WO2016056361A1 - Électrolyte pour batterie secondaire, batterie secondaire, bloc-batterie, véhicule électrique, système d'accumulation d'énergie, outil électrique et équipement d'appreil électronique - Google Patents

Électrolyte pour batterie secondaire, batterie secondaire, bloc-batterie, véhicule électrique, système d'accumulation d'énergie, outil électrique et équipement d'appreil électronique Download PDF

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WO2016056361A1
WO2016056361A1 PCT/JP2015/076171 JP2015076171W WO2016056361A1 WO 2016056361 A1 WO2016056361 A1 WO 2016056361A1 JP 2015076171 W JP2015076171 W JP 2015076171W WO 2016056361 A1 WO2016056361 A1 WO 2016056361A1
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secondary battery
represented
hydrocarbon group
formula
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遼平 津田
窪田　忠彦
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ソニー株式会社
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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
    • 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
    • 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 technology relates to an electrolytic solution used for a secondary battery, a secondary battery using the electrolytic solution, a battery pack using the secondary battery, an electric vehicle, an electric power storage system, an electric tool, and an electronic device.
  • a variety of electronic devices such as mobile phones and personal digital assistants (PDAs) are widely used, and there is a demand for further downsizing, weight reduction, and longer life of the electronic devices. Accordingly, as a power source, development of a battery, in particular, a secondary battery that is small and lightweight and capable of obtaining a high energy density is in progress.
  • Secondary batteries are not limited to the electronic devices described above, but are also being considered for other uses.
  • a battery pack detachably mounted on an electronic device, an electric vehicle such as an electric vehicle, an electric power storage system such as a household electric power server, and an electric tool such as an electric drill.
  • Secondary batteries that use various charge / discharge principles have been proposed to obtain battery capacity.
  • secondary batteries that use the storage and release of electrode reactants, and those that use precipitation and dissolution of electrode reactants. Secondary batteries are attracting attention. This is because these secondary batteries can provide a higher energy density than lead batteries and nickel cadmium batteries.
  • the secondary battery includes an electrolyte along with a positive electrode and a negative electrode. Since the composition of the electrolytic solution greatly affects the battery characteristics, various studies have been made on the composition of the electrolytic solution.
  • lithium salts such as lithium difluorooxalate borate are used as the electrolyte salt in order to improve the initial charge / discharge efficiency (see, for example, Patent Document 1).
  • various compounds such as phosphazene are used as an additive for the electrolytic solution (see, for example, Patent Documents 2 to 9).
  • JP 2012-094369 A Patent No. 5258353 Japanese Patent No. 4793378 Japanese Patent No. 5298419 Japanese Patent No. 5109329 Japanese Patent No. 5109310 Japanese Patent No. 5034352 JP 2012-190699 A JP 2012-079593 A
  • An electrolytic solution for a secondary battery includes a boron fluorine oxygen (BFO) -containing metal salt represented by the following formula (1), a dinitrile compound represented by the formula (2), a formula ( And at least one of an unsaturated cyclic carbonate represented by 3) and a disulfonic anhydride represented by formula (4).
  • BFO boron fluorine oxygen
  • NC-R1-CN (2) (R1 is a divalent hydrocarbon group.)
  • R2 and R3 are each a hydrogen group or a monovalent hydrocarbon group.
  • R4 is a divalent group represented by> CR5R6, and each of R5 and R6 is a hydrogen group. And a monovalent hydrocarbon group.
  • “Divalent hydrocarbon group” is a general term for divalent groups composed of carbon and hydrogen.
  • the divalent hydrocarbon group may be linear or branched including one or more side chains.
  • the divalent hydrocarbon group may be a saturated hydrocarbon group that does not include an unsaturated bond, or may be an unsaturated hydrocarbon group that includes one or more unsaturated bonds.
  • the unsaturated bond is one or both of a carbon-carbon double bond (> C ⁇ C ⁇ ) and a carbon-carbon triple bond (—C ⁇ C—).
  • “Monovalent hydrocarbon group” is a general term for monovalent groups composed of carbon and hydrogen. Other configurations (other than linear or branched, presence or absence of unsaturated bond) are the same as those of the above-described divalent hydrocarbon group.
  • a secondary battery according to an embodiment of the present technology includes a positive electrode, a negative electrode, and an electrolytic solution, and the electrolytic solution has the same configuration as the above-described electrolytic solution for a secondary battery according to an embodiment of the present technology. It is.
  • Each of the battery pack, the electric vehicle, the power storage system, the electric tool, and the electronic device according to the embodiment of the present technology includes a secondary battery, and the secondary battery includes the secondary battery according to the embodiment of the present technology described above. It has the same configuration.
  • the electrolyte is at least one of a BFO-containing metal salt, a dinitrile compound, an unsaturated cyclic carbonate, and a disulfonic anhydride. Therefore, excellent battery characteristics can be obtained. In addition, similar effects can be obtained in each of the battery pack, the electric vehicle, the power storage system, the electric tool, and the electronic device according to the embodiment of the present technology.
  • effect described here is not necessarily limited, and may be any effect described in the present technology.
  • FIG. 4 is a cross-sectional view taken along line IV-IV of the spirally wound electrode body illustrated in FIG. 3.
  • It is a block diagram showing the structure of the battery pack shown in FIG. It is a block diagram showing the structure of the application example (battery pack: assembled battery) of a secondary battery.
  • Electrolytic solution for secondary battery Secondary battery 2-1. Lithium ion secondary battery (cylindrical type) 2-2. Lithium ion secondary battery (laminate film type) 2-3. Lithium metal secondary battery Applications of secondary batteries 3-1. Battery pack (single cell) 3-2. Battery pack (assembled battery) 3-3. Electric vehicle 3-4. Electric power storage system 3-5. Electric tool
  • Electrolyte for secondary battery First, a secondary battery electrolyte solution according to an embodiment of the present technology will be described.
  • electrolyte The secondary battery electrolyte described here (hereinafter simply referred to as “electrolyte”) is used in, for example, a secondary battery.
  • electrolytic solution is not limited to the secondary battery.
  • This electrolytic solution contains any one or more of the solvents and any one or more of the electrolyte salts.
  • the electrolyte solution may further contain any one kind or two or more kinds of various materials such as additives.
  • the electrolyte salt includes a metal salt represented by the following formula (1). There may be only one kind of metal salt, or two or more kinds.
  • This metal salt contains boron (B), fluorine (F), and oxygen (O) as constituent elements. Therefore, hereinafter, the metal salt represented by the formula (1) is referred to as “BFO-containing metal salt”.
  • the type of M is not particularly limited as long as it is one of alkali metal elements.
  • the alkali metal element is, for example, any one of lithium (Li), sodium (Na), and potassium (K).
  • the content of the BFO-containing metal salt in the electrolytic solution is not particularly limited, but is, for example, 0.02 mol / kg to 1 mol / kg with respect to the solvent.
  • the solvent is a dinitrile compound represented by the following formula (2), one or both of an unsaturated cyclic carbonate represented by the formula (3) and a disulfonic anhydride represented by the formula (4): Is included.
  • the solvent may be only one kind of dinitrile compound, or two or more kinds. The fact that one kind or two or more kinds may be used in this way is the same for each of the unsaturated cyclic carbonate and the disulfonic anhydride.
  • the solvent may contain only an unsaturated cyclic carbonate of unsaturated cyclic carbonate and disulfonic anhydride, or may contain only disulfonic anhydride, or an unsaturated cyclic carbonate. And disulfonic anhydride may be included.
  • NC-R1-CN (2) (R1 is a divalent hydrocarbon group.)
  • R2 and R3 are each a hydrogen group or a monovalent hydrocarbon group.
  • R4 is a divalent group represented by> CR5R6, and each of R5 and R6 is a hydrogen group. And a monovalent hydrocarbon group.
  • the dinitrile compound is a chain compound containing two cyano groups (—CN) as shown in the formula (2).
  • the “divalent hydrocarbon group” relating to R1 is a general term for divalent groups composed of carbon and hydrogen.
  • the divalent hydrocarbon group may be linear or branched including one or more side chains.
  • the divalent hydrocarbon group may be a saturated hydrocarbon group that does not include an unsaturated bond, or may be an unsaturated hydrocarbon group that includes one or more unsaturated bonds.
  • the unsaturated bond is one or both of a carbon-carbon double bond (> C ⁇ C ⁇ ) and a carbon-carbon triple bond (—C ⁇ C—).
  • the type of R1 is not particularly limited as long as it is a divalent hydrocarbon group.
  • the divalent hydrocarbon group includes, for example, an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, an arylene group, and a divalent group in which two or more of them are bonded (hereinafter, “2 Valent bonding group ”).
  • the carbon number of the divalent hydrocarbon group is not particularly limited.
  • the alkylene group preferably has 1 to 12 carbon atoms.
  • Each of the alkenylene group and the alkynylene group preferably has 2 to 12 carbon atoms.
  • the cycloalkylene group preferably has 3 to 18 carbon atoms.
  • the carbon number of the arylene group is preferably 6-18. This is because the solubility and compatibility of the dinitrile compound are ensured.
  • alkylene group examples include a methylene group (—CH 2 —), an ethylene group (—C 2 H 4 —), a propylene group (—C 3 H 6 —), and a butylene group (—C 4 H 8 —). is there.
  • alkynylene group include an ethynyl group (—C ⁇ C—) and the like.
  • cycloalkylene group examples include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, and a cyclooctylene group.
  • arylene group examples include a phenyl group and a naphthyl group.
  • Examples of the divalent linking group include a group in which an alkylene group and an alkenylene group are bonded, a group in which an alkylene group and an alkynylene group are bonded, and a group in which an alkenylene group and an alkynylene group are bonded.
  • Examples of the divalent linking group include a group in which an alkylene group and an arylene group are bonded, and a group in which an alkylene group and a cycloalkylene group are bonded.
  • the dinitrile compound examples include succinonitrile (NC-C 2 H 4 -CN), glutaronitrile (NC-C 3 H 6 -CN), adiponitrile (NC-C 4 H 8 -CN), pimeonitrile (NC -C 5 H 10 -CN), Suberonitrile (NC-C 6 H 12 -CN), Azeronitrile (NC-C 7 H 14 -CN), Sevacononitrile (NC-C 8 H 16 -CN) and Phthalonitrile (NC- C 6 H 4 -CN).
  • the content of the dinitrile compound in the electrolytic solution is not particularly limited, but is, for example, 0.2 wt% to 5 wt%.
  • the “monovalent hydrocarbon group” relating to R2, R3, R5 and R6 is a general term for monovalent groups composed of carbon and hydrogen as described above.
  • the monovalent hydrocarbon group may be linear or branched including one or more side chains.
  • the monovalent hydrocarbon group may be a saturated hydrocarbon group that does not include an unsaturated bond, or may be an unsaturated hydrocarbon group that includes one or more unsaturated bonds.
  • the unsaturated bond is one or both of a carbon-carbon double bond (> C ⁇ C ⁇ ) and a carbon-carbon triple bond (—C ⁇ C—).
  • R2 and R3 may be the same group or different groups.
  • R5 and R6 may be the same group or different groups.
  • R2 and R3 are not particularly limited as long as it is either a hydrogen group or a monovalent hydrocarbon group.
  • the monovalent hydrocarbon group includes, for example, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, and a monovalent group in which two or more of them are bonded (hereinafter, “1 Valent bonding group ”).
  • the carbon number of the monovalent hydrocarbon group is not particularly limited.
  • the alkyl group preferably has 1 to 12 carbon atoms.
