WO2009157261A1 - 難燃剤含有非水系二次電池 - Google Patents
難燃剤含有非水系二次電池 Download PDFInfo
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- WO2009157261A1 WO2009157261A1 PCT/JP2009/059086 JP2009059086W WO2009157261A1 WO 2009157261 A1 WO2009157261 A1 WO 2009157261A1 JP 2009059086 W JP2009059086 W JP 2009059086W WO 2009157261 A1 WO2009157261 A1 WO 2009157261A1
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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
- H01M10/05—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
- H01M10/0569—Liquid materials characterised by the solvents
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/30—Arrangements for facilitating escape of gases
- H01M50/383—Flame arresting or ignition-preventing means
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/30—Arrangements for facilitating escape of gases
- H01M50/394—Gas-pervious parts or elements
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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 flame retardant-containing non-aqueous secondary battery. More specifically, the present invention relates to a flame retardant-containing non-aqueous secondary battery that has the same battery performance as that of the prior art and is superior to the conventional safety.
- Non-aqueous secondary battery a secondary battery using a non-aqueous electrolyte such as a lithium ion secondary battery (hereinafter referred to as a non-aqueous secondary battery).
- a non-aqueous electrolyte is used for the lithium ion secondary battery, and the non-aqueous electrolyte is composed of an electrolyte salt such as a lithium salt and a non-aqueous solvent.
- Non-aqueous solvents are required to have a high dielectric constant, a high oxidation potential, and stability in a battery, regardless of the operating environment.
- an aprotic solvent is used as such a non-aqueous solvent.
- cyclic carbonates such as ethylene carbonate and propylene carbonate
- high dielectric constant solvents such as cyclic carboxylic acid esters such as ⁇ -butyllactone
- diethyl Low-viscosity solvents such as chain carbonates such as carbonate and dimethyl carbonate and ethers such as dimethoxyethane are known.
- a high dielectric constant solvent and a low viscosity solvent are used in combination.
- the non-aqueous electrolyte may leak due to an abnormality such as an increase in internal pressure due to damage to the battery or some other cause.
- the leaked non-aqueous electrolyte may ignite or burn due to a short circuit between the positive electrode and the negative electrode constituting the lithium ion secondary battery.
- the non-aqueous solvent based on the organic solvent may vaporize and / or decompose to generate gas due to heat generation of the lithium ion secondary battery.
- the generated gas has a problem that it ignites or ruptures the lithium ion secondary battery.
- researches are being made to add flame retardants to non-aqueous electrolytes to impart flame retardancy.
- Patent Document 1 Japanese Patent Application Laid-Open No. 6-13108
- Patent Document 2 Japanese Patent Application Laid-Open No. 2002-25615
- Patent Document 3 Japanese Translation of PCT International Publication No. 2001-525597
- Patent Document 4 Japanese Patent Laid-Open No. 11-329495
- phosphazene derivatives have been proposed in JP-A-6-13108 and JP-A-2002-25615
- azobis (isobutyronitrile) (AIBN) in JP-T-2001-525597.
- An imidazole compound is proposed in Japanese Patent Application Laid-Open No. 11-329495.
- JP-A-6-13108 Japanese Patent Laid-Open No. 2002-25615 JP 2001-5255597 A Japanese Patent Laid-Open No. 11-329495
- phosphazene derivatives exhibit excellent flame retardancy, the operation of lithium ion secondary batteries at high temperatures is expected to become unstable depending on the type of non-aqueous solvent used and the combination ratio with the non-aqueous solvent. .
- a lithium ion secondary battery generates heat for some reason, a thermal decomposition reaction occurs at the interface between the negative electrode or the positive electrode and the electrolytic solution, and this reaction causes thermal runaway, resulting in the explosion of the lithium ion secondary battery. Or it may ignite. This phenomenon can occur even when a phosphazene derivative is blended.
- characteristics such as cycle characteristics and operational environment stability may be deteriorated.
- a phosphazene derivative is used at a high content of 40% by volume with respect to a non-aqueous solvent. Since the phosphazene derivative has a relatively high viscosity and a low dielectric constant, when the content is high, the conductivity of the non-aqueous electrolyte solution is lowered, and there is a concern that the battery performance may deteriorate due to the decrease. Furthermore, AIBN has a low solubility in non-aqueous solvents, mainly aprotic solvents, and the content cannot be increased, so that flame retardancy may not be sufficiently improved.
- AIBN may be electrolyzed by charging / discharging of a lithium ion secondary battery, and there is a concern about deterioration of battery performance.
- an imidazole compound in the case of an imidazole compound, sufficient flame retardancy cannot be obtained unless the addition amount is increased, and if the addition amount is increased, there is a concern that the cycle characteristics and the operating environment stability are deteriorated. Therefore, further improvement in flame retardancy is desired without deteriorating battery performance.
- the inventors of the present invention have made extensive studies on flame retardants for non-aqueous secondary batteries. As a result, it is sufficient for a battery to contain a cyclic compound containing a nitrogen-nitrogen unsaturated bond in the molecule in the non-aqueous electrolyte. Surprisingly, it was found that the flame retardancy can be exhibited, and the present invention has been achieved. As a result that sufficient flame retardancy can be exhibited, it becomes possible to ensure safety and reliability during abnormal heating of the non-aqueous secondary battery. Furthermore, since this flame retardant does not affect the electrical characteristics of the non-aqueous secondary battery even in a wide temperature range, it is possible to provide a non-aqueous secondary battery exhibiting stable cycle characteristics.
- a positive electrode, a negative electrode, and a non-aqueous electrolyte are provided, and the non-aqueous electrolyte is represented by the general formula (1).
- a non-aqueous secondary battery characterized by containing at least a compound is provided. Furthermore, according to this invention, the flame retardant for non-aqueous secondary batteries which consists of said cyclic nitrogen containing compound is provided.
- a non-aqueous secondary battery by including in the non-aqueous electrolyte a cyclic compound containing a nitrogen-nitrogen unsaturated bond in the molecule.
- this cyclic compound has little influence on electrical characteristics such as cycle characteristics of a non-aqueous secondary battery. Therefore, a non-aqueous secondary battery with improved safety and reliability can be provided.
