Non-aqueous electrolyte and non-aqueous electrolyte battery

Abstract

This nonaqueous electrolytic solution is for a nonaqueous electrolytic solution battery including a positive electrode and a negative electrode which are capable of occluding and releasing metal ions, and is characterized by comprising: an alkali metal salt; a nonaqueous solvent; a compound represented by general formula (A); and at least one of specific compounds represented by general formula (α) and specific compounds represented by general formula (β).

Description

[Technical Field]

[0001] The present invention relates to a nonaqueous electrolyte and a nonaqueous electrolyte battery, and more particularly to a nonaqueous electrolyte containing a specific compound and a nonaqueous electrolyte battery using this nonaqueous electrolyte. [Background technology]

[0002] BACKGROUND ART Non-aqueous electrolyte batteries such as lithium secondary batteries have been put to practical use in a wide range of applications, such as power sources for so-called small consumer devices such as mobile phones such as smartphones and laptop computers, and on-board power sources for driving electric vehicles and the like.

[0003] As a means for improving the battery characteristics of non-aqueous electrolyte batteries, many studies have been conducted in the fields of positive and negative electrode active materials and additives for non-aqueous electrolytes.

[0004] For example, Patent Document 1 discloses a study on improving the high-temperature cycle capacity retention rate and the change in thickness of a battery during high-temperature storage by adding a cyclic sulfate compound to a non-aqueous electrolyte solution consisting of a lithium salt, a specific carbamate compound, and an organic solvent such as carbonate. Patent Document 2 discloses a study to improve the storage stability of a silyl group-containing compound by adding a trialkylsilyl compound of a protonic acid, sulfonic acid, or carboxylic acid having a phosphorus atom and / or a boron atom, and a basic compound or a specific silicon compound to a non-aqueous electrolyte solution, and further to improve the 4.9 V high voltage cycle capacity retention rate and the amount of gas generated during battery operation. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Special Publication No. 2016-532989 [Patent Document 2] International Publication No. 2015 / 098471 Summary of the Invention [Problem to be solved by the invention]

[0006] In recent years, the trend toward higher-capacity lithium batteries for use as power sources in electric vehicles and mobile phones such as smartphones has accelerated, resulting in a smaller proportion of voids within the battery than before. Therefore, the large amount of gas generated during initial conditioning is a fatal drawback.

[0007] An object of the present invention is to provide a nonaqueous electrolyte that can suppress the amount of gas generated during initial conditioning of a nonaqueous electrolyte battery, and to provide a nonaqueous electrolyte battery in which the amount of gas generated during initial conditioning is suppressed. [Means for solving the problem]

[0008] As a result of intensive research to solve the above problems, the present inventors have come up with the idea that gas generation during initial conditioning can be suppressed by using a nonaqueous electrolyte solution containing a compound represented by general formula (A) and at least one of a compound represented by general formula (α) and a compound represented by general formula (β), and have completed the present invention.

[0009] The present invention provides the following specific embodiments. <1> A non-aqueous electrolyte solution for a non-aqueous electrolyte battery having a positive electrode and a negative electrode capable of absorbing and releasing metal ions, the non-aqueous electrolyte solution comprising an alkali metal salt, a non-aqueous solvent, a compound represented by general formula (A), and at least one of a compound represented by general formula (α) and a compound represented by general formula (β). [ka] (In formula (A), Q 1 and Q 2 each independently represents an alkylene group having 1 to 10 carbon atoms which may have a substituent. 1 represents an integer of 0 or 1. 1 When is 0, the sulfur atom and the oxygen atom form a direct bond.) [ka] (In formula (α), R 1 and R 2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or -SiR 3 R 4 R 5 R represents a silyl group represented by 3 ~R 5 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; Y represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, -NR 6 -SiR 7 R 8 R 9 or a group represented by -NR 10 -R 11 R represents a group represented by 6 , R 10 and R 11 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent; R 7 ~R 9 R each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 1 or R 2 and Y may be bonded to each other to form a ring. [ka] (In formula (β), R 21 ~R 23 each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 18 carbon atoms, or an optionally substituted aralkyl group having 7 to 18 carbon atoms; and Z represents an optionally substituted alkenyl group or alkynyl group having 2 to 10 carbon atoms. <2> 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, <1> The non-aqueous electrolyte solution according to claim 1. <3> the content of the compound represented by the general formula (α) or the compound represented by the general formula (β) is 0.01 mass ppm or more and 0.5 mass % or less with respect to the total amount of the nonaqueous electrolyte solution; <1> or <2> The non-aqueous electrolyte solution according to claim 1. <4> The mass ratio of the content of the compound represented by the general formula (A) to the content of the compound represented by the general formula (α) or the compound represented by the general formula (β) in the nonaqueous electrolyte solution is 1.0 or more and 1.0 × 10 4 Below is the <1> ~ <3> The non-aqueous electrolyte solution according to any one of the preceding claims. <5> Y in the compound represented by the general formula (α) is —NR 6 -SiR 7 R 8 R 9 or a group represented by -NR 10 -R 11 represents a group represented by <1> ~ <4> The non-aqueous electrolyte solution according to any one of the preceding claims. <6> A non-aqueous electrolyte solution for a non-aqueous electrolyte battery having a positive electrode and a negative electrode capable of absorbing and releasing metal ions, the non-aqueous electrolyte solution comprising an alkali metal salt, a non-aqueous solvent, a compound represented by general formula (AA), and a compound represented by general formula (αα). [ka] (In formula (AA), Q 31 and Q 32 are each independently an alkylene group having 1 to 10 carbon atoms. The alkylene group may be substituted with a hydrocarbon group, or a hydrogen atom of the alkylene group may be substituted with a halogen atom. 31 represents an integer of 0 or 1. 31 When is 0, the sulfur atom and the oxygen atom form a direct bond.) [ka] (In formula (αα), R 31 and R 32 are each independently a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or -SiR 33 R34 R 35 R represents a silyl group represented by 33 ~R 35 each independently represents a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, or an optionally substituted alkoxy group having 1 to 12 carbon atoms; Y 31 R represents an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 31 or R 32 and Y 31 may be bonded to each other to form a ring. <7> 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, <6> The non-aqueous electrolyte solution according to claim 1. <8> The content of the compound represented by the general formula (αα) is 0.01 mass ppm or more and 0.5 mass % or less with respect to the total amount of the nonaqueous electrolyte solution. <6> or <7> The non-aqueous electrolyte solution according to claim 1. <9> 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 (αα) in the nonaqueous electrolyte solution is 1.0 or more and 1.0 × 10 4 Below is the <6> ~ <8> The non-aqueous electrolyte solution according to any one of the preceding claims. <10> 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 solution, <1> ~ <9> 10. A non-aqueous electrolyte battery comprising the non-aqueous electrolyte according to any one of claims 1 to 9. [Effects of the Invention]

