WO2001039314A1 - Accumulateur secondaire a electrolyte non aqueux, agent prevenant la deterioration pour accumulateur secondaire a electrolyte non aqueux et additif correspondant - Google Patents
Accumulateur secondaire a electrolyte non aqueux, agent prevenant la deterioration pour accumulateur secondaire a electrolyte non aqueux et additif correspondant Download PDFInfo
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- WO2001039314A1 WO2001039314A1 PCT/JP2000/008041 JP0008041W WO0139314A1 WO 2001039314 A1 WO2001039314 A1 WO 2001039314A1 JP 0008041 W JP0008041 W JP 0008041W WO 0139314 A1 WO0139314 A1 WO 0139314A1
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- aqueous electrolyte
- electrolyte secondary
- secondary battery
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- phosphazene derivative
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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
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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
- H01M10/052—Li-accumulators
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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
- 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
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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
- H01M10/42—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
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- 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
Definitions
- the present invention relates to a non-aqueous electrolyte secondary battery, a deterioration inhibitor for the non-aqueous electrolyte secondary battery, and an additive for the non-aqueous electrolyte secondary battery.
- Non-aqueous electrolyte secondary battery having fire-extinguishing or flame-retardant properties, additive for non-aqueous electrolyte used therein, and non-aqueous electrolyte secondary battery capable of effectively suppressing deterioration of the non-aqueous electrolyte secondary battery
- the present invention relates to a battery deterioration inhibitor.
- nickel-cadmium batteries have been the mainstream, especially as secondary batteries for memory backup of personal computers, VTRs and other AV and information equipment, and for driving power for them.
- non-aqueous electrolyte secondary batteries have attracted much attention as an alternative to nickel-cadmium batteries because they have the advantages of high voltage and high energy density and exhibit excellent self-discharge properties. Attempts have been made, some of which have been commercialized. For example, more than half of notebook computers and mobile phones are driven by non-aqueous electrolyte secondary batteries.
- non-aqueous electrolyte secondary batteries for cameras use alkali metals (particularly lithium metals and lithium alloys) as negative electrode materials, they reduce the danger of violent reaction with water.
- an aprotic organic solvent such as an ester organic solvent is usually used as the electrolytic solution.
- these non-aqueous electrolyte secondary batteries also have the following problems in safety.
- an alkali metal particularly, lithium metal, lithium alloy, or the like
- the alkali metal has a very high activity with respect to moisture.
- the anode material and water react with each other to generate hydrogen, and there is a high risk of ignition.
- lithium metal has a low melting point (approximately 170 ° C)
- the battery may overheat, causing the battery to be extremely dangerous.
- the electrolyte generated based on the organic solvent is vaporized and decomposed to generate gas as the battery generates heat, and the generated gas causes the battery to burst or ignite.
- a first object of the present invention is to provide a non-aqueous electrolyte solution having excellent resistance to deterioration, low interfacial resistance of the non-aqueous electrolyte solution, and excellent low-temperature discharge characteristics while maintaining battery characteristics and the like required as a battery. It is to provide a secondary battery.
- a second object of the present invention is to provide a non-aqueous electrolyte having excellent self-extinguishing properties or excellent flame retardancy, low interfacial resistance of a non-aqueous electrolyte, and excellent low-temperature discharge characteristics while maintaining battery characteristics required for a battery.
- An electrolytic solution is to provide a secondary battery.
- a third object of the present invention is to add a non-aqueous electrolyte to a non-aqueous electrolyte in a non-aqueous electrolyte secondary battery while maintaining battery characteristics such as charge / discharge capacity required as a battery.
- An object of the present invention is to provide an anti-degradation agent for a non-aqueous electrolyte secondary battery that can prevent deterioration and reduce the resistance of an interface and can provide excellent low-temperature discharge characteristics.
- a fourth object of the present invention is to provide excellent self-extinguishing while adding the non-aqueous electrolyte to a non-aqueous electrolyte in a non-aqueous electrolyte secondary battery while maintaining the battery characteristics required for the battery.
- An object of the present invention is to provide an additive for a non-aqueous electrolyte secondary battery, which can impart low temperature / discharge characteristics and low-temperature discharge characteristics and can have low interface resistance.
- a first embodiment of the nonaqueous electrolyte secondary battery according to the present invention for achieving the first object includes a positive electrode, a negative electrode, a phosphazene derivative of 2% by volume or more and less than 20% by volume, and And a non-aqueous electrolyte containing a salt.
- a second embodiment of the non-aqueous electrolyte secondary battery of the present invention for achieving the second object is a non-aqueous electrolyte containing a positive electrode, a negative electrode, 20% by volume or more of a phosphazene derivative, and a supporting salt. And a liquid.
- the deterioration preventing agent for a non-aqueous electrolyte secondary battery of the present invention for achieving the third object is a non-aqueous electrolyte secondary battery having a non-aqueous electrolyte containing a supporting salt and an organic solvent, It is characterized by being added to the non-aqueous electrolyte and containing at least a phosphazene derivative.
- the additive for a non-aqueous electrolyte secondary battery of the present invention for achieving the fourth object is a non-aqueous electrolyte secondary battery having a non-aqueous electrolyte containing a supporting salt and an organic solvent. It is added to the solution and contains at least a phosphazene derivative.
- BEST MODE FOR CARRYING OUT THE INVENTION The non-aqueous electrolyte secondary battery of the present invention has a positive electrode, a negative electrode, and a non-aqueous electrolyte, and has other members as necessary.
- the deterioration inhibitor for nonaqueous electrolyte secondary batteries and the additive for nonaqueous electrolyte secondary batteries of the present invention contain a phosphazene derivative and, if necessary, other components.
- the material of the positive electrode is not particularly limited, and may be appropriately selected from known positive electrode materials and used.
- V 2 0 5, V 6 0, M n 0 2, M o 0 3, L i C o 0 2, L i N i 0 2, L i M n 2 ⁇ metal oxides such as 4, T i Metal sulfides such as S 2 and Mo S 2 , conductive polymers such as polyaniline, and the like are preferable.
- high capacity, high safety, and excellent wettability of the electrolyte are preferred.
- L i C O_ ⁇ 2, L i n I_ ⁇ 2, L i M n 2 0 4 is particularly preferred.
- These materials may be used alone or in combination of two or more.
- the shape of the positive electrode is not particularly limited, and may be appropriately selected from known shapes as electrodes. For example, a sheet shape, a column shape, a plate shape, a spiral shape, and the like can be given.