- the flame retardant for non-aqueous secondary batteries which can improve the safety
- the non-aqueous secondary battery of the present invention includes a positive electrode, a negative electrode, and a non-aqueous electrolyte, and the non-aqueous electrolyte contains at least a cyclic nitrogen-containing compound having a structure of the following general formula (1).
- the mechanism by which the cyclic nitrogen-containing compound used as a flame retardant in the present invention exhibits flame retardancy is decomposed by heat at the time of thermal runaway (generation of fire) of a non-aqueous secondary battery, and nitrogen (N 2 ) gas is removed.
- the inventor believes that this is a mechanism that extinguishes the source of fire by reducing the surrounding oxygen concentration (suffocation extinction). In order to realize such a mechanism, it is essential that the cyclic nitrogen-containing compound has a double bond (azo bond) between nitrogen atoms.
- the cyclic nitrogen-containing compound used in the present invention has the general formula (1)
- the divalent group derived from a chain saturated hydrocarbon there are a linear group and a branched group.
- the linear divalent group include a methylene group, an ethylene group, a trimethylene group, a tetraethylene group, and a pentaethylene group.
- the branched divalent group include a methylmethylene group, an ethylmethylene group, a methylethylene group, an ethylethylene group, a methyltrimethylene group, an ethyltrimethylene group, and a methyltetramethylene group.
- These divalent groups are preferably linear groups. By being a linear group, better flame retardancy can be obtained, and there is an advantage that synthesis is easy.
- a 1 and A 2 are the same or different and are a methylene group which may have a substituent, ⁇ C ⁇ O or ⁇ SO 2 .
- substituent of the methylene group include a halogen atom, a lower alkyl group, a lower alkoxy group, an ester group, a cycloalkyl group which may have a substituent, or an aryl group which may have a substituent.
- a 2 is a methylene group
- the cyclic nitrogen-containing compound is specifically represented by the general formula (2)
- X and A 1 are the same as those in the general formula (1).
- R 1 and R 2 are the same or different and are a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, an ester group, an optionally substituted cycloalkyl group or an optionally substituted aryl. It is a group.
- a 2 in the general formula (2) is also a methylene group, the cyclic nitrogen-containing compound is represented by the general formula (3)
- X, R 1 and R 2 are the same as those in the general formula (2).
- R 3 and R 4 are the same or different and are a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, an ester group, an optionally substituted cycloalkyl group or an optionally substituted aryl. It is a group.
- the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and the like. Among these, a chlorine atom or a fluorine atom is preferable, and a chlorine atom is particularly preferable.
- the lower alkyl group includes an alkyl group having 1 to 4 carbon atoms, and specifically includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, Examples thereof include a tert-butyl group.
- the lower alkoxy group includes an alkyl group having 1 to 4 carbon atoms bonded via a single terminal ether bond, and specifically includes a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, Examples thereof include an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.
- the ester group includes an alkyl group having 1 to 4 carbon atoms bonded through a single terminal ester bond.
- the cycloalkyl group includes a cycloalkyl group having 3 to 6 carbon atoms, and specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like.
- substituent of the cycloalkyl group include a halogen atom such as a chlorine atom and a fluorine atom, and a lower alkyl group having 1 to 4 carbon atoms.
- Examples of the aryl group include a phenyl group and a naphthyl group.
- Examples of the substituent for the aryl group include a halogen atom such as a chlorine atom and a fluorine atom, and a lower alkyl group having 1 to 4 carbon atoms.
- R 1 to R 4 are selected from a hydrogen atom, a chlorine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a cycloalkyl group from the viewpoint of achieving both high flame retardancy and battery performance. It is preferable to select.
- R 1 to R 4 are each a hydrogen atom, a chlorine atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a methyl ester group, an ethyl ester group, More preferably, it is selected from a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
- R 1 to R 4 are different types of substituents
- the positions of the substituents are not particularly limited.
- R 1 and R 2 may be the same substituent
- R 3 and R 4 may be the same substituent
- R 1 and R 2 are different substituents.
- the groups R 3 and R 4 may be different substituents.
- a mixture of structural isomers may be used.
- X is a divalent group derived from a chain-like saturated hydrocarbon
- the cyclic nitrogen-containing compound is represented by the general formula (4).
- n is an integer of 1 to 5
- R 1 to R 4 are the same as in the general formula (3).
- the cyclic nitrogen-containing compound can control the solubility with the aprotic solvent by controlling, for example, the types of R 1 to R 4 and the size of the ring. Therefore, the cyclic nitrogen-containing compound does not affect the electrical characteristics of the non-aqueous secondary battery at normal times, and it is possible to control thermal runaway by decomposing at an abnormal time and generating nitrogen gas.
- the solubility can be further increased by increasing the number of carbon atoms of R 1 to R 4 , using an aromatic group, or enlarging the ring, for example.
- the cyclic nitrogen-containing compound is selected from the above-mentioned types of atomic groups A 1 and A 2 , so that it does not affect the electrical characteristics of the non-aqueous secondary battery at normal times, and decomposes at the time of abnormality. Generation of gas makes it possible to control thermal runaway.
- a cyclic nitrogen-containing compound is a compound that generates nitrogen gas when heated to a temperature equal to or higher than the decomposition temperature.
- the decomposition temperature is preferably a temperature that is 100 ° C. or more higher than the environmental temperature at which a normal non-aqueous secondary battery is used. Specifically, the decomposition temperature is preferably 100 to 300 ° C., more preferably 140 to 250 ° C.
- the decomposition temperature can be controlled by controlling the ring size and substituent effect.
- a dibromo compound is cyclized with hydrazine, and a diaziridine derivative is used with a dehydrogenation catalyst (for example, tungstate, molybdate, nickelate, etc.)
- a dehydrogenation catalyst for example, tungstate, molybdate, nickelate, etc.
- a dibromo derivative can be easily obtained by converting a hydrogen group into a bromo group by a known method.
- the compound of the general formula (4) is obtained by cyclizing the diamine derivative in the presence of a dehydrogenation catalyst (for example, tungstate, molybdate, nickelate, etc.) as shown in the following formula, for example.
- a dehydrogenation catalyst for example, tungstate, molybdate, nickelate, etc.
- the diamine derivative can be easily obtained by converting the hydroxyl group in the diol derivative into an amino group by a known method.
- the nonaqueous electrolytic solution contains an electrolyte salt, a nonaqueous solvent, and optionally other additives.