[0010] According to the present invention, it is possible to obtain a nonaqueous electrolyte that is excellent in suppressing the amount of gas generated during initial conditioning of a nonaqueous electrolyte battery, and a nonaqueous electrolyte battery in which the amount of gas generated during initial conditioning is suppressed. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, embodiments of the present invention will be described in detail. The following embodiments are examples (representative examples) of the present invention, and the present invention is not limited to these. Furthermore, the present invention can be implemented with any modifications within the scope of the gist thereof.

[0012] [First invention] <1-1. Non-aqueous electrolyte> The non-aqueous electrolyte solution according to the present invention contains a compound represented by general formula (A) and at least one of a compound represented by general formula (α) and a compound represented by general formula (β), which will be explained below. The mechanism by which the amount of gas generated during initial conditioning is suppressed by using a nonaqueous electrolyte solution containing a compound represented by general formula (A) and at least one of a compound represented by general formula (α) and a compound represented by general formula (β) is not clear, but is presumed to be as follows.

[0013] Compounds represented by general formula (A) have a cyclic structure and a polar structure (—SO2—O—) in the cyclic backbone, resulting in a higher dielectric constant than chain-like compounds. Compounds represented by general formula (α) also have a polar structure (—N—(C═O)—) in their molecules. Therefore, these compounds tend to interact with surface functional groups of negative electrode active materials, such as carbon, and / or the surface of positive electrode active materials, such as transition metal oxides, and localize near the surface of the active materials. Furthermore, it is speculated that the interaction between the compounds localized on the active material surface (compounds represented by general formula (A) and compounds represented by general formula (α)) increases the amount of localized compounds adhering to the positive electrode active material and / or negative electrode active material surface. In particular, the RN-(C═O)-Y structure of compounds represented by general formula (α) has a high adsorption property to the electrode surface, which promotes the adsorption of compounds represented by general formula (A) to the electrode starting from the adsorption of compounds represented by general formula (α) to the electrode. As a result, the compound represented by general formula (α) and the compound represented by general formula (A), which are localized on the electrode, electrochemically decompose during the initial charge, forming a composite insulating coating. Furthermore, the compound represented by general formula (A) undergoes a ring-opening reaction favorably during the reaction, which is thought to facilitate efficient formation of the composite coating. It is presumed that this composite coating suppresses side reactions in the electrolyte during initial conditioning and suppresses gas generation. In addition, the compound represented by the general formula (A) has a cyclic structure and a polar structure (-SO2-O-) in the cyclic skeleton, and therefore has a higher dielectric constant than a chain compound. Therefore, 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 a transition metal oxide, and to be localized near the surface. In addition, the compound represented by the general formula (β) has an unsaturated bond with π electrons in the molecule and a nonpolar structure (-SiR 21 R 22 R 11). In general, silicon atoms have a wide electron cloud, and because there are no steric hindrances when forming bonds, they easily form bonds with π electrons or unpaired electrons via vacant d orbitals. Therefore, compounds represented by general formula (A) localized on the surface of the active material interact with compounds represented by general formula (β), promoting the attachment of these compounds to the electrode. As a result, during the first charge, the compounds represented by general formula (β) and the compounds represented by general formula (A) electrochemically decompose to form a composite insulating coating. It is believed that this composite coating suppresses side reactions in the electrolyte during initial conditioning and suppresses gas generation.

[0014] <1-1-1. Compound represented by general formula (A)> [ka] (In formula (A), Q 1 and Q 2 each independently represents an alkylene group having 1 to 10 carbon atoms which may have a substituent. 1 represents an integer of 0 or 1. 1 When is 0, the sulfur atom and the oxygen atom form a direct bond.)

[0015] Q relating to general formula (A) 1 and Q 2 each independently represents an alkylene group having 1 to 10 carbon atoms which may have a substituent. Q 1 As for n 1 = 0, an alkylene group having 1 to 5 carbon atoms which may have a substituent is preferred, an alkylene group having 1 to 3 carbon atoms which may have a substituent is more preferred, and an alkylene group having 2 to 3 carbon atoms which may have a substituent is particularly preferred. Also, Q 1 As for n 1 When = 1, an alkylene group having 1 to 5 carbon atoms which may have a substituent is preferred, an alkylene group having 1 to 3 carbon atoms which may have a substituent is more preferred, and an optionally substituted methylene group is particularly preferred. Q 2As the alkylene group, an alkylene group having 1 to 5 carbon atoms which may have a substituent is preferred, an alkylene group having 1 to 3 carbon atoms which may have a substituent is more preferred, and an optionally substituted methylene group is particularly preferred. When the alkylene group has a substituent, the number of carbon atoms contained in the substituent is not included in the number of carbon atoms.