  • the alkenyl group and alkynyl group preferably have 2 to 12 carbon atoms.
  • the cycloalkyl group preferably has 3 to 18 carbon atoms.
  • the aryl group preferably has 6 to 18 carbon atoms. This is because the solubility and compatibility of the unsaturated cyclic carbonate are ensured.
  • alkyl group examples include a methyl group (—CH 3 ), an ethyl group (—C 2 H 5 ), a propyl group (—C 3 H 7 ), an n-butyl group (—C 4 H 8 ), and a t-butyl group. (—C (—CH 3 ) 2 —CH 3 ) and the like.
  • alkenyl group examples include a vinyl group (—CH ⁇ CH 2 ) and an allyl group (—CH 2 —CH ⁇ CH 2 ).
  • the alkynyl group is, for example, an ethynyl group (—C ⁇ CH).
  • Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
  • Examples of the aryl group include a phenyl group and a naphthyl group.
  • Examples of the monovalent linking group include a group in which an alkyl group and an alkenyl group are bonded, a group in which an alkyl group and an alkynyl group are bonded, and a group in which an alkenyl group and an alkynyl group are bonded.
  • Examples of the monovalent linking group include a group in which an alkyl group and an aryl group are bonded, and a group in which an alkyl group and a cycloalkyl group are bonded.
  • unsaturated cyclic carbonates include 4-methylene-1,3-dioxolan-2-one, 4,4-dimethyl-5-methylene-1,3-dioxolan-2-one, and 4,4-diethyl. -5-methylene-1,3-dioxolan-2-one and the like.
  • the content of the unsaturated cyclic carbonate in the electrolytic solution is not particularly limited, but is, for example, 0.1 wt% to 10 wt%.
  • the disulfonic anhydride is a cyclic anhydride containing a group (—S ( ⁇ O) 2 —O—S ( ⁇ O) 2 —) in which two sulfonic acid groups are dehydrated as shown in the formula (4). It is.
  • the content of disulfonic anhydride in the electrolytic solution is not particularly limited, but is, for example, 0.1% by weight to 5% by weight.
  • This electrolyte contains specific three compounds together as described above. These three compounds are a BFO-containing metal salt, a dinitrile compound, and one or both of an unsaturated cyclic carbonate and a disulfonic anhydride.
  • the chemical stability of the electrolytic solution is specifically improved by the synergistic action of the three, so that the decomposition reaction of the electrolytic solution is remarkably suppressed during the charge / discharge process. Thereby, even if charging / discharging is repeated, the discharge capacity is unlikely to decrease. In this case, it is further difficult to generate gas resulting from the decomposition reaction of the electrolytic solution. This advantage is not achieved if only one of the three is missing, as is evident from the synergistic effect of the three, and is only obtained when the three are together. This is an advantageous technical trend.
  • solvent other solvents
  • other solvents one or more of other materials (hereinafter referred to as “other solvents”) are used. May be included.
  • the other solvent is, for example, any one or more of non-aqueous solvents (organic solvents).
  • the electrolytic solution containing the nonaqueous solvent is a so-called nonaqueous electrolytic solution.
  • solvents include, for example, cyclic carbonates, chain carbonates, lactones, chain carboxylates and nitriles (mononitrile). This is because excellent battery capacity, cycle characteristics, storage characteristics, and the like can be obtained.
  • cyclic carbonate are ethylene carbonate, propylene carbonate and butylene carbonate.
  • chain carbonate include dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and methyl propyl carbonate.
  • lactones include ⁇ -butyrolactone and ⁇ -valerolactone.
  • chain carboxylic acid ester include methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, methyl isobutyrate, methyl trimethyl acetate, and ethyl trimethyl acetate.
  • nitriles include acetonitrile, methoxyacetonitrile and 3-methoxypropionitrile.
  • solvents include, for example, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 4-methyl-1,3-dioxolane, 1,3-dioxane, 1 , 4-dioxane, N, N-dimethylformamide, N-methylpyrrolidinone, N-methyloxazolidinone, N, N′-dimethylimidazolidinone, nitromethane, nitroethane, sulfolane, trimethyl phosphate and dimethyl sulfoxide. This is because similar advantages can be obtained.
  • any one or two or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate are preferable. This is because better battery capacity, cycle characteristics, storage characteristics, and the like can be obtained.
  • high viscosity (high dielectric constant) solvents such as ethylene carbonate and propylene carbonate (for example, dielectric constant ⁇ ⁇ 30) and low viscosity solvents such as dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate (for example, viscosity ⁇ 1 mPas).
  • -A combination with s is more preferred. This is because the dissociation property of the electrolyte salt and the ion mobility are improved.
  • the other solvent may contain any one or more of other unsaturated cyclic carbonates, halogenated carbonates, sulfonates, acid anhydrides and diisocyanate compounds. This is because the chemical stability of the electrolytic solution is improved.
  • the unsaturated cyclic carbonate described above is excluded from the other unsaturated cyclic carbonates described here. Further, the above-described disulfonic anhydride is excluded from the acid anhydrides described herein.
  • Other unsaturated cyclic carbonates are cyclic carbonates containing one or more unsaturated bonds (carbon-carbon double bonds), and are represented by, for example, the following formulas (5) and (6), respectively. And the like.
  • the content of the other unsaturated cyclic ester carbonate in the solvent is not particularly limited, but is, for example, 0.01 wt% to 10 wt%.
  • Each of R11 and R12 is any one of a hydrogen group and an alkyl group.
  • Each of R13 to R16 is any one of a hydrogen group, an alkyl group, a vinyl group, and an allyl group. At least one of which is either a vinyl group or an allyl group.
  • the compound represented by the formula (5) is a vinylene carbonate type compound.
  • R11 and R12 may be the same group or different groups. Details regarding the alkyl group are as described above.
  • Specific examples of this vinylene carbonate type compound include vinylene carbonate (1,3-dioxol-2-one), methyl vinylene carbonate (4-methyl-1,3-dioxol-2-one), ethyl vinylene carbonate (4- Ethyl-1,3-dioxol-2-one), 4,5-dimethyl-1,3-dioxol-2-one, 4,5-diethyl-1,3-dioxol-2-one, 4-fluoro-1 , 3-dioxol-2-one and 4-trifluoromethyl-1,3-dioxol-2-one.
  • the compound represented by the formula (6) is a vinyl ethylene carbonate type compound.
  • R13 to R16 may be the same group or different groups. Of course, some of R13 to R16 may be the same group.
  • Specific examples of the vinyl ethylene ethylene type compound include vinyl ethylene carbonate (4-vinyl-1,3-dioxolan-2-one), 4-methyl-4-vinyl-1,3-dioxolan-2-one, 4 -Ethyl-4-vinyl-1,3-dioxolane-2-one, 4-n-propyl-4-vinyl-1,3-dioxolan-2-one, 5-methyl-4-vinyl-1,3-dioxolane -2-one, 4,4-divinyl-1,3-dioxolan-2-one, 4,5-divinyl-1,3-dioxolan-2-one, and the like.
  • the other unsaturated cyclic carbonate may be catechol carbonate having a benzene ring.
  • the halogenated carbonate is a cyclic or chain carbonate containing 1 or 2 or more halogens as a constituent element.
  • the halogenated carbonate is a compound represented by each of the following formulas (7) and (8). is there.
  • the content of the halogenated carbonate in the solvent is not particularly limited, but is, for example, 0.01% by weight to 50% by weight.
  • R17 to R20 are any one of a hydrogen group, a halogen group, an alkyl group, and a halogenated alkyl group, and at least one of R17 to R20 is any one of a halogen group and a halogenated alkyl group.
  • R21 to R26 are any one of a hydrogen group, a halogen group, an alkyl group and a halogenated alkyl group, and at least one of R21 to R26 is a halogen group or a halogenated alkyl group. Either.
  • R17 to R20 may be the same group or different groups. Of course, some of R17 to R20 may be the same group.
  • the type of the halogen group is not particularly limited. Among them, any one or two of a fluorine group (—F), a chlorine group (—Cl), a bromine group (—Br), and an iodine group (—I) The above is preferable, and a fluorine group is more preferable. This is because a fluorine group is easier to form the protective film than other halogen groups.
  • the number of halogen groups is preferably two rather than one, and may be three or more. This is because the ability to form a protective film becomes higher and the protective film becomes stronger.
  • the halogenated alkyl group is a group in which one or two or more hydrogen groups in an alkyl group are substituted (halogenated) with a halogen group. Details regarding the halogen group are as described above.
  • cyclic halogenated carbonate examples include compounds represented by the following formulas (7-1) to (7-21), and the compounds include geometric isomers.
  • 4,5-difluoro-1,3-dioxolan-2-one represented by formula (7-3) Is preferred.
  • a trans isomer is preferable to a cis isomer. This is because it can be easily obtained and a high effect can be obtained.
  • the compound represented by the formula (8) is a chain halogenated carbonate.
  • R21 to R26 may be the same group or different groups. Of course, a part of R21 to R26 may be the same group.
  • chain halogenated carbonate examples include fluoromethyl methyl carbonate, bis (fluoromethyl) carbonate, and difluoromethyl methyl carbonate.
  • Sulfonic acid esters include, for example, monosulfonic acid esters and disulfonic acid esters.
  • the content of the sulfonic acid ester in the solvent is not particularly limited, and is, for example, 0.5% by weight to 5% by weight.
  • the monosulfonic acid ester may be a cyclic monosulfonic acid ester or a chain monosulfonic acid ester.
  • cyclic monosulfonic acid esters are sultone such as 1,3-propane sultone and 1,3-propene sultone.
  • chain monosulfonic acid ester include a compound in which a cyclic monosulfonic acid ester is cleaved on the way.
  • the disulfonic acid ester may be a cyclic disulfonic acid ester or a chain disulfonic acid ester.
  • Specific examples of the cyclic disulfonic acid ester include compounds represented by the following formulas (9-1) to (9-3).
  • Specific examples of the chain disulfonic acid ester include a compound in which a cyclic disulfonic acid ester is cleaved on the way.
  • Examples of the acid anhydride include a carboxylic acid anhydride and a carboxylic acid sulfonic acid anhydride.
  • the content of the acid anhydride in the solvent is not particularly limited, but is, for example, 0.5% by weight to 5% by weight.
  • carboxylic acid anhydride examples include succinic anhydride, glutaric anhydride, and maleic anhydride.
  • carboxylic acid sulfonic acid anhydride examples include anhydrous sulfobenzoic acid, anhydrous sulfopropionic acid, and anhydrous sulfobutyric acid.
  • the diisocyanate compound is, for example, a compound represented by OCN—C n H 2n —NCO (n is an integer of 1 or more).
  • the content of the diisocyanate compound in the solvent is not particularly limited and is, for example, 0.5% by weight to 5% by weight.
  • Specific examples of the diisocyanate compound include OCN—C 6 H 12 —NCO.
  • the electrolyte salt may contain one or more of other materials (hereinafter referred to as “other electrolyte salts”) together with the above-described BFO-containing metal salt.
  • the other electrolyte salt is, for example, any one or more of electrolyte salts such as other metal salts.
  • the above-mentioned BFO-containing metal salt is excluded from the other electrolyte salts described here.
  • a lithium salt is taken as an example of the metal salt, but the metal salt may contain a salt other than the lithium salt.
  • the salt other than the lithium salt include salts of light metals other than lithium.
  • electrolyte salts include lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium perchlorate (LiClO 4 ), and lithium hexafluoroarsenate (LiAsF 6 ).
