Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0567—Liquid materials characterised by the additives
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to a non-aqueous electrolyte and a non-aqueous electrolyte battery, and more specifically to a non-aqueous electrolyte containing a specific compound and a non-aqueous electrolyte battery using this non-aqueous electrolyte.
• Non-aqueous electrolyte batteries such as lithium secondary batteries are practically used in a wide range of applications such as power sources for small consumer devices such as mobile phones such as smartphones and notebook computers, and vehicle power sources for driving electric vehicles. has been made
• Patent Document 1 discloses that a cyclic sulfuric acid compound is added to a non-aqueous electrolytic solution composed of an organic solvent such as a lithium salt, a specific carbamate compound, and a carbonate to improve the high-temperature cycle capacity retention rate and the battery performance during high-temperature storage. Studies have been disclosed to improve thickness variation.
• Patent Document 2 a trialkylsilyl compound of protonic acid, sulfonic acid, and carboxylic acid having a phosphorus atom and/or a boron atom and a basic compound or a specific silicon compound are added to a non-aqueous electrolytic solution to convert silyl Studies are disclosed to improve the storage stability of the group-containing compound and, in addition, to improve the 4.9 V high voltage cycle capacity retention rate and the amount of gas generated during battery operation.
• the present inventors have found that at least the compound represented by the general formula (A), the compound represented by the general formula ( ⁇ ), and the compound represented by the general formula ( ⁇ ) By using a non-aqueous electrolytic solution containing one of them, the present invention was completed based on the idea of suppressing gas generation during initial conditioning.
• a non-aqueous electrolytic solution for a non-aqueous electrolytic battery comprising a positive electrode and a negative electrode capable of absorbing and releasing metal ions, comprising an alkali metal salt, a non-aqueous solvent, and a compound represented by the general formula (A), and at least one of a compound represented by general formula ( ⁇ ) and a compound represented by general formula ( ⁇ ).
• Q 1 and Q 2 each independently represent an optionally substituted alkylene group having 1 to 10 carbon atoms.
• n 1 represents an integer of 0 or 1.
• R 1 and R 2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a silyl group represented by —SiR 3 R 4 R 5 ;
• R 3 to R 5 are each independently a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, or an optionally substituted C 1 to 12 represents an alkoxy group;
• Y is a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, a group represented by —NR 6 —SiR 7 R 8 R 9 , or a group represented by —NR 10 —R 11 ;
• R 6 , R 10 and R 11 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent;
• R 7 to R 9 are each independently a hydrogen atom,
• R 1 or R 2 and Y may combine with each other to form a ring.
• R 21 to R 23 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a carbon represents an aralkyl group having a number of 7 to 18; Z represents an optionally substituted alkenyl group having 2 to 10 carbon atoms or an alkynyl group.
• the content of the compound represented by the general formula (A) is 1.0 ⁇ 10 -3 % by mass or more and 10% by mass or less with respect to the total amount of the non-aqueous electrolyte solution.
• Non-aqueous electrolyte is 1.0 ⁇ 10 -3 % by mass or more and 10% by mass or less with respect to the total amount of the non-aqueous electrolyte solution.
• ⁇ 3> The content of the compound represented by the general formula ( ⁇ ) or the compound represented by the general formula ( ⁇ ) is 0.01 mass ppm or more and 0.5 mass% or less with respect to the total amount of the non-aqueous electrolytic solution
• ⁇ 4> The content of the compound represented by the general formula (A) with respect to the content of the compound represented by the general formula ( ⁇ ) or the compound represented by the general formula ( ⁇ ) in the non-aqueous electrolyte
• Y relating to the compound represented by the general formula ( ⁇ ) represents a group represented by —NR 6 —SiR 7 R 8 R 9 or a group represented by —NR 10 —R 11 ;
• the non-aqueous electrolytic solution according to any one of ⁇ 1> to ⁇ 4>.
• ⁇ 6> A non-aqueous electrolyte for a non-aqueous electrolyte battery comprising a positive electrode and a negative electrode capable of absorbing and releasing metal ions, comprising an alkali metal salt, a non-aqueous solvent, and a compound represented by the general formula (AA), and a compound represented by general formula ( ⁇ ).
• Q 31 and Q 32 each independently represent an alkylene group having 1 to 10 carbon atoms.
• the alkylene group may be substituted with a hydrocarbon group, and the hydrogen atom of the alkylene group is a halogen atom, n31 represents an integer of 0 or 1.
• R 31 and R 32 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a silyl group represented by —SiR 33 R 34 R 35 ;
• R 33 to R 35 are each independently a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, or an optionally substituted C 1 to 12
• Y 31 represents an optionally substituted alkoxy group having 1 to 12 carbon atoms, and R 31 or R 32 and Y 31 may combine with each other to form a ring.
• the content of the compound represented by the general formula (AA) is 1.0 ⁇ 10 -3 % by mass or more and 10% by mass or less with respect to the total amount of the non-aqueous electrolyte solution.
• the mass ratio of the content of the compound represented by the general formula (AA) to the content of the compound represented by the general formula ( ⁇ ) in the non-aqueous electrolytic solution is 1.0 or more and 1.0.
• a non-aqueous electrolyte battery comprising a positive electrode and a negative electrode capable of absorbing and releasing metal ions, and a non-aqueous electrolyte, wherein the non-aqueous electrolyte is any one of ⁇ 1> to ⁇ 9>.
• non-aqueous electrolyte solution that is excellent in suppressing the amount of gas generated during the initial conditioning of a non-aqueous electrolyte battery, and a non-aqueous electrolyte battery that suppresses the amount of gas generated during the initial conditioning.
• Non-aqueous electrolytic solution is a compound represented by the general formula (A) described below, and at least one of the compound represented by the general formula ( ⁇ ) and the compound represented by the general formula ( ⁇ ) contains one
• the compound represented by the general formula (A) has a cyclic structure and a polar structure ( --SO.sub.2 --O--) in the cyclic skeleton, and thus has a higher dielectric constant than a chain compound.
• the compounds localized on the surface of the active material also interact with each other, so that the localized compounds It is presumed that the amount of fixation on the surface of the positive electrode active material and/or the negative electrode active material also increases.
• the compound represented by the general formula ( ⁇ ) and the compound represented by the general formula (A) localized on the electrode during the initial charge are electrochemically decomposed to form a composite insulating film. do.
• the compound represented by the general formula (A) has a cyclic structure and a polar structure ( --SO.sub.2 --O--) in the cyclic skeleton, and therefore has a higher dielectric constant than a chain compound.
• the compound represented by the general formula (A) tends to interact with the surface of the negative electrode active material such as carbon and/or the positive electrode active material such as transition metal oxide, and localize near the surface.
• the compound represented by the general formula ( ⁇ ) has an unsaturated bond having ⁇ electrons in the molecule and a nonpolar structure (-SiR 21 R 22 R 11 ).
• silicon atoms have a large electron cloud and do not have steric hindrance when forming bonds, so they easily form bonds with ⁇ electrons and unpaired electrons via empty d orbitals. .
• the compound represented by the general formula (A) localized on the surface of the active material interacts with the compound represented by the general formula ( ⁇ ), thereby promoting the fixation of these compounds to the electrode.
• the compound represented by the general formula ( ⁇ ) and the compound represented by the general formula (A) are electrochemically decomposed during the initial charging to form a composite insulating coating. It is presumed that this composite coating suppresses side reactions of the electrolyte during initial conditioning and suppresses gas generation.