- the material of the negative electrode is not particularly limited as long as it can occlude and release lithium or lithium ions, for example, and can be appropriately selected from known negative electrode materials and used, for example, a material containing lithium, Suitable examples include lithium metal itself, alloys of lithium with aluminum, indium, lead or zinc, and carbon materials such as lithium-doped graphite. Among these, carbon materials such as graphite are preferable in terms of higher safety. These materials may be used alone or in combination of two or more.
- the shape of the negative electrode is not particularly limited, and may be appropriately selected from known shapes similar to the shape of the positive electrode. [Non-aqueous electrolyte]
- the non-aqueous electrolyte contains a supporting salt and a phosphazene derivative, and if necessary, other components such as a non-protonic organic solvent.
- the non-aqueous electrolyte to which the non-aqueous electrolyte secondary battery deterioration inhibitor and the non-aqueous electrolyte secondary battery are added contains a supporting salt and an organic solvent.
- a supporting salt serving as an ion source of lithium ions is preferable.
- the lithium ion ion source is not particularly limited.
- L i C 1 O 4 , L i BF 4 , L i PF 6 , L i CF 3 S 0 3 , L i As F 6 , L i C 4 F 9 S0 3, L i (CF 3 S0 2) 2 N, L i (C 2 F 5 S0 2) lithium salts such as 2 N are preferably exemplified. These may be used alone or in combination of two or more.
- the content of the supporting salt in the nonaqueous electrolyte is preferably from 0.2 to 1 mol, more preferably from 0.5 to 1 mol, per 1 kg of the nonaqueous electrolyte (solvent component).
- the non-aqueous electrolyte secondary battery In the first embodiment of the non-aqueous electrolyte secondary battery, the non-aqueous electrolyte
- the reason for containing the conductor (compound) and the reason for adding the above-mentioned deterioration preventing agent for a non-aqueous electrolyte secondary battery containing a phosphazene derivative (compound) to the non-aqueous electrolyte are as follows. Degraded in conventional non-aqueous electrolyte secondary battery, in the electrolytic solution ester such as for example, lithium ion sources, etc. L i PF 6 salt is a supporting salt, to the L i F and PF 5 with time It is considered that the corrosion progresses and deteriorates due to the generated PF 5 gas or the hydrogen fluoride gas generated by further reacting the generated PF 5 gas with water or the like.
- the conductivity of the non-aqueous electrolyte decreases and the generated hydrogen fluoride gas degrades the electrode material.
- the phosphazene derivative can be, for example, to suppress the decomposition of the lithium ion source such as the aforementioned i PF 6 contributes to the stabilization. Therefore, when the phosphazene derivative is contained in the conventional non-aqueous electrolyte, the decomposition reaction of the non-aqueous electrolyte is suppressed, so that corrosion and deterioration can be suppressed.
- the reason why the non-aqueous electrolyte contains a phosphazene derivative (compound), and the non-aqueous electrolyte secondary battery contains a phosphazene derivative (compound) is as follows.
- the content of the phosphazene derivative in the nonaqueous electrolyte needs to be 2% by volume or more and less than 20% by volume, and 2.5. Preferably, it is more than 3% by volume and less than 20% by volume, more preferably more than 3% by volume and less than 20% by volume. If the content is within the numerical range, preferably Deterioration can be suppressed.
- the deterioration refers to the decomposition of the supporting salt (for example, lithium salt).
- the effect of preventing the deterioration can be evaluated by the following “stability evaluation method”.
- the content of the phosphazene derivative in the non-aqueous electrolyte needs to be 20% by volume or more, and more preferably 30% by volume or more.
- the upper limit of the content is not particularly limited, and 100% by volume of the nonaqueous electrolyte may be the phosphazene derivative.
- the self-extinguishing property means a property in which the ignited flame is extinguished on a 25 to 100 mm line in the following method for evaluating self-extinguishing property, and no ignition is observed even on a falling object. Further, the above-mentioned flame retardancy refers to a property in which the ignited flame does not reach the 25 mm line and the falling object is not ignited in the following flame retardancy evaluation method. 11 Self-extinguishing properties
- the self-extinguishing property and the flame retardancy were evaluated by measuring and evaluating the burning behavior of a flame ignited in an atmospheric environment by using a method that is an arrangement of the UL (Underwriting Laboratory) standard UL 94 HB method. At that time, the ignitability, flammability, carbide formation, and the phenomenon during secondary ignition were also observed. Specifically, based on UL test standards, non-combustible quartz fiber Each sample was impregnated with 1.0 ml of various electrolytic solutions to prepare a test piece of 127 mm ⁇ 12.7 mm.
- the amount of the nonaqueous electrolyte secondary battery deterioration inhibitor added to the nonaqueous electrolyte is preferably 2 to 90% by volume, more preferably more than 2.5% by volume and 90% by volume or less, ⁇ 75% by volume is particularly preferred.
- the amount is less than 2% by volume, a sufficient effect of preventing deterioration may not be exhibited. If the amount is more than 90% by volume, the viscosity of the non-aqueous electrolyte increases and a suitable electrical conductivity can be secured. There may not be.
- the deterioration refers to the decomposition of the supporting salt (for example, lithium salt).
- the supporting salt for example, lithium salt
- the effect of preventing the deterioration can be evaluated by the following “stability evaluation method”.
- the amount of the additive for the non-aqueous electrolyte secondary battery added to the non-aqueous electrolyte depends on the effect obtained by adding the non-aqueous electrolyte secondary battery to the non-aqueous electrolyte secondary battery.
- the first addition amount is preferably 20 to 90% by volume, more preferably 40 to 75% by volume, and the phosphazene derivative has a substituent containing a halogen element in a molecular structure.
- the content is preferably from 10 to 90% by volume, and more preferably from 20 to 75% by volume. If the amount is less than 20% by volume, sufficient self-extinguishing properties may not be imparted. On the other hand, if the amount exceeds 90% by volume, the viscosity of the non-aqueous electrolyte increases and the conductivity becomes extremely high. May drop.
- the support salt comprises L i PF 6, when the organic solvent comprises E Ji Ren carbonate, as the first additive amount is 1.5 to 2.5 body % Is preferred.
- the self-extinguishing property refers to a property in which the ignited flame is extinguished on a 25 to 100 mm line in the following method for evaluating self-extinguishing property, and no ignition is observed even on a falling object.