  • Lithium tetraphenylborate LiB (C 6 H 5 ) 4
  • LiCH 3 SO 3 lithium methanesulfonate
  • LiCF 3 SO 3 lithium trifluoromethanesulfonate
  • LiAlCl 4 Lithium tetraphenylborate
  • LiCH 3 SO 3 lithium methanesulfonate
  • LiCF 3 SO 3 lithium trifluoromethanesulfonate
  • LiAlCl 4 Li tetrachloroaluminate
  • Dilithium hexafluorosilicate Li 2 SiF 6
  • lithium chloride LiCl
  • lithium bromide LiBr
  • any one or two or more of LiPF 6 , LiBF 4 , LiClO 4 and LiAsF 6 are preferable, and LiPF 6 is more preferable. This is because the internal resistance is lowered.
  • R31 and 32 may be the same group or different groups.
  • R41 to R43 may be the same group or different groups. Of course, any two of R41 to R43 may be the same group.
  • R51 and R52 may be the same group or different groups.
  • X31 is any one of group 1 element and group 2 element in the long-period periodic table, and aluminum (Al).
  • M31 is a transition metal, group 13 element, group 14 in the long-period periodic table And any one of elements and Group 15.
  • R31 is a halogen group
  • Y31 is —C ( ⁇ O) —R32—C ( ⁇ O) —, —C ( ⁇ O) —CR33 2 —.
  • R33 is any one of an alkyl group, a halogenated alkyl group, an aryl group, and a halogenated aryl group, wherein a3 is an integer of 1 to 4, and b3 is an integer of 0, 2, or 4. c3, d3, each of m3 and n3 is an integer of 1-3.)
  • X41 is one of group 1 and group 2 elements in the long-period periodic table.
  • M41 is a transition metal and group 13 element, group 14 element and group 15 element in the long-period periodic table.
  • any of the alkyl groups provided that at least one of R41 is It is either a halogen group or a halogenated alkyl group, and at least one of R43 is any one of a halogen group and a halogenated alkyl group, and R42 is a hydrogen group, an alkyl group, or a halogen group.
  • a4, e4 and n4 are each an integer of 1 or 2
  • b4 and d5 are each an integer of 1 to 4
  • c4 is 0 to 4
  • each of f4 and m4 is an integer of 1 to 3.
  • X51 is one of Group 1 and Group 2 elements in the long-period periodic table.
  • M51 is a transition metal, and Group 13 element, Group 14 element and Group 15 element in the long-period periodic table.
  • Rf is any one of a fluorinated alkyl group and a fluorinated aryl group, and each of the fluorinated alkyl group and the fluorinated aryl group has 1 to 10 carbon atoms.
  • R51 is any one of a hydrogen group, an alkyl group, a halogen group and a halogenated alkyl group
  • R52 is any one of a hydrogen group, an alkyl group, a halogen group and a halogenated alkyl group.
  • R52 is any one of a halogen group and a halogenated alkyl group, wherein each of a5, f5 and n5 is an integer of 1 or 2, and each of b5, c5 and e5 Is an integer from 1 to 4, d5 is an integer from 0 to 4, and each of g5 and m5 is an integer from 1 to 3.)
  • the Group 1 elements are hydrogen (H), lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr).
  • Group 2 elements are beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra).
  • Group 13 elements are boron (B), aluminum (Al), gallium (Ga), indium (In), and thallium (Tl).
  • Group 14 elements are carbon (C), silicon (Si), germanium (Ge), tin (Sn), and lead (Pb).
  • Group 15 elements are nitrogen (N), phosphorus (P), arsenic (As), antimony (Sb), and bismuth (Bi).
  • Specific examples of the compound represented by the formula (10) include compounds represented by the following formulas (10-1) to (10-5).
  • Specific examples of the compound represented by the formula (11) include compounds represented by the following formulas (11-1) to (11-8).
  • Specific examples of the compound represented by the formula (12) include a compound represented by the following formula (12-1).
  • the other electrolyte salt may be a compound represented by each of the following formulas (13) to (15).
  • m and n may be the same value or different values.
  • p, q, and r may be the same value or different values. Of course, any two of p, q, and r may have the same value.
  • R71 is a linear or branched perfluoroalkylene group having 2 to 4 carbon atoms.
  • the compound shown in Formula (13) is a chain imide compound.
  • this chain imide compound include bis (fluorosulfonyl) imide lithium (LiN (SO 2 F) 2 ), bis (trifluoromethanesulfonyl) imide lithium (LiN (CF 3 SO 2 ) 2 ), bis (pentafluoro Ethanesulfonyl) imidolithium (LiN (C 2 F 5 SO 2 ) 2 ), (trifluoromethanesulfonyl) (pentafluoroethanesulfonyl) imide lithium (LiN (CF 3 SO 2 ) (C 2 F 5 SO 2 )), ( Trifluoromethanesulfonyl) (heptafluoropropanesulfonyl) imidolithium (LiN (CF 3 SO 2 ) (C 3 F 7 SO 2 )), and (trifluoromethanesulfonyl) (nonafluorobut
  • the compound represented by the formula (14) is a cyclic imide compound.
  • Specific examples of the cyclic imide compound include compounds represented by the following formulas (14-1) to (14-4).
  • the compound represented by the formula (15) is a chain methide compound.
  • Specific examples of the chain methide compound include lithium tris (trifluoromethanesulfonyl) methide (LiC (CF 3 SO 2 ) 3 ).
  • the content of the electrolyte salt is not particularly limited, but is preferably 0.3 mol / kg to 3.0 mol / kg with respect to the solvent. This is because high ionic conductivity is obtained.
  • the other material may be any one type or two or more types of materials other than those described above.
  • Materials other than the above are, for example, phosphorous fluorine-containing salts such as lithium difluorophosphate (LiPF 2 O 2 ) and lithium fluorophosphate (Li 2 PFO 3 ).
  • the content of the additive in the electrolytic solution is not particularly limited.
  • the BFO-containing metal salt content is 0.02 mol / kg to 1 mol / kg
  • the dinitrile compound content is 0.2 wt% to 5 wt%
  • the unsaturated cyclic carbonate content is 0.1 wt%.
  • the content is ⁇ 10 wt% and the disulfonic anhydride content is 0.1 wt% to 5 wt%, a higher effect can be obtained.
  • FIG. 1 shows a cross-sectional configuration of the secondary battery
  • FIG. 2 shows a partial cross-sectional configuration of the spirally wound electrode body 20 shown in FIG.
  • the secondary battery described here is, for example, a lithium ion secondary battery in which the capacity of the negative electrode 22 is obtained by occlusion / release of lithium (Li), which is an electrode reactant.
  • the secondary battery has a so-called cylindrical battery structure.
  • a pair of insulating plates 12 and 13 and a battery element are provided inside a hollow cylindrical battery can 11.
  • the wound electrode body 20 is housed.
  • the wound electrode body 20 for example, after the positive electrode 21 and the negative electrode 22 are stacked via the separator 23, the positive electrode 21, the negative electrode 22, and the separator 23 are wound.
  • the wound electrode body 20 is impregnated with an electrolytic solution (electrolytic solution for a secondary battery) that is a liquid electrolyte.
  • the battery can 11 has, for example, a hollow structure in which one end is closed and the other end is opened.
  • any of iron (Fe), aluminum (Al), and alloys thereof It is formed of one type or two or more types.
  • Nickel or the like may be plated on the surface of the battery can 11.
  • the pair of insulating plates 12 and 13 are arranged so as to sandwich the wound electrode body 20 and to extend perpendicularly to the wound peripheral surface.
  • a battery lid 14, a safety valve mechanism 15, and a heat sensitive resistance element (PTC element) 16 are caulked to the open end of the battery can 11 via a gasket 17. Thereby, the battery can 11 is sealed.
  • the battery lid 14 is formed of the same material as the battery can 11, for example.
  • Each of the safety valve mechanism 15 and the thermal resistance element 16 is provided inside the battery lid 14, and the safety valve mechanism 15 is electrically connected to the battery lid 14 via the thermal resistance element 16.
  • the disk plate 15 ⁇ / b> A is reversed when the internal pressure becomes a certain level or more due to an internal short circuit or external heating. Thereby, the electrical connection between the battery lid 14 and the wound electrode body 20 is cut.
  • the resistance of the heat sensitive resistor 16 increases as the temperature rises.
  • the gasket 17 is formed of, for example, an insulating material, and asphalt or the like may be applied to the surface of the gasket 17.
  • a center pin 24 is inserted into the winding center of the wound electrode body 20.
  • the center pin 24 may not be inserted into the winding center of the wound electrode body 20.
  • a positive electrode lead 25 is attached to the positive electrode 21, and a negative electrode lead 26 is attached to the negative electrode 22.
  • the positive electrode lead 25 is formed of a conductive material such as aluminum, for example.
  • the positive electrode lead 25 is attached to the safety valve mechanism 15 and is electrically connected to the battery lid 14.
  • the negative electrode lead 26 is formed of a conductive material such as nickel, for example.
  • the negative electrode lead 26 is attached to the battery can 11 and is electrically connected to the battery can 11.
  • the positive electrode 21 includes a positive electrode current collector 21 ⁇ / b> A and a positive electrode active material layer 21 ⁇ / b> B provided on both surfaces of the positive electrode current collector 21 ⁇ / b> A.
  • the positive electrode active material layer 21B may be provided only on one surface of the positive electrode current collector 21A.
  • the positive electrode current collector 21A includes, for example, any one type or two or more types of conductive materials. Although the kind of conductive material is not specifically limited, For example, they are metal materials, such as aluminum (Al), nickel (Ni), and stainless steel.
  • the positive electrode current collector 21A may be a single layer or a multilayer.
  • the positive electrode active material layer 21B contains any one or more of positive electrode materials capable of occluding and releasing lithium as a positive electrode active material.
  • the positive electrode active material layer 21 ⁇ / b> B may include any one type or two or more types of other materials such as a positive electrode binder and a positive electrode conductive agent in addition to the positive electrode active material.
  • the positive electrode material is preferably a lithium-containing compound, and more specifically, preferably one or both of a lithium-containing composite oxide and a lithium-containing phosphate compound. This is because a high energy density can be obtained.
  • the lithium-containing composite oxide is an oxide containing lithium and one or more elements other than lithium (hereinafter referred to as “other elements”) as constituent elements, for example, a layered rock salt type and a spinel type It has one of the following crystal structures.
  • the lithium-containing phosphate compound is a phosphate compound containing lithium and one or more other elements as constituent elements, and has, for example, an olivine type crystal structure.
  • the type of other element is not particularly limited as long as it is any one or more of arbitrary elements.
  • the other elements are preferably any one or more of elements belonging to Groups 2 to 15 in the long-period periodic table. More specifically, it is more preferable that the other elements include one or more metal elements of nickel (Ni), cobalt (Co), manganese (Mn), and iron (Fe). preferable. This is because a high voltage can be obtained.
  • the lithium-containing composite oxide having a layered rock salt type crystal structure is, for example, a compound represented by each of the following formulas (21) to (23).
  • M1 is cobalt (Co), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zinc (Zn), zirconium (Zr), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), and tungsten (W), a to e being 0.8 ⁇ a ⁇ 1.2, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.5, (b + c) ⁇ 1, ⁇ 0.1 ⁇ d ⁇ 0.2 and 0 ⁇ e ⁇ 0.1 are satisfied.
  • the composition of lithium varies depending on the charge / discharge state, and a is the value of the fully discharged state.