[0016] Specific examples of the alkylene group include a methylene group, an ethylene group, an n-propylene group, a butylene group, and a hexylene group.

[0017] Here, the substituents include hydrocarbon groups having 1 to 10 carbon atoms, cyano groups, isocyanato groups, and acyl groups (-(C=O)-R a ), acyloxy group (-O(C=O)-R a ), alkoxycarbonyl group (-(C=O)OR a ), sulfonyl group (-SO2-R a ), sulfonyloxy group (-O(SO2)-R a ), alkoxysulfonyl group (-(SO2)-OR a ), alkoxysulfonyloxy group (-O-(SO2)-OR a ), alkoxycarbonyloxy group (-O-(C=O)-OR a ), alkoxy group (-OR a ), a halogen atom (preferably a fluorine atom), a trifluoromethyl group, etc. 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. a When is an alkylene group, it may be bonded to a part of the hydrocarbon group that substitutes it to form a ring. Among these substituents, preferred are hydrocarbon groups having 1 to 10 carbon atoms, cyano groups, isocyanato groups, and acyloxy groups (—O(C═O)—R a ), alkoxycarbonyl group (-(C=O)OR a ), sulfonyloxy group (-O(SO2)-R a), a halogen atom (preferably a fluorine atom), a trifluoromethyl group, and more preferably a hydrocarbon group having 1 to 10 carbon atoms, an isocyanato group, an alkoxycarbonyl group (-(C=O)OR a ), sulfonyloxy group (-O(SO2)-R a ), acyloxy group (-O(C=O)-R a ), a halogen atom (preferably a fluorine atom), or a trifluoromethyl group, and particularly preferably a hydrocarbon group having 1 to 10 carbon atoms, or an alkoxycarbonyl group (—(C═O)OR a ), sulfonyloxy group (-O(SO2)-R a ), a halogen atom (preferably a fluorine atom), or a trifluoromethyl group.

[0018] Specific examples of 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, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a cyclohexyl group. Among these, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, a hexyl group, and a cyclohexyl group are preferred, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, and a cyclohexyl group are more preferred, and a methyl group, an ethyl group, an n-butyl group, a tert-butyl group, and a cyclohexyl group are particularly preferred.

[0019] Specific examples of the alkenyl group include a vinyl group, an allyl group, a methallyl group, a 2-butenyl group, a 3-methyl-2-butenyl group, a 3-butenyl group, a 4-pentenyl group, etc. Among these, a vinyl group, an allyl group, a methallyl group, and a 2-butenyl group are preferred, a vinyl group, an allyl group, and a methallyl group are more preferred, and a vinyl group or an allyl group is particularly preferred.

[0020] Specific examples of the alkynyl group include an ethynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 4-pentynyl group, a 5-hexynyl group, etc. Among these, an ethynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group are preferred, a 2-propynyl group, a 3-butynyl group are more preferred, and a 2-propynyl group is particularly preferred.

[0021] Specific examples of the aryl group include a phenyl group and a tolyl group, with the phenyl group being preferred. Specific examples of the aralkyl group include a benzyl group and a phenethyl group. Alkoxycarbonyl group (-(C=O)OR a Specific examples of -(C=O)O-CH3, -(C=O)O-CH2CH3, etc. Sulfonyloxy group (-O(SO2)-R a Specific examples of -O(SO2)-CH3, -O(SO2)-CH2CH3, etc.

[0022] Specific examples of the compound represented by formula (A) include the following compounds.

[0023] [ka]

[0024] Preferred are the following compounds: [ka]

[0025] More preferably, the following compounds are used: [ka]

[0026] Particularly preferred are the following compounds: [ka]

[0027] The compound represented by general formula (A) may be used alone or in combination of two or more kinds. The content of the compound represented by general formula (A) (when there are two or more kinds, the total amount thereof) relative to the total amount of the nonaqueous electrolyte solution according to one embodiment of the present invention is usually 1.0 × 10 -3 % by mass or more, preferably 1.0 × 10 -2 It is preferably 10% by mass or less, more preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1% by mass or less. When the content of the compound represented by general formula (A) relative to the total amount of the nonaqueous electrolyte solution is within the above range, concentration of the compound in the active material proceeds more suitably, and it becomes possible to produce a battery that generates less gas during initial conditioning.

[0028] <1-1-2. Compound represented by general formula (α)> A non-aqueous electrolyte solution according to one embodiment of the present invention contains a compound represented by general formula (α). [ka] (In formula (α), R 1 and R 2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or -SiR 3 R 4 R 5 R represents a silyl group represented by 3 ~ 5 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; Y represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, -NR 6 -SiR 7 R 8 R 9 or a group represented by -NR10 -R 11 R represents a group represented by 6 , R 10 and R 11 each independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 12 carbon atoms; R 7 ~R 9 R each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 1 or R 2 and Y may be bonded to each other to form a ring. Below, R 1 ~R 11 and Y, etc. will be explained.