- the second addition amount is preferably 30 to 90% by volume, more preferably 40 to 60% by volume.
- Is preferably 20 to 90% by volume, more preferably 30 to 60% by volume. If the addition amount is less than 30% by volume, sufficient flame retardancy may not be imparted. On the other hand, if it exceeds 90% by volume, the viscosity of the non-aqueous electrolyte increases, and good electrical conductivity is obtained. May not be maintained.
- the support salt comprises L i PF 6, when the organic solvent comprises E Ji Ren carbonate, as the second amount, 2. 5 vol% exceeded 90 vol% or less is preferable, and 3 vol% or more and 90 vol% or less is more preferable.
- the above-mentioned flame retardancy refers to a property in which the ignited flame does not reach the 25 mm line and ignition of falling objects is not recognized in the following flame retardancy evaluation method.
- the self-extinguishing property and the flame retardancy were evaluated by measuring the combustion behavior of a flame ignited in an atmospheric environment using a method that is an arrangement of the UL (underwriting laboratory) standard UL 94 HB method. At that time, the ignitability, flammability, carbide formation, and the phenomenon during secondary ignition were also observed. Specifically, based on UL testing standards, Each sample was impregnated with 1.0 ml of various electrolytic solutions to prepare a specimen of 127 mm ⁇ 12.7 mm.
- the content is preferably more than 2.5% by volume.
- the phosphazene derivative may have a substituent containing a halogen element in a molecular structure. Is preferred.
- the halogen gas derived from the phosphazene derivative may cause a smaller content in the numerical range of the content of the phosphazene derivative.
- the non-aqueous electrolyte can exhibit self-extinguishing properties or flame retardancy.
- a halogen radical may be a problem.
- the phosphorus element in the molecular structure promotes the halogen radical, and the compound is stable. Such a problem does not occur because phosphorus halide is formed.
- the content of the halogen element in the phosphazene derivative is preferably 2 to 80% by weight, more preferably 2 to 60% by weight, and still more preferably 2 to 50% by weight. If the content is less than 2% by weight, the effect of including the halogen element may not be sufficiently exhibited. If the content is more than 80% by weight, the viscosity increases, and thus the content of the halogen element is increased. When added, its conductivity may decrease.
- the phosphazene derivative is not particularly limited as long as it is a liquid at normal temperature (25 ° C.) in terms of the conductivity of the nonaqueous electrolyte, and for example, a chain represented by the following general formula (1)
- a phosphazene derivative or a cyclic phosphazene derivative represented by the following general formula (2) is preferably exemplified.
- RR 2 and R 3 represent a monovalent substituent or a halogen element.
- X represents a group containing at least one element selected from the group consisting of carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, zeolite, selenium, tellurium, and polonium.
- Y 1 , Y 2 and Y 3 represent a divalent linking group, a divalent element or a single bond.
- R 4 represents a monovalent substituent or a halogen element.
- N represents 3 to 15.
- R ′, R 2 and R 3 is not particularly limited as long as it is a monovalent substituent or a halogen element, and can be appropriately selected depending on the purpose. Examples of the monovalent substituent include an alkoxy group, an alkyl group, a carboxyl group
- halogen element examples include the halogen element.
- an alkoxy group is particularly preferred in that the viscosity of the non-aqueous electrolyte can be reduced.
- ⁇ To 3 may be of the same type or different types.
- the alkoxy group include an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and an alkoxy-substituted alkoxy group such as a methoxyethoxy group and a methoxyethoxyoxy group. Can be Of these, 1 to!
- ⁇ 3 are preferably all methoxy, ethoxy, methoxyethoxy or methoxyethoxyethoxy groups, and all are preferred from the viewpoint of low viscosity and high dielectric constant. Particularly preferred is a methoxy group or an ethoxy group.
- alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and the like.
- Examples of the acryl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isoptyryl group, and a valeryl group.
- aryl group examples include a phenyl group, a tolyl group, and a naphthyl group.
- Y ", ⁇ 2 and Upsilon The group represented by I, for example, addition of CH 2 group, oxygen, sulfur, selenium, nitrogen, boron, aluminum, scandium, Galli ⁇ beam , Yttrium, indium, lanthanum, thallium, carbon, silicon, titanium, tin, germanium, zirconium, lead, phosphorus, vanadium, arsenic, niobium, antimony, tantalum, bismuth, chromium, molybdenum, tellurium, polonium, tungsten, A group containing an element such as iron, cobalt, nickel, etc.
- a CH 2 group, a group containing oxygen, sulfur, selenium or nitrogen, etc. are preferable, and sulfur or selenium is preferable. Groups containing are more preferred.
- ⁇ 2 and ⁇ 3 contain sulfur or selenium. This is preferable because the flame retardancy of the liquid is significantly improved. Yi ⁇ Y 3 may be homologous derconnection also may together or they may be heterologous.
- X is a group containing at least one element selected from the group consisting of carbon, silicon, nitrogen, phosphorus, oxygen and zeo in consideration of harmfulness, environment, and the like. And a group having a structure represented by the following general formula (3) is more preferable.
- R 5 to R 9 represent a monovalent substituent or a halogen element.
- Y 5 to Y 9 represent a divalent linking group, a divalent element or a single bond.
- ⁇ represents a divalent group or a divalent element.
- the R 5 to R 9, substituent or a halogen element similar monovalent to that described in R' ⁇ R 3 can be mentioned as preferred either in the general formula (1) . These may be the same or different in the same group.
- the R 5 and R B, and the R s and R 9, may be bonded to each other to form a ring.
- Z represents, for example, a CH 2 group, a CHR (R represents an alkyl group, an alkoxyl group, a phenyl group, etc .; the same applies hereinafter), an NR group, and oxygen , Sulfur, selenium, boron, aluminum, scandium, gallium, yttrium, indium, lanthanum, thallium, carbon, silicon, titanium, tin, tin, germanium, zirconia, lead, phosphorus, vanadium, arsenic, niobium, antimony, tantalum, bismuth And chromium, molybdenum, tellurium, polonium, tungsten, iron, cobalt, nickel, and other groups.
- a group containing oxygen, sulfur or selenium in addition to a CH 2 group, a CHR group, and an NR group is preferable, and the second embodiment of the non-aqueous electrolyte secondary battery and the non-aqueous electrolyte secondary battery
- a group containing sulfur or selenium is preferable because the flame retardancy of the non-aqueous electrolyte is significantly improved.