• Q 1 and Q 2 in general formula (A) each independently represent an optionally substituted alkylene group having 1 to 10 carbon atoms.
• Q 1 is preferably an optionally substituted alkylene group having 1 to 5 carbon atoms, more preferably an optionally substituted 1 to 3 carbon atom group.
• Q 1 is preferably an optionally substituted alkylene group having 1 to 5 carbon atoms, more preferably an optionally substituted alkylene group having 1 to 5 carbon atoms. 3, preferably a methylene group which may have a substituent.
• Q 2 is preferably an optionally substituted alkylene group having 1 to 5 carbon atoms, more preferably an optionally substituted alkylene group having 1 to 3 carbon atoms, particularly A methylene group which may have a substituent is preferred.
• the alkylene group has a substituent, the number of carbon atoms included in the substituent is not included in the number of carbon atoms.
• alkylene groups include methylene, ethylene, n-propylene, butylene, and hexylene groups.
• R a represents an alkyl group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms.
• Ra When Ra is an alkylene group, it may combine with part of the substituted hydrocarbon group to form a ring.
• hydrocarbon groups having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 1 to 10 carbon atoms, alkynyl groups having 1 to 10 carbon atoms, and aryl groups having 6 to 10 carbon atoms. and aralkyl groups having 7 to 10 carbon atoms.
• alkyl groups include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, n-pentyl group, hexyl group, heptyl group, octyl group and nonyl group.
• decyl group cyclohexyl group and the like.
• methyl group, ethyl group, n-propyl group, n-butyl group, tert-butyl group, n-pentyl group, hexyl group and cyclohexyl group more preferably methyl group, ethyl group and n-propyl group, n-butyl group, tert-butyl group, n-pentyl group and cyclohexyl group, particularly preferably methyl group, ethyl group, n-butyl group, tert-butyl group and cyclohexyl group.
• alkenyl groups include vinyl, allyl, methallyl, 2-butenyl, 3-methyl-2-butenyl, 3-butenyl, and 4-pentenyl groups.
• preferred are vinyl group, allyl group, methallyl group and 2-butenyl group, more preferred are vinyl group, allyl group and methallyl group, and particularly preferred is vinyl group or allyl group.
• alkynyl groups include ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, 4-pentynyl, and 5-hexynyl groups.
• ethynyl group, 2-propynyl group, 2-butynyl group and 3-butynyl group are more preferred, 2-propynyl group and 3-butynyl group are more preferred, and 2-propynyl group is particularly preferred.
• aryl groups include a phenyl group and a tolyl group. Among them, a phenyl group is preferred.
• aralkyl groups include benzyl and phenethyl groups.
• Specific examples of the sulfonyloxy group (--O(SO 2 )--R a ) include --O(SO 2 )--CH 3 and --O(SO 2 )--CH 2 CH 3 .
• the compounds represented by formula (A) may be used singly or in combination of two or more.
• the content of the compound represented by the general formula (A) with respect to the total amount of the non-aqueous electrolyte according to one embodiment of the present invention is usually 1.0 ⁇ 10 -3 % by mass or more, preferably 1.0 ⁇ 10 ⁇ 2 mass % or more, more preferably 0.1 mass % or more, and usually 10 mass % or less, preferably 5 mass % or less, more preferably is 3% by mass or less, more preferably 2% by mass or less, and particularly preferably 1% by mass or less.
• the content of the compound represented by the general formula (A) with respect to the total amount of the non-aqueous electrolyte is within the above range, the concentration of the compound in the active material proceeds more favorably, and the gas generation during the initial conditioning is more likely. It becomes possible to manufacture a small number of batteries.
• a non-aqueous electrolytic solution contains a compound represented by general formula ( ⁇ ).
• R 1 and R 2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a silyl group represented by —SiR 3 R 4 R 5 ;
• R 3 to 5 are each independently a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, or an optionally substituted alkoxy having 1 to 12 carbon atoms
• Y is a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, a group represented by —NR 6 —SiR 7 R 8 R 9 , or — represents a group represented by NR 10 -R 11 ;
• R 6 , R 10 and R 11 each independently represents a hydrogen atom or a hydrocarbon group having 1
• R 1 and R 2 in general formula ( ⁇ ) each independently represent a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a silyl group represented by —SiR 3 R 4 R 5 , and R 3 to R 5 are each independently a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, or an optionally substituted carbon number 1 to 12 represents an alkoxy group of In the silyl group represented by —SiR 3 R 4 R 5 , R 3 to R 5 are each independently a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent.
• an optionally substituted alkoxy group having 1 to 12 carbon atoms is preferable, and particularly preferably having a substituent is a hydrocarbon group having 1 to 12 carbon atoms which may be substituted.
• the hydrocarbon group has a substituent, the number of carbon atoms included in the substituent is not included in the number of carbon atoms.
• at least one of R 3 to R 5 is an alkyl group having 1 to 12 carbon atoms, from the viewpoint that the compound represented by the general formula ( ⁇ ) tends to be favorably localized on the electrode surface. is preferred.
• R 3 to R 5 are particularly preferably alkyl groups having 1 to 12 carbon atoms.
• R 3 to R 5 in general formula ( ⁇ ) may be the same or different, but preferably at least two or more of them are the same from the viewpoint of facilitating synthesis of the compound, and all three are the same. It is even more preferable in view of the foregoing.
• a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned as a halogen atom.
• a fluorine atom is preferable from the viewpoint of less electrochemical side reactions.
• the hydrocarbon group having 1 to 12 carbon atoms is preferably a hydrocarbon group having 1 to 6 carbon atoms, particularly preferably a hydrocarbon group having 1 to 4 carbon atoms.
• hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, aralkyl groups and aryl groups.
• alkyl groups include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, n-pentyl group, hexyl group, heptyl group, octyl group and nonyl group.
• a chain alkyl group such as a decyl group
• a cyclic alkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
• methyl group, ethyl group, n-propyl group, n-butyl group, tert-butyl group, n-pentyl group, hexyl group and cyclohexyl group more preferably methyl group, ethyl group and n-propyl group, n-butyl group, tert-butyl group, n-pentyl group and cyclohexyl group, particularly preferably methyl group, ethyl group, n-butyl group, tert-butyl group and cyclohexyl group.
• the alkyl group described above is preferred because the compound represented by the general formula ( ⁇ ) tends to localize near the surface of the positive electrode active material and/or the negative electrode active material.
• alkenyl groups include vinyl, allyl, methallyl, 2-butenyl, 3-methyl-2-butenyl, 3-butenyl, and 4-pentenyl groups.
• preferred are vinyl group, allyl group, methallyl group and 2-butenyl group, more preferred are vinyl group, allyl group and methallyl group, and particularly preferred is vinyl group or allyl group.
• the above alkenyl group is preferable because the compound represented by the general formula ( ⁇ ) tends to localize near the surface of the positive electrode active material and/or the negative electrode active material.
• alkynyl groups include ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, 4-pentynyl, and 5-hexynyl groups. Among them, ethynyl group, 2-propynyl group, 2-butynyl group and 3-butynyl group are more preferred, 2-propynyl group and 3-butynyl group are more preferred, and 2-propynyl group is particularly preferred.