- the cyclic nitrogen-containing compound can also function as a non-aqueous solvent. Therefore, other organic solvents may not be used as long as a non-aqueous electrolyte having sufficient characteristics can be obtained using only the above cyclic nitrogen-containing compound.
- the non-aqueous solvent is preferably a mixed solvent with other organic solvents.
- aprotic organic solvents can usually be used.
- the aprotic solvent is not particularly limited, and examples thereof include dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dipropyl carbonate, propylene carbonate, ethylene carbonate, butylene carbonate, ⁇ -butyllactone ( ⁇ -butyrolactone), and ⁇ -valero.
- These organic solvents can be used alone or in combination of two or more.
- the blending ratio of the nitrogen-containing cyclic compound is usually in the range of 1 to 60% (v / v), preferably in the range of 10 to 40% in terms of volume fraction in the non-aqueous electrolyte solution. If it is less than 1%, rupture and ignition of the nonaqueous secondary battery may not be sufficiently suppressed. On the other hand, if it exceeds 60%, the performance of the non-aqueous secondary battery may deteriorate in a low temperature environment.
- a lithium salt is usually used as the electrolyte salt.
- the lithium salt is not particularly limited as long as it is soluble in a non-aqueous solvent.
- LiClO 4 , LiCl, LiBF 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiN (SO 2 CF 3 ) 2 , LiC (SO 2 CF 3 ) 2 , lower aliphatic carboxylic acid, chloroborane lithium, 4-phenylborane Examples include lithium acid. These lithium salts can be used alone or in combination of two or more.
- the preferable addition amount of the electrolyte salt is preferably 0.1 to 3 mol, more preferably 0.5 to 2 mol, with respect to 1 kg of the non-aqueous solvent.
- Examples of other additives include conventionally known dehydrating agents and deoxidizing agents. Specifically, vinylene carbonate, fluoroethylene carbonate, trifluoropropylene carbonate, phenylethylene carbonate, succinic anhydride, glutaric anhydride, maleic anhydride, ethylene sulfite, 1,3-propane sultone, 1,4-butane sultone, Examples include methyl methanesulfonate, dibutyl sulfide, heptane, octane, and cycloheptane. When these are contained in a non-aqueous solvent at a concentration of usually 0.1 wt% or more and 5 wt% or less, capacity maintenance characteristics and cycle characteristics after high-temperature storage can be improved.
- the positive electrode can be produced, for example, by applying, drying, and pressing a paste containing a positive electrode active material, a conductive material, a binder, and an organic solvent on the positive electrode current collector.
- the compounding amount of the positive electrode active material, the conductive material, the binder and the organic solvent is 1 to 20 parts by weight of the conductive material, 1 to 15 parts by weight of the binder and 1 to 15 parts by weight of the organic solvent when the positive electrode active material is 100 parts by weight. It can be 30 to 60 parts by weight.
- the positive electrode active material examples include LiNiO 2 , LiCoO 2 , LiMn 2 O 4 lithium composite oxide, and some elements in these oxides other elements (eg, Fe, Si, Mo, Cu, Zn, etc.) ) Can be used.
- Examples of the conductive material include carbonaceous materials such as acetylene black and ketjen black.
- the binder include polyvinylidene fluoride (PVdF), polyvinyl pyridine, and polytetrafluoroethylene.
- Examples of the organic solvent include N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF) and the like.
- Examples of the positive electrode current collector include foils and thin plates of conductive metal such as SUS and aluminum.
- the negative electrode can be produced, for example, by applying, drying, and pressing a paste containing a negative electrode active material, a conductive material, a binder, and an organic solvent on the negative electrode current collector.
- the compounding amount of the negative electrode active material, the conductive material, the binder and the organic solvent is such that the negative electrode active material is 100 parts by weight, the conductive material is 1 to 15 parts by weight, the binder is 1 to 10 parts by weight, and the organic solvent is The amount can be 40 to 70 parts by weight.
- the negative electrode active material include pyrolytic carbons, cokes, graphites, glassy carbons, organic polymer compound sintered bodies, carbon fibers, activated carbon, and the like.
- Examples of the conductive material include carbonaceous materials such as acetylene black and ketjen black.
- the binder include polyvinylidene fluoride, polyvinyl pyridine, and polytetrafluoroethylene.
- Examples of the organic solvent include N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF) and the like.
- Examples of the negative electrode current collector include a metal foil such as copper.
- a separator is interposed between the negative electrode and the positive electrode.
- the separator is usually made of a porous film, and the material is selected in consideration of solvent resistance and reduction resistance.
- a porous film or a nonwoven fabric made of a polyolefin resin such as polyethylene or polypropylene is suitable.
- a material made of such a material can be used as a single layer or a plurality of layers. In the case of a plurality of layers, it is preferable to use at least one nonwoven fabric from the viewpoints of cycle characteristics, low temperature performance, load characteristics, and the like.
- a non-aqueous secondary battery can be obtained by arbitrarily sandwiching a separator between the negative electrode and the positive electrode and injecting a non-aqueous electrolyte. Alternatively, a plurality of one unit may be stacked with this non-aqueous secondary battery as one unit.
- the form of the non-aqueous secondary battery is not particularly limited, and various forms such as a button type, a coin type, a square type, a spiral type cylindrical type, and a laminated type battery may be mentioned. Accordingly, various sizes such as a thin shape and a large size can be obtained.
- Compound (in general formula (3), R 1 to R 4 are methyl groups, and X is a hydrocarbon group having 2 carbon atoms (ethylene group) (non-aqueous secondary battery flame retardant, 3, 20 ml of 3,6,6-tetramethyl-3,4,5,6-tetrahydropyridazine (decomposition temperature 146 ° C.) was added to the resulting mixed solvent, and 1.0 mol / kg of LiPF 6 as a lithium salt.
- a non-aqueous electrolyte was prepared by dissolving at a concentration of 1 to 5%
- a positive electrode forming paste was prepared.
- the produced paste was uniformly coated on both surfaces of a 20 ⁇ m-thick strip-shaped aluminum foil as a positive electrode current collector using a coating apparatus.
- the uncoated part for terminal connection was set to the edge part of aluminum foil.
