Example 3.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 0.8M LiBF 4 0.2M LiBETI EC/DMC (1/2 by volume), 0.1M of PS5, and 5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 930 mAh (up to 4.2 V) and an overcharging capacity of 420 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.45, which is equal to that of the battery in Example 32 which employs a mixture of lithium salts.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiBF 4 PC, 0.1M of PS5, and 0.5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 900 mAh (up to 4.2 V) and an overcharging capacity of 430 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.48 and the storage characteristic was 92%. This result suggests that even a single solvent greatly improves the battery safety and storage characteristics compared with the battery in Example 21.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiBF 4 GBL, 0.1M of PS5, and 0.5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 910 mAh (up to 4.2 V) and an overcharging capacity of 420 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.46 and the storage characteristic was 92%.
  • the battery in this example is much better in safety and storage characteristic than the battery in Example 22.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiBF 4 EC/PC (1/2 by volume), 0.1M of PS5, and 0.5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 910 mAh (up to 4.2 V) and an overcharging capacity of 400 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.44, which is best among all the batteries obtained in the foregoing Examples.
  • the storage characteristic of the battery was as high as 93%.
  • a manganese-based battery was prepared which contains an electrolytic solution consisting of 1M LiBF 4 EC/GBL/PC (1/1/1 by volume), 0.1M of PS5, and 0.5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 920 mAh (up to 4.2 V) and an overcharging capacity of 390 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.42, which is best among all the batteries obtained in the foregoing Examples.
  • the storage characteristic of the battery was 93%, which also best among all the batteries obtained in the foregoing Examples.
  • a battery of the same shape as in Comparative Example 4 was prepared in which the anode active material is LiNi 0.5 Mn 1.5 O 4 and the cathode active material is graphite carbon and the electrolytic solution is 1M LiPF 6 EC/DMC (1/2 by volume).
  • This battery will be referred to as “5V-class Mn-graphite battery” hereinafter.
  • This battery was charged under the condition of constant current and constant voltage (V 1 ) of 4.9 V.
  • the charging voltage was set at 4.9 V because this battery has a high average discharge voltage.
  • the current at the end of charging was 20 mA.
  • the battery was discharged at a constant current of 1 A until the voltage decreased to 3.7 V.
  • a 5V-class Mn-graphite battery was prepared which contains an electrolytic solution consisting of 1M LiBF 4 EC/DMC (1/2 by volume), 0.1 M of An, and 5 vol % of HFE1.
  • the resulting battery was found to have a charging capacity of 1110 mAh and an overcharging capacity of 660 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.6, which is lower by 0.19 than that of the battery in Comparative Example 5.
  • the storage characteristic of the battery was 82%.
  • a 5V-class Mn-graphite battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/DMC (1/2 by volume), 0.1 M of An, and 5 vol % of HFE2.
  • the resulting battery was found to have a charging capacity of 1110 mAh and an overcharging capacity of 650 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.59, which is lower by 0.01 than that of the battery in Example 38.
  • the storage characteristic of the battery was 83%, which is 1% higher than that of the battery in Example 38.
  • a 5V-class Mn-graphite battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/DMC (1/2 by volume), 0.1 M of An, and 5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 1120 mAh and an overcharging capacity of 630 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.57, which is lower by 0.02 than that of the battery in Example 39.
  • the storage characteristic of the battery was 85%, which is 2% higher than that of the battery in Example 39.
  • fluorinated solvent and overcharge inhibiting agent improves the safety effect and prevents the storage characteristics from decreasing also in the case of 5V-class Mn-graphite battery.
  • ether-type fluorinated solvents are more effective than ester-type ones also in the case of 5V-class Mn-graphite battery.
  • a 5V-class Mn-graphite battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/GBL (1/2 by volume), 0.1 M of An, and 1 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 1120 mAh and an overcharging capacity of 580 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.52, which is lower by 0.05 than that of the battery in Example 40.
  • the storage characteristic of the battery was 86%, which is 1% higher than that of the battery in Example 40. This result suggests that the battery is improved in safety effect and storage characteristic when the solvent for electrolytic solution is switched from DMC to GBL.