• the aforementioned alkynyl group is preferable because the compound represented by the general formula ( ⁇ ) tends to localize near the surface of the positive electrode active material and/or the negative electrode active material.
• aryl groups include a phenyl group and a tolyl group.
• a phenyl group is preferable from the viewpoint that the compound represented by the general formula ( ⁇ ) tends to localize near the surface of the positive electrode active material and/or the negative electrode active material.
• aralkyl groups include benzyl and phenethyl groups.
• the alkoxy group having 1 to 12 carbon atoms is preferably an alkoxy group having 1 to 6 carbon atoms, and particularly preferably an alkoxy group having 1 to 4 carbon atoms.
• alkoxy groups having 1 to 12 carbon atoms include methoxy, ethoxy, propoxy, butoxy, and isopropoxy groups.
• a methoxy group and an ethoxy group are preferable in that the steric hindrance of the compound is small and they are preferably concentrated on the surface of the active material.
• alkoxycarbonyl group (-(C O)O-R b ), sulfonyl group (-SO 2 -R b ), sulfonyloxy group (-O(SO 2 )-R b ), alkoxysulfonyl group (-(SO 2 ) —OR b ), alkoxysulfonyloxy group (—O—(SO 2 )—OR b ), alkoxycarbonyloxy group (—O—(C ⁇ O)—OR b ), alkoxy group (-OR b ), acryl group, methacryl group, halogen atom (preferably fluorine atom), trifluoromethyl group and the like.
• R b represents an alkyl group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms.
• Rb is an alkylene group, it may combine with part of the substituted hydrocarbon group to form a ring.
• Y in the general formula ( ⁇ ) is a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, or a group represented by —NR 6 —SiR 7 R 8 R 9 or a group represented by —NR 10 —R 11 , wherein R 6 , R 10 and R 11 are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent and R 7 to R 9 are each independently a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, or an optionally substituted carbon represents an alkoxy group of numbers 1-12; Among them, the group represented by -NR 6 -SiR 7 R 8 R 9 or the group represented by -NR 10 -R 11 more favorably interacts with the compound represented by general formula (A).
• R 3 to R 5 applies to both halogen atoms and hydrocarbon groups having 1 to 12 carbon atoms which may have a substituent.
• R 6 is a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 12 carbon atoms
• R 1 applies to the hydrocarbon group having 1 to 12 carbon atoms which may be present, and the preferred embodiments are also the same.
• the group represented by -SiR 7 R 8 R 9 is explained in the same manner as the group represented by -SiR 3 R 4 R 5 , and the preferred embodiments are also the same.
• R 10 and R 11 are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent.
• R 1 applies to the optionally substituted hydrocarbon group having 1 to 12 carbon atoms, and the preferred embodiments are also the same.
• the compounds represented by formula ( ⁇ ) may be used singly or in combination of two or more.
• the content of the compound represented by the general formula ( ⁇ ) with respect to the total amount of the non-aqueous electrolytic solution according to one embodiment of the present invention is not particularly limited, but is preferably is 0.01 mass ppm or more, more preferably 0.1 mass ppm or more, still more preferably 1.0 mass ppm or more, particularly preferably 10 mass ppm or more, and preferably 1.0 mass ppm or less , more preferably 0.75% by mass or less, still more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less.
• the content of the compound represented by the general formula ( ⁇ ) with respect to the total amount of the non-aqueous electrolyte is within the above range, the concentration of the compound in the active material proceeds more favorably, and the gas generation during the initial conditioning is more likely. It becomes possible to manufacture a small number of batteries.
• the mass ratio of the compound represented by the general formula (A) to the content of the compound represented by the general formula ( ⁇ ) in the non-aqueous electrolyte is not particularly limited, but is usually 1.0 or more, preferably 2.0 or more, and is usually 1.0 ⁇ 10 4 or less, preferably 7.0 ⁇ 10 3 or less, more preferably 4.0 ⁇ 10 3 or less, still more preferably 2.0 ⁇ 10 3 or less, even more preferably 1.0 ⁇ 10 3 or less, particularly preferably 5.0 ⁇ 10 2 or less.
• a non-aqueous electrolytic solution according to one embodiment of the present invention contains an unsaturated silane compound represented by the general formula ( ⁇ ).
• each of R 21 to R 23 is independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a carbon represents an aralkyl group having a number of 7 to 18;
• Z represents an optionally substituted alkenyl group or alkynyl group having 2 to 10 carbon atoms.
• R c represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms.
• the carbon atoms in these substituents are not counted in the number of carbon atoms in the hydrocarbon groups of R 21 to R 23 and Z having 1 to 12 carbon atoms.
• alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, n-pentyl group, hexyl group and heptyl group. , an octyl group, a nonyl group, or a decyl group.
• methyl group, ethyl group, n-propyl group, n-butyl group, tert-butyl group, n-pentyl group and hexyl group preferred are methyl group, ethyl group, n-propyl group and n- A butyl group, a tert-butyl group or an n-pentyl group, particularly preferably a methyl group or an ethyl group.
• aryl group having 6 to 18 carbon atoms include a phenyl group and a tolyl group. Among them, a phenyl group is preferable because it facilitates the progress of concentration into the active material.
• aralkyl group having 7 to 18 carbon atoms include phenylmethyl group (benzyl group), phenylethyl group (phenethyl group), phenylpropyl group, phenylbutyl group, phenylisopropyl group and the like.
• a benzyl group and a phenethyl group are preferable, and a benzyl group is particularly preferable, from the viewpoint that the compound represented by the general formula ( ⁇ ) tends to localize near the surface of the positive electrode active material and/or the negative electrode active material. .
• alkenyl group having 2 to 10 carbon atoms include vinyl group, allyl group, methallyl group, 2-butenyl group, 3-methyl-2-butenyl group, 3-butenyl group, or 4-pentenyl group. .
• vinyl group, allyl group, methallyl group or 2-butenyl group is preferred, vinyl group, allyl group or methallyl group is more preferred, and allyl group or methallyl group is particularly preferred. This is because the above alkenyl group can suitably form an insulating film.
• alkynyl groups having 2 to 10 carbon atoms include ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, 4-pentynyl, and 5-hexynyl groups.
• an ethynyl group, a 2-propynyl group, a 2-butynyl group or a 3-butynyl group is preferred, an ethynyl group, a 2-propynyl group or a 3-butynyl group is more preferred, and an ethynyl group or a 2- It is a propynyl group. This is because the above alkynyl group can suitably form an insulating film.
• R 21 to R 23 is substituted.
• an alkyl group having 1 to 10 carbon atoms which may have a group preferably at least two are alkyl groups having 1 to 10 carbon atoms which may have a substituent, more preferably all is an optionally substituted alkyl group having 1 to 10 carbon atoms, and is most preferably a methyl group or an ethyl group.
• any one of R 21 to R 23 is a methyl group, all of R 21 to R 23 need not be methyl groups. For example, the following combinations are preferred.
• R 21 , R 22 , R 23 (methyl group, methyl group, ethyl group), (methyl group, methyl group, n-butyl group), (methyl group, methyl group, tert-butyl group), (methyl group, methyl group, phenyl group), (methyl group, ethyl group, ethyl group), (methyl group, phenyl group, phenyl group).
• Z is preferably an optionally substituted alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 10 carbon atoms, still more preferably vinyl group, allyl group or methallyl group, particularly preferably allyl group or methallyl group. This is because an insulating film can be suitably formed.