[0029] R according to general formula (α) 1 and R 2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or -SiR 3 R 4 R 5 R represents a silyl group represented by 3 ~R 5 each independently represents a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group of 1 to 12 carbon atoms, or an optionally substituted alkoxy group of 1 to 12 carbon atoms. -SiR 3 R 4 R 5 In the silyl group represented by the formula 3 ~R 5 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 12 carbon atoms which may have a substituent, or an alkoxy group of 1 to 12 carbon atoms which may have a substituent. Of these, a hydrocarbon group of 1 to 12 carbon atoms which may have a substituent and an alkoxy group of 1 to 12 carbon atoms which may have a substituent are preferred, and a hydrocarbon group of 1 to 12 carbon atoms which may have a substituent is particularly preferred. When the hydrocarbon group has a substituent, the number of carbon atoms contained in the substituent is not included in this carbon number. Also, R 3 ~R 5It is preferable that at least one of R is an alkyl group having 1 to 12 carbon atoms, since the compound represented by general formula (α) tends to be suitably localized on the electrode surface. 3 ~R 5 All of these are alkyl groups having 1 to 12 carbon atoms. R according to general formula (α) 3 ~R 5 may be the same or different, but it is preferable that at least two of them are the same in terms of ease of compound synthesis, and it is even more preferable that all three of them are the same in terms of the above.

[0030] Examples of halogen atoms include fluorine atoms, chlorine atoms, and bromine atoms. Fluorine atoms are preferred because they cause fewer electrochemical side reactions. The hydrocarbon group having 1 to 12 carbon atoms is preferably a hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a hydrocarbon group having 1 to 4 carbon atoms.

[0031] Specific examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, and an aryl group. Specific examples of the alkyl group include chain alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, hexyl, heptyl, octyl, nonyl, and decyl; and cyclic alkyl groups such as cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. Among these, preferred are methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, hexyl, and cyclohexyl; more preferred are methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, and cyclohexyl; and most preferred are methyl, ethyl, n-butyl, tert-butyl, and cyclohexyl. The alkyl groups mentioned above are preferred because they tend to localize the compound represented by general formula (α) near the surface of the positive electrode active material and / or negative electrode active material.

[0032] Specific examples of the alkenyl group include a vinyl group, an allyl group, a methallyl group, a 2-butenyl group, a 3-methyl-2-butenyl group, a 3-butenyl group, and a 4-pentenyl group. Among these, a vinyl group, an allyl group, a methallyl group, and a 2-butenyl group are preferred, a vinyl group, an allyl group, and a methallyl group are more preferred, and a vinyl group or an allyl group is particularly preferred. The above-mentioned alkenyl groups are preferred because the compound represented by general formula (α) tends to be localized near the surface of the positive electrode active material and / or the negative electrode active material.

[0033] Specific examples of the alkynyl group include an ethynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 4-pentynyl group, and a 5-hexynyl group. Among these, an ethynyl group, a 2-propynyl group, a 2-butynyl group, and a 3-butynyl group are preferred, a 2-propynyl group and a 3-butynyl group are more preferred, and a 2-propynyl group is particularly preferred. The above-mentioned alkynyl groups are preferred because the compound represented by general formula (α) tends to be localized near the surface of the positive electrode active material and / or the negative electrode active material.

[0034] Specific examples of the aryl group include a phenyl group and a tolyl group, etc. Among these, a phenyl group is preferred from the viewpoint that the compound represented by general formula (α) tends to be localized near the surface of the positive electrode active material and / or the negative electrode active material. Specific examples of the aralkyl group include a benzyl group and a phenethyl group. 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. Specific examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an isopropoxy group, etc. Among these, a methoxy group and an ethoxy group are preferred because they cause less steric hindrance to the compound and are suitably concentrated on the surface of the active material.

[0035] Here, the substituents include a cyano group, an isocyanato group, an oxo group (=O), an acyl group (-(C=O)-R b), acyloxy group (-O(C=O)-R b ), alkoxycarbonyl group (-(C=O)OR b ), sulfonyl group (-SO2-R b ), sulfonyloxy group (-O(SO2)-R b ), alkoxysulfonyl group (-(SO2)-OR b ), alkoxysulfonyloxy group (-O-(SO2)-OR b ), alkoxycarbonyloxy group (-O-(C=O)-OR b ), alkoxy group (-OR b ), an acrylic group, a methacrylic group, a halogen atom (preferably a fluorine atom), a trifluoromethyl group, etc. 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. b When is an alkylene group, it may be bonded to a part of the hydrocarbon group that substitutes it to form a ring. Among these substituents, a cyano group, an isocyanato group, an oxo group (=O), an acyloxy group (-O(C=O)-R b ), a halogen atom (preferably a fluorine atom), or a trifluoromethyl group, and more preferably an oxo group (=O), an isocyanato group, or an acyloxy group (-O(C=O)-R b ), a halogen atom (preferably a fluorine atom), or a trifluoromethyl group, and particularly preferably an oxo group (=O), an acyloxy group (-O(C=O)-R b ), a halogen atom (preferably a fluorine atom), or a trifluoromethyl group. -SiR 3 R 4 R 5Specific examples of the group represented by the formula are -Si(CH3)3, -Si(CH3)2(C2H5), -Si(CH3)2(CH=CH2), -Si(CH3)2(CH2CH2CH3), -Si(CH3)2(CH2CH=CH2), -Si(CH3)2[CH(CH3)2], -Si(CH3)2[(CH2)3CH3], -Si(CH3)2[CH2CH(CH3)2], -Si(CH3)2[C(CH 3)3], -Si(CH3)2(C6H5), -Si(CH3)(C6H5)2, -Si(C6H5)3, -Si(C2H5)3, -Si(CH=CH2)3, -Si(CH2CH2CH3)3, - Examples include Si[CH(CH3)2]3, -Si(CH2CH=CH2)3, -Si(CH3)(C6H5)(CH=CH2), -Si(C6H5)2(CH=CH2), and -Si(CF3)3. Of these, -Si(CH3)3, -Si(CH3)2(CH=CH2), -Si(CH3)2(CH2CH=CH2), -Si(C2H5)3, -Si(CH3)(C6H5)(CH=CH2), and -Si(C6H5)2(CH=CH2) are preferred, with -Si(CH3)2(CH=CH2) and -Si(CH3)2(CH2CH=CH2) being particularly preferred.