  • a 5V-class Mn-graphite battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/GBL (1/2 by volume), 0.1 M of PS1, and 1 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 1120 mAh and an overcharging capacity of 550 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.49, which is lower by 0.03 than that of the battery in Example 41.
  • the storage characteristic of the battery was 87%, which is 1% higher than that of the battery in Example 41. This result suggests that PS1 (phenyltrimethylsilane) as the overcharge inhibiting agent contributes to safety and storage characteristic also in the case of 5V-class Mn-graphite battery.
  • a 5V-class Mn-graphite battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/GBL (1/2 by volume), 0.1 M of PS2, and 1 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 1110 mAh and an overcharging capacity of 510 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.45, which is lower by 0.03 than that of the battery in Example 42.
  • the storage characteristic of the battery was 88%, which is 1% higher than that of the battery in Example 42.
  • a 5V-class Mn-graphite battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/GBL (1/2 by volume), 0.1 M of PS3, and 1 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 1110 mAh and an overcharging capacity of 460 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.41, which is lower by 0.05 than that of the battery in Example 43.
  • the storage characteristic of the battery was 89%, which is equal to that of the battery in Comparative Example 5.
  • a 5V-class Mn-graphite battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/GBL (1/2 by volume), 0.1 M of PS4, and 1 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 1120 mAh and an overcharging capacity of 450 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.40, which is lower by 0.01 than that of the battery in Example 44.
  • the storage characteristic of the battery was 89%, which is equal to that of the battery in Comparative Example 5.
  • a 5V-class Mn-graphite battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/GBL (1/2 by volume), 0.1 M of PS5, and 1 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 1120 mAh and an overcharging capacity of 420 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.38, which is lower by 0.02 than that of the battery in Example 45.
  • the storage characteristic of the battery was 89%, which is equal to that of the battery in Comparative Example 5.
  • a battery of the same shape as in Comparative Example 4 was prepared in which the anode active material is LiNi 0.5 Mn 1.5 O 4 and the cathode active material is amorphous carbon and the electrolytic solution is 1M LiPF 6 EC/DMC (1/2 by volume).
  • This battery will be referred to as “5V-class Mn-amorphous battery” hereinafter.
  • This battery was charged under the condition of constant current and constant voltage (V 1 ) of 4.9 V.
  • the charging voltage was set at 4.9 V because this battery has a high average discharge voltage.
  • the current at the end of charging was 20 mA.
  • the battery was discharged at a constant current of 1 A until the voltage decreased to 3.7 V.
  • a 5V-class Mn-amorphous battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/DMC (1/2 by volume), 0.1 M of An, and 5 vol % of HFE1.
  • the resulting battery was found to have a charging capacity of 950 mAh and an overcharging capacity of 660 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.69, which is lower by 0.26 than that of the battery in Comparative Example 6.
  • the storage characteristic of the battery was 81%.
  • a 5V-class Mn-amorphous battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/DMC (1/2 by volume), 0.1 M of An, and 5 vol % of HFE2.
  • the resulting battery was found to have a charging capacity of 960 mAh and an overcharging capacity of 650 mAh. Therefore, the safety effect (4) of the battery was 0.67, which is lower by 0.02 than that of the battery in Example 47.
  • the storage characteristic of the battery was 82%, which is higher by 1% than that of the battery in Example 47.
  • a 5V-class Mn-amorphous battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/DMC (1/2 by volume), 0.1 M of An, and 5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 960 mAh and an overcharging capacity of 630 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.66, which is lower by 0.01 than that of the battery in Example 48.
  • the storage characteristic of the battery was 84%, which is higher by 2% than that of the battery in Example 48.
  • fluorinated solvent and overcharge inhibiting agent improves the safety effect and prevents the storage characteristics from decreasing also in the case of 5V-class Mn-amorphous battery.
  • ether-type fluorinated solvents are more effective than ester-type ones also in the case of 5V-class Mn-amorphous battery.