• the compounds represented by formula ( ⁇ ) may be used singly or in combination of two or more.
• the content of the compound represented by the general formula ( ⁇ ) with respect to the total amount of the non-aqueous electrolytic solution according to one embodiment of the present invention is usually 0.01 mass ppm or more, Preferably 0.001% by mass or more, more preferably 0.005% by mass or more, still more preferably 0.01% by mass or more, and usually 5% by mass or less, preferably 2% by mass or less, more preferably is 1% by mass or less, more preferably 0.5% by mass or less, even more preferably less than 0.5% by mass, particularly preferably 0.2% by mass or less, and most preferably 0.1% by mass or less.
• the content of the compound represented by the general formula ( ⁇ ) with respect to the total amount of the non-aqueous electrolyte is within the above range, the concentration of the compound represented by the general formula ( ⁇ ) into the active material proceeds more favorably. , it is possible to fabricate a battery that generates less gas during initial conditioning. Further, the mass ratio of the compound represented by the general formula (A) to the content of the compound represented by the general formula ( ⁇ ) in the non-aqueous electrolytic solution is the compound represented by the general formula (A).
• the It is 3.0 or more, most preferably 5.0 or more, preferably 1.0 ⁇ 10 4 or less, more preferably 0.5 ⁇ 10 4 or less, still more preferably 1.0 ⁇ 10 3 or less.
• the content of the compound represented by the general formula ( ⁇ ) or the compound represented by the general formula ( ⁇ ) in the non-aqueous electrolytic solution is the compound represented by the general formula (A) and the general formula ( ⁇ )
• the mass ratio of the compound represented by the general formula (A) to the total content when both the compounds represented by the formula ( ⁇ ) are included is the compound represented by the general formula (A) and the general formula ( ⁇ )
• the above particularly preferably 3.0 or more, most preferably 5.0 or more, preferably 1.0 ⁇ 10 4 or less, more preferably 0.5 ⁇ 10 4 or less, still more preferably 1.0 ⁇ 10 3 It is below.
• the method of incorporating the compound represented by the general formula ( ⁇ ) or the compound represented by the general formula ( ⁇ ) and the compound represented by the general formula (A) into the non-aqueous electrolytic solution is not particularly limited. .
• the method of adding the above compound directly to the non-aqueous electrolyte there is a method of generating the above compound in the battery or in the non-aqueous electrolyte.
• the content of the compound means the content at the time of manufacturing the non-aqueous electrolyte, at the time of pouring the non-aqueous electrolyte into the battery, or at the time of shipment as a battery.
• the non-aqueous electrolytic solution of the present embodiment normally contains an electrolyte as its component, like a general non-aqueous electrolytic solution.
• the electrolyte used in the non-aqueous electrolytic solution of the present embodiment is not particularly limited as long as it is an alkali metal salt, such as LiBF 4 , LiPF 6 , LiN(FSO 2 ) 2 , LiN(CF 3 SO 2 ) 2 , and lithium difluorooxa.
• Lithium salts such as latoborate can be suitably used.
• these lithium salts can also be used individually or in combination of 2 or more types.
• the total concentration of the alkali metal salt in the non-aqueous electrolyte is not particularly limited, but is usually 8% by mass or more, preferably 8.5% by mass or more, more preferably 9% by mass, relative to the total amount of the non-aqueous electrolyte. % or more. Also, it is usually 18% by mass or less, preferably 17% by mass or less, and more preferably 16% by mass or less.
• the electrical conductivity is appropriate for battery operation, so there is a tendency to obtain sufficient output characteristics.
• Non-aqueous solvent normally contains, as its main component, a non-aqueous solvent that dissolves the above-described electrolyte, like a general non-aqueous electrolytic solution.
• the non-aqueous solvent is not particularly limited, and known organic solvents can be used.
• organic solvents include saturated cyclic carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate; chain carbonates such as dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate; carboxylic acid esters; ether compounds such as dimethoxymethane, diethoxymethane, ethoxymethoxymethane, tetrahydrofuran, 1,3-dioxane, and 1,4-dioxane; 2-methylsulfolane, 3-methylsulfolane, 2-fluorosulfolane, sulfone compounds such as 3-fluorosulfolane, dimethylsulfone, ethylmethylsulfone, and monofluoromethylmethylsulfone; and the like.
• saturated cyclic carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate
• chain carbonates such as dimethyl carbonate, diethyl carbonate, and ethyl
• the non-aqueous electrolytic solution of the present embodiment may contain an auxiliary agent within a range in which the effects of the present invention are exhibited.
• an adjuvant difluorophosphate anion-containing compound; fluorosulfonate anion-containing compound; oxalate anion-containing compounds; a sulfonylimide anion-containing compound; Alkyl sulfate anion-containing compound; Unsaturated cyclic carbonates such as vinylene carbonate, vinylethylene carbonate and ethynylethylene carbonate; fluorinated cyclic carbonates such as monofluoroethylene carbonate, 4,4-difluoroethylene carbonate, 4,5-difluoroethylene carbonate and 4,5-difluoro-4,5-dimethylethylene carbonate; carbonate compounds such as methoxyethyl-methyl carbonate; Spiro compounds such as methyl-2-propynyl oxalate; Diisocyanates
• a difluorophosphate anion-containing compound, a fluorosulfonate anion-containing compound, an oxalate anion-containing compound, a sulfonylimide anion-containing compound, and an alkyl sulfate anion (hereinafter , these are also referred to as "specific anion-containing compounds")
• specific anion-containing compounds / or unsaturated cyclic carbonates and cyclic carbonates having a fluorine atom
• auxiliary agent is usually 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, more preferably 0.1% by mass or more in 100% by mass of the non-aqueous electrolyte It is 0.2% by mass or more, and usually 10% by mass or less, preferably 8% by mass or less, and more preferably 5% by mass or less.
• the total amount preferably satisfies the above range.
• a particular anion-containing compound is usually an acid or a salt, preferably a salt.
• Counter cations of salts of specific anion-containing compounds are not particularly limited, but are lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, and NR 123 R 124 R 125 R 126 (wherein R 123 to R 126 each independently represent a hydrogen atom or an organic group having 1 to 12 carbon atoms. Among them, lithium is preferable.
• the organic group having 1 to 12 carbon atoms represented by R 123 to R 126 of the ammonium is not particularly limited, but for example, an alkyl group optionally substituted with a halogen atom, a halogen atom or an alkyl group substituted with an optionally substituted cycloalkyl group, an optionally substituted aryl group with a halogen atom or an alkyl group, and an optionally substituted nitrogen atom-containing heterocyclic group.
• R 123 to R 126 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or a nitrogen atom-containing heterocyclic group.
• the difluorophosphate anion-containing compounds may be used singly or in combination of two or more in any desired ratio.
• the content of the difluorophosphate anion-containing compound relative to the total amount of the non-aqueous electrolytic solution is not particularly limited, and is arbitrary as long as it does not significantly impair the effects of the present invention, but usually 0.001 to 8% by mass, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and preferably 5.0% by mass or less, more preferably 3.0% by mass Below, more preferably 2.0% by mass or less, most preferably 1.5% by mass or less.
• the fluorosulfonate anion-containing compounds may be used singly or in combination of two or more in any combination and ratio.