  • M2 is cobalt (Co), manganese (Mn), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), and tungsten (W), and a to d are 0.8.
  • composition of lithium depends on the charge / discharge state Unlikely, a is the value of the fully discharged state.
  • M3 is nickel (Ni), manganese (Mn), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), and tungsten (W), and a to d are 0.8.
  • lithium-containing composite oxide having a layered rock salt type crystal structure LiNiO 2 , LiCoO 2 , LiCo 0.98 Al 0.01 Mg 0.01 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2.
  • LiNi 0.33 Co 0.33 Mn 0.33 O 2 Li 1.2 Mn 0.52 Co 0.175 Ni 0.1 O 2 and Li 1.15 (Mn 0.65 Ni 0.22 Co 0.13 ) O 2 .
  • the lithium-containing composite oxide having a layered rock salt type crystal structure contains nickel, cobalt, manganese, and aluminum as constituent elements
  • the atomic ratio of nickel is preferably 50 atomic% or more. This is because a high energy density can be obtained.
  • the lithium-containing composite oxide having a spinel crystal structure is, for example, a compound represented by the following formula (24).
  • M4 is cobalt (Co), nickel (Ni), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), copper At least one of (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), and tungsten (W), wherein a to d are 0.9.
  • composition of lithium differs depending on the charge / discharge state, and a Is the value of the fully discharged state.
  • lithium-containing composite oxide having a spinel crystal structure examples include LiMn 2 O 4 .
  • the lithium-containing phosphate compound having an olivine type crystal structure is, for example, a compound represented by the following formula (25).
  • Li a M5PO 4 (25) (M5 is cobalt (Co), manganese (Mn), iron (Fe), nickel (Ni), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), niobium It is at least one of (Nb), copper (Cu), zinc (Zn), molybdenum (Mo), calcium (Ca), strontium (Sr), tungsten (W), and zirconium (Zr). 0.9 ⁇ a ⁇ 1.1, where the composition of lithium varies depending on the charge / discharge state, and a is the value of the complete discharge state.)
  • lithium-containing phosphate compound having an olivine type crystal structure examples include LiFePO 4 , LiMnPO 4 , LiFe 0.5 Mn 0.5 PO 4, and LiFe 0.3 Mn 0.7 PO 4 .
  • the lithium-containing composite oxide may be a compound represented by the following formula (26).
  • the positive electrode material may be any one kind or two or more kinds of oxides, disulfides, chalcogenides, conductive polymers, and the like.
  • oxide include titanium oxide, vanadium oxide, and manganese dioxide.
  • disulfide include titanium disulfide and molybdenum sulfide.
  • chalcogenide is niobium selenide.
  • conductive polymer include sulfur, polyaniline, and polythiophene.
  • the positive electrode material may be a material other than the above.
  • the positive electrode binder contains, for example, one or more of synthetic rubber and polymer material.
  • synthetic rubber include styrene butadiene rubber, fluorine rubber, and ethylene propylene diene.
  • polymer material include polyvinylidene fluoride and polyimide.
  • the positive electrode conductive agent includes, for example, one or more of carbon materials.
  • the carbon material include graphite, carbon black, acetylene black, and ketjen black.
  • the positive electrode conductive agent may be a metal material or a conductive polymer as long as it is a conductive material.
  • the negative electrode 22 includes a negative electrode current collector 22A and negative electrode active material layers 22B provided on both surfaces of the negative electrode current collector 22A.
  • the negative electrode active material layer 22B may be provided only on one surface of the negative electrode current collector 22A.
  • the negative electrode current collector 22A includes, for example, any one type or two or more types of conductive materials. Although the kind of conductive material is not specifically limited, For example, they are metal materials, such as copper (Cu), aluminum (Al), nickel (Ni), and stainless steel.
  • the anode current collector 22A may be a single layer or a multilayer.
  • the surface of the negative electrode current collector 22A is preferably roughened. This is because the so-called anchor effect improves the adhesion of the negative electrode active material layer 22B to the negative electrode current collector 22A. In this case, the surface of the negative electrode current collector 22A only needs to be roughened at least in a region facing the negative electrode active material layer 22B.
  • the roughening method is, for example, a method of forming fine particles using electrolytic treatment. In the electrolytic treatment, fine particles are formed on the surface of the negative electrode current collector 22A by an electrolysis method in an electrolytic bath, so that the surface of the negative electrode current collector 22A is provided with irregularities.
  • a copper foil produced by an electrolytic method is generally called an electrolytic copper foil.
  • the negative electrode active material layer 22B includes one or more of negative electrode materials capable of occluding and releasing lithium as a negative electrode active material.
  • the negative electrode active material layer 22B may include any one type or two or more types of other materials such as a negative electrode binder and a negative electrode conductive agent in addition to the negative electrode active material.
  • the chargeable capacity of the negative electrode material is larger than the discharge capacity of the positive electrode 21 in order to prevent unintentional deposition of lithium metal on the negative electrode 22 during charging. That is, the electrochemical equivalent of the negative electrode material capable of occluding and releasing lithium is preferably larger than the electrochemical equivalent of the positive electrode 21.
  • the negative electrode material is, for example, one or more of carbon materials. This is because the change in crystal structure at the time of occlusion and release of lithium is very small, so that a high energy density can be obtained stably. Moreover, since the carbon material also functions as a negative electrode conductive agent, the conductivity of the negative electrode active material layer 22B is improved.
  • Examples of the carbon material include graphitizable carbon, non-graphitizable carbon, and graphite.
  • the interplanar spacing of the (002) plane in non-graphitizable carbon is preferably 0.37 nm or more, and the interplanar spacing of the (002) plane in graphite is preferably 0.34 nm or less.
  • examples of the carbon material include pyrolytic carbons, cokes, glassy carbon fibers, organic polymer compound fired bodies, activated carbon, and carbon blacks.
  • the cokes include pitch coke, needle coke, petroleum coke and the like.
  • the organic polymer compound fired body is obtained by firing (carbonizing) a polymer compound such as a phenol resin and a furan resin at an appropriate temperature.
  • the carbon material may be low crystalline carbon heat-treated at a temperature of about 1000 ° C. or less, or may be amorphous carbon.
  • the shape of the carbon material may be any of a fibrous shape, a spherical shape, a granular shape, and a scale shape.
  • the negative electrode material is, for example, a material (metal material) containing any one or more of metal elements and metalloid elements as constituent elements. This is because a high energy density can be obtained.
  • the metal-based material may be any of a simple substance, an alloy, and a compound, or two or more of them, or a material having one or two or more phases thereof at least in part.
  • the alloy includes a material including one or more metal elements and one or more metalloid elements in addition to a material composed of two or more metal elements.
  • the alloy may contain a nonmetallic element.
  • the structure of this metal material is, for example, a solid solution, a eutectic (eutectic mixture), an intermetallic compound, and two or more kinds of coexisting materials.
  • the metal element and metalloid element described above are, for example, any one or more metal elements and metalloid elements capable of forming an alloy with lithium. Specifically, for example, magnesium (Mg), boron (B), aluminum (Al), gallium (Ga), indium (In), silicon (Si), germanium (Ge), tin (Sn), lead (Pb) ), Bismuth (Bi), cadmium (Cd), silver (Ag), zinc, hafnium (Hf), zirconium, yttrium (Y), palladium (Pd) and platinum (Pt).
  • silicon and tin is preferable. This is because the ability to occlude and release lithium is excellent, so that a significantly high energy density can be obtained.
  • the material containing one or both of silicon and tin as a constituent element may be any of a simple substance, an alloy and a compound of silicon, or any of a simple substance, an alloy and a compound of tin. It may be a kind or more, and may be a material having at least a part of one kind or two or more kinds of phases.
  • the simple substance described here means a simple substance (which may contain a small amount of impurities) in a general sense, and does not necessarily mean 100% purity.
  • the alloy of silicon is, for example, any one of tin, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony, chromium and the like as a constituent element other than silicon or Includes two or more.
  • the compound of silicon contains, for example, one or more of carbon and oxygen as constituent elements other than silicon.
  • the compound of silicon may contain any 1 type or 2 types or more of the series of elements demonstrated regarding the alloy of silicon as structural elements other than silicon, for example.
  • silicon alloys and silicon compounds are SiB 4 , SiB 6 , Mg 2 Si, Ni 2 Si, TiSi 2 , MoSi 2 , CoSi 2 , NiSi 2 , CaSi 2 , CrSi 2 , Cu 5 Si, FeSi 2.
  • v in SiO v may be 0.2 ⁇ v ⁇ 1.4.
  • the alloy of tin for example, as a constituent element other than tin, any one of silicon, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony, chromium, etc. Includes two or more.
  • the tin compound contains, for example, one or more of carbon and oxygen as constituent elements other than tin.
  • the compound of tin may contain any 1 type in the series of elements demonstrated regarding the alloy of tin, or 2 or more types as structural elements other than tin, for example.
  • tin alloy and the tin compound include SnO w (0 ⁇ w ⁇ 2), SnSiO 3 , LiSnO, and Mg 2 Sn.
  • the material containing tin as a constituent element is preferably, for example, a material containing Sn (first constituent element) and a second constituent element and a third constituent element (Sn-containing material).
  • the second constituent element is, for example, cobalt, iron, magnesium, titanium, vanadium, chromium, manganese, nickel, copper, zinc, gallium, zirconium, niobium, molybdenum, silver, indium, cesium (Ce), hafnium (Hf), Any one or more of tantalum, tungsten, bismuth, silicon and the like are included.
  • the third constituent element includes, for example, any one or more of boron, carbon, aluminum, phosphorus (P), and the like. This is because, when the Sn-containing material contains the second and third constituent elements, a high battery capacity and excellent cycle characteristics can be obtained.
  • the Sn-containing material is preferably a material (SnCoC-containing material) containing tin, cobalt, and carbon as constituent elements.
  • the carbon content is 9.9 mass% to 29.7 mass%, and the ratio of the content of tin and cobalt (Co / (Sn + Co)) is 20 mass% to 70 mass%. . This is because a high energy density can be obtained.
  • the SnCoC-containing material has a phase containing tin, cobalt, and carbon, and the phase is preferably low crystalline or amorphous. Since this phase is a reaction phase capable of reacting with lithium, excellent characteristics can be obtained due to the presence of the reaction phase.
  • the half-width (diffraction angle 2 ⁇ ) of the diffraction peak obtained by X-ray diffraction of this reaction phase is 1 ° or more when CuK ⁇ ray is used as the specific X-ray and the insertion speed is 1 ° / min. Is preferred. This is because lithium is occluded and released more smoothly and the reactivity with the electrolytic solution is reduced.
  • the SnCoC-containing material may include a phase containing a simple substance or a part of each constituent element in addition to the low crystalline or amorphous phase.
  • a diffraction peak obtained by X-ray diffraction corresponds to a reaction phase capable of reacting with lithium can be easily determined by comparing X-ray diffraction charts before and after electrochemical reaction with lithium. .
  • the position of the diffraction peak changes before and after the electrochemical reaction with lithium, it corresponds to a reaction phase capable of reacting with lithium.
  • Such a reaction phase contains, for example, each of the above-described constituent elements, and is considered to be low crystallized or amorphous mainly due to the presence of carbon.
  • the SnCoC-containing material it is preferable that at least a part of carbon as a constituent element is bonded to a metal element or a metalloid element as another constituent element. This is because aggregation or crystallization of tin or the like is suppressed.
  • the bonding state of the elements can be confirmed using, for example, X-ray photoelectron spectroscopy (XPS).