- a phosphorus-containing group represented by the group (A) is particularly preferable in that it can effectively impart deterioration resistance, self-extinguishing property, or flame retardancy.
- R 4 is not particularly limited as long as it is a monovalent substituent or a halogen element, and can be appropriately selected depending on the purpose.
- Examples of the monovalent substituent include an alkoxy group, an alkyl group, a carboxyl group, an acyl group, and an aryl group.
- halogen element examples include the halogen element.
- an alkoxy group is preferable in that the viscosity of the nonaqueous electrolyte can be particularly reduced.
- the alkoxy group include a methoxy group, an ethoxy group, a methoxyethoxy group, a propoxy group, and a phenoxy group. Among them, methoxy group, An ethoxy group and a methoxyethoxy group are particularly preferred.
- the hydrogen element in these substituents is preferably substituted with a halogen element as described above.
- Formula (1) ⁇ R in (3) 'R 9, ⁇ ' by appropriately selecting the ⁇ 3, Y 5 ⁇ Y 9 or Z, said having a more preferable viscosity, suitable for mixing and dissolving, etc. It is possible to synthesize a non-aqueous electrolyte secondary battery, a deterioration inhibitor for the non-aqueous electrolyte secondary battery, and an additive for the non-aqueous electrolyte secondary battery.
- These phosphazene derivatives may be used alone or in a combination of two or more.
- the flash point of the phosphazene derivative is not particularly limited, but is preferably 100 ° C.
- the non-aqueous electrolytic solution is prepared by adding the non-aqueous electrolyte secondary battery deterioration inhibitor containing at least the phosphazene derivative to the non-aqueous electrolytic solution in a known non-aqueous electrolytic solution secondary battery. It is possible to prevent the deterioration of the electrolyte, to reduce the interfacial resistance of the non-aqueous electrolyte, to provide excellent low-temperature discharge characteristics, and to have high stability over a long period of time, equivalent to ordinary batteries. A non-aqueous electrolyte secondary battery having excellent battery characteristics can be easily manufactured.
- non-aqueous electrolyte secondary battery containing at least the phosphazene derivative
- the non-aqueous electrolyte can have a low interface resistance, high safety, and excellent battery characteristics equivalent to ordinary batteries.
- a non-aqueous electrolyte secondary battery having the same can be easily manufactured.
- the organic solvent is preferably an aprotic organic solvent from the viewpoint of safety.
- the non-aqueous electrolyte contains the aprotic organic solvent
- the material of the negative electrode High safety can be obtained without reacting with the nonaqueous electrolyte, and the viscosity of the nonaqueous electrolyte can be reduced, and the optimum ionic conductivity as a nonaqueous electrolyte secondary battery can be easily achieved.
- the aprotic organic solvent is not particularly limited, but is preferably an ether compound, an ester compound, or the like from the viewpoint of reducing the viscosity of the nonaqueous electrolytic solution.
- cyclic ester compounds such as ethylene carbonate, propylene carbonate and arbutyrolactone, and chain ester compounds such as 1,2-dimethylxetane, dimethyl carbonate, ethylmethyl carbonate and getyl carbonate are preferred.
- a cyclic ester compound is preferable because it has a high relative dielectric constant and is excellent in solubility of a lithium salt or the like, has a low viscosity, and has a low chain viscosity in that the nonaqueous electrolyte solution can have a low viscosity.
- These may be used alone or in combination of two or more.
- the viscosity of the aprotic organic solvent at 25 ° C. is not particularly limited, but is preferably 1 OmPa ⁇ s (10 cP) or less.
- Examples of the other members include a separator which is interposed between the positive electrode and the negative electrode in a non-aqueous electrolyte secondary battery so as to prevent a current short circuit due to contact between the two electrodes.
- the material of the separation it is possible to reliably prevent contact between the two electrodes, and to be capable of receiving or containing the electrolyte, for example, a synthetic resin such as polytetrafluoroethylene, polypropylene, or polyethylene.
- a nonwoven fabric, a thin film and the like are preferably mentioned.
- polypropylene or polyethylene microporous with a thickness of about 20 to 50 / zm Films are particularly preferred.
- well-known other members commonly used in batteries are preferably used as the other members.
- the form of the non-aqueous electrolyte secondary battery of the present invention described above is not particularly limited, and various known forms such as a coin type, a button type, a paper type, a square type or a spiral type cylindrical battery are preferable. It is listed.
- a nonaqueous electrolyte secondary battery is manufactured by forming a sheet-shaped positive electrode, sandwiching a current collector, and stacking and winding a negative electrode (sheet-shaped) on the current collector.
- the first embodiment of the non-aqueous electrolyte secondary battery is excellent in deterioration resistance
- the second embodiment of the non-aqueous electrolyte secondary battery is self-extinguishing or flame retardant. All non-aqueous electrolyte secondary batteries have low interface resistance of non-aqueous electrolyte and excellent low-temperature discharge characteristics while maintaining the battery characteristics required for batteries.
- Example 2 and Comparative Example 1 of the first embodiment of the nonaqueous electrolyte secondary battery will be described, but the present invention is not limited thereto.
- Arptyrolactone an aprotic organic solvent 49 ml was added to a phosphazene derivative (a linear EO-type phosphazene derivative (in the above general formula (1), X represents a group (A) represented by the general formula (3)).
- to ⁇ 3 and ⁇ 5 to ⁇ 6 are all single bonds, shaku 1 to! ⁇ And R 5 to R 6 are all ethoxy groups and Z is oxygen ) and lml of) was added (2% by volume), and further, is dissolved L i PF 6 a (lithium salt) 0. at a concentration of 5 mol / kg To prepare a non-aqueous electrolyte. Evaluation of deterioration
- the water content (ppm) immediately after the preparation of the non-aqueous electrolyte and after leaving it in a glove box for 2 months and the concentration of hydrogen fluoride in the same manner as in the above-mentioned “Method for evaluating stability” (P pm) and charge / discharge capacity (mAhZg) were measured and calculated to evaluate deterioration.
- the charge / discharge capacity (mAhZg) is obtained by measuring the charge / discharge curve using a known weight of the positive electrode or the negative electrode and dividing by the weight of the electrode or the negative electrode using the obtained charge and discharge amounts. It was asked by. The results are shown in Table 1.
- Binder resin (Binder resin), kneaded with an organic solvent (50/50 volume% mixed solvent of ethyl acetate and ethanol), and roll-rolled to form a thin cathode of 100 Aim in thickness and 40 mm in width.