- the coating film was dried under reduced pressure at 130 ° C. for 8 hours to remove the solvent, and then pressed using a hydraulic press to form a positive electrode plate.
- the obtained positive electrode plate was cut into a predetermined size and used.
- the obtained negative electrode plate was cut into a predetermined size and used.
- the obtained positive electrode plate and negative electrode plate were laminated via a polypropylene porous film as a separator, and then the non-aqueous electrolyte was injected into the laminate to produce a non-aqueous secondary battery. .
- Example 2 A nonaqueous secondary battery was produced in the same manner as in Example 1, except that the amount of the mixed solvent of ethylene carbonate and diethylene carbonate was 1 ml and the amount of the cyclic nitrogen-containing compound was 99 ml.
- Example 3 A nonaqueous secondary battery was produced in the same manner as in Example 1 except that the amount of the mixed solvent of ethylene carbonate and diethylene carbonate was 40 ml and the amount of the cyclic nitrogen-containing compound was 60 ml.
- Example 4 As the cyclic nitrogen-containing compound, a 6-membered ring compound is obtained by replacing X in the general formula (3) with a hydrocarbon group having 1 carbon atom (methylene group) and two of R 1 to R 4 are hydrogen atoms, The same as in Example 1, except that a 5-membered ring compound represented by the following formula (Chemical Formula 9) in which two are chlorine atoms (dichloro-4,5-dihydro-3H-pyrazole: decomposition temperature 179 ° C.) was used. A non-aqueous secondary battery was produced.
- a 5-membered ring compound represented by the following formula (Chemical Formula 9) in which two are chlorine atoms (dichloro-4,5-dihydro-3H-pyrazole: decomposition temperature 179 ° C.) was used.
- a non-aqueous secondary battery was produced.
- the 5-membered ring compounds are compounds in which R 1 and R 3 are hydrogen atoms and R 2 and R 4 are chlorine atoms, and compounds in which R 1 and R 4 are hydrogen atoms and R 2 and R 3 are chlorine atoms. A mixture of was used.
- a 6-membered ring compound is represented by the following formula (X) wherein X is a hydrocarbon group having 5 carbon atoms (pentamethylene group) and R 1 to R 4 are hydrogen atoms.
- X is a hydrocarbon group having 5 carbon atoms (pentamethylene group) and R 1 to R 4 are hydrogen atoms.
- a cyclic nitrogen-containing compound represented by the following formula (Formula 11) (in the general formula (1), X is an oxygen atom, A 1 and A 2 are carbon atoms, and R 1 to R 4 are methyl groups. Except for the 5-membered ring compound (2,2,5,5-tetramethyl-1,3,4-oxadiazoline: decomposition temperature 127 ° C.) that is a non-aqueous secondary compound as in Example 1. A battery was produced.
- Example 7 As the cyclic nitrogen-containing compound, a cyclic nitrogen-containing compound represented by the following formula (Chemical Formula 12) (in the general formula (3), X is ⁇ C ⁇ O, and R 1 to R 4 are methyl groups ( 3,3,5,5-tetramethyl-1-pyrazol-4-one: decomposition temperature was changed to 141 ° C.), and a nonaqueous secondary battery was produced in the same manner as in Example 1.
- a cyclic nitrogen-containing compound represented by the following formula (Chemical Formula 12) in the general formula (3), X is ⁇ C ⁇ O, and R 1 to R 4 are methyl groups ( 3,3,5,5-tetramethyl-1-pyrazol-4-one: decomposition temperature was changed to 141 ° C.), and a nonaqueous secondary battery was produced in the same manner as in Example 1.
- Example 1 except that the 5-membered cyclic compound (4,4-dimethyl-4,5-dihydro- [1,2,3] thiadiazole-1,1-dioxide: decomposition temperature 162 ° C.) was used. Similarly, a non-aqueous secondary battery was produced.
- a 6-membered ring compound is represented by the following formula (Formula 15) in which X is a hydrocarbon group having 6 carbon atoms and R 1 to R 4 are hydrogen atoms in the general formula (3).
- a non-aqueous two-component system was used in the same manner as in Example 1 except that it was replaced with a 10-membered ring compound (3,4,5,6,7,8,9,10-octahydro- [1,2] diaphonen: decomposition temperature 206 ° C.)
- a secondary battery was produced.
- Example 2 A nonaqueous secondary battery was produced in the same manner as in Example 1 except that no cyclic nitrogen-containing compound was used.
- Comparative Example 3 A nonaqueous two-component system was used in the same manner as in Example 1 except that the amount of the mixed solvent of ethylene carbonate and diethylene carbonate was 98 ml, and azobisisobutyronitrile (AIBN) was 2 ml instead of the cyclic nitrogen-containing compound.
- AIBN azobisisobutyronitrile
- the initial discharge capacity at 20 ° C. and 60 ° C. the measurement of the discharge capacity retention rate, and the nail penetration test as a safety test are as follows: The procedure was performed. (1) Measurement of initial discharge capacity at 20 ° C. After charging a non-aqueous secondary battery until it reaches 4.2 V at a 0.1 CmA rate, it discharges at a 0.1 CmA rate until the voltage reaches 3.0 V The capacity when discharged is the initial discharge capacity (mAh / g). The measurement is carried out in a constant temperature chamber at 20 ° C.
- the total charge / discharge cycle is performed 500 times, and the capacity when one charge / discharge cycle is performed under the same charge / discharge conditions as the initial discharge capacity is obtained.
- the discharge capacity maintenance rates (%) for the 100th and 500th times are the ratios of the 100th discharge capacity to the initial discharge capacity and the 500th discharge capacity to the initial discharge capacity, respectively.
- the measurement is carried out in a constant temperature chamber at 20 ° C.
- a general nonaqueous secondary battery (Comparative Example 2) that uses a general organic solvent as a nonaqueous solvent and does not contain a flame retardant generates smoke and ignition in the nail penetration test.
- the nonaqueous secondary batteries (Examples 1 to 9) in which the cyclic nitrogen-containing compound was added to the nonaqueous solvent, no abnormality such as smoke or ignition occurred even in the nail penetration test. Further, regarding the battery performance, the non-aqueous secondary batteries of Examples 1 to 9 are not inferior to the general non-aqueous secondary battery of Comparative Example 2.