• the content of the fluorosulfonate anion-containing compound relative to the total amount of the non-aqueous electrolyte is not particularly limited, and is arbitrary as long as it does not significantly impair the effects of the present invention, but usually 0.001 to 8% by mass, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and preferably 5.0% by mass or less, more preferably 3.0% by mass or less , more preferably 2.0% by mass or less, and most preferably 1.5% by mass or less.
• the initial gas generation can be more suitably suppressed.
• sulfonylimide anion-containing compound Specific examples of the sulfonylimide anions constituting the sulfonylimide anion-containing compound include N ⁇ (FSO 2 ) 2 , N ⁇ (FSO 2 )(CF 3 SO 2 ), N ⁇ (CF 3 SO 2 ) 2 , N ⁇ (C 2 F 5 SO 2 ) 2 , cyclic 1,2-perfluoroethanedisulfonylimide anion, cyclic 1,3-perfluoropropanedisulfonylimide anion, N ⁇ (CF 3 SO 2 )(C 4 F 9 SO 2 ), and N- ( FSO 2 ) 2, N- ( CF 3 SO 2 ) 2 and N- ( C 2 F 5 SO 2 ) 2 are preferred, and N- ( FSO 2 ) 2 is particularly preferred.
• the sulfonylimide anion-containing compounds may be used alone, or two or more of them may be used in any combination and ratio.
• the content of the sulfonylimide anion-containing compound relative to the total amount of the non-aqueous electrolytic solution is not particularly limited, and is arbitrary as long as it does not significantly impair the effects of the present invention, but usually 0 0.001 to 8% by mass, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and preferably 5.0% by mass or less, more preferably 3.0% by mass or less , more preferably 2.0% by mass or less, and most preferably 1.5% by mass or less.
• alkyl sulfate anion-containing compound Specific examples of the alkylsulfate anion constituting the alkylsulfate anion-containing compound include compounds represented by C n H 2n+1 OSO 3 ⁇ (1 ⁇ n ⁇ 10), preferably methylsulfate anion or ethylsulfate anion.
• the content of the alkyl sulfate anion-containing compound is not particularly limited, and is arbitrary as long as it does not significantly impair the effects of the present invention. It is preferably 0.1% by mass or more, and is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, still more preferably 2.0% by mass or less, and most preferably 1.5% by mass. It is below.
• the oxalate complex anion-containing compounds may be used singly, or two or more of them may be used in any combination and ratio.
• the content of the oxalate complex anion-containing compound (the total content in the case of two or more kinds) is not particularly limited and is arbitrary as long as the effects of the present invention are not significantly impaired, but is usually 0.001 to 8% by mass. , preferably 0.01% by mass or more, more preferably 0.1% by mass or more, preferably 5.0% by mass or less, more preferably 3.0% by mass or less, still more preferably 2.0% by mass % or less, most preferably 1.5 mass % or less.
• the non-aqueous electrolytic solution preferably contains at least one carbonate compound selected from the group consisting of unsaturated cyclic carbonates having carbon-carbon unsaturated bonds and cyclic carbonates having fluorine atoms. Among these, it preferably contains an unsaturated cyclic carbonate, and more preferably contains a vinylene carbonate. These can be used alone or in combination of two or more in any ratio, and preferably contain an unsaturated cyclic carbonate and a fluorinated cyclic carbonate, and preferably contain vinylene carbonate and a fluorinated cyclic carbonate. , or unsaturated cyclic carbonate and monofluoroethylene carbonate, more preferably vinylene carbonate and monofluoroethylene carbonate.
• the unsaturated cyclic carbonate is not particularly limited as long as it is a cyclic carbonate having a carbon-carbon double bond or a carbon-carbon triple bond.
• a cyclic carbonate having an aromatic ring is also included in the unsaturated cyclic carbonate.
• unsaturated cyclic carbonates examples include vinylene carbonates, ethylene carbonates substituted with a substituent having an aromatic ring, carbon-carbon double bond or carbon-carbon triple bond, phenyl carbonates, vinyl carbonates, allyl carbonates, catechol carbonates and the like.
• vinylene carbonates and ethylene carbonates substituted with a substituent having an aromatic ring or a carbon-carbon double bond or a carbon-carbon triple bond are preferred.
• Vinylene carbonates include vinylene carbonate, methylvinylene carbonate, 4,5-dimethylvinylene carbonate, phenylvinylene carbonate, 4,5-diphenylvinylene carbonate, vinylvinylene carbonate, 4,5-vinylvinylene carbonate, allylvinylene carbonate, 4 , 5-diallyl vinylene carbonate and the like.
• Ethylene carbonates substituted with a substituent having an aromatic ring or a carbon-carbon double bond or carbon-carbon triple bond include vinylethylene carbonate, 4,5-divinylethylene carbonate, and 4-methyl-5-vinylethylene carbonate.
• vinylene carbonate, vinylethylene carbonate, and ethynylethylene carbonate are preferred because they form a more stable composite coating on the electrode.
• One or more selected from vinylene carbonate and vinylethylene carbonate is more preferred, and vinylene carbonate is even more preferred.
• An unsaturated cyclic carbonate can be used individually by 1 type or in combination of 2 or more types by arbitrary ratios.
• Fluoroethylene carbonate having 1 to 8 fluorine atoms and derivatives thereof, and ethylene carbonate having a fluorine-containing group include monofluoroethylene carbonate, 4,4-difluoroethylene carbonate, 4,5-difluoroethylene carbonate, 4-fluoro -4-methylethylene carbonate, 4,5-difluoro-4-methylethylene carbonate, 4-fluoro-5-methylethylene carbonate, 4,4-difluoro-5-methylethylene carbonate, 4-(fluoromethyl)-ethylene carbonate , 4-(difluoromethyl)-ethylene carbonate, 4-(trifluoromethyl)-ethylene carbonate, 4-(fluoromethyl)-4-fluoroethylene carbonate, 4-(fluoromethyl)-5-fluoroethylene carbonate, 4- fluoro-4,5-dimethylethylene carbonate, 4,5-difluoro-4,5-dimethylethylene carbonate, 4,4-difluoro-5,5-dimethylethylene carbonate and the like.
• monofluoroethylene carbonate, 4,4-difluoroethylene carbonate, and 4,5-difluoroethylene carbonate are used from the viewpoint of imparting high ionic conductivity to the electrolytic solution and facilitating the formation of a stable interfacial protective film.
• One or more selected are preferable.
• Cyclic carbonates having a fluorine atom can be used singly or in combination of two or more at any ratio.
• the content of the specific carbonate compound in the total amount of the non-aqueous electrolytic solution is usually 0.001 to 10% by mass, preferably 0.01% by mass or more, more preferably 0 .1% by mass or more, more preferably 0.5% by mass or more, preferably 8.0% by mass or less, more preferably 6.0% by mass or less, and still more preferably 5.0% by mass or less . preferably 0.001 to 10% by mass, more preferably 0.001 to 8.0% by mass, even more preferably 0.001 to 6.0% by mass, most preferably 0.001 to 5.0% by mass be .
• the represented compound [g]) is usually 1-200. It is preferably 3 or more, more preferably 5 or more, preferably 100 or less, more preferably 70 or less, and still more preferably 50 or less. It is preferably 1-100, more preferably 1-70, still more preferably 1-50. If the mass ratio is within the above range, gas generation during initial conditioning can be significantly suppressed.