- a sheet was prepared.
- a 25 / xm-thick aluminum foil (current collector) with a conductive adhesive applied to the surface was sandwiched, and a 25-m-thick separator was placed between them.
- a microporous film: polypropylene with a 150-mm-thick lithium metal foil laminated and rolled up to produce a cylindrical electrode.
- the length of the positive electrode of the cylindrical electrode was about 260 mm.
- the nonaqueous electrolytic solution was injected into the cylindrical electrode and sealed to prepare an AA lithium battery. Since the obtained battery used the non-aqueous electrolyte, the battery had excellent deterioration resistance while maintaining battery characteristics required for the battery. Evaluation of low-temperature discharge characteristics (measurement of low-temperature discharge capacity)
- the obtained non-aqueous electrolyte secondary battery was charged and discharged up to 50 cycles under the conditions of an upper limit voltage of 4.5 V, a lower limit voltage of 3.0 V, a discharge current of 100 mA, and a charging current of 50 mA. Repeated. At this time, charging was performed at 20 ° C, and discharging was performed at a low temperature (120 ° C, 110). At this time, the discharge capacity at low temperature was compared with the discharge capacity when charge and discharge were repeated up to 50 cycles at 20. The discharge capacity reduction rate was calculated from the following equation. Table 1 shows the results.
- Example 1 the phosphazene derivative (chain EO-type phosphazene derivative (in the general formula (1), X represents a group (A) represented by the general formula (3)) a structure, ⁇ 1 ⁇ 3 and ⁇ 5- ⁇ 6 Ari in all single bonds, 1 ⁇ to 1 ⁇ and continuous 5 to 1 ⁇ is a all ethoxy group, and Z is oxygen
- a non-aqueous electrolyte was prepared in the same manner as in Example 1 except that the addition amount of)) was changed to 20% by volume, and the deterioration and the low-temperature discharge characteristics were evaluated.
- Example 2 145 20 145 0 20 40% or less 70% or less
- a cobalt oxide represented by the chemical formula i Coo 2 as a positive electrode active material Against 2 1 0 0 parts of acetylene black (conductive additive) 1 0 parts of Teflon binder (binder resin) 1 0 parts was added, 5 0 Z 5 0 bodies of an organic solvent (acetic Echiru and ethanol % Mixed solvent), and roll-rolled to produce a thin layered positive electrode sheet having a thickness of 100 m and a width of 40 mm.
- a 25-m-thick aluminum foil (current collector) with a conductive adhesive applied to the surface was sandwiched, and a 25-m-thick separator was inserted between them.
- a microporous film: polypropylene was interposed, and a 150-m-thick lithium metal foil was overlapped and rolled up to produce a cylindrical electrode.
- the length of the positive electrode of the cylindrical electrode was about 260 mm.
- the nonaqueous electrolytic solution was injected into the cylindrical electrode and sealed to prepare an AA lithium battery. Measurement and evaluation of battery characteristics
- Example 3 the phosphazene derivative (chain EO-type phosphazene derivative (in the above general formula (1), X represents a group (A) represented by the general formula (3)) a structure, ⁇ 1 ⁇ 3 and ⁇ 5- ⁇ 6 Ari in all single bond, R ⁇ R 3 and R 5 to R 6 is a all ethoxy group, and Z is oxygen)
- a non-aqueous electrolyte was prepared in the same manner as in Example 3 except that the addition amount was changed to 80% by volume, and the self-extinguishing property or the flame retardancy was evaluated.
- a non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 3, and the initial battery characteristics (voltage, internal resistance), charge / discharge cycle performance, and low-temperature discharge characteristics were measured and evaluated. The results are shown in Table 2.
- the phosphazene derivative (chain EO-type phosphazene derivative (in the above general formula (1), X represents a group (A) represented by the general formula (3)) ⁇
- Example 3 A non-aqueous electrolyte was prepared and evaluated for self-extinguishing properties or flame retardancy, and a non-aqueous electrolyte secondary battery was fabricated in the same manner as in Example 3. And the initial cell characteristics (voltage, internal resistance), the charge-discharge cycle performance was measured and evaluated respectively low temperature discharge conductive properties. The results are shown in Table 2.
- Example 3 In “Preparation of non-aqueous electrolyte" in Example 3, the phosphazene derivative (chain EO-type phosphazene derivative (in the above general formula (1), X represents a group (A) represented by the general formula (3)) ⁇ and ⁇ to ⁇ ⁇ are all single bonds, RR 3 and R 5 to R 6 are all ethoxy groups, and Z is oxygen.))
- a non-aqueous electrolyte was prepared and evaluated for self-extinguishing or flame retardancy.
- a non-aqueous electrolyte secondary battery was fabricated in the same manner as in Example 3, and the initial battery characteristics (voltage, internal resistance), charge / discharge cycle performance, and low-temperature discharge characteristics were measured and evaluated. The results are shown in Table 2. Evaluation of low temperature discharge characteristics
- Example 3 2.85 200 5 40% or less 70% or less With self-extinguishing property
- Example 4 2.85 215 5 40% or less 70% or less Flame retardant
- Example 5 2.90 225 5 40% or less 70% or less Flame retardant
- Example 6 2.85 200 5 40% or less 70% or less Flame retardant Comparative Example 2 2.80 190 4 50% or more 85% or more Flammable
- the non-aqueous electrolyte has excellent self-extinguishing properties or flame retardancy
- the second embodiment of the non-aqueous electrolyte secondary battery of the present invention has excellent safety.
- Examples 7 to 8 and Comparative Examples 3 and 4 of the deterioration inhibitor for a non-aqueous electrolyte secondary battery are shown, but the present invention is not limited thereto.