- the non-aqueous secondary battery of Comparative Example 1 using a cyclic nitrogen-containing compound having a 10-membered ring compound did not cause abnormalities such as smoke and ignition in the nail penetration test as in Examples 1 to 9. .
- the battery performance is inferior compared with the general non-aqueous secondary battery of Comparative Example 2.
- the battery performance of Comparative Example 1 when heated to 60 ° C. is significantly inferior to Examples 1-5.
- Comparative Example 3 the non-aqueous secondary battery using AIBN shows deterioration in cycle characteristics due to the electrolysis of AIBN during charging / discharging at 20 ° C., and due to the thermal decomposition of AIBN during charging / discharging at 60 ° C. Stable electrical characteristics are not obtained. Furthermore, Comparative Examples 3 and 4 produced smoke and fire in the nail penetration test. Therefore, in a non-aqueous secondary battery using a known flame retardant such as AIBN or an imidazole compound, flame retardance at the time of abnormality cannot be secured while preventing deterioration of battery performance during charging and discharging.
- a known flame retardant such as AIBN or an imidazole compound
- Example 4 the diol derivative was 1,3-dichloropropane-1,3-diol, for Example 5, heptane-1,7-diol, and for Comparative Example 1, octane-1,8- A cyclic nitrogen-containing compound (Example 4: dichloro-4,5-dihydro-3H-pyrazole, Example 5: 4, 5, 6, 7) , 8,9-hexahydro-3H- [1,2] diazonine, Comparative Example 1: 3,4,5,6,7,8,9,10-octahydro- [1,2] diazecine).
- Example 7 (Synthesis of cyclic nitrogen-containing compounds of Examples 7 to 9)
- the starting material was 2,4-dimethyl-3-pentanone, for Example 8, methanedisulfonyl dichloride, for Example 9, 2-chloro-2-methylpropanesulfonyl chloride,
- a cyclic nitrogen-containing compound is obtained in the same manner as in Example 6 except that each is changed.
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Abstract
Description
リチウムイオン二次電池には、非水電解液が使用され、非水電解液は、リチウム塩のような電解質塩と、非水系溶媒とから構成されている。非水系溶媒には、動作環境によらず、高い誘電率を有すること、酸化電位が高いこと、電池中で安定であること等が要求されている。
具体的には、難燃剤として、特開平6-13108号公報及び特開2002-25615号公報ではホスファゼン誘導体が提案され、特表2001-525597号公報ではアゾビス(イソブチロニトリル)(AIBN)が提案され、特開平11-329495号公報ではイミダゾール系化合物が提案されている。
更に、AIBNは、非プロトン性溶媒を主とする非水系溶媒に対して溶解度が低く、含有量を増やすことができないため、難燃性を十分向上できないことがある。更に、AIBNは、リチウムイオン二次電池の充放電により電気分解することがあり、電池性能の悪化が懸念される。
また、イミダゾール系化合物においても、添加量を多くしないと十分な難燃性が得られず、添加量を多くすると、サイクル特性、動作環境安定性の悪化が懸念される。
従って、電池性能を悪化させることなく、更なる難燃性の向上が望まれている。
更に、本発明によれば、上記環状窒素含有化合物からなる非水系二次電池用難燃剤が提供される。
また、上記作用により非水系二次電池の安全性、信頼性を向上しうる非水系二次電池用難燃剤を提供できる。
本発明で難燃剤として使用される環状窒素含有化合物が難燃性を示す機構は、非水系二次電池の熱暴走(火元が発生する)時に熱により分解し、窒素(N2)ガスを発生し、その結果、周囲の酸素濃度を低下させることにより火元を消す(窒息消火)機構であると発明者は考えている。そのような機構を実現するために、環状窒素含有化合物は、窒素原子同士の二重結合(アゾ結合)を有することが必須である。
式中、Xは、炭素数1~5の分岐していてもよい鎖状の飽和炭化水素由来の二価の基、=C=CH2、=C=O、=C=S=O、=O又は=Sである。これら置換基からXを選択することで、難燃性と電池性能をより高度に両立できる。
メチレン基の置換基としては、ハロゲン原子、低級アルキル基、低級アルコキシ基、エステル基、置換基を有してもよいシクロアルキル基又は置換基を有してもよいアリール基が挙げられる。A2がメチレン基の場合、環状窒素含有化合物は、具体的には、一般式(2)
式中、X及びA1は、一般式(1)と同じである。
R1及びR2は、同一又は異なって、水素原子、ハロゲン原子、低級アルキル基、低級アルコキシ基、エステル基、置換基を有してもよいシクロアルキル基又は置換基を有してもよいアリール基である。
一般式(2)中のA2もメチレン基の場合、環状窒素含有化合物は、一般式(3)
式中、X、R1及びR2は、一般式(2)と同じである。
R3及びR4は、同一又は異なって、水素原子、ハロゲン原子、低級アルキル基、低級アルコキシ基、エステル基、置換基を有してもよいシクロアルキル基又は置換基を有してもよいアリール基である。