  • XPS X-ray photoelectron spectroscopy
  • Al—K ⁇ ray or Mg—K ⁇ ray is used as the soft X-ray.
  • the energy calibration is performed so that the peak of the 4f orbit (Au4f) of the gold atom is obtained at 84.0 eV.
  • the C1s peak of the surface-contaminated carbon is set to 284.8 eV, and the peak is used as an energy reference.
  • the waveform of the C1s peak is obtained in a form including the surface contamination carbon peak and the carbon peak in the SnCoC-containing material. For this reason, for example, both peaks are separated by analyzing using commercially available software. In the waveform analysis, the position of the main peak existing on the lowest bound energy side is used as the energy reference (284.8 eV).
  • This SnCoC-containing material is not limited to a material (SnCoC) whose constituent elements are only tin, cobalt and carbon.
  • This SnCoC-containing material is, for example, any one of silicon, iron, nickel, chromium, indium, niobium, germanium, titanium, molybdenum, aluminum, phosphorus, gallium, and bismuth in addition to tin, cobalt, and carbon
  • One kind or two or more kinds may be included as constituent elements.
  • SnCoC-containing materials materials containing tin, cobalt, iron and carbon as constituent elements
  • SnCoFeC-containing materials materials containing tin, cobalt, iron and carbon as constituent elements
  • the composition of the SnCoFeC-containing material is arbitrary.
  • the iron content is set to be small, the carbon content is 9.9 mass% to 29.7 mass%, and the iron content is 0.3 mass% to 5.9 mass%.
  • the content ratio of tin and cobalt (Co / (Sn + Co)) is 30% by mass to 70% by mass.
  • the carbon content is 11.9% to 29.7% by mass
  • the ratio of the content of tin, cobalt and iron ((Co + Fe) / (Sn + Co + Fe)) Is 26.4% by mass to 48.5% by mass
  • the content ratio of cobalt and iron (Co / (Co + Fe)) is 9.9% by mass to 79.5% by mass.
  • the physical properties (half-value width, etc.) of the SnCoFeC-containing material are the same as the above-described physical properties of the SnCoC-containing material.
  • the negative electrode material may be any one kind or two or more kinds of metal oxides and polymer compounds, for example.
  • the metal oxide include iron oxide, ruthenium oxide, and molybdenum oxide.
  • the polymer compound include polyacetylene, polyaniline, and polypyrrole.
  • the negative electrode material preferably contains both a carbon material and a metal-based material for the following reasons.
  • Metal materials in particular, materials containing one or both of silicon and tin as constituent elements have the advantage of high theoretical capacity, but they have a concern that they tend to violently expand and contract during charging and discharging.
  • the carbon material has a concern that the theoretical capacity is low, but has an advantage that it is difficult to expand and contract during charging and discharging. Therefore, by using both a carbon material and a metal-based material, expansion and contraction during charging and discharging are suppressed while obtaining a high theoretical capacity (in other words, battery capacity).
  • the negative electrode active material layer 22B is formed by any one method or two or more methods among, for example, a coating method, a gas phase method, a liquid phase method, a thermal spray method, and a firing method (sintering method).
  • the coating method is, for example, a method in which a particulate (powder) negative electrode active material is mixed with a negative electrode binder and the mixture is dispersed in an organic solvent and then applied to the negative electrode current collector 22A.
  • the vapor phase method include a physical deposition method and a chemical deposition method.
  • a vacuum deposition method for example, a vacuum deposition method, a sputtering method, an ion plating method, a laser ablation method, a thermal chemical vapor deposition, a chemical vapor deposition (CVD) method, and a plasma chemical vapor deposition method.
  • the liquid phase method include an electrolytic plating method and an electroless plating method.
  • the thermal spraying method is a method of spraying a molten or semi-molten negative electrode active material onto the negative electrode current collector 22A.
  • the firing method is, for example, a method in which a mixture dispersed in an organic solvent or the like is applied to the negative electrode current collector 22A using a coating method and then heat-treated at a temperature higher than the melting point of the negative electrode binder or the like.
  • an atmosphere firing method, a reaction firing method, a hot press firing method, or the like can be used.
  • the electrochemical equivalent of the negative electrode material capable of occluding and releasing lithium is the electrical equivalent of the positive electrode. Greater than the chemical equivalent.
  • the open circuit voltage (that is, the battery voltage) at the time of full charge is 4.25 V or more, compared with the case where it is 4.20 V, even when the same positive electrode active material is used, the amount of lithium released per unit mass Therefore, the amounts of the positive electrode active material and the negative electrode active material are adjusted accordingly. Thereby, a high energy density is obtained.
  • the separator 23 is disposed between the positive electrode 21 and the negative electrode 22.
  • the separator 23 separates the positive electrode 21 and the negative electrode 22 and allows lithium ions to pass through while preventing a short circuit of current due to contact between the two electrodes.
  • the separator 23 is, for example, one kind or two or more kinds of porous films such as synthetic resin and ceramic, and may be a laminated film of two or more kinds of porous films.
  • the synthetic resin include polytetrafluoroethylene, polypropylene, and polyethylene.
  • the separator 23 may include, for example, the above-described porous film (base material layer) and a polymer compound layer provided on one or both surfaces of the base material layer. This is because the adhesion of the separator 23 to each of the positive electrode 21 and the negative electrode 22 is improved, so that the distortion of the wound electrode body 20 is suppressed. As a result, the decomposition reaction of the electrolytic solution is suppressed, and the leakage of the electrolytic solution impregnated in the base material layer is also suppressed. Therefore, the resistance is not easily increased even if charging and discharging are repeated, and the battery swelling is also suppressed. Is done.
  • the polymer compound layer includes, for example, a polymer material such as polyvinylidene fluoride. This is because it has excellent physical strength and is electrochemically stable.
  • the polymer material may be a material other than polyvinylidene fluoride.
  • the wound electrode body 20 is impregnated with the electrolytic solution.
  • This electrolytic solution has the same configuration as the electrolytic solution of the present technology described above. That is, the electrolytic solution contains a BFO-containing metal salt, a dinitrile compound, and one or both of an unsaturated cyclic carbonate and a disulfonic anhydride.
  • This secondary battery operates as follows, for example.
  • lithium ions are released from the positive electrode 21, and the lithium ions are occluded in the negative electrode 22 through the electrolytic solution.
  • lithium ions are released from the negative electrode 22, and the lithium ions are occluded in the positive electrode 21 through the electrolytic solution.
  • This secondary battery is manufactured by the following procedure, for example.
  • the positive electrode 21 When the positive electrode 21 is produced, first, a positive electrode active material and, if necessary, a positive electrode binder and a positive electrode conductive agent are mixed to obtain a positive electrode mixture. Subsequently, the positive electrode mixture is dispersed in an organic solvent or the like to obtain a paste-like positive electrode mixture slurry. Subsequently, after applying the positive electrode mixture slurry to both surfaces of the positive electrode current collector 21A, the positive electrode mixture slurry is dried to form the positive electrode active material layer 21B. Subsequently, the positive electrode active material layer 21B is compression-molded using a roll press or the like while heating the positive electrode active material layer 21B as necessary. In this case, compression molding may be repeated a plurality of times.
  • the negative electrode active material layer 22B is formed on the negative electrode current collector 22A by the same procedure as that of the positive electrode 21 described above. Specifically, a negative electrode active material, a negative positive electrode binder, a negative electrode conductive agent, and the like are mixed to form a negative electrode mixture, and then the negative electrode mixture is dispersed in an organic solvent or the like to obtain a paste-like negative electrode mixture. A slurry is obtained. Subsequently, after applying the negative electrode mixture slurry to both surfaces of the negative electrode current collector 22A, the negative electrode mixture slurry is dried to form the negative electrode active material layer 22B. Finally, the negative electrode active material layer 22B is compression molded using a roll press or the like.
  • an electrolyte salt is dissolved in a solvent, and then a BFO-containing metal salt, a dinitrile compound, an unsaturated cyclic carbonate, and a disulfonic anhydride are added to the solvent.
  • the positive electrode lead 25 is attached to the positive electrode current collector 21A using a welding method or the like, and the negative electrode lead 26 is attached to the negative electrode current collector 22A using a welding method or the like. Subsequently, after the positive electrode 21 and the negative electrode 22 are laminated via the separator 23, the positive electrode 21, the negative electrode 22, and the separator 23 are wound to form the wound electrode body 20. Subsequently, the center pin 24 is inserted into the center of the wound electrode body 20.
  • the wound electrode body 20 is accommodated in the battery can 11 while the wound electrode body 20 is sandwiched between the pair of insulating plates 12 and 13.
  • the tip of the positive electrode lead 25 is attached to the safety valve mechanism 15 using a welding method or the like
  • the tip of the negative electrode lead 26 is attached to the battery can 11 using a welding method or the like.
  • an electrolytic solution is injected into the battery can 11 and the separator 23 is impregnated with the electrolytic solution.
  • the battery lid 14, the safety valve mechanism 15, and the heat sensitive resistance element 16 are caulked to the opening end of the battery can 11 through the gasket 17. Thereby, a cylindrical secondary battery is completed.
  • the electrolytic solution contains a BFO-containing metal salt, a dinitrile compound, and one or both of an unsaturated cyclic carbonate and a disulfonic anhydride.
  • the decomposition reaction of the electrolytic solution is suppressed even when charging and discharging are repeated, the discharge capacity is unlikely to decrease. Therefore, excellent battery characteristics can be obtained.
  • FIG. 3 shows a perspective configuration of another secondary battery
  • FIG. 4 shows a cross section taken along line IV-IV of the spirally wound electrode body 30 shown in FIG.
  • FIG. 3 shows a state where the wound electrode body 30 and the exterior member 40 are separated from each other.
  • This secondary battery is a lithium ion secondary battery having a so-called laminate film type battery structure.
  • a wound electrode as a battery element is provided inside a film-shaped exterior member 40.
  • the body 30 is stored.
  • the positive electrode 33 and the negative electrode 34 are stacked via the separator 35 and the electrolyte layer 36, the positive electrode 33, the negative electrode 34, the separator 35, and the electrolyte layer 36 are wound.
  • a positive electrode lead 31 is attached to the positive electrode 33, and a negative electrode lead 32 is attached to the negative electrode 34.
  • the outermost peripheral part of the wound electrode body 30 is protected by a protective tape 37.
  • the positive electrode lead 31 and the negative electrode lead 32 is led out in the same direction from the inside of the exterior member 40 to the outside, for example.
  • the positive electrode lead 31 is formed of any one type or two or more types of conductive materials such as aluminum (Al).
  • the negative electrode lead 32 is formed of any one type or two or more types of conductive materials such as copper (Cu), nickel (Ni), and stainless steel, for example. These conductive materials have, for example, a thin plate shape or a mesh shape.
  • the exterior member 40 is, for example, a single film that can be folded in the direction of the arrow R shown in FIG. 3, and a recess for accommodating the wound electrode body 30 is provided in a part of the exterior member 40. It has been.
  • the exterior member 40 is, for example, a laminate film in which a fusion layer, a metal layer, and a surface protective layer are laminated in this order. In the manufacturing process of the secondary battery, after the exterior member 40 is folded so that the fusion layers face each other with the wound electrode body 30 therebetween, the outer peripheral edges of the fusion layers are fused.
  • the exterior member 40 may be one in which two laminated films are bonded together with an adhesive or the like.
  • the fusion layer is, for example, any one kind or two or more kinds of films such as polyethylene and polypropylene.
  • the metal layer is, for example, one or more of aluminum foils.