- a phosphazene derivative (a linear EO-type phosphazene derivative (in the above-mentioned general formula (1), represents a group represented by the general formula (3)) a structure, Y ⁇ Y 3 and ⁇ Y 6 is that all single bonds, RR 3 and R 5 to R 6 is a all ethoxy group, and Z is oxygen)) (non-aqueous electrolyte solution added lm l for a secondary battery deterioration inhibitor) and (2 vol%), further, L i PF 6 (the supporting salt) dissolved at a concentration of 0.5 mol / kg, to prepare a non-aqueous electrolyte solution . Evaluation of degradation
- Example 7 In “Preparation of non-aqueous electrolyte” of Example 7, the addition amount of arptyrolactone (aprotic organic solvent) was set to 50 ml, and the phosphazene derivative (chain EO-type phosphazene derivative (the general formula In (1), X is the structure of the group (A) represented by the general formula (3), and
- Example 8 145 20 145 0 20 40% or less 70% or less
- Comparative Example 3 145 20 20 40 2 50% or more 85% or more
- the nonaqueous electrolytic solution was injected into the cylindrical electrode and sealed to prepare an AA lithium battery. Measurement and evaluation of battery characteristics
- Charge / discharge was repeated up to 50 cycles under the conditions of an upper limit voltage of 4.5 V, a lower limit voltage of 3.0 V, a discharge current of 100 mA, and a charge current of 50 mA.
- the charge / discharge capacity at this time was compared with the charge / discharge capacity at the initial stage, and the capacity reduction rate after 50 cycles was calculated. Similar measurements and calculations were made for a total of three batteries, and the average of these values was used as an evaluation of charge / discharge cycle performance.
- Non-aqueous Electrolyte Solution the phosphazene derivative (chain EO-type phosphazene derivative (in the above general formula (1), represents a structure of a group (A) represented by the general formula (3)) in and, ⁇ ' ⁇ 3 and - Y 6 is that all single bonds,! ⁇ ⁇ ! ⁇ and! ⁇ ⁇ ⁇ is a all ethoxy group, compound ⁇ is oxygen))
- nonaqueous was prepared in the same manner as in Example 9 except that the amount of the additive for the electrolyte secondary battery) in the non-aqueous electrolyte was changed to be 80% by volume. The flame retardancy was evaluated.
- a non-aqueous electrolyte secondary battery was prepared in the same manner as in Example 9, and the initial battery characteristics (voltage, internal resistance), charge / discharge cycle performance, and low-temperature discharge characteristics were measured and evaluated. The results are shown in Table 4.
- Non-Aqueous Electrolyte Solution the additive for a non-aqueous electrolyte secondary battery was a phosphazene derivative (chain-type ⁇ ⁇ -type phosphazene derivative (X in the above general formula (1)) a structure of group (Alpha) of the formula (3), ⁇ 1 ⁇ 3 and ⁇ 5 ⁇ 6 is that all single bond, R 'R 3 and R 5 to R 6 are all A compound in which Z is oxygen, which is an ethoxy group)) (Hydrogen element in ethoxy group in (non-aqueous electrolyte secondary battery additive) is replaced with elemental fluorine (content of elemental fluorine in phosphazene derivative: 15) (Wt%), a non-aqueous electrolyte solution was prepared in the same manner as in Example 9 except that the compound was replaced with the same compound and evaluated for self-extinguishing properties or flame retardancy.
- a non-aqueous electrolyte solution was prepared in the same manner
- a non-aqueous electrolyte secondary battery was fabricated in the same manner as in Example 9, and the initial battery characteristics (voltage and internal resistance), charge / discharge cycle performance, and low-temperature discharge characteristics were measured and evaluated. Table 4 shows the results. (Example 12)
- ⁇ 6 are all ethoxy groups, and Z is oxygen Certain compounds)) (except for using a non-aqueous electrolyte secondary battery additive) and changing the addition amount of a mixed solvent of ethylene carbonate and getyl carbonate (non-protonic organic solvent) to 100 ml Prepared a non-aqueous electrolyte in the same manner as in Example 9, and evaluated self-extinguishing properties or flame retardancy.
- a non-aqueous electrolyte secondary battery was fabricated in the same manner as in Example 9, and the initial battery characteristics (voltage and internal resistance), charge / discharge cycle performance, and low-temperature discharge characteristics were measured and evaluated. Table 4 shows the results. Evaluation of low temperature discharge characteristics
- Example 9 2.85 200 5 40% or less 70% or less With self-extinguishing property
- Example 1 0 2.85 210 5 40% or less 70% or less Flame retardant
- Example 1 1 2.90 230 5 40% or less 70% or less Flame retardant
- Example 1 2 2.85 200 5 40% or less 70% or less Flame retardant Comparative Example 5 2.80 180 3 50% or more 85% or more Flammable
- the non-aqueous electrolyte has excellent self-extinguishing properties or flame retardancy.
- the additive for a non-aqueous electrolyte secondary battery of the present invention when used, it has excellent safety. You can see that In particular, in Examples 11 and 12, it can be seen that excellent flame retardancy can be imparted even when the additive amount of the non-aqueous electrolyte secondary battery additive is small.
- Industrial Applicability The first form of the non-aqueous electrolyte secondary battery has excellent resistance to deterioration while maintaining the battery characteristics and the like required as a battery, and has a low interfacial resistance of the non-aqueous electrolyte. Has excellent low-temperature discharge characteristics.
- the second embodiment of the non-aqueous electrolyte secondary battery has excellent self-extinguishing properties or flame retardancy while maintaining the battery characteristics and the like required as a battery, and has a low non-aqueous electrolyte with low interfacial resistance. Has low-temperature discharge characteristics.
- the deterioration preventing agent for a non-aqueous electrolyte secondary battery is added to a non-aqueous electrolyte in a non-aqueous electrolyte secondary battery to maintain battery characteristics such as charge / discharge capacity required as a battery. It prevents degradation of the lysate, reduces the interfacial resistance of the non-aqueous electrolyte, and provides excellent low-temperature discharge characteristics.
- the additive for a non-aqueous electrolyte secondary battery is added to a non-aqueous electrolyte in a non-aqueous electrolyte secondary battery, and while maintaining battery characteristics and the like required for a battery, the additive for the non-aqueous electrolyte is reduced. Interfacial resistance can be achieved, and the nonaqueous electrolyte can be provided with excellent self-extinguishing properties, flame retardancy, and low-temperature discharge characteristics.