  • a 5V-class Mn-amorphous battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/PC (1/2 by volume), 0.1 M of An, and 0.5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 940 mAh and an overcharging capacity of 560 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.60, which is lower by 0.06 than that of the battery in Example 49.
  • the storage characteristic of the battery was 85%, which is higher by 1% than that of the battery in Example 49. This result suggests that the battery improves in safety and storage characteristic when the solvent for electrolytic solution is switched from DMC to PC.
  • a 5V-class Mn-amorphous battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/PC (1/2 by volume), 0.1 M of PS1, and 0.5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 950 mAh and an overcharging capacity of 520 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.55, which is lower by 0.05 than that of the battery in Example 50.
  • the storage characteristic of the battery was 87%, which is higher by 2% than that of the battery in Example 50. This result suggests that the battery improves in safety and storage characteristic when phenylsilane is used as the overcharge inhibiting agent.
  • a 5V-class Mn-amorphous battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/PC (1/2 by volume), 0.1 M of PS2, and 0.5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 950 mAh and an overcharging capacity of 490 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.52, which is lower by 0.03 than that of the battery in Example 51.
  • the storage characteristic of the battery was 88%, which is higher by 1% than that of the battery in Example 51.
  • a 5V-class Mn-amorphous battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/PC (1/2 by volume), 0.1 M of PS3, and 0.5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 940 mAh and an overcharging capacity of 470 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.50, which is lower by 0.02 than that of the battery in Example 52.
  • the storage characteristic of the battery was 88%.
  • a 5V-class Mn-amorphous battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/PC (1/2 by volume), 0.1 M of PS4, and 0.5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 950 mAh and an overcharging capacity of 430 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.45, which is lower by 0.05 than that of the battery in Example 53.
  • the storage characteristic of the battery was 88%.
  • a 5V-class Mn-amorphous battery was prepared which contains an electrolytic solution consisting of 1M LiPF 6 EC/PC (1/2 by volume), 0.1 M of PS5, and 0.5 vol % of HFE3.
  • the resulting battery was found to have a charging capacity of 1120 mAh and an overcharging capacity of 420 mAh. Therefore, the safety effect ( ⁇ ) of the battery was 0.44, which is lower by 0.01 than that of the battery in Example 54.
  • the storage characteristic of the battery was 88%.
  • the lithium secondary battery according to the present invention has a lower overcharge current than the conventional one by more than 20%. Therefore, it can be increased in capacity with safety.
  • the first commercialized lithium secondary battery had a capacity of 1000 mAh; the capacity has increased to 2000 mAh since then. The increase in capacity is accompanied by danger.
  • the battery with a capacity of 1000 mAh has an energy of 17.1 kJ if overcharged up to 5V
  • the battery with a capacity of 2000 mAh has an energy of 34.2 kJ if overcharged up to 5V.
  • the latter battery has twice as much energy as the former battery.
  • the battery according to the present invention has a safety effect of, say, 0.6 and hence it has an energy of 28.8 kJ in its overcharged state even though it has a capacity of 2000 mAh.
  • the magnitude of this energy is 1.68 times that of the battery with a capacity of 1000 mAh.
  • the battery with an overcharge capacity of 2400 mAh will have the same energy of the conventional battery with an overcharge capacity of 2000 mAh which has a safety effect of 0.9.
  • the present invention can be utilized in any electrical appliance as well.
  • an electrical appliance is defined to include any electrical object capable of utilizing a lithium secondary battery.