• the mass ratio of the content of the specific carbonate compound (the total amount when there are two or more) to the content of the electrolyte (preferably LiPF 6 ) (specific carbonate compound [g] / electrolyte [g] ) is usually between 0.001 and 0.8. It is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, and is preferably 0.5 or less, more preferably 0.4 or less, and still more preferably 0.35 or less. be. It is preferably 0.001 to 0.5, more preferably 0.001 to 0.4, still more preferably 0.001 to 0.35.
• a non-aqueous electrolyte battery according to one embodiment of the present invention is a non-aqueous electrolyte battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte, and the non-aqueous electrolyte according to one embodiment of the present invention described above Prepare. More specifically, a positive electrode having a positive electrode active material layer on at least a part of a current collector and the surface of the current collector and capable of absorbing and releasing metal ions, and at least one of the current collector and the surface of the current collector.
• the non-aqueous electrolyte battery of the present embodiment is the same as conventionally known non-aqueous electrolyte batteries except for the above non-aqueous electrolyte.
• a positive electrode and a negative electrode are laminated via a porous film (separator) impregnated with the non-aqueous electrolytic solution, and these are housed in a case (exterior body).
• the shape of the non-aqueous electrolyte battery of the present embodiment is not particularly limited, and may be cylindrical, rectangular, laminated, coin-shaped, large, or the like.
• Non-aqueous electrolytic solution As the non-aqueous electrolytic solution, the above-described non-aqueous electrolytic solution according to one embodiment of the present invention is used. It should be noted that other non-aqueous electrolytic solutions may be blended with the above-described non-aqueous electrolytic solution without departing from the scope of the present invention.
• the positive electrode has a current collector and a positive electrode active material on at least part of the surface of the current collector. For other configurations, conventionally known ones can be adopted.
• a transition metal oxide represented by the following compositional formula (11) is preferable.
• M represents at least one element selected from the group consisting of Mn, Al, Mg, Zr, Fe, Ti and Er.
• the transition metal is less likely to be eluted from the positive electrode, and even if Ni and Co are eluted, Ni and Co will not be used in the non-aqueous secondary battery. It has the advantage of having less adverse effects.
• Preferred specific examples include LiNi0.85Co0.10Al0.05O2 , LiNi0.80Co0.15Al0.05O2 , LiNi0.5Co0.2Mn0 .
• the negative electrode has a current collector and a negative electrode active material on at least part of the surface of the current collector. For other configurations, conventionally known ones can be adopted.
• the negative electrode active material is not particularly limited as long as it can electrochemically occlude and release metal ions.
• Specific examples include carbonaceous materials, materials containing metallic elements and/or metalloid elements capable of being alloyed with Li, lithium-containing metal composite oxide materials, and mixtures thereof. These may be used individually by 1 type, and may be used in arbitrary combinations of 2 or more types.
• Carbon-based materials include natural graphite, artificial graphite, amorphous carbon, carbon-coated graphite, graphite-coated graphite, and resin-coated graphite. Among them, natural graphite is preferable.
• Examples of natural graphite include scaly graphite, scaly graphite, and/or graphite particles obtained by spheroidizing or densifying these graphites.
• spherical or ellipsoidal graphite particles subjected to a spheroidizing treatment are particularly preferable from the viewpoint of the packing properties of the particles and the charge/discharge rate characteristics.
• the average particle size (d50) of graphite particles is usually 1 ⁇ m or more and 100 ⁇ m or less.
• any conventionally known material can be used. It is preferably a single substance or a compound of a metallic element and/or semi-metallic element that can be alloyed with Li selected from the group consisting of Al, As, and Zn.
• the material containing a metal element and/or metalloid element that can be alloyed with Li contains two or more elements, the material may be an alloy material made of an alloy of these elements.
• metal oxides, metal nitrides, metal carbides and the like are examples of compounds containing metal elements and/or metalloid elements that can be alloyed with Li.
• the compound may contain two or more metal elements and/or metalloid elements that can be alloyed with Li.
• metal Si hereinafter sometimes referred to as Si
• Si-containing compounds are preferable from the viewpoint of increasing the capacity.
• the average particle diameter (d50) of the particle is usually 0.01 ⁇ m or more and 10 ⁇ m or less from the viewpoint of cycle life.
• It may be a mixture in which particles of a material containing and the above-mentioned graphite particles are mixed in a state of independent particles, or particles of a material containing a metal element and / or metalloid element that can be alloyed with Li It may be a composite existing on the surface or inside the graphite particles.
• the content ratio of the particles of the material containing the metal element and/or metalloid element that can be alloyed with Li to the total of the particles of the material containing the metal element and/or metalloid element that can be alloyed with Li and the graphite particles is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and still more preferably 2.0% by mass or more.
• the compound represented by the general formula (AA) has a cyclic structure and a polar structure (--SO 2 --O--) in the cyclic skeleton, it has a higher dielectric constant than a chain compound.
• the compounds localized on the surface of the active material also interact with each other, so that the localized compounds It is presumed that the amount of fixation on the surface of the positive electrode active material and/or the negative electrode active material also increases.
• the compound represented by the general formula ( ⁇ ) and the compound represented by the general formula (AA) localized on the electrode during the initial charge are electrochemically decomposed to form a composite insulating film. do.
• the compound represented by the general formula (AA) undergoes a ring-opening reaction favorably during the reaction, so that the formation of the composite coating proceeds efficiently. It is presumed that this composite coating suppresses side reactions of the electrolyte during initial conditioning and suppresses gas generation.
• the compound represented by the general formula (AA) has a cyclic structure and a polar structure ( --SO.sub.2 --O--) in the cyclic skeleton, and thus has a higher dielectric constant than a chain compound. Therefore, the compound represented by general formula (AA) tends to interact with the surface of a negative electrode active material such as carbon and/or a positive electrode active material such as a transition metal oxide, and localize near the surface.
• Q 31 and Q 32 each independently represent an alkylene group having 1 to 10 carbon atoms.
• the alkylene group may be substituted with a hydrocarbon group, and the hydrogen atom of the alkylene group is a halogen atom, n31 represents an integer of 0 or 1. When n31 is 0, the sulfur atom and the oxygen atom form a direct bond.
• Q 31 and Q 32 in general formula (AA) each independently represent an alkylene group having 1 to 10 carbon atoms.
• the alkylene group may be substituted with a hydrocarbon group, and a hydrogen atom of the alkylene group may be substituted with a halogen atom.
• Q 1 is preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, and particularly preferably an alkylene group having 2 to 3 carbon atoms. be.
• Q 1 is preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, and particularly preferably a methylene group.
• Q 2 is preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, and particularly preferably a methylene group.
• the alkylene group has a hydrocarbon group as a substituent, the number of carbon atoms contained in the substituent is not included in the number of carbon atoms.
• alkylene groups include methylene, ethylene, n-propylene, butylene, and hexylene groups.
• examples of the substituent include a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom (preferably a fluorine atom), and the like.
• hydrocarbon groups having 1 to 8 carbon atoms and halogen atoms are preferred, and hydrocarbon groups having 1 to 6 carbon atoms and fluorine atoms are particularly preferred.
• hydrocarbon groups having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 1 to 10 carbon atoms, alkynyl groups having 1 to 10 carbon atoms, and aryl groups having 6 to 10 carbon atoms. and aralkyl groups having 7 to 10 carbon atoms.