  • the surface protective layer is, for example, any one film or two or more films selected from nylon and polyethylene terephthalate.
  • the exterior member 40 is an aluminum laminate film in which a polyethylene film, an aluminum foil, and a nylon film are laminated in this order.
  • the exterior member 40 may be a laminate film having another laminated structure, a polymer film such as polypropylene, or a metal film.
  • an adhesive film 41 is inserted between the exterior member 40 and the positive electrode lead 31 in order to prevent intrusion of outside air. Further, for example, the adhesion film 41 described above is inserted between the exterior member 40 and the negative electrode lead 32.
  • the adhesion film 41 is formed of a material having adhesion to both the positive electrode lead 31 and the negative electrode lead 32.
  • the material having this adhesion is, for example, a polyolefin resin, and more specifically, any one or more of polyethylene, polypropylene, modified polyethylene, modified polypropylene, and the like.
  • the positive electrode 33 includes, for example, a positive electrode current collector 33A and a positive electrode active material layer 33B
  • the negative electrode 34 includes, for example, a negative electrode current collector 34A and a negative electrode active material layer 34B.
  • the configurations of the positive electrode current collector 33A, the positive electrode active material layer 33B, the negative electrode current collector 34A, and the negative electrode active material layer 34B are, for example, the positive electrode current collector 21A, the positive electrode active material layer 21B, the negative electrode current collector 22A, and the negative electrode
  • the configuration is the same as that of each of the active material layers 22B.
  • the configuration of the separator 35 is the same as that of the separator 23, for example.
  • the electrolyte layer 36 contains an electrolytic solution and a polymer compound. This electrolytic solution has the same configuration as the electrolytic solution of the present technology described above.
  • the electrolyte layer 36 described here is a so-called gel electrolyte, and an electrolytic solution is held by a polymer compound. This is because high ionic conductivity (for example, 1 mS / cm or more at room temperature) is obtained and leakage of the electrolytic solution is prevented.
  • the electrolyte layer 36 may further include any one kind or two or more kinds of other materials such as additives.
  • polymer compound examples include polyacrylonitrile, polyvinylidene fluoride, polytetrafluoroethylene, polyhexafluoropropylene, polyethylene oxide, polypropylene oxide, polyphosphazene, polysiloxane, polyvinyl fluoride, polyvinyl acetate, polyvinyl alcohol, polymethacryl It includes any one or more of methyl acid, polyacrylic acid, polymethacrylic acid, styrene-butadiene rubber, nitrile-butadiene rubber, polystyrene and polycarbonate.
  • the polymer compound may be a copolymer.
  • This copolymer is, for example, a copolymer of vinylidene fluoride and hexafluoropyrene.
  • a copolymer of vinylidene fluoride and hexafluoropyrene is preferable. This is because it is electrochemically stable.
  • the solvent contained in the electrolytic solution is a wide concept including not only a liquid material but also a material having ion conductivity capable of dissociating the electrolyte salt. Therefore, when using a polymer compound having ion conductivity, the polymer compound is also included in the non-aqueous solvent.
  • the wound electrode body 30 is impregnated with the electrolytic solution.
  • This secondary battery operates as follows, for example.
  • lithium ions are released from the positive electrode 33 and the lithium ions are occluded in the negative electrode 34 through the electrolyte layer 36.
  • lithium ions are released from the negative electrode 34 and the lithium ions are occluded in the positive electrode 33 through the electrolyte layer 36.
  • the secondary battery provided with the gel electrolyte layer 36 is manufactured, for example, by the following three types of procedures.
  • the positive electrode 33 and the negative electrode 34 are manufactured by the same manufacturing procedure as that of the positive electrode 21 and the negative electrode 22. That is, when the positive electrode 33 is produced, the positive electrode active material layer 33B is formed on both surfaces of the positive electrode current collector 33A, and when the negative electrode 34 is produced, the negative electrode active material layer is formed on both surfaces of the negative electrode current collector 34A. 34B is formed. Subsequently, an electrolytic solution, a polymer compound, an organic solvent, and the like are mixed to prepare a precursor solution. Subsequently, after applying a precursor solution to each of the positive electrode 33 and the negative electrode 34, the precursor solution is dried to form a gel electrolyte layer 36.
  • the positive electrode lead 31 is attached to the positive electrode current collector 33A using a welding method or the like, and the negative electrode lead 32 is attached to the negative electrode current collector 34A using a welding method or the like.
  • the positive electrode 33 and the negative electrode 34 are stacked via the separator 35, the positive electrode 33, the negative electrode 34, and the separator 35 are wound to form the wound electrode body 30.
  • the protective tape 37 is attached to the outermost peripheral portion of the wound electrode body 30.
  • the outer peripheral edge portions of the exterior member 40 are bonded to each other using a heat fusion method or the like, and the wound member 40 is wound inside the exterior member 40.
  • the electrode body 30 is encapsulated. In this case, the adhesion film 41 is inserted between the positive electrode lead 31 and the exterior member 40, and the adhesion film 41 is inserted between the negative electrode lead 32 and the exterior member 40.
  • the positive electrode lead 31 is attached to the positive electrode 33 and the negative electrode lead 32 is attached to the negative electrode 34.
  • the positive electrode 33 and the negative electrode 34 are stacked via the separator 35 and wound to produce a wound body that is a precursor of the wound electrode body 30, and then the outermost peripheral portion of the wound body.
  • a protective tape 37 is affixed to the surface.
  • the remaining outer peripheral edge portion excluding the outer peripheral edge portion of one side of the exterior member 40 is bonded using a heat fusion method or the like.
  • the wound body is housed inside the bag-shaped exterior member 40.
  • an electrolyte solution is prepared by mixing the electrolytic solution, a monomer that is a raw material of the polymer compound, a polymerization initiator, and other materials such as a polymerization inhibitor as necessary.
  • the electrolyte composition is injected into the bag-shaped exterior member 40, the exterior member 40 is sealed using a heat fusion method or the like.
  • the monomer is thermally polymerized to form a polymer compound. Thereby, since the electrolytic solution is held by the polymer compound, the gel electrolyte layer 36 is formed.
  • a wound body is produced and stored in the bag-shaped exterior member 40 in the same manner as in the second procedure described above except that the separator 35 on which the polymer compound layer is formed is used.
  • the opening of the exterior member 40 is sealed using a thermal fusion method or the like.
  • the exterior member 40 is heated while applying a load so that the separator 35 is in close contact with the positive electrode 33 through the polymer compound layer, and the separator 35 is in close contact with the negative electrode 34 through the polymer compound layer.
  • each of the polymer compound layers is impregnated with the electrolytic solution, and each of the polymer compound layers is gelled, so that the electrolyte layer 36 is formed.
  • the electrolyte layer 36 includes an electrolytic solution, and the electrolytic solution includes one or both of a BFO-containing metal salt, a dinitrile compound, an unsaturated cyclic carbonate, and a disulfonic anhydride. Together with. Therefore, excellent battery characteristics can be obtained for the same reason as the above-described cylindrical secondary battery. Other operations and effects are the same as those of the cylindrical secondary battery.
  • Lithium metal secondary battery The secondary battery described here is a cylindrical secondary battery (lithium metal secondary battery) in which the capacity of the negative electrode 22 is expressed by precipitation and dissolution of lithium metal.
  • This secondary battery has the same configuration as the above-described lithium ion secondary battery (cylindrical type) except that the negative electrode active material layer 22B is formed of lithium metal, and is manufactured by the same procedure. Is done.
  • the negative electrode active material layer 22B may already exist from the time of assembly, but does not exist at the time of assembly, and may be formed of lithium metal deposited during charging. Further, the anode current collector 22A may be omitted by using the anode active material layer 22B as a current collector.
  • This secondary battery operates as follows, for example. At the time of charging, lithium ions are released from the positive electrode 21, and the lithium ions are deposited as lithium metal on the surface of the negative electrode current collector 22A through the electrolytic solution. On the other hand, at the time of discharging, lithium metal is converted into lithium ions from the negative electrode active material layer 22B and eluted into the electrolytic solution, and the lithium ions are occluded in the positive electrode 21 through the electrolytic solution.
  • the electrolytic solution contains a BFO-containing metal salt, a dinitrile compound, and one or both of an unsaturated cyclic carbonate and a disulfonic anhydride. . Therefore, excellent battery characteristics can be obtained for the same reason as the above-described lithium ion secondary battery.
  • the configuration of the lithium metal secondary battery described here is not limited to the cylindrical secondary battery, and may be applied to a laminate film type secondary battery. In this case, the same effect can be obtained.
  • the secondary battery can be used for machines, devices, instruments, devices, and systems (a collection of multiple devices) that can use the secondary battery as a power source for driving or a power storage source for storing power.
  • the secondary battery used as a power source may be a main power source (a power source used preferentially) or an auxiliary power source (a power source used in place of the main power source or switched from the main power source).
  • the type of the main power source is not limited to the secondary battery.
  • the usage of the secondary battery is, for example, as follows.
  • Electronic devices including portable electronic devices
  • portable electronic devices such as video cameras, digital still cameras, mobile phones, notebook computers, cordless phones, headphone stereos, portable radios, portable televisions, and portable information terminals.
  • It is a portable living device such as an electric shaver.
  • Storage devices such as backup power supplies and memory cards.
  • Electric tools such as electric drills and electric saws.
  • It is a battery pack used for a notebook computer or the like as a detachable power source.
  • Medical electronic devices such as pacemakers and hearing aids.
  • An electric vehicle such as an electric vehicle (including a hybrid vehicle).
  • It is an electric power storage system such as a home battery system that stores electric power in case of an emergency. Of course, applications other than those described above may be used.
  • the battery pack is a power source using a secondary battery, and is a so-called assembled battery.
  • An electric vehicle is a vehicle that operates (runs) using a secondary battery as a driving power source, and may be an automobile (such as a hybrid automobile) that includes a drive source other than the secondary battery as described above.
  • the power storage system is a system that uses a secondary battery as a power storage source.
  • a secondary battery which is a power storage source
  • An electric power tool is a tool in which a movable part (for example, a drill etc.) moves, using a secondary battery as a driving power source.
  • An electronic device is a device that exhibits various functions using a secondary battery as a driving power source (power supply source).
  • FIG. 5 shows a perspective configuration of a battery pack using single cells
  • FIG. 6 shows a block configuration of the battery pack shown in FIG. FIG. 5 shows a state where the battery pack is disassembled.
  • the battery pack described here is a simple battery pack (so-called soft pack) using one secondary battery of the present technology, and is mounted on, for example, an electronic device typified by a smartphone.
  • the battery pack includes a power supply 111 that is a laminate film type secondary battery, and a circuit board 116 connected to the power supply 111.
  • a positive electrode lead 112 and a negative electrode lead 113 are attached to the power source 111.
  • a pair of adhesive tapes 118 and 119 are attached to both side surfaces of the power source 111.
  • a protection circuit (PCM: Protection Circuit Module) is formed on the circuit board 116.
  • the circuit board 116 is connected to the positive electrode 112 through the tab 114 and is connected to the negative electrode lead 113 through the tab 115.
  • the circuit board 116 is connected to a lead wire 117 with a connector for external connection. In the state where the circuit board 116 is connected to the power supply 111, the circuit board 116 is protected from above and below by the label 120 and the insulating sheet 121. By attaching the label 120, the circuit board 116, the insulating sheet 121, and the like are fixed.
  • the battery pack includes, for example, a power supply 111 and a circuit board 116 as shown in FIG.