[0036] Y in the general formula (α) is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, -NR 6 -SiR 7 R 8 R 9 or a group represented by -NR 10 -R 11 R represents a group represented by 6 , R 10 and R 11 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, and R 7 ~R 9 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 6 -SiR 7 R 8 R 9 or a group represented by -NR10 -R 11 is preferred in that it interacts more favorably with the compound represented by general formula (A). Here, the halogen atom and the hydrocarbon group having 1 to 12 carbon atoms which may have a substituent are all represented by R 3 ~R 5 The same explanations as those set out in 2. above apply. -NR 6 -SiR 7 R 8 R 9 In the group represented by 6 is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, and the hydrocarbon group having 1 to 12 carbon atoms which may have a substituent is R 1 The same applies to the description of the preferred embodiments. 7 R 8 R 9 The group represented by -SiR 3 R 4 R 5 The same explanation as for the group represented by the formula (I) applies, and the same preferred embodiments also apply. -NR 10 -R 11 In the group represented by 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. Here, the hydrocarbon group having 1 to 12 carbon atoms which may have a substituent is R 1 The explanations given in the previous paragraph apply, and the preferred embodiments are similar.

[0037] Specific examples of the compound represented by general formula (α) include the following compounds.

[0038] [ka] [ka] [ka] [ka]

[0039] Preferred examples of the compounds include the following: [ka] [ka] [ka] [ka]

[0040] More preferred compounds include the following: [ka] [ka] [ka] [ka]

[0041] Particularly preferred are the following compounds: [ka] [ka] [ka] [ka]

[0042] The compound represented by general formula (α) may be used alone or in combination of two or more kinds. The content of the compound represented by general formula (α) (when there are two or more types, the total content thereof) relative to the total amount of the nonaqueous electrolyte solution according to one embodiment of the present invention is not particularly limited, but is preferably 0.01 ppm by mass or more, more preferably 0.1 ppm by mass or more, even more preferably 1.0 ppm by mass or more, particularly preferably 10 ppm by mass or more, and is preferably 1.0% by mass or less, more preferably 0.75% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less. When the content of the compound represented by general formula (α) relative to the total amount of the nonaqueous electrolyte solution is within the above range, the concentration of the compound in the active material proceeds more favorably, making it possible to produce a battery that generates less gas during initial conditioning.

[0043] The mass ratio of the compound represented by general formula (A) to the content of the compound represented by general formula (α) in the non-aqueous electrolyte solution (content of the compound represented by general formula (A) / content of the compound represented by general formula (α)) is not particularly limited, but is usually 1.0 or more, preferably 2.0 or more, and is usually 1.0 × 10 4 Less than or equal to 7.0 × 10 3 or less, preferably 4.0 × 10 3 or less, more preferably 2.0 × 10 3 Below, particularly preferably 1.0 × 10 3 Below 5.0 × 10, particularly preferably 2 The following is the result.

[0044] <1-1-3. Compounds represented by general formula (β)> A non-aqueous electrolyte solution according to one embodiment of the present invention contains an unsaturated silane compound represented by general formula (β).

[0045] [ka]

[0046] In the general formula (β), R 21 ~R 23each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 18 carbon atoms, or an optionally substituted aralkyl group having 7 to 18 carbon atoms; and Z represents an optionally substituted alkenyl group or alkynyl group having 2 to 10 carbon atoms.

[0047] Here, the substituents include a cyano group, an isocyanato group, an acyl group (—(C═O)—R c ), acyloxy group (-O(C=O)-R c ), alkoxycarbonyl group (-(C=O)OR c ), sulfonyl group (-SO2-R c ), sulfonyloxy group (-O(SO2)-R c ), alkoxysulfonyl group (-(SO2)-OR c ), alkoxycarbonyloxy group (-O-(C=O)-OR c ), ether group (-OR c ), an acrylic group, a methacrylic group, a halogen (preferably fluorine), or a trifluoromethyl group. 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 21 ~R 23 and Z is not counted as the number of carbon atoms in the hydrocarbon group having 1 to 12 carbon atoms.

[0048] Among these substituents, a cyano group, an isocyanato group, an acyl group (—(C═O)—R c ), acyloxy group (-O(C=O)-R c ), alkoxycarbonyl group (-(C=O)OR c ), and more preferably a cyano group, an isocyanato group, an acyl group (—(C═O)—R c ), or an alkoxycarbonyl group (-(C=O)OR c ), and particularly preferably a cyano group, an isocyanato group, or an alkoxycarbonyl group (—(C═O)OR c ), and most preferably a cyano group.

[0049] Specific examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Among these, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, or a hexyl group is preferred, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a tert-butyl group, or an n-pentyl group is more preferred, and a methyl group or an ethyl group is particularly preferred.

[0050] Specific examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a tolyl group, etc. Among these, a phenyl group is preferred because it facilitates concentration in the active material. Specific examples of the aralkyl group having 7 to 18 carbon atoms include a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group. Of these, benzyl and phenethyl groups are preferred, with benzyl groups being particularly preferred, from the viewpoint that the compound represented by general formula (β) tends to be localized near the surface of the positive electrode active material and / or the negative electrode active material.

[0051] Specific examples of alkenyl groups having 2 to 10 carbon atoms include vinyl, allyl, methallyl, 2-butenyl, 3-methyl-2-butenyl, 3-butenyl, and 4-pentenyl groups. Among these, vinyl, allyl, methallyl, and 2-butenyl groups are preferred, vinyl, allyl, and methallyl groups are more preferred, and allyl and methallyl groups are particularly preferred. The above-mentioned alkenyl groups are preferred because they allow for the formation of an insulating coating film.