• alkyl groups include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, n-pentyl group, hexyl group, heptyl group, octyl group and nonyl group.
• decyl group cyclohexyl group and the like.
• methyl group, ethyl group, n-propyl group, n-butyl group, tert-butyl group, n-pentyl group, hexyl group and cyclohexyl group more preferably methyl group, ethyl group and n-propyl group, n-butyl group, tert-butyl group, n-pentyl group and cyclohexyl group, particularly preferably methyl group, ethyl group, n-butyl group, tert-butyl group and cyclohexyl group.
• alkenyl groups include vinyl, allyl, methallyl, 2-butenyl, 3-methyl-2-butenyl, 3-butenyl, and 4-pentenyl groups.
• preferred are vinyl group, allyl group, methallyl group and 2-butenyl group, more preferred are vinyl group, allyl group and methallyl group, and particularly preferred is vinyl group or allyl group.
• alkynyl groups include ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, 4-pentynyl, and 5-hexynyl groups.
• ethynyl group, 2-propynyl group, 2-butynyl group and 3-butynyl group are more preferred, 2-propynyl group and 3-butynyl group are more preferred, and 2-propynyl group is particularly preferred.
• aryl groups include a phenyl group and a tolyl group. Among them, a phenyl group is preferred.
• aralkyl groups include benzyl and phenethyl groups.
• Specific examples of compounds represented by general formula (AA) include the following compounds.
• the compounds represented by formula (AA) may be used singly or in combination of two or more.
• the content of the compound represented by the general formula (AA) with respect to the total amount of the non-aqueous electrolyte according to one embodiment of the present invention is usually 1.0 ⁇ 10 -3 % by mass or more, preferably 1.0 ⁇ 10 -2 % by mass or more, more preferably 0.1% by mass or more, and usually 10% by mass or less, preferably 5% by mass or less, and more It is preferably 3% by mass or less, more preferably 2% by mass or less, and particularly preferably 1% by mass or less.
• the content of the compound represented by the general formula (AA) with respect to the total amount of the non-aqueous electrolyte is within the above range, the concentration of the compound in the active material proceeds more favorably, and the gas generation during the initial conditioning is more likely. It becomes possible to manufacture a small number of batteries.
• a non-aqueous electrolytic solution according to one embodiment of the present invention contains a compound represented by the general formula ( ⁇ ).
• R 31 and R 32 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a silyl group represented by —SiR 33 R 34 R 35 ;
• R 33 to R 35 are each independently a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, or an optionally substituted C 1 to 12
• Y 31 represents an optionally substituted alkoxy group having 1 to 12 carbon atoms, and R 31 or R 32 and Y 31 may combine with each other to form a ring.
• R 31 to R 32 , Y, etc. will be described below.
• R 31 and R 32 in general formula ( ⁇ ) each independently represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or a silyl group represented by —SiR 33 R 34 R 35 , and R 33 to R 35 are each independently a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, or an optionally substituted carbon number of 1 to 12 represents an alkoxy group of The same explanation as defined for R 1 to R 5 applies to the hydrocarbon group having 1 to 12 carbon atoms.
• R 31 and R 32 is preferably a silyl group represented by —SiR 33 R 34 R 35 .
• Y 31 in general formula ( ⁇ ) represents an optionally substituted alkoxy group having 1 to 12 carbon atoms.
• methoxy group, ethoxy group, propoxy group, butoxy group, isopropoxy group and the like can be mentioned.
• a methoxy group and an ethoxy group are preferable in that the steric hindrance of the compound is small and they are preferably concentrated on the surface of the active material.
• alkoxycarbonyl group (-(C O)O-R d ), sulfonyl group (-SO 2 -R d ), sulfonyloxy group (-O(SO 2 )-R d ), alkoxysulfonyl group (-(SO 2 ) —OR d ), alkoxysulfonyloxy group (—O—(SO 2 )—OR d ), alkoxycarbonyloxy group (—O—(C ⁇ O)—OR d ), alkoxy group (-OR d ), acryl group, methacryl group, halogen atom (preferably fluorine atom), trifluoromethyl group and the like.
• R d represents an alkyl group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms.
• R d is an alkylene group, it may combine with part of the substituted hydrocarbon group to form a ring.
• the compounds represented by the general formula ( ⁇ ) may be used singly or in combination of two or more.
• the content of the compound represented by the general formula ( ⁇ ) (in the case of two or more, the total thereof) with respect to the total amount of the non-aqueous electrolytic solution according to one embodiment of the present invention is not particularly limited, but is preferably is 0.01 mass ppm or more, more preferably 0.1 mass ppm or more, still more preferably 1.0 mass ppm or more, particularly preferably 10 mass ppm or more, and preferably 1.0 mass ppm or less , more preferably 0.75% by mass or less, still more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less.
• the content of the compound represented by the general formula ( ⁇ ) with respect to the total amount of the non-aqueous electrolyte is within the above range, the concentration of the compound in the active material proceeds more favorably, and the gas generation during the initial conditioning is more likely. It becomes possible to manufacture a small number of batteries.
• the mass ratio of the compound represented by the general formula (AA) to the content of the compound represented by the general formula ( ⁇ ) in the non-aqueous electrolyte is not particularly limited, but is usually 1.0 or more, preferably 2.0 or more, and is usually 1.0 ⁇ 10 4 or less, preferably 7.0 ⁇ 10 3 or less, more preferably 4.0 ⁇ 10 3 or less, still more preferably 2.0 ⁇ 10 3 or less, even more preferably 1.0 ⁇ 10 3 or less, particularly preferably 5.0 ⁇ 10 2 or less.
• the content of the compound means the content at the time of manufacturing the non-aqueous electrolyte, at the time of pouring the non-aqueous electrolyte into the battery, or at the time of shipment as a battery.
• Identification and measurement of the content of the compound represented by the general formula ( ⁇ ) and the compound represented by the general formula (AA) in the non-aqueous electrolyte can be performed by nuclear magnetic resonance (NMR) spectroscopy or gas chromatography. (GC) or the like.
• the non-aqueous electrolytic solution of the present embodiment normally contains an electrolyte as its component, like a general non-aqueous electrolytic solution.
• the electrolyte used in the non-aqueous electrolytic solution of the present embodiment is ⁇ 1-1-4. Electrolyte> applies, and preferred embodiments are also the same.
• Non-aqueous solvent> The non-aqueous electrolytic solution of the present embodiment normally contains, as its main component, a non-aqueous solvent that dissolves the above-described electrolyte, like a general non-aqueous electrolytic solution.
• Non-Aqueous Solvent> is applied, and preferred embodiments are also the same.
• the non-aqueous electrolytic solution of the present embodiment may contain an auxiliary agent within a range in which the effects of the present invention are exhibited.
• Auxiliaries that may be used in the non-aqueous electrolytic solution of the present embodiment are described in ⁇ 1-1-6.
• Auxiliary Agent> applies, and preferred embodiments are also the same.
• a non-aqueous electrolyte battery according to one embodiment of the present invention is a non-aqueous electrolyte battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte, and the non-aqueous electrolyte according to one embodiment of the present invention described above Prepare. More specifically, a positive electrode having a positive electrode active material layer on at least a part of a current collector and the surface of the current collector and capable of absorbing and releasing metal ions, and at least one of the current collector and the surface of the current collector.
• a non-aqueous electrolytic solution containing a compound represented by formula ( ⁇ ) is provided.