ハロゲン原子には、フッ素原子、塩素原子、臭素原子等が含まれる。この内、塩素原子又はフッ素原子が好ましく、特に好ましくは、塩素原子である。
低級アルキル基には、炭素数1~4のアルキル基が含まれ、具体的には、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基等が挙げられる。
エステル基には、単一の末端エステル結合を介して結合された炭素数1~4のアルキル基が含まれる。
シクロアルキル基には、炭素数3~6のシクロアルキル基が含まれ、具体的には、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等が挙げられる。シクロアルキル基の置換基としては、塩素原子、フッ素原子等のハロゲン原子、炭素数1~4の低級アルキル基等が挙げられる。
上記R1~R4は、難燃性と電池性能を高度に両立させる観点から、水素原子、塩素原子及び炭素数1~4のアルキル基、炭素数1~4のアルコキシ基、シクロアルキル基から選択することが好ましい。更に、難燃性と電池性能をより高度に両立させる観点から、R1~R4は、水素原子、塩素原子、メチル基、エチル基、メトキシ基、エトキシ基、メチルエステル基、エチルエステル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基から選択することがより好ましい。
なお、Xが鎖状の飽和炭化水素由来の二価の基である場合、環状窒素含有化合物は、一般式(4)
更に、環状窒素含有化合物は、例えば、R1~R4の種類、環の大きさを制御することで、非プロトン性溶媒と溶解性を制御できる。そのため、環状窒素含有化合物は、通常時に非水系二次電池の電気特性に影響を及ぼさず、かつ、異常時に分解して窒素ガスを発生することで熱暴走を制御することが可能になる。なお、溶解性は、例えば、R1~R4の炭素数を多くしたり、芳香族系の基を使用したり、環を大きくしたりすることで、より高めることができる。更に、Xとして、=C=CH2、=C=O、=C=S=O、=O又は=Sを選択することで、非水溶媒への溶解性を高めることもできる。
環状窒素含有化合物は、分解温度以上の加熱で、窒素ガスを生じる化合物である。分解温度は、通常の非水系二次電池を使用する環境温度よりも100℃以上高い温度であることが好ましく、具体的には、100~300℃が好ましく、140~250℃がより好ましい。分解温度と通常の環境温度との差が100℃未満の場合、通常の使用時に環状窒素含有化合物が分解することがあり、その場合には非水系二次電池の電気特性が低下することになる。ここで、分解温度の制御は、環の大きさ、置換基効果の制御により、制御可能となる。
また、一般式(4)の化合物は、例えば、下記式のように、脱水素触媒(例えば、タングステン酸塩、モリブデン酸塩、ニッケル酸塩等)の存在下で、ジアミン誘導体を環化することで得ることができる。
非水電解液は、電解質塩と、非水系溶媒と、任意に他の添加剤とを含んでいる。上記環状窒素含有化合物は、非水系溶媒としても機能させることができる。従って、上記環状窒素含有化合物のみで十分な特性の非水電解液を得ることができるのであれば、他の有機溶媒を使用しなくてもよい。しかしながら、非水系二次電池の充放電特性、耐低温性等を向上させる観点から、非水系溶媒は、他の有機溶媒との混合溶媒とすることが好ましい。
電解質塩としては、通常リチウム塩が使用される。リチウム塩としては、非水系溶媒に溶解するものであれば特に限定されない。例えば、LiClO4、LiCl、LiBF4、LiPF6、LiAsF6、LiSbF6、LiN(SO2CF3)2、LiC(SO2CF3)2、低級脂肪族カルボン酸、クロロボランリチウム、4-フェニルホウ酸リチウム等が挙げられる。これらのリチウム塩は、1種又は2種以上組み合わせて使用できる。電解質塩の好ましい添加量は、非水系溶媒1Kgに対して、0.1~3モルが好ましく、0.5~2モルがより好ましい。
正極活物質としては、例えば、LiNiO2、LiCoO2、LiMn2O4のリチウム複合酸化物、及びこれら酸化物中の一部の元素を他元素(例えば、Fe、Si、Mo、Cu及びZn等)で置換した化合物を用いることができる。
結着剤としては、例えば、ポリフッ化ビニリデン(PVdF)、ポリビニルピリジンや、ポリテトラフルオロエチレン等が挙げられる。
有機溶剤としては、例えば、N-メチル-2-ピロリドン(NMP)、N,N-ジメチルホルムアミド(DMF)等が挙げられる。
正極集電体としては、例えば、SUS、アルミニウム等の導電性金属の箔や薄板が挙げられる。
負極活物質としては、例えば、熱分解炭素類、コークス類、黒鉛類、ガラス状炭素類、有機高分子化合物焼結体、炭素繊維、活性炭等が挙げられる。
結着剤としては、例えば、ポリフッ化ビニリデン、ポリビニルピリジンやポリテトラフルオロエチレン等が挙げられる。
有機溶剤としては、例えば、N-メチル-2-ピロリドン(NMP)、N,N-ジメチルホルムアミド(DMF)等が挙げられる。
負極集電体としては、例えば、銅のような金属の箔が挙げられる。
セパレータは、通常多孔質フィルムよりなり、耐溶剤性や耐還元性を考慮して材質が選定される。例えば、ポリエチレン、ポリプロピレン等のポリオレフィン樹脂からなる多孔質フィルムあるいは不織布が好適である。このような材質からなるものを単層又は複数層にして用いることができる。複数層の場合は、サイクル特性、低温性能、負荷特性等の観点から少なくとも1枚は不織布を用いることが好ましい。
負極と正極間に、任意にセパレータを挟み、非水電解液を注入することで非水系二次電池が得られる。また、この非水系二次電池を一単位として、一単位を複数積層してもよい。
また、非水系二次電池の形態としては、特に制限されず、ボタン型、コイン型、角型、スパイラル構造の円筒型、ラミネート型電池等の種々の形態が挙げられ、これらは、その用途に応じて、薄型、大型等の種々の大きさにすることができる。
(実施例1)
エチレンカーボネートとジエチレンカーボネートとの混合溶媒(混合比(体積比):エチレンカーボネート/ジエチレンカーボネート=1/2)(非プロトン性有機溶媒)80mlに、下記式(化8)で表される環状窒素含有化合物(一般式(3)において、R1~R4がメチル基、Xが、炭素数2の炭化水素基(エチレン基)である6員環化合物(非水系二次電池用難燃剤、3,3,6,6-テトラメチル-3,4,5,6-テトラヒドロピリダジン:分解温度146℃)20mlを添加した。得られた混合溶媒に、リチウム塩として、LiPF6を1.0モル/kgの濃度で溶解させ、非水電解液を調製した。
得られた正極板と負極板とを、セパレータとしてのポリプロピレンの多孔質フィルムを介して積層し、次いで、積層体に前記非水電解液を注液することで、非水系二次電池を作製した。
エチレンカーボネートとジエチレンカーボネートとの混合溶媒の使用量を1mlとし、環状窒素含有化合物の使用量を99mlとしたほかは、実施例1と同様に非水系二次電池を作製した。
(実施例3)
エチレンカーボネートとジエチレンカーボネートとの混合溶媒の使用量を40mlとし、環状窒素含有化合物の使用量を60mlとしたほかは、実施例1と同様に非水系二次電池を作製した。
環状窒素含有化合物として、6員環化合物を、一般式(3)においてXが炭素数1の炭化水素基(メチレン基)でありかつR1~R4の内、2つが水素原子であって、2つが塩素原子である下記式(化9)で表される5員環化合物(ジクロロ-4,5-ジヒドロ-3H-ピラゾール:分解温度179℃)に代えたほかは、実施例1と同様に非水系二次電池を作製した。なお、5員環化合物は、R1とR3が水素原子かつR2とR4が塩素原子である化合物と、R1とR4が水素原子かつR2とR3が塩素原子である化合物の混合物を使用した。