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/130,069 US6955867B1 (en) | 1999-11-25 | 2000-11-15 | Non-aqueous electrolyte secondary cell and, deterioration-preventing agent for non-aqueous electrolyte secondary cell and additive for non-aqueous electrolyte secondary cell for use therein |
EP00976252A EP1253662B1 (en) | 1999-11-25 | 2000-11-15 | Non-aqueous electrolyte secondary cell and, deterioration-preventing agent for non-aqueous electrolyte secondary cell and additive for non-aqueous electrolyte secondary cell for use therein |
DE60043266T DE60043266D1 (de) | 1999-11-25 | 2000-11-15 | Nichtwässrige elektrolyt-sekundärzelle, alterungsverhinderndes mittel und additive für den gebrauch in solch einer zelle |
Applications Claiming Priority (16)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP33495699 | 1999-11-25 | ||
JP33495399 | 1999-11-25 | ||
JP11/334954 | 1999-11-25 | ||
JP11/334953 | 1999-11-25 | ||
JP33495499 | 1999-11-25 | ||
JP11/334956 | 1999-11-25 | ||
JP11/334955 | 1999-11-25 | ||
JP33495599 | 1999-11-25 | ||
JP2000126569A JP2001217002A (ja) | 1999-11-25 | 2000-04-26 | 非水電解液二次電池用劣化防止剤 |
JP2000/126570 | 2000-04-26 | ||
JP2000/126568 | 2000-04-26 | ||
JP2000126571A JP2001217004A (ja) | 1999-11-25 | 2000-04-26 | 非水電解液二次電池 |
JP2000/126569 | 2000-04-26 | ||
JP2000/126571 | 2000-04-26 | ||
JP2000126570A JP2001217003A (ja) | 1999-11-25 | 2000-04-26 | 非水電解液二次電池 |
JP2000126568A JP2001217001A (ja) | 1999-11-25 | 2000-04-26 | 非水電解液二次電池用添加剤 |
Publications (1)
Publication Number | Publication Date |
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WO2001039314A1 true WO2001039314A1 (fr) | 2001-05-31 |
Family
ID=27573661
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2000/008041 WO2001039314A1 (fr) | 1999-11-25 | 2000-11-15 | Accumulateur secondaire a electrolyte non aqueux, agent prevenant la deterioration pour accumulateur secondaire a electrolyte non aqueux et additif correspondant |
Country Status (5)
Country | Link |
---|---|
US (1) | US6955867B1 (ja) |
EP (1) | EP1253662B1 (ja) |
KR (1) | KR100775566B1 (ja) |
DE (1) | DE60043266D1 (ja) |
WO (1) | WO2001039314A1 (ja) |
Cited By (6)
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WO2003041197A1 (en) | 2001-11-07 | 2003-05-15 | Bridgestone Corporation | Non-aqueous electrolyte primary cell and additive for non-aqueous electrolyte of the cell |
EP1328036A1 (en) * | 2000-09-07 | 2003-07-16 | Bridgestone Corporation | Additive for nonaqueous-electrolyte secondary battery |
EP1414096A1 (en) * | 2001-07-05 | 2004-04-28 | Bridgestone Corporation | Polymer cell and polymer electrolyte |
EP1414097A1 (en) * | 2001-07-05 | 2004-04-28 | Bridgestone Corporation | Non-aqueous electrolyte cell, electrolyte stabilizing agent, and phosphazene derivative and method for preparation thereof |
WO2004059671A1 (ja) * | 2002-12-26 | 2004-07-15 | Bridgestone Corporation | 電気二重層キャパシタの非水電解液用添加剤及び非水電解液電気二重層キャパシタ |
US7099142B2 (en) | 2000-09-07 | 2006-08-29 | Bridgestone Corporation | Additive for non-aqueous liquid electrolyte secondary cell, non-aqueous liquid electrolyte secondary cell, additive for non-aqueous liquid electrolyte electric double layer capacitor and non-aqueous liquid electrolyte electric double layer capacitor |
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WO2001086746A1 (fr) | 2000-05-08 | 2001-11-15 | Bridgestone Corporation | Batterie d'accumulateurs a electrolyte non aqueux |
CN100502129C (zh) * | 2000-09-07 | 2009-06-17 | 株式会社普利司通 | 非水性电解液添加剂、非水性电解液蓄电池以及非水性电解液电双层电容器 |
US20030190531A1 (en) * | 2000-09-07 | 2003-10-09 | Masashi Otsuki | Additive for non-aqueous liquid electrolyte, non-aqueous liquid electrolyte secondary cell and non-aqueous liquid electrolyte electric double layer capacitor |
US6797437B2 (en) | 2001-12-28 | 2004-09-28 | Quallion Llc | Electrolyte system and energy storage device using same |
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EP1580832B1 (en) * | 2002-12-26 | 2009-11-04 | Bridgestone Corporation | Additive for nonaqueous electrolytic solution of secondary battery and nonaqueous electrolyte secondary battery |
WO2005091421A1 (ja) * | 2004-03-23 | 2005-09-29 | Bridgestone Corporation | 電池の非水電解液用添加剤、電池用非水電解液及び非水電解液電池 |
US7285362B2 (en) * | 2004-05-17 | 2007-10-23 | Battelle Energy Alliance, Llc | Safe battery solvents |
US8039138B2 (en) * | 2007-08-14 | 2011-10-18 | Millennium Engineering And Integration Company | Chloride-free, sodium ion-free, and water-free thermal batteries using molten nitrate electrolytes |
US10497970B2 (en) | 2013-03-14 | 2019-12-03 | Arizona Board Of Regents On Behalf Of Arizona State University | Alkali ion conducting plastic crystals |
US10490847B2 (en) | 2013-03-14 | 2019-11-26 | Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University | Alkali ion conducting plastic crystals |
KR102272272B1 (ko) | 2014-07-11 | 2021-07-02 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 전해액 및 이를 포함하는 리튬 이차 전지 |
EP3353844B1 (en) | 2015-03-27 | 2022-05-11 | Mason K. Harrup | All-inorganic solvents for electrolytes |
US10707531B1 (en) | 2016-09-27 | 2020-07-07 | New Dominion Enterprises Inc. | All-inorganic solvents for electrolytes |
CN114709478A (zh) * | 2022-03-30 | 2022-07-05 | 厦门大学 | 含Se=P双键有机化合物在制备二次电池电解液中的应用 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5166009A (en) * | 1991-03-28 | 1992-11-24 | The United States Of America As Represented By The Secretary Of The Navy | Mixed polymer electrolyte and mixed polymer electrolyte battery |