  • the circuit board 116 includes, for example, a control unit 121, a switch unit 122, a PTC 123, and a temperature detection unit 124. Since the power source 111 can be connected to the outside via the positive electrode terminal 125 and the negative electrode terminal 127, the power source 111 is charged / discharged via the positive electrode terminal 125 and the negative electrode terminal 127.
  • the temperature detector 124 can detect the temperature using a temperature detection terminal (so-called T terminal) 126.
  • the control unit 121 controls the operation of the entire battery pack (including the usage state of the power supply 111), and includes, for example, a central processing unit (CPU) and a memory.
  • CPU central processing unit
  • the control unit 121 disconnects the switch unit 122 so that the charging current does not flow in the current path of the power supply 111. For example, when a large current flows during charging, the control unit 121 disconnects the charging current by cutting the switch unit 122.
  • the control unit 121 disconnects the switch unit 122 so that the discharge current does not flow in the current path of the power supply 111. For example, when a large current flows during discharging, the control unit 121 cuts off the switch unit 122 and cuts off the discharging current.
  • the overcharge detection voltage of the secondary battery is, for example, 4.20V ⁇ 0.05V, and the overdischarge detection voltage is, for example, 2.4V ⁇ 0.1V.
  • the switch unit 122 switches the usage state of the power source 111 (whether the power source 111 can be connected to an external device) in accordance with an instruction from the control unit 121.
  • the switch unit 122 includes, for example, a charge control switch and a discharge control switch.
  • Each of the charge control switch and the discharge control switch is, for example, a semiconductor switch such as a field effect transistor (MOSFET) using a metal oxide semiconductor.
  • MOSFET field effect transistor
  • the temperature detection unit 124 measures the temperature of the power supply 111 and outputs the measurement result to the control unit 121, and includes a temperature detection element such as a thermistor, for example.
  • the measurement result by the temperature detection unit 124 is used when the control unit 121 performs charge / discharge control during abnormal heat generation, or when the control unit 121 performs correction processing when calculating the remaining capacity.
  • circuit board 116 may not include the PTC 123.
  • a PTC element may be attached to the circuit board 116 separately.
  • FIG. 7 shows a block configuration of a battery pack using an assembled battery.
  • This battery pack includes, for example, a control unit 61, a power source 62, a switch unit 63, a current measurement unit 64, a temperature detection unit 65, a voltage detection unit 66, and a switch control unit 67 inside the housing 60.
  • the housing 60 is made of, for example, a plastic material.
  • the control unit 61 controls the operation of the entire battery pack (including the usage state of the power supply 62), and includes, for example, a CPU.
  • the power source 62 includes one or more secondary batteries of the present technology.
  • the power source 62 is, for example, an assembled battery including two or more secondary batteries, and the connection form of these secondary batteries may be in series, in parallel, or a mixture of both.
  • the power source 62 includes six secondary batteries connected in two parallel three series.
  • the switch unit 63 switches the usage state of the power source 62 (whether or not the power source 62 can be connected to an external device) according to an instruction from the control unit 61.
  • the switch unit 63 includes, for example, a charge control switch, a discharge control switch, a charging diode, a discharging diode, and the like.
  • the charge control switch and the discharge control switch are semiconductor switches such as a field effect transistor (MOSFET) using a metal oxide semiconductor, for example.
  • the current measurement unit 64 measures current using the current detection resistor 70 and outputs the measurement result to the control unit 61.
  • the temperature detection unit 65 measures the temperature using the temperature detection element 69 and outputs the measurement result to the control unit 61. This temperature measurement result is used, for example, when the control unit 61 performs charge / discharge control during abnormal heat generation, or when the control unit 61 performs correction processing when calculating the remaining capacity.
  • the voltage detection unit 66 measures the voltage of the secondary battery in the power supply 62, converts the measured voltage from analog to digital, and supplies the converted voltage to the control unit 61.
  • the switch control unit 67 controls the operation of the switch unit 63 in accordance with signals input from the current measurement unit 64 and the voltage detection unit 66.
  • the switch control unit 67 disconnects the switch unit 63 (charge control switch) and controls the charging current not to flow through the current path of the power source 62. .
  • the power source 62 can only discharge through the discharging diode.
  • the switch control unit 67 cuts off the charging current when a large current flows during charging, for example.
  • the switch control unit 67 disconnects the switch unit 63 (discharge control switch) so that the discharge current does not flow in the current path of the power source 62 when the battery voltage reaches the overdischarge detection voltage, for example. .
  • the power source 62 can only be charged via the charging diode.
  • the switch control part 67 interrupts
  • the overcharge detection voltage is 4.20V ⁇ 0.05V
  • the overdischarge detection voltage is 2.4V ⁇ 0.1V.
  • the memory 68 is, for example, an EEPROM which is a nonvolatile memory.
  • the memory 68 stores, for example, numerical values calculated by the control unit 61, secondary battery information (for example, internal resistance in an initial state) measured in the manufacturing process stage, and the like. If the full charge capacity of the secondary battery is stored in the memory 68, the control unit 61 can grasp information such as the remaining capacity.
  • the temperature detection element 69 measures the temperature of the power supply 62 and outputs the measurement result to the control unit 61, and is, for example, a thermistor.
  • the positive electrode terminal 71 and the negative electrode terminal 72 are connected to an external device (for example, a notebook personal computer) operated using a battery pack, an external device (for example, a charger) used to charge the battery pack, or the like. Terminal. Charging / discharging of the power source 62 is performed via the positive terminal 71 and the negative terminal 72.
  • an external device for example, a notebook personal computer
  • an external device for example, a charger
  • FIG. 8 shows a block configuration of a hybrid vehicle which is an example of an electric vehicle.
  • This electric vehicle includes, for example, a control unit 74, an engine 75, a power source 76, a driving motor 77, a differential device 78, a generator 79, and a transmission 80 inside a metal casing 73. And a clutch 81, inverters 82 and 83, and various sensors 84.
  • the electric vehicle includes, for example, a front wheel drive shaft 85 and a front wheel 86 connected to the differential device 78 and the transmission 80, and a rear wheel drive shaft 87 and a rear wheel 88.
  • This electric vehicle can run using, for example, either the engine 75 or the motor 77 as a drive source.
  • the engine 75 is a main power source, such as a gasoline engine.
  • the driving force (rotational force) of the engine 75 is transmitted to the front wheels 86 or the rear wheels 88 via, for example, a differential device 78, a transmission 80, and a clutch 81 which are driving units.
  • the rotational force of the engine 75 is also transmitted to the generator 79, and the generator 79 generates AC power using the rotational force.
  • the AC power is converted into DC power via the inverter 83, and the power source 76.
  • the motor 77 which is the conversion unit when used as a power source, the power (DC power) supplied from the power source 76 is converted into AC power via the inverter 82, and the motor 77 is driven using the AC power. .
  • the driving force (rotational force) converted from electric power by the motor 77 is transmitted to the front wheels 86 or the rear wheels 88 via, for example, a differential device 78, a transmission 80, and a clutch 81, which are driving units.
  • the resistance force at the time of deceleration may be transmitted as a rotational force to the motor 77, and the motor 77 may generate AC power using the rotational force.
  • This AC power is preferably converted into DC power via the inverter 82, and the DC regenerative power is preferably stored in the power source 76.
  • the control unit 74 controls the operation of the entire electric vehicle and includes, for example, a CPU.
  • the power source 76 includes one or more secondary batteries of the present technology.
  • the power source 76 may be connected to an external power source and can store power by receiving power supply from the external power source.
  • the various sensors 84 are used, for example, to control the rotational speed of the engine 75 and to control the throttle valve opening (throttle opening).
  • the various sensors 84 include, for example, a speed sensor, an acceleration sensor, an engine speed sensor, and the like.
  • the electric vehicle may be a vehicle (electric vehicle) that operates using only the power source 76 and the motor 77 without using the engine 75.
  • FIG. 9 shows a block configuration of the power storage system.
  • This power storage system includes, for example, a control unit 90, a power source 91, a smart meter 92, and a power hub 93 in a house 89 such as a general house and a commercial building.
  • the power source 91 is connected to an electric device 94 installed inside the house 89 and can be connected to an electric vehicle 96 stopped outside the house 89.
  • the power source 91 is connected to, for example, a private generator 95 installed in a house 89 via a power hub 93 and can be connected to an external centralized power system 97 via a smart meter 92 and the power hub 93. is there.
  • the electric device 94 includes, for example, one or more home appliances, and the home appliances are, for example, a refrigerator, an air conditioner, a television, and a water heater.
  • the private generator 95 is, for example, any one type or two types or more of a solar power generator and a wind power generator.
  • the electric vehicle 96 is, for example, any one type or two or more types of electric vehicles, electric motorcycles, hybrid vehicles, and the like.
  • the centralized power system 97 is, for example, any one type or two or more types among a thermal power plant, a nuclear power plant, a hydroelectric power plant, and a wind power plant.
  • the control unit 90 controls the operation of the entire power storage system (including the usage state of the power supply 91), and includes, for example, a CPU.
  • the power source 91 includes one or more secondary batteries of the present technology.
  • the smart meter 92 is, for example, a network-compatible power meter installed in a house 89 on the power demand side, and can communicate with the power supply side. Accordingly, for example, the smart meter 92 enables efficient and stable energy supply by controlling the balance between supply and demand in the house 89 while communicating with the outside.
  • the power storage system for example, power is accumulated in the power source 91 from the centralized power system 97 that is an external power source via the smart meter 92 and the power hub 93, and from the private power generator 95 that is an independent power source via the power hub 93.
  • electric power is accumulated in the power source 91. Since the electric power stored in the power supply 91 is supplied to the electric device 94 and the electric vehicle 96 in accordance with an instruction from the control unit 91, the electric device 94 can be operated and the electric vehicle 96 can be charged.
  • the power storage system is a system that makes it possible to store and supply power in the house 89 using the power source 91.
  • the power stored in the power supply 91 can be used arbitrarily. For this reason, for example, power is stored in the power source 91 from the centralized power system 97 at midnight when the electricity usage fee is low, and the power stored in the power source 91 is used during the day when the electricity usage fee is high. it can.
  • the power storage system described above may be installed for each house (one household), or may be installed for each of a plurality of houses (multiple households).
  • FIG. 10 shows a block configuration of the electric power tool.
  • This electric tool is, for example, an electric drill, and includes a control unit 99 and a power supply 100 inside a tool main body 98 formed of a plastic material or the like.
  • a drill portion 101 which is a movable portion is attached to the tool body 98 so as to be operable (rotatable).
  • the control unit 99 controls the operation of the entire power tool (including the usage state of the power supply 100), and includes, for example, a CPU.
  • the power supply 100 includes one or more secondary batteries of the present technology.
  • the control unit 99 supplies power from the power supply 100 to the drill unit 101 in accordance with the operation of the operation switch.
  • the coin type secondary battery (lithium ion secondary battery) shown in FIG. 11 was produced as a test secondary battery by the following procedure.
  • test electrode 51 accommodated in the exterior can 52 and the counter electrode 53 accommodated in the exterior cup 54 are laminated via the separator 55, and the exterior can 52 and the exterior cup 54 are connected to the gasket 56. Is being squeezed through.