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050053843A1 (en) * 2003-09-09 2005-03-10 Sanyo Electric Co., Ltd. Non-aqueous solvent secondary battery
US20060160000A1 (en) * 2005-01-14 2006-07-20 Kim Jin H Electrolyte for lithium rechargeable battery and lithium rechargeable battery comprising the same
US20070077495A1 (en) * 2005-10-05 2007-04-05 California Institute Of Technology Subfluorinated Graphite Fluorides as Electrode Materials
US20070218364A1 (en) * 2005-10-05 2007-09-20 Whitacre Jay F Low temperature electrochemical cell
US20080171268A1 (en) * 2006-08-11 2008-07-17 Rachid Yazami Dissociating agents, formulations and methods providing enhanced solubility of fluorides
US20080206631A1 (en) * 2007-02-27 2008-08-28 3M Innovative Properties Company Electrolytes, electrode compositions and electrochemical cells made therefrom
US20080280201A1 (en) * 2006-01-30 2008-11-13 Isamu Konishiike Negative electrode for use with secondary battery and secondary battery using such negative electrode
US20090061326A1 (en) * 2007-05-23 2009-03-05 Sony Corporation Current collector, anode, and battrey
US20090111021A1 (en) * 2007-03-14 2009-04-30 Rachid Yazami High discharge rate batteries
US20090123831A1 (en) * 2007-11-08 2009-05-14 Samsung Sdi Co., Ltd Cap assembly and secondary battery using the same
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US20100141211A1 (en) * 2008-11-04 2010-06-10 Rachid Yazami Hybrid electrochemical generator with a soluble anode
US20100221603A1 (en) * 2006-03-03 2010-09-02 Rachid Yazami Lithium ion fluoride battery
US7794880B2 (en) 2005-11-16 2010-09-14 California Institute Of Technology Fluorination of multi-layered carbon nanomaterials
US8232007B2 (en) 2005-10-05 2012-07-31 California Institute Of Technology Electrochemistry of carbon subfluorides
US8377586B2 (en) 2005-10-05 2013-02-19 California Institute Of Technology Fluoride ion electrochemical cell
CN103227346A (zh) * 2012-01-27 2013-07-31 三洋电机株式会社 非水电解质二次电池的制造方法、非水电解质二次电池
US20150056503A1 (en) * 2006-04-27 2015-02-26 Mitsubishi Chemical Corporation Non-aqueous liquid electrolyte and non-aqueous liquid electrolyte secondary battery
US10050305B2 (en) * 2013-12-16 2018-08-14 Samsung Sdi Co., Ltd. Electrolyte for lithium secondary battery and lithium secondary battery employing the same
US10096858B2 (en) 2014-03-14 2018-10-09 Adeka Corporation Nonaqueous electrolyte and nonaqueous secondary battery
US20200185755A1 (en) 2009-02-09 2020-06-11 Varta Microbattery Gmbh Button cells and method of producing same
US10804506B2 (en) 2009-06-18 2020-10-13 Varta Microbattery Gmbh Button cell having winding electrode and method for the production thereof
US11024880B2 (en) 2018-05-29 2021-06-01 Hyundai Motor Company Electrolyte for lithium secondary battery and lithium secondary battery including the same
CN114583259A (zh) * 2020-12-01 2022-06-03 泰星能源解决方案有限公司 锂离子二次电池的非水电解液和锂离子二次电池
WO2022265259A1 (ko) * 2021-06-16 2022-12-22 삼성에스디아이주식회사 리튬이차전지용 전해질 및 이를 포함하는 리튬이차전지

Families Citing this family (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100422942B1 (ko) 2001-05-22 2004-03-18 주식회사 엘지화학 안전성을 향상시키는 비수전해액 첨가제 및 이를 포함하는리튬이온 2차 전지