JPH0613108A (ja) * | 1992-04-09 | 1994-01-21 | Bridgestone Corp | 非水電解質電池 |
DE4420095C1 (de) * | 1994-06-09 | 1995-10-19 | Daimler Benz Ag | Ionenleiter für elektrochemische Speicher und Verfahren zu dessen Herstellung |
US5830600A (en) * | 1996-05-24 | 1998-11-03 | Sri International | Nonflammable/self-extinguishing electrolytes for batteries |
JPH11144757A (ja) * | 1992-04-09 | 1999-05-28 | Bridgestone Corp | 非水電解質電池 |
JPH11191431A (ja) * | 1997-12-26 | 1999-07-13 | Sony Corp | 非水電解液電池 |
JP2000021442A (ja) * | 1998-06-30 | 2000-01-21 | Shin Kobe Electric Mach Co Ltd | 非水電解液二次電池 |
JP2000030740A (ja) * | 1998-07-15 | 2000-01-28 | Toyota Central Res & Dev Lab Inc | リチウム二次電池 |
JP2001023687A (ja) * | 1999-07-09 | 2001-01-26 | Sony Corp | 非水電解質電池 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5707760A (en) * | 1996-12-09 | 1998-01-13 | Valence Technology, Inc. | Additives for inhibiting decomposition of lithium salts and electrolytes containing said additives |
KR100644850B1 (ko) * | 1998-11-30 | 2006-11-10 | 소니 가부시키가이샤 | 비수 전해액 이차 전지 |
JP4314503B2 (ja) | 1999-08-04 | 2009-08-19 | 株式会社豊田中央研究所 | リチウム二次電池 |
-
2000
- 2000-11-15 EP EP00976252A patent/EP1253662B1/en not_active Expired - Lifetime
- 2000-11-15 DE DE60043266T patent/DE60043266D1/de not_active Expired - Lifetime
- 2000-11-15 WO PCT/JP2000/008041 patent/WO2001039314A1/ja not_active Application Discontinuation
- 2000-11-15 US US10/130,069 patent/US6955867B1/en not_active Expired - Fee Related
- 2000-11-15 KR KR1020027006644A patent/KR100775566B1/ko active IP Right Grant
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5166009A (en) * | 1991-03-28 | 1992-11-24 | The United States Of America As Represented By The Secretary Of The Navy | Mixed polymer electrolyte and mixed polymer electrolyte battery |
JPH0613108A (ja) * | 1992-04-09 | 1994-01-21 | Bridgestone Corp | 非水電解質電池 |
JPH11144757A (ja) * | 1992-04-09 | 1999-05-28 | Bridgestone Corp | 非水電解質電池 |
DE4420095C1 (de) * | 1994-06-09 | 1995-10-19 | Daimler Benz Ag | Ionenleiter für elektrochemische Speicher und Verfahren zu dessen Herstellung |
US5830600A (en) * | 1996-05-24 | 1998-11-03 | Sri International | Nonflammable/self-extinguishing electrolytes for batteries |
JPH11191431A (ja) * | 1997-12-26 | 1999-07-13 | Sony Corp | 非水電解液電池 |
JP2000021442A (ja) * | 1998-06-30 | 2000-01-21 | Shin Kobe Electric Mach Co Ltd | 非水電解液二次電池 |
JP2000030740A (ja) * | 1998-07-15 | 2000-01-28 | Toyota Central Res & Dev Lab Inc | リチウム二次電池 |
JP2001023687A (ja) * | 1999-07-09 | 2001-01-26 | Sony Corp | 非水電解質電池 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1253662A4 * |
Cited By (13)
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US7099142B2 (en) | 2000-09-07 | 2006-08-29 | Bridgestone Corporation | Additive for non-aqueous liquid electrolyte secondary cell, non-aqueous liquid electrolyte secondary cell, additive for non-aqueous liquid electrolyte electric double layer capacitor and non-aqueous liquid electrolyte electric double layer capacitor |
EP1328036A1 (en) * | 2000-09-07 | 2003-07-16 | Bridgestone Corporation | Additive for nonaqueous-electrolyte secondary battery |
EP1328036A4 (en) * | 2000-09-07 | 2006-12-06 | Bridgestone Corp | ADDITIVE FOR A SECONDARY BATTERY WITH A WATER-FREE ELECTROLYTE |
EP1414097A4 (en) * | 2001-07-05 | 2005-03-09 | Bridgestone Corp | NONAQUEOUS ELECTROLYTE ELEMENT, ELECTROLYTE STABILIZING AGENT, PHOSPHAZENE DERIVATIVE, AND PROCESS FOR PREPARING THE SAME |
EP1414096A4 (en) * | 2001-07-05 | 2005-03-09 | Bridgestone Corp | POLYMER ELEMENT AND POLYMER ELECTROLYTE |
EP1414097A1 (en) * | 2001-07-05 | 2004-04-28 | Bridgestone Corporation | Non-aqueous electrolyte cell, electrolyte stabilizing agent, and phosphazene derivative and method for preparation thereof |
EP1414096A1 (en) * | 2001-07-05 | 2004-04-28 | Bridgestone Corporation | Polymer cell and polymer electrolyte |
US7560595B2 (en) | 2001-07-05 | 2009-07-14 | Bridgestone Corporation | Non-aqueous electrolyte cell, electrolyte stabilizing agent, and phosphazene derivative and method for preparation thereof |
US8168831B2 (en) | 2001-07-05 | 2012-05-01 | Bridgestone Corporation | Non-aqueous electrolyte cell, electrode stabilizing agent, phosphazene derivative and method of producing the same |
EP1443578A1 (en) * | 2001-11-07 | 2004-08-04 | Bridgestone Corporation | Non-aqueous electrolyte primary cell and additive for non-aqueous electrolyte of the cell |
WO2003041197A1 (en) | 2001-11-07 | 2003-05-15 | Bridgestone Corporation | Non-aqueous electrolyte primary cell and additive for non-aqueous electrolyte of the cell |
EP1443578A4 (en) * | 2001-11-07 | 2006-09-27 | Bridgestone Corp | NONAQUEOUS ELECTROLYTE PRIMARY CELL AND ADDITIVE FOR NONAQUEOUS ELECTROLYTE OF SAID CELL |
WO2004059671A1 (ja) * | 2002-12-26 | 2004-07-15 | Bridgestone Corporation | 電気二重層キャパシタの非水電解液用添加剤及び非水電解液電気二重層キャパシタ |
Also Published As
Publication number | Publication date |
---|---|
DE60043266D1 (de) | 2009-12-17 |
EP1253662B1 (en) | 2009-11-04 |
KR20020053882A (ko) | 2002-07-05 |
EP1253662A4 (en) | 2006-11-02 |
US6955867B1 (en) | 2005-10-18 |
KR100775566B1 (ko) | 2007-11-09 |
EP1253662A1 (en) | 2002-10-30 |
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