[0052] Specific examples of alkynyl groups having 2 to 10 carbon atoms include ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, 4-pentynyl, and 5-hexynyl groups. Among these, ethynyl, 2-propynyl, 2-butynyl, and 3-butynyl groups are preferred, ethynyl, 2-propynyl, and 3-butynyl groups are more preferred, and ethynyl and 2-propynyl groups are particularly preferred. The above-mentioned alkynyl groups are preferred because they allow for the formation of an insulating coating film.

[0053] Since the compound represented by general formula (β) and the compound represented by general formula (A) tend to interact favorably, R 21 ~R 23 At least one of R is an alkyl group having 1 to 10 carbon atoms which may have a substituent, preferably at least two are alkyl groups having 1 to 10 carbon atoms which may have a substituent, more preferably all are alkyl groups having 1 to 10 carbon atoms which may have a substituent, and most preferably a methyl group or an ethyl group. 21 ~R 23 If any one of the groups is a methyl group, then R 21 ~R 23 It is not necessary that all of R are methyl groups. For example, the following combinations are preferable: 21 , R 22 , R 23 ): (methyl, methyl, ethyl), (methyl, methyl, n-butyl), (methyl, methyl, tert-butyl), (methyl, methyl, phenyl), (methyl, ethyl, ethyl), (methyl, phenyl, phenyl).

[0054] In general formula (β), Z is preferably an alkenyl group having 2 to 10 carbon atoms which may have a substituent, more preferably an alkenyl group having 2 to 10 carbon atoms, still more preferably a vinyl group, an allyl group, or a methallyl group, and particularly preferably an allyl group or a methallyl group, because this allows for the suitable formation of an insulating coating.

[0055] Specific examples of the compound represented by general formula (β) include compounds having the following structures.

[0056] [ka]

[0057] More preferred are compounds having the following structures: The compounds having the following structures are more likely to interact favorably with the compound represented by general formula (A).

[0058] [ka]

[0059] Particularly preferred are compounds having the following structures: The compounds having the following structures are more likely to interact favorably with the compound represented by general formula (A).

[0060] [ka]

[0061] Most preferably, compounds having the following structure are mentioned: Compounds having the following structure are highly reactive and suitably form insulating layers.

[0062] [ka]

[0063] The compound represented by general formula (β) may be used alone or in combination of two or more kinds. The content of the compound represented by general formula (β) (when there are two or more types, the total content thereof) relative to the total amount of the nonaqueous electrolyte solution according to one embodiment of the present invention is usually 0.01 mass ppm or more, preferably 0.001 mass% or more, more preferably 0.005 mass% or more, and even more preferably 0.01 mass% or more, and is usually 5 mass% or less, preferably 2 mass% or less, more preferably 1 mass% or less, even more preferably 0.5 mass% or less, particularly preferably less than 0.5 mass%, particularly preferably 0.2 mass% or less, and most preferably 0.1 mass% or less. When the content of the compound represented by general formula (β) relative to the total amount of the nonaqueous electrolyte solution is within the above range, the concentration of the compound represented by general formula (β) in the active material proceeds more suitably, and it becomes possible to produce a battery that generates less gas during initial conditioning. Furthermore, the mass ratio of the compound represented by the general formula (A) to the content of the compound represented by the general formula (β) in the non-aqueous electrolyte solution is preferably 1.0 or more, more preferably 1.5 or more, even more preferably 2.0 or more, particularly preferably 3.0 or more, and most preferably 5.0 or more, from the viewpoint of more suitably forming a composite coating film consisting of the compound represented by the general formula (A) and the compound represented by the general formula (β), and is preferably 1.0 × 10 4 Less than or equal to 0.5 × 10 4 or less, more preferably 1.0 × 10 3 The following is the result. Furthermore, the mass ratio of the compound represented by general formula (A) to the content of the compound represented by general formula (α) or the compound represented by general formula (β) in the non-aqueous electrolyte solution (the total content when both the compound represented by general formula (α) and the compound represented by general formula (β) are included) is preferably 1.0 or more, more preferably 1.5 or more, even more preferably 2.0 or more, particularly preferably 3.0 or more, and most preferably 5.0 or more, from the viewpoint of more suitably forming a composite coating film composed of the compound represented by general formula (A) and the compound represented by general formula (α) or the compound represented by general formula (β), and is preferably 1.0 × 10 4 Less than or equal to 0.5 × 10 4 or less, more preferably 1.0 × 10 3The following is the result. The method for incorporating the compound represented by general formula (α) or the compound represented by general formula (β) and the compound represented by general formula (A) into the non-aqueous electrolyte solution is not particularly limited. In addition to a method of directly adding the compound to the non-aqueous electrolyte solution, a method of generating the compound in the battery or the non-aqueous electrolyte solution can be mentioned. In this specification, the content of the compounds means the content at the time of manufacturing the nonaqueous electrolyte solution, at the time of injecting the nonaqueous electrolyte solution into a battery, or at the time of shipping the battery. The identification and content measurement of the compound represented by general formula (α), the compound represented by general formula (β), and the compound represented by general formula (A) in the nonaqueous electrolyte solution are performed by nuclear magnetic resonance (NMR) spectroscopy, gas chromatography (GC), or the like.

[0064] <1-1-4. Electrolyte> The nonaqueous electrolyte solution of this embodiment, like a general nonaqueous electrolyte solution, typically contains an electrolyte as a component. The electrolyte used in the nonaqueous electrolyte solution of this embodiment is not particularly limited as long as it is an alkali metal salt, and lithium salts such as LiBF, LiPF, LiN(FSO), LiN(CFSO), and lithium difluorooxalatoborate are suitable. These lithium salts can also be used alone or in combination of two or more.