• positive electrode, negative electrode, and separator see ⁇ 1-2-1.
• Non-aqueous electrolytic solution> As the non-aqueous electrolytic solution, the above-described non-aqueous electrolytic solution according to one embodiment of the present invention is used. It should be noted that other non-aqueous electrolytic solutions may be blended with the above-described non-aqueous electrolytic solution without departing from the scope of the present invention.
• Example 1 The compounds used in Examples and Comparative Examples are shown below.
• a battery element was produced by stacking the positive electrode, the negative electrode, and the separator made of polyethylene in the order of negative electrode, separator, and positive electrode. After inserting this battery element into a bag made of a laminate film in which both sides of aluminum (thickness 40 ⁇ m) are coated with a resin layer so that the terminals of the positive electrode and the negative electrode protrude, the non-aqueous electrolyte solution prepared as described above is placed in the bag. It was injected into the inside and vacuum-sealed to fabricate a laminate type non-aqueous electrolyte battery.
• Table 1 shows the value of the initial gas amount of each example and comparative example when the initial gas amount of Comparative Example 1-1 is 100 as “initial gas”.
• compound (A) indicates “compound represented by formula (A)
• compound ( ⁇ ) indicates “compound represented by formula ( ⁇ )”.
• the batteries produced in Examples 1-1 to 1-27 have smaller initial gas amounts than the batteries produced in Comparative Examples 1-1 to 1-26. . From the comparison of Comparative Example 1-1 with Comparative Examples 1-2, 1-25, and 1-26, it does not contain the compound represented by formula ( ⁇ ), but contains only the compound represented by formula (A). It can be seen that the initial gas amount tends to be larger than that of Comparative Example 1 when the non-aqueous electrolytic solution is used.
• Comparative Example 1-1 by comparing Comparative Example 1-1 with Comparative Examples 1-3, 1-4, 1-6, 1-10 to 1-23, without containing the compound represented by formula (A), It can be seen that when the non-aqueous electrolytic solution containing only the compound represented by formula ( ⁇ ) is used, the initial gas amount tends to be larger than in Comparative Example 1-1. From the results of Comparative Examples 1-1 to 1-3, it was predicted that the initial gas amount of the battery using the electrolyte solution containing the compound of the combination of Example 1-1 would be larger than that of Comparative Example 1-1. However, in the battery of Example 1-1, the generation of the initial amount of gas was remarkably suppressed as compared with Comparative Example 1-1.
• the initial gas amount of the battery using the electrolyte solution containing the compound of the combination of Example 1-6 is greater than that of Comparative Example 1-1.
• the generation of the initial gas amount was significantly suppressed as compared with Comparative Example 1-1.
• the initial gas amount of the battery using the electrolyte solution containing the compound of the combination of Example 1-7 is significantly increased compared to Comparative Example 1-1.
• the generation of initial gas amount was significantly suppressed as compared with Comparative Example 1-1.
• the initial gas amount of the battery using the electrolyte solution containing the compound of the combination of Example 1-8 is greater than that of Comparative Example 1-1.
• the generation of the initial amount of gas was suppressed more than in Comparative Example 1-1.
• the initial gas amount of the battery using the electrolyte solution containing the compound of the combination of Example 1-10 is greater than that of Comparative Example 1-1.
• the generation of the initial gas amount was significantly suppressed as compared with Comparative Example 1-1.
• Comparative Example 1-24 in which the compound represented by formula (A) and the compound not corresponding to the compound represented by formula ( ⁇ ) were used in combination, the compound represented by formula ( ⁇ ) and the compound represented by formula (A) The initial amount of gas increased compared to Comparative Example 1-1, unlike the battery using the electrolytic solution in combination with the compound represented by the following.
• the compound represented by the general formula ( ⁇ ) and the compound represented by the general formula (A) are preferably adsorbed on the positive electrode active material and/or the negative electrode active material.
• the compound localized on the electrode was electrochemically decomposed during the initial charge, forming a composite insulating film on the surface of the positive electrode active material and/or the negative electrode active material.
• the adsorption of the compound to the electrode can be controlled, and the initial gas generation amount can be reduced. It can be suitably suppressed.
• Example 2 The compounds used in Examples and Comparative Examples are shown below.
• a battery element was produced by stacking the positive electrode, the negative electrode, and the separator made of polyethylene in the order of negative electrode, separator, and positive electrode. After inserting this battery element into a bag made of a laminate film in which both sides of aluminum (thickness 40 ⁇ m) are coated with a resin layer so that the terminals of the positive electrode and the negative electrode protrude, the non-aqueous electrolyte solution prepared as described above is placed in the bag. It was injected into the inside and vacuum-sealed to fabricate a laminate type non-aqueous electrolyte battery.
• Table 2 shows the value of the initial gas amount of each example and comparative example when the initial gas amount of Comparative Example 2-1 is 100 as “initial gas”. Further, in Table 2, “compound (A)” indicates “compound represented by formula (A)”, and “compound ( ⁇ )” indicates “compound represented by formula ( ⁇ )”.
• Example 2-1 has a smaller initial gas amount than the batteries produced in Comparative Examples 2-1 to 2-6.
• the adsorption of the compound to the electrode can be controlled, and the initial gas generation amount can be reduced. It can be suitably suppressed.
• Example 3 The compounds used in Examples and Comparative Examples are shown below.
• a battery element was produced by stacking the positive electrode, the negative electrode, and the separator made of polyethylene in the order of negative electrode, separator, and positive electrode. After inserting this battery element into a bag made of a laminate film in which both sides of aluminum (thickness 40 ⁇ m) are coated with a resin layer so that the terminals of the positive electrode and the negative electrode protrude, the non-aqueous electrolyte solution prepared as described above is placed in the bag. It was injected into the inside and vacuum-sealed to fabricate a laminate type non-aqueous electrolyte battery.
• Table 3 shows the value of the initial gas amount of each example and comparative example when the initial gas amount of Comparative Example 3-1 is set to 100 as “initial gas”.
• compound (AA) indicates “compound represented by formula (AA)
• compound ( ⁇ ) indicates “compound represented by formula ( ⁇ )”.
• the batteries produced in Examples 3-1 to 3-3 have smaller initial gas amounts than the batteries produced in Comparative Examples 3-1 to 3-6.
• the adsorption of the compound to the electrode can be controlled, and the initial gas generation amount can be reduced. It can be suitably suppressed.
• the non-aqueous electrolyte solution of the present invention is useful because it can suppress the amount of gas generated during the initial conditioning of a non-aqueous electrolyte battery, and can improve the deterioration of a high-capacity battery.
• the non-aqueous electrolytic solution of the present invention and the non-aqueous electrolytic solution battery using the same can be used for various known applications using non-aqueous electrolytic solution batteries. Specific examples include notebook computers, pen-input computers, mobile computers, e-book players, mobile phones, mobile faxes, mobile copiers, mobile printers, headphone stereos, video movies, liquid crystal televisions, handy cleaners, portable CDs, and minidiscs.
• walkie-talkies electronic notebooks, calculators, memory cards, portable tape recorders, radios, backup power supplies, motors, motorcycles, motorized bicycles, bicycles, lighting fixtures, toys, game devices, clocks, power tools, strobes, cameras, household backups Power sources, backup power sources for business establishments, load leveling power sources, natural energy storage power sources, and the like.

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• 2022
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