  • the test electrode 51 When preparing the test electrode 51, first, 96 parts by mass of an active material (LiCoO 2 ), 3 parts by mass of a binder (polyvinylidene fluoride), and 1 part by mass of a conductive agent (carbon black) are mixed. The mixture was used. Subsequently, the mixture was dispersed in an organic solvent (N-methyl-2-pyrrolidone) to obtain a paste mixture slurry. Subsequently, the mixture slurry was applied to both surfaces of the current collector (20 ⁇ m-thick striped aluminum foil) using a coating apparatus, and then the mixture slurry was dried to form an active material layer. Finally, the active material layer was compression molded using a roll press.
  • an active material LiCoO 2
  • 3 parts by mass of a binder polyvinylidene fluoride
  • a conductive agent carbon black
  • an active material mixture of graphite and silicon
  • a binder polyvinylidene fluoride
  • an electrolyte salt was dissolved in a solvent.
  • Solvents include ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), and cyclic halogenated carbonate 4-fluoro-1,3-dioxolan-2-one (FEC).
  • the mixed solvent was used.
  • LiDFOB lithium difluorooxalate borate
  • LiPF 6 lithium hexafluorophosphate
  • the composition of the electrolyte salt and the content (mol / kg) of each component with respect to the solvent are as shown in Tables 1 and 2.
  • a dinitrile compound, an unsaturated cyclic carbonate, a disulfonic anhydride and other materials were added to the solvent in which the electrolyte salt was dissolved, as necessary.
  • the respective types of dinitrile compounds, unsaturated cyclic carbonates, disulfonic anhydrides and other materials and the content (% by weight) in the electrolytic solution are as shown in Tables 1 and 2.
  • Succinonitrile was used as the dinitrile compound.
  • 4-methylene-1,3-dioxolan-2-one was used as the unsaturated cyclic carbonate.
  • PSAH Propane disulfonic anhydride
  • Other materials include 1,3-propane sultone (PS) which is a sulfonate ester, lithium difluorophosphate (LiPF 2 O 2 ) and lithium fluorophosphate (Li 2 PFO 3 ) which are phosphorus fluorine-containing salts.
  • the test electrode 51 was punched out into a pellet shape, and then the test electrode 51 was accommodated in an outer can 52. Subsequently, after punching the counter electrode 53 into a pellet, the counter electrode 53 was accommodated in the exterior cup 54. Subsequently, the test electrode 51 accommodated in the outer can 52 and the counter electrode 53 accommodated in the outer cup 54 are laminated through the separator 55 (23 ⁇ m-thick microporous polypropylene film), and then the gasket 56 is interposed. The outer can 52 and the outer cup 54 were caulked. Thereby, a coin-type secondary battery was completed.
  • laminate film type secondary battery (lithium ion secondary battery) shown in FIGS. 3 and 4 was produced by the following procedure. In the following, the components of the coin-type secondary battery already described will be quoted as needed.
  • the positive electrode active material layer 33 ⁇ / b> B was formed on both surfaces of the positive electrode current collector 33 ⁇ / b> A by the same procedure as the production procedure of the test electrode 51. Further, when producing the negative electrode 34, the negative electrode active material layer 34 ⁇ / b> B was formed on both surfaces of the negative electrode current collector 34 ⁇ / b> A by the same procedure as the production procedure of the counter electrode 53.
  • the positive electrode lead 31 made of aluminum was welded to the positive electrode current collector 33A, and the negative electrode lead 32 made of copper was welded to the negative electrode current collector 34A.
  • the positive electrode 33 and the negative electrode 34 are laminated via the separator 35 (23 ⁇ m-thick microporous polypropylene film)
  • the positive electrode 33, the negative electrode 34, and the separator 35 are wound in the longitudinal direction.
  • a rotating electrode body 30 was formed.
  • a protective tape 37 was attached to the outermost peripheral portion of the wound electrode body 30.
  • the exterior member 40 was bent so as to sandwich the wound electrode body 30, the outer peripheral edge portions on the three sides of the exterior member 40 were heat-sealed.
  • the exterior member 40 includes a nylon film (30 ⁇ m thickness), an aluminum foil (40 ⁇ m thickness), and an unstretched polypropylene film (30 ⁇ m thickness) laminated in this order from the outside in a moisture resistant aluminum laminate film (total thickness 100 ⁇ m). ) was used. Finally, an electrolyte solution was injected into the exterior member 40 and the wound electrode body 30 was impregnated with the electrolyte solution, and then the remaining one side of the exterior member 40 was heat-sealed in a reduced pressure environment.
  • the adhesion film 41 (50 ⁇ m thick acid-modified propylene film) is inserted between the positive electrode lead 31 and the exterior member 40, and the adhesion film 41 is similarly inserted between the negative electrode lead 32 and the exterior member 40. Inserted. Thereby, a laminated film type secondary battery was completed.
  • the thickness of the positive electrode active material layer 33B is adjusted so that the charge / discharge capacity of the negative electrode 34 is larger than the charge / discharge capacity of the positive electrode 33, and the negative electrode 34 is fully charged. Lithium metal was not precipitated.
  • 0.2 C is a current value at which the battery capacity (theoretical capacity) can be discharged in 5 hours
  • 0.05 C is a current value at which the battery capacity can be discharged in 20 hours.
  • the capacity retention rate and the swelling rate varied greatly depending on the composition of the electrolyte.
  • the capacity retention rate when the electrolyte does not contain a BFO-containing metal salt (LiDFOB) (Experimental Examples 23 to 28) will be examined.
  • the capacity retention rate in the case where the electrolytic solution does not contain any of a dinitrile compound, an unsaturated cyclic carbonate, and a disulfonic anhydride (Experimental Example 23) is used as a comparison reference.
  • the unsaturated cyclic carbonate functions to increase the capacity retention rate, while the dinitrile compound functions to decrease the capacity retention ratio. Due to the difference in these functions, when the electrolyte contains a dinitrile compound and an unsaturated cyclic carbonate, the unsaturated cyclic carbonate increases the capacity retention rate, while the dinitrile compound has a capacity retention rate. Decrease. For this reason, the capacity maintenance rate when the electrolytic solution contains the dinitrile compound and the unsaturated cyclic carbonate is much larger than the capacity maintenance rate when the electrolytic solution contains only the unsaturated cyclic carbonate. It will decrease.
  • the unsaturated cyclic carbonate functions to increase the capacity retention rate
  • the dinitrile compound functions to decrease the capacity retention ratio. Therefore, when the electrolytic solution contains the dinitrile compound and the unsaturated cyclic carbonate together, the same tendency as in the case where the electrolytic solution does not contain the BFO-containing metal salt (Experimental Examples 23 to 28) is obtained. Expected to be. Specifically, the capacity retention rate when the electrolyte solution contains a dinitrile compound and an unsaturated cyclic carbonate ester greatly increases the capacity retention rate when the electrolyte solution contains only an unsaturated cyclic carbonate ester. Expected to be less than
  • the electrolytic solution contains a BFO-containing metal salt, a dinitrile compound, and an unsaturated cyclic carbonate together (Experimental Examples 3, 5, and 6), the electrolytic solution contains a BFO-containing metal salt, a dinitrile compound, and an unsaturated cyclic carbonate. Compared with the case where the saturated cyclic carbonate was not included (Experimental Examples 29 to 31), the swelling rate was greatly reduced.
  • the electrolytic solution contains a BFO-containing metal salt, a dinitrile compound, and a disulfonic anhydride (Experimental Examples 8, 11, and 12)
  • the electrolytic solution contains a BFO-containing metal salt, a dinitrile compound, and a disulfone.
  • the swelling rate was greatly reduced.
  • the electrolytic solution included a BFO-containing metal salt, a dinitrile compound, and an unsaturated cyclic carbonate or disulfonic anhydride.
  • the battery structure is a cylindrical type, a laminate film type, and a coin type and the battery element has a winding structure
  • the secondary battery of the present technology can be similarly applied even when other battery structures such as a square type and a button type are provided. Further, the secondary battery of the present technology can be similarly applied when the battery element has another structure such as a laminated structure.
  • the electrolyte solution for a secondary battery of the present technology is not limited to a secondary battery, and may be applied to other electrochemical devices.
  • Other electrochemical devices are, for example, capacitors.
  • a secondary battery comprising: an electrolyte solution containing at least one of disulfonic anhydrides represented by: (M is an alkali metal element.) NC-R1-CN (2) (R1 is a divalent hydrocarbon group.) (R2 and R3 are each a hydrogen group or a monovalent hydrocarbon group. R4 is a divalent group represented by> CR5R6, and each of R5 and R6 is a hydrogen group.
  • R7 is a divalent hydrocarbon group.
  • the alkali metal element is any one of lithium (Li), sodium (Na), and potassium (K)
  • the monovalent hydrocarbon group is any one of an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, and a monovalent group in which two or more of them are bonded
  • the divalent hydrocarbon group is any one of an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, an arylene group, and a divalent group in which two or more of them are bonded.
  • the secondary battery as described in said (1).
  • Each of the alkyl group and the alkylene group has 1 to 12 carbon atoms; Each of the alkenyl group, the alkynyl group, the alkenylene group, and the alkynylene group has 2 to 12 carbon atoms, Each of the cycloalkyl group and the cycloalkylene group has 3 to 18 carbon atoms, Each of the aryl group and the arylene group has 6 to 18 carbon atoms.
  • the content of the BFO-containing metal salt in the electrolytic solution is 0.02 mol / kg to 1 mol / kg,
  • the dinitrile compound content in the electrolytic solution is 0.2 wt% to 5 wt%,
  • the content of the unsaturated cyclic carbonate in the electrolytic solution is 0.1 wt% to 10 wt%,
  • the content of the disulfonic anhydride in the electrolytic solution is 0.1 wt% to 5 wt%.
  • M is an alkali metal element.
  • NC-R1-CN (2) R1 is a divalent hydrocarbon group.
  • R2 and R3 are each a hydrogen group or a monovalent hydrocarbon group.
  • R4 is a divalent group represented by> CR5R6, and each of R5 and R6 is a hydrogen group.
  • An electronic apparatus comprising the secondary battery according to any one of (1) to (5) as a power supply source.

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Abstract

L'invention conerne une batterie secondaire comprenant : une électrode positive; une électrode négative; et un électrolyte contenant au moins un élément sélectionné parmi un sel métallique contenant du bore, du fluor, et de l'oxygène (BFO), un composé dinitrile, un ester de carbone cyclique insaturé, et un anhydride disulfonique.
PCT/JP2015/076171 2014-10-10 2015-09-15 Électrolyte pour batterie secondaire, batterie secondaire, bloc-batterie, véhicule électrique, système d'accumulation d'énergie, outil électrique et équipement d'appreil électronique WO2016056361A1 (fr)

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CN109449480A (zh) * 2018-11-27 2019-03-08 桑顿新能源科技有限公司 一种添加剂及电解液及三元锂离子电池
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CN105958118A (zh) * 2016-05-18 2016-09-21 东莞市凯欣电池材料有限公司 一种高电压锂离子电池用非水电解质溶液及一种锂电池
EP3766122A4 (fr) * 2018-03-12 2022-05-04 Tesla, Inc. Nouveaux systèmes de batterie basés sur des systèmes d'électrolyte à deux additifs comprenant du 1,2,6-oxodithiane-2,2,6,6-tétraoxyde
CN109449480A (zh) * 2018-11-27 2019-03-08 桑顿新能源科技有限公司 一种添加剂及电解液及三元锂离子电池
CN110380113A (zh) * 2019-08-02 2019-10-25 湖州昆仑动力电池材料有限公司 高电压锂离子电池电解液用添加剂及其应用
CN114175342A (zh) * 2019-12-24 2022-03-11 宁德时代新能源科技股份有限公司 二次电池及含有该二次电池的装置
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