環状窒素含有化合物として、6員環化合物を、一般式(3)においてXが炭素数5の炭化水素基(ペンタメチレン基)でありかつR1~R4が水素原子である下記式(化10)で表される9員環化合物(4,5,6,7,8,9-ヘキサヒドロ-3H-[1,2]ジアゾニン:分解温度192℃)に代えたほかは、実施例1と同様に非水系二次電池を作製した。
環状窒素含有化合物として、下記式(化11)で表される環状窒素含有化合物(一般式(1)において、Xが酸素原子、A1、A2が炭素原子、R1~R4がメチル基である5員環化合物(2,2,5,5-テトラメチル-1,3,4-オキサジアゾリン:分解温度127℃))に代えたほかは、実施例1と同様に非水系二次電池を作製した。
環状窒素含有化合物として、下記式(化12)で表される環状窒素含有化合物(一般式(3)において、Xが=C=O、R1~R4がメチル基である5員環化合物(3,3,5,5-テトラメチル-1-ピラゾール-4-オン:分解温度141℃))に代えたほかは、実施例1と同様に非水系二次電池を作製した。
環状窒素含有化合物として、下記式(化13)で表される環状窒素含有化合物(一般式(1)において、Xがメチレン基、A1及びA2が=SO2である5員環環状化合物([1,4,2,3]ジチアジアゾール-1,1,4,4-テトラオキサイド:分解温度187℃))に代えたほかは、実施例1と同様に非水系二次電池を作製した。
環状窒素含有化合物として、下記式(化14)で表される環状窒素含有化合物(一般式(2)において、Xがメチレン基、A1が=SO2、R1及びR2がメチル基である5員環環状化合物(4,4-ジメチル-4,5-ジヒドロ-[1,2,3]チアジアゾール-1,1-ジオキサイド:分解温度162℃))に代えたほかは、実施例1と同様に非水系二次電池を作製した。
環状窒素含有化合物として、6員環化合物を、一般式(3)においてXが炭素数6の炭化水素基でありかつR1~R4が水素原子である下記式(化15)で表される10員環化合物(3,4,5,6,7,8,9,10-オクタヒドロ-[1,2]ジアゼシン:分解温度206℃)に代えたほかは、実施例1と同様に非水系二次電池を作製した。
環状窒素含有化合物を使用しないことのほかは、実施例1と同様に非水系二次電池を作製した。
(比較例3)
エチレンカーボネートとジエチレンカーボネートとの混合溶媒の使用量を98mlとし、環状窒素含有化合物に代えてアゾビスイソブチロニトリル(AIBN)を2mlとしたことのほかは、実施例1と同様に非水系二次電池を作製した。
(比較例4)
エチレンカーボネートとジエチレンカーボネートとの混合溶媒の使用量を90mlとし、環状窒素含有化合物に代えて1-エチル-3-メチルイミダゾリウム/6フッ化リン酸アニオン(EMI-HF)を10mlとしたことのほかは、実施例1と同様に非水系二次電池を作製した。
実施例1~9及び比較例1~4で得られた非水系二次電池について、20℃及び60℃における初回放電容量の測定、放電容量維持率の測定、安全性試験として釘刺し試験を以下の手順で行った。
(1)20℃における初回放電容量の測定
0.1CmAレートにて4.2Vになるまで非水系二次電池を充電した後、0.1CmAレートにて放電し、電圧が3.0Vになるまで放電したときの容量を初回放電容量(mAh/g)とする。なお、測定は、20℃一定の恒温器の中で実施する。
1CmAレートにて4.2Vになるまで非水系二次電池を充電した後、1CmAレートにて電圧が3.0Vになるまで放電することを1サイクルとし、このサイクルを99回行い、100回目として、初回放電容量と同一の充放電条件で充放電を1サイクル行ったときの容量を求める。
100回目測定終了後、1CmAレートにて4.2Vになるまで非水系二次電池を充電した後、1CmAレートにて電圧が3.0Vになるまで放電することを1サイクルとし、このサイクルを399回行い、トータル充放電サイクル500回目として、初回放電容量と同一の充放電条件で充放電を1サイクル行ったときの容量を求める。
100回目、及び500回目の放電容量維持率(%)は、それぞれ、初回放電容量に対する100回目、及び、初回放電容量に対する500回目の放電容量の割合とする。なお、測定は、20℃一定の恒温器の中で実施する。
60℃における初回放電容量(mAh/g)及び放電容量維持率(%)は、恒温器の温度を60℃一定にすること以外は、20℃における初回放電容量及び放電容量維持率と同様にして測定した値とする。
釘刺し試験は、0.1CmAレートにて4.2Vになるまで充電した非水系二次電池に、室温20℃において、直径3mmの釘を速度1mm/sで貫通させた時の状態を確認する試験である。
試験結果を表1に示す。
また、10員環化合物を有する環状窒素含有化合物を用いた比較例1の非水系二次電池は、釘刺し試験において、実施例1~9と同様に発煙、発火のような異常が生じていない。しかし、電池性能が、比較例2の一般的な非水系二次電池と比較して、劣っている。特に、60℃に加温したときの比較例1の電池性能は、実施例1~5よりも顕著に劣っている。
以上のように、表1から、特定の構造の環状窒素含有化合物を非水電解液の難燃剤として使用することで、難燃性を向上できるだけなく、従来と同等程度の電気特性を備えた非水系二次電池が得られることが分かる。
実施例1~5及び比較例1の環状窒素含有化合物を以下の合成スキームで以下のようにして得た。
1H-NMR(ppm,CDCl3) δ;1.56(s,4H)、1.29(s,12H)
IR;ν(KBr)cm-1;2966,2893,1576,1303,1242,1131,1004,962
上記値から、得られた環状窒素含有化合物が、3,3,6,6-テトラメチル-3,4,5,6-テトラヒドロピリダジンであることが確認できた。
実施例6の環状窒素含有化合物を以下の合成スキームで以下のようにして得た。
撹拌機、滴下漏斗、冷却管を備えた3口フラスコ中を窒素雰囲気下にした後、無水ヒドラジン14.4g(0.45mol)及び無水エタノールをml加え、撹拌する。次に、ジブロモ誘導体129g(0.5mol)をゆっくりと滴下した。滴下終了後、約1時間還流した後、蒸留にてジアジリジン誘導体48.4g(収率82.7%)を得た。
1H-NMR(ppm,CDCl3) δ;1.37(s,12H)
IR;ν(KBr)cm-1;3081,1952,1390,1242,943,522
上記値から、得られた環状窒素含有化合物が、2,2,5,5-テトラメチル-1,3,4-オキサジアゾリンであることが確認できた。
実施例7については、出発原料を2,4-ジメチル-3-ペンタノンに、実施例8については、メタンジスルホニルジクロリドに、実施例9については、2-クロロ-2-メチルプロパンスルホニルクロリドに、それぞれ変更すること以外は、実施例6と同様にして、環状窒素含有化合物が得られる。
Claims (9)
- 前記環状窒素含有化合物が、前記非水電解液中に、1~60体積%で含まれる請求項1~4のいずれか1つに記載の非水系二次電池。
- 前記環状窒素含有化合物が、分解温度以上の加熱で、窒素ガスを生じる化合物である請求項1~5のいずれか1つに記載の非水系二次電池。
- 前記環状窒素含有化合物が、120~250℃の分解温度を有する化合物である請求項6に記載の非水系二次電池。
- 前記R1~R4が、メチル基又はフェニル基である請求項3~7のいずれか1つに記載の非水系二次電池。