CN100370641C (zh) * 2001-12-21 2008-02-20 三洋电机株式会社 非水电解质二次电池
US20050123834A1 (en) * 2003-12-03 2005-06-09 Nec Corporation Secondary battery
JP4022889B2 (ja) * 2004-02-12 2007-12-19 ソニー株式会社 電解液および電池
JP5053834B2 (ja) * 2004-04-01 2012-10-24 スリーエム イノベイティブ プロパティズ カンパニー 再充電可能なリチウム−イオンバッテリーの過放電保護のためのレドックスシャトル
ATE491240T1 (de) * 2004-04-01 2010-12-15 3M Innovative Properties Co Redox-shuttle für eine wiederaufladbare lithiumionenzelle
JP2006024392A (ja) * 2004-07-06 2006-01-26 Tdk Corp リチウムイオン二次電池の充電方法
US7611801B2 (en) 2004-10-13 2009-11-03 Samsung Sdi Co., Ltd. Non-aqueous electrolyte, rechargeable lithium battery, and rechargeable battery system
JP5073161B2 (ja) 2004-10-13 2012-11-14 三星エスディアイ株式会社 リチウム二次電池用の非水電解液およびリチウム二次電池および二次電池システム
JP2006172775A (ja) * 2004-12-14 2006-06-29 Hitachi Ltd エネルギー貯蔵デバイスとそのモジュール及びそれを用いた自動車
JP2007019012A (ja) * 2005-06-10 2007-01-25 Mitsubishi Chemicals Corp 非水系電解液及び非水系電解液二次電池
DE102005048802A1 (de) * 2005-10-10 2007-04-12 Solvay Fluor Gmbh Fluorierte Additive für Lithiumionenbatterien
KR20140020334A (ko) 2006-06-02 2014-02-18 미쓰비시 가가꾸 가부시키가이샤 비수계 전해액 및 비수계 전해액 전지
KR100760763B1 (ko) * 2006-10-17 2007-10-04 삼성에스디아이 주식회사 고전압 리튬 이차 전지용 전해액 및 이를 채용하는 고전압리튬 이차 전지
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KR100816208B1 (ko) * 2007-03-27 2008-03-28 삼성에스디아이 주식회사 리튬 이온 이차 전지용 전해액 및 이를 포함하는 리튬 이온이차 전지
US8101302B2 (en) * 2008-02-12 2012-01-24 3M Innovative Properties Company Redox shuttles for high voltage cathodes
KR101004399B1 (ko) 2008-05-29 2010-12-28 삼성에스디아이 주식회사 리튬 이차 전지용 전해액 및 이를 포함하는 리튬 이차 전지
US8993177B2 (en) * 2009-12-04 2015-03-31 Envia Systems, Inc. Lithium ion battery with high voltage electrolytes and additives
CN102097647B (zh) 2009-12-09 2014-03-26 微宏动力系统（湖州）有限公司 锂离子电池
WO2013008439A1 (ja) * 2011-07-08 2013-01-17 パナソニック株式会社 非水電解質およびそれを用いた非水電解質二次電池
US9325000B2 (en) * 2012-04-18 2016-04-26 Lg Chem, Ltd. Cathode active material and the secondary battery comprising the same
US10411299B2 (en) 2013-08-02 2019-09-10 Zenlabs Energy, Inc. Electrolytes for stable cycling of high capacity lithium based batteries
KR102216069B1 (ko) * 2013-12-13 2021-02-16 한양대학교 산학협력단 전해질 및 이를 포함하는 리튬 이차전지
JP2015198052A (ja) * 2014-04-02 2015-11-09 旭化成株式会社 リチウムイオン二次電池の使用方法及びリチウムイオン二次電池
US10199687B2 (en) 2016-08-30 2019-02-05 Wildcat Discovery Technologies, Inc Electrolyte formulations for electrochemical cells containing a silicon electrode
KR20180089244A (ko) 2017-01-31 2018-08-08 삼성전자주식회사 모노플루오로실란 화합물을 함유하는 전해액을 포함하는 리튬이차전지
KR102518992B1 (ko) * 2017-02-03 2023-04-07 주식회사 엘지에너지솔루션 고온 저장 특성이 향상된 리튬 이차전지의 제조 방법
JP2018206641A (ja) * 2017-06-06 2018-12-27 リチウム エナジー アンド パワー ゲゼルシャフト ミット ベシュレンクテル ハフッング ウント コンパニー コマンディトゲゼルシャフトＬｉｔｈｉｕｍ Ｅｎｅｒｇｙ ａｎｄ Ｐｏｗｅｒ ＧｍｂＨ ＆ Ｃｏ． ＫＧ 非水電解質蓄電素子
JP6980502B2 (ja) * 2017-11-29 2021-12-15 三井化学株式会社 電池用非水電解液及びリチウム二次電池
US11973178B2 (en) 2019-06-26 2024-04-30 Ionblox, Inc. Lithium ion cells with high performance electrolyte and silicon oxide active materials achieving very long cycle life performance
CN113113573B (zh) * 2021-03-30 2022-06-21 天能电池集团股份有限公司 一种用于干荷电池负极板处理的浸渍液、负极板及电池

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0617447A (ja) 1991-02-27 1994-01-25 Yutani Heavy Ind Ltd 小型ショベルの油圧回路