[0065] The total concentration of the alkali metal salts 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 or more, based on the total amount of the non-aqueous electrolyte. Also, it is usually 18% by mass or less, preferably 17% by mass or less, more preferably 16% by mass or less. When the total concentration of the alkali metal salts in the electrolyte is within the above range, the electrical conductivity is appropriate for battery operation, and thus sufficient output characteristics tend to be obtained.

[0066] <1-1-5. Non-aqueous solvents> The non-aqueous electrolyte solution of this embodiment, like a general non-aqueous electrolyte solution, usually contains a non-aqueous solvent that dissolves the above-mentioned electrolyte as its main component. There are no particular limitations on the non-aqueous solvent, and known organic solvents can be used. Examples of organic solvents include saturated cyclic carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate; linear carbonates such as dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate; carboxylic acid esters such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; ether compounds such as dimethoxymethane, diethoxymethane, ethoxymethoxymethane, tetrahydrofuran, 1,3-dioxane, and 1,4-dioxane; sulfone compounds such as 2-methylsulfolane, 3-methylsulfolane, 2-fluorosulfolane, 3-fluorosulfolane, dimethyl sulfone, ethyl methyl sulfone, and monofluoromethyl methyl sulfone; and the like. Preferred are saturated cyclic carbonates, chain carbonates, and carboxylic acid esters, and more preferred are saturated cyclic carbonates and chain carbonates. These non-aqueous solvents can be used alone or in combination of two or more.

[0067] <1-1-6. Auxiliaries> The nonaqueous electrolyte solution of this embodiment may contain an auxiliary agent within a range that allows the effects of the present invention to be achieved. As an auxiliary agent, Difluorophosphate anion-containing compounds; Fluorosulfonate anion-containing compounds; Oxalate anion-containing compounds; Sulfonylimide anion-containing compounds; Alkyl sulfate anion-containing compounds; 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 having a cycloalkylene group, such as 1,3-bis(isocyanatomethyl)cyclohexane; isocyanate compounds such as trimer compounds derived from compounds having at least two isocyanate groups in the molecule, such as triallyl isocyanurate, or aliphatic polyisocyanates obtained by adding a polyhydric alcohol thereto; Nitrogen-containing compounds such as 1-methyl-2-pyrrolidinone; hydrocarbon compounds such as cycloheptane; Fluorinated aromatic compounds such as fluorobenzene; Ester compounds such as 2-propynyl 2-(methanesulfonyloxy)propionate; Lithium salts such as lithium ethylmethyloxycarbonylphosphonate; These may be used alone or in combination of two or more. The addition of these auxiliary agents can suppress gas generation during initial conditioning and improve capacity retention and cycle characteristics after high-temperature storage.

[0068] In particular, in the nonaqueous electrolyte solution according to one embodiment of the present invention, the combined use of one or more compounds selected from difluorophosphate anion-containing compounds, fluorosulfonate anion-containing compounds, oxalate anion-containing compounds, sulfonylimide anion-containing compounds, and alkylsulfate anions (hereinafter, these may also be referred to as "specific anion-containing compounds"), and / or one or more compounds selected from unsaturated cyclic carbonates and cyclic carbonates having fluorine atoms (hereinafter, these may also be referred to as "specific carbonate compounds") is preferred in that gas generation during initial conditioning is further suppressed and a battery that is less likely to swell can be obtained. When two or more of the specific anion-containing compound and the specific carbonate compound are used in combination, it is preferable to use the specific anion-containing compound and the specific carbonate compound in combination. Among the specific anion-containing compounds, difluorophosphate anion-containing compounds are particularly preferred. The content of the 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, and even more preferably 0.2% by mass or more, relative to 100% by mass of the nonaqueous electrolyte solution, and is usually 10% by mass or less, preferably 8% by mass or less, and more preferably 5% by mass or less. When two or more auxiliary agents are used in combination, it is preferable that the total amount satisfies the above range.

[0069] [1-1-6-1. Specific anion-containing compounds] The specific anion-containing compound is usually an acid or a salt, and preferably a salt. The counter cation of the salt of the specific anion-containing compound is not particularly limited, but includes lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, and NR 123 R 124 R 125 R 126 (In the formula, R 123 ~R 126 and each independently represent a hydrogen atom or an organic group having 1 to 12 carbon atoms. Examples include ammonium represented by the following formula: Among these, lithium is preferred.

[0070] The above ammonium R 123 ~R 126 The organic group having 1 to 12 carbon atoms represented by the formula (I) is not particularly limited, but examples thereof include an alkyl group which may be substituted with a halogen atom, a cycloalkyl group which may be substituted with a halogen atom or an alkyl group, an aryl group which may be substituted with a halogen atom or an alkyl group, or a nitrogen atom-containing heterocyclic group which may have a substituent. 123 ~R 126 are each preferably independently a hydrogen atom, an alkyl group, a cycloalkyl group, or a nitrogen atom-containing heterocyclic group.

[0071] (Difluorophosphate anion-containing compounds) The difluorophosphate anion-containing compound may be used alone or in any combination and ratio of two or more. The content of the difluorophosphate anion-containing compound (the total content when two or more compounds are used) relative to the total amount of the nonaqueous electrolyte is not particularly limited and may be any amount as long as it does not significantly impair the effects of the present invention. It is typically 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, even more preferably 2.0% by mass or less, and most preferably 1.5% by mass or less. It is preferably 0.001 to 5.0% by mass, more preferably 0.001 to 3.0% by mass, even more preferably 0.001 to 2.0% by mass, and most preferably 0.001 to 1.5% by mass. If the content of the difluorophosphate anion-containing compound is within this range, the initial gas generation can be more suitably suppressed.