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CN2009801245075A CN102077403B (zh) | 2008-06-25 | 2009-05-15 | 含有阻燃剂的非水二次电池 |
JP2010517816A JP5228045B2 (ja) | 2008-06-25 | 2009-05-15 | 難燃剤含有非水系二次電池 |
US13/001,351 US8420266B2 (en) | 2008-06-25 | 2009-05-15 | Flame retardant-containing nonaqueous secondary battery |
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JP (1) | JP5228045B2 (ja) |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013012350A (ja) * | 2011-06-28 | 2013-01-17 | Sharp Corp | 非水系二次電池及びその難燃剤 |
WO2013091413A1 (zh) * | 2011-12-21 | 2013-06-27 | 华为技术有限公司 | 一种锂离子电池电解液及含有该电解液的锂离子电池 |
WO2014123074A1 (ja) * | 2013-02-05 | 2014-08-14 | 富士フイルム株式会社 | 非水二次電池用電解液および非水二次電池、電解液用添加剤 |
JP2020510278A (ja) * | 2017-02-17 | 2020-04-02 | ヴェストファーレン ヴィルヘルム−ウニヴェルジテート ミュンスター | リチウムイオンバッテリーシステム用の電解質添加物 |
WO2020256373A1 (ko) | 2019-06-18 | 2020-12-24 | 주식회사 엘지화학 | 리튬 이차전지용 전해질 및 이를 포함하는 리튬 이차전지 |
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WO2016160703A1 (en) | 2015-03-27 | 2016-10-06 | Harrup Mason K | All-inorganic solvents for electrolytes |
US10355310B2 (en) * | 2015-05-28 | 2019-07-16 | Shenzhen Capchem Technology Co., Ltd. | Electrolyte compositions for electrochemical devices |
US10707531B1 (en) | 2016-09-27 | 2020-07-07 | New Dominion Enterprises Inc. | All-inorganic solvents for electrolytes |
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JP2002025615A (ja) | 2000-07-10 | 2002-01-25 | Toyota Central Res & Dev Lab Inc | リチウム二次電池 |
GB0406867D0 (en) * | 2004-03-26 | 2004-04-28 | F2G Ltd | Antifungal agents |
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- 2009-05-15 WO PCT/JP2009/059086 patent/WO2009157261A1/ja active Application Filing
- 2009-05-15 US US13/001,351 patent/US8420266B2/en not_active Expired - Fee Related
- 2009-05-15 JP JP2010517816A patent/JP5228045B2/ja not_active Expired - Fee Related
- 2009-05-15 CN CN2009801245075A patent/CN102077403B/zh not_active Expired - Fee Related
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JPH0613108A (ja) * | 1992-04-09 | 1994-01-21 | Bridgestone Corp | 非水電解質電池 |
JP2004331521A (ja) * | 2003-04-30 | 2004-11-25 | Toyo Kasei Kogyo Co Ltd | イオン性液体 |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013012350A (ja) * | 2011-06-28 | 2013-01-17 | Sharp Corp | 非水系二次電池及びその難燃剤 |
US9130245B2 (en) | 2011-06-28 | 2015-09-08 | Sharp Kabushiki Kaisha | Nonaqueous secondary battery and flame retardant for use in the same |
WO2013091413A1 (zh) * | 2011-12-21 | 2013-06-27 | 华为技术有限公司 | 一种锂离子电池电解液及含有该电解液的锂离子电池 |
WO2014123074A1 (ja) * | 2013-02-05 | 2014-08-14 | 富士フイルム株式会社 | 非水二次電池用電解液および非水二次電池、電解液用添加剤 |
JP2014154247A (ja) * | 2013-02-05 | 2014-08-25 | Fujifilm Corp | 非水二次電池用電解液および非水二次電池、電解液用添加剤 |
JP2020510278A (ja) * | 2017-02-17 | 2020-04-02 | ヴェストファーレン ヴィルヘルム−ウニヴェルジテート ミュンスター | リチウムイオンバッテリーシステム用の電解質添加物 |
JP7088565B2 (ja) | 2017-02-17 | 2022-06-21 | ヴェストファーレン ヴィルヘルム-ウニヴェルジテート ミュンスター | リチウムイオンバッテリーシステム用の電解質添加物 |
WO2020256373A1 (ko) | 2019-06-18 | 2020-12-24 | 주식회사 엘지화학 | 리튬 이차전지용 전해질 및 이를 포함하는 리튬 이차전지 |
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JP5228045B2 (ja) | 2013-07-03 |
CN102077403A (zh) | 2011-05-25 |
CN102077403B (zh) | 2013-06-19 |
US20110104565A1 (en) | 2011-05-05 |
JPWO2009157261A1 (ja) | 2011-12-08 |
US8420266B2 (en) | 2013-04-16 |
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