JP3259436B2 (ja) 1993-05-31 2002-02-25 ソニー株式会社 非水電解液二次電池
JP3809657B2 (ja) 1994-03-07 2006-08-16 ソニー株式会社 非水電解液二次電池
JP3304187B2 (ja) * 1994-03-14 2002-07-22 日本電信電話株式会社 リチウム２次電池用電解液
JP3669024B2 (ja) 1995-05-26 2005-07-06 ソニー株式会社 非水電解液二次電池
CA2156800C (en) 1995-08-23 2003-04-29 Huanyu Mao Polymerizable aromatic additives for overcharge protection in non-aqueous rechargeable lithium batteries
JP3354057B2 (ja) * 1996-10-03 2002-12-09 日立マクセル株式会社 有機電解液二次電池
JPH117932A (ja) 1997-06-18 1999-01-12 Hitachi Ltd 二次電池
JP4328915B2 (ja) * 1997-09-10 2009-09-09 ダイキン工業株式会社 二次電池用非水電解液及びそれを用いた二次電池
JP3428910B2 (ja) * 1997-09-25 2003-07-22 キヤノン株式会社 電解質の製造方法及び二次電池の製造方法
US6277525B1 (en) * 1997-09-25 2001-08-21 Canon Kabushiki Kaisha Method for producing electrolyte and method for producing secondary battery
CA2216898C (en) 1997-09-26 2005-03-22 Moli Energy (1990) Limited Improved additives for overcharge protection in non-aqueous rechargeable lithium batteries
TW434923B (en) * 1998-02-20 2001-05-16 Hitachi Ltd Lithium secondary battery and liquid electrolyte for the battery
JP3408152B2 (ja) 1998-05-19 2003-05-19 三洋電機株式会社 非水系電解液二次電池
JP2939468B1 (ja) 1998-07-31 1999-08-25 三洋電機株式会社 非水系電池用電解液およびこの電解液を用いた二次電池
JP2983205B1 (ja) 1998-07-31 1999-11-29 三洋電機株式会社 非水系二次電池
JP2928779B1 (ja) 1998-07-31 1999-08-03 三洋電機株式会社 非水系電池用電解液およびこの電解液を用いた二次電池
JP2963898B1 (ja) 1998-07-31 1999-10-18 三洋電機株式会社 非水系電池用電解液およびこの電解液を用いた二次電池
JP2939469B1 (ja) 1998-07-31 1999-08-25 三洋電機株式会社 非水系電池用電解液およびこの電解液を用いた二次電池
JP4296620B2 (ja) 1998-11-18 2009-07-15 ソニー株式会社 非水電解液電池

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US20050053843A1 (en) * 2003-09-09 2005-03-10 Sanyo Electric Co., Ltd. Non-aqueous solvent secondary battery
US7582388B2 (en) * 2003-09-09 2009-09-01 Sanyo Electric Co., Ltd. Non-aqueous solvent secondary battery
US20100074832A1 (en) * 2004-03-17 2010-03-25 California Institute Of Technology Methods for purifying carbon materials
US7537682B2 (en) 2004-03-17 2009-05-26 California Institute Of Technology Methods for purifying carbon materials
US20060160000A1 (en) * 2005-01-14 2006-07-20 Kim Jin H Electrolyte for lithium rechargeable battery and lithium rechargeable battery comprising the same
US8968921B2 (en) 2005-10-05 2015-03-03 California Institute Of Technology Fluoride ion electrochemical cell
US8377586B2 (en) 2005-10-05 2013-02-19 California Institute Of Technology Fluoride ion electrochemical cell
US8232007B2 (en) 2005-10-05 2012-07-31 California Institute Of Technology Electrochemistry of carbon subfluorides
US7563542B2 (en) 2005-10-05 2009-07-21 California Institute Of Technology Subfluorinated graphite fluorides as electrode materials
US20070218364A1 (en) * 2005-10-05 2007-09-20 Whitacre Jay F Low temperature electrochemical cell
US20090258294A1 (en) * 2005-10-05 2009-10-15 California Institute Of Technology Subfluorinated Graphite Fluorides as Electrode Materials
US20070077495A1 (en) * 2005-10-05 2007-04-05 California Institute Of Technology Subfluorinated Graphite Fluorides as Electrode Materials
US7794880B2 (en) 2005-11-16 2010-09-14 California Institute Of Technology Fluorination of multi-layered carbon nanomaterials
US20110003149A1 (en) * 2005-11-16 2011-01-06 Rachid Yazami Fluorination of Multi-Layered Carbon Nanomaterials
US20080280201A1 (en) * 2006-01-30 2008-11-13 Isamu Konishiike Negative electrode for use with secondary battery and secondary battery using such negative electrode
US8802286B2 (en) * 2006-01-30 2014-08-12 Sony Corporation Negative electrode for use with secondary battery and secondary battery using such negative electrode
US20100221603A1 (en) * 2006-03-03 2010-09-02 Rachid Yazami Lithium ion fluoride battery
US20150056503A1 (en) * 2006-04-27 2015-02-26 Mitsubishi Chemical Corporation Non-aqueous liquid electrolyte and non-aqueous liquid electrolyte secondary battery
US20080171268A1 (en) * 2006-08-11 2008-07-17 Rachid Yazami Dissociating agents, formulations and methods providing enhanced solubility of fluorides
US8658309B2 (en) 2006-08-11 2014-02-25 California Institute Of Technology Dissociating agents, formulations and methods providing enhanced solubility of fluorides
US20080206631A1 (en) * 2007-02-27 2008-08-28 3M Innovative Properties Company Electrolytes, electrode compositions and electrochemical cells made therefrom
US20090111021A1 (en) * 2007-03-14 2009-04-30 Rachid Yazami High discharge rate batteries
US20090061326A1 (en) * 2007-05-23 2009-03-05 Sony Corporation Current collector, anode, and battrey
US8932744B2 (en) * 2007-05-23 2015-01-13 Sony Corporation Current collector, anode, and battery
US20090123831A1 (en) * 2007-11-08 2009-05-14 Samsung Sdi Co., Ltd Cap assembly and secondary battery using the same
US8399125B2 (en) * 2007-11-08 2013-03-19 Samsung Sdi Co., Ltd. Cap assembly and secondary battery using the same
US20100141211A1 (en) * 2008-11-04 2010-06-10 Rachid Yazami Hybrid electrochemical generator with a soluble anode
US11791493B2 (en) 2009-02-09 2023-10-17 Varta Microbattery Gmbh Button cells and method of producing same
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US11217844B2 (en) 2009-06-18 2022-01-04 Varta Microbattery Gmbh Button cell having winding electrode and method for the production thereof
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US11362385B2 (en) 2009-06-18 2022-06-14 Varta Microbattery Gmbh Button cell having winding electrode and method for the production thereof
US20130230748A1 (en) * 2012-01-27 2013-09-05 Toyota Jidosha Kabushiki Kaisha Nonaqueous electrolyte secondary battery, method for manufacturing nonaqueous electrolyte secondary battery, and vehicle comprising nonaqueous electrolyte secondary battery
CN103227346A (zh) * 2012-01-27 2013-07-31 三洋电机株式会社 非水电解质二次电池的制造方法、非水电解质二次电池
US10050305B2 (en) * 2013-12-16 2018-08-14 Samsung Sdi Co., Ltd. Electrolyte for lithium secondary battery and lithium secondary battery employing the same
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US10096858B2 (en) 2014-03-14 2018-10-09 Adeka Corporation Nonaqueous electrolyte and nonaqueous secondary battery
US11024880B2 (en) 2018-05-29 2021-06-01 Hyundai Motor Company Electrolyte for lithium secondary battery and lithium secondary battery including the same
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