[0072] (Fluorosulfonate anion-containing compounds) The fluorosulfonate anion-containing compound may be used alone or in any combination and ratio of two or more. The content of the fluorosulfonate anion-containing compound (the total content when two or more compounds are used) relative to the total amount of the nonaqueous electrolyte is not particularly limited and may be any amount as long as it does not significantly impair the effects of the present invention. It is typically 0.001 to 8 mass%, preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and preferably 5.0 mass% or less, more preferably 3.0 mass% or less, even more preferably 2.0 mass% or less, and most preferably 1.5 mass% or less. It is preferably 0.001 to 5.0 mass%, more preferably 0.001 to 3.0 mass%, even more preferably 0.001 to 2.0 mass%, and most preferably 0.001 to 1.5 mass%. If the content of the fluorosulfonate anion-containing compound is within this range, the initial gas generation can be more suitably suppressed.

[0073] (Sulfonylimide anion-containing compounds) Specific examples of the sulfonylimide anion constituting the sulfonylimide anion-containing compound include N - (FSO2)2, N - (FSO2)(CF3SO2), N - (CF3SO2)2, N - (C2F5SO2)2, cyclic 1,2-perfluoroethanedisulfonylimide anion, cyclic 1,3-perfluoropropanedisulfonylimide anion, N - (CF3SO2)(C4F9SO2), and N - (FSO2) 2、 N - (CF3SO2)2, N - (C2F5SO2)2 is preferred, especially N - (FSO2)2 is preferred.

[0074] The sulfonylimide anion-containing compound may be used alone or in any combination and ratio of two or more. The content of the sulfonylimide anion-containing compound (the total content when two or more compounds are used) relative to the total amount of the nonaqueous electrolyte is not particularly limited and may be any amount as long as it does not significantly impair the effects of the present invention. It is 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, even more preferably 2.0% by mass or less, and most preferably 1.5% by mass or less. It is preferably 0.001 to 5.0% by mass, more preferably 0.001 to 3.0% by mass, even more preferably 0.001 to 2.0% by mass, and most preferably 0.001 to 1.5% by mass. If the content of the sulfonylimide anion-containing compound is within this range, the initial gas generation can be more suitably suppressed.

[0075] (Alkyl sulfate anion-containing compounds) Specific examples of alkyl sulfate anions constituting alkyl sulfate anion-containing compounds include C n H 2n+1 OSO3 -(1≦n≦10), and a methyl sulfate anion or an ethyl sulfate anion is preferred. The content of the alkyl sulfate anion-containing compound is not particularly limited and can be any amount as long as it does not significantly impair the effects of the present invention, but is 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, even more preferably 2.0% by mass or less, and most preferably 1.5% by mass or less. Preferably, it is 0.001 to 5.0% by mass, more preferably 0.001 to 3.0% by mass, even more preferably 0.001 to 2.0% by mass, and most preferably 0.001 to 1.5% by mass. If the content of the alkyl sulfate anion-containing compound is within this range, the initial gas generation can be more suitably suppressed.

[0076] (Oxalate complex anion-containing compounds) Specific examples of the oxalate complex anion constituting the oxalate complex anion-containing compound include (oxalate)borate anion, bis(oxalate)borate anion, tetrafluorooxalate phosphate anion, difluorobis(oxalate)phosphate anion, and tris(oxalate)phosphate anion, of which bis(oxalate)borate and difluorobis(oxalate)phosphate anion are preferred, and bis(oxalate)borate anion is particularly preferred.

[0077] The oxalate complex anion-containing compound may be used alone or in any combination of two or more in any ratio. The content of the oxalate complex anion-containing compound (the total content when two or more types are used) is not particularly limited and can be any amount as long as it does not significantly impair the effects of the present invention, but is 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, even more preferably 2.0% by mass or less, and most preferably 1.5% by mass or less. Preferably, it is 0.001 to 5.0% by mass, more preferably 0.001 to 3.0% by mass, even more preferably 0.001 to 2.0% by mass, and most preferably 0.001 to 1.5% by mass. When the content of the oxalate complex anion-containing compound is within this range, the initial gas generation can be more suitably suppressed.

[0078] [1-1-6-2. Specific carbonate compounds] The non-aqueous electrolyte preferably contains at least one carbonate compound selected from the group consisting of unsaturated cyclic carbonates having a carbon-carbon unsaturated bond and cyclic carbonates having a fluorine atom. Among these, it is preferable to contain an unsaturated cyclic carbonate, and more preferable to contain vinylene carbonate. These can be used alone or in combination of two or more in any ratio. It is preferable to contain an unsaturated cyclic carbonate and a fluorinated cyclic carbonate, more preferably vinylene carbonate and a fluorinated cyclic carbonate, or an unsaturated cyclic carbonate and monofluoroethylene carbonate, and even more preferably vinylene carbonate and monofluoroethylene carbonate.

[0079] (Unsaturated cyclic 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. Cyclic carbonates having an aromatic ring are also included in the unsaturated cyclic carbonate.

[0080] Examples of unsaturated cyclic carbonates include vinylene carbonates, ethylene carbonates substituted with a substituent having an aromatic ring, a carbon-carbon double bond, or a carbon-carbon triple bond, phenyl carbonates, vinyl carbonates, allyl carbonates, catechol carbonates, etc. Among these, vinylene carbonates and ethylene carbonates substituted with a substituent having an aromatic ring, a carbon-carbon double bond, or a carbon-carbon triple bond are preferred.

[0081] Examples of vinylene carbonates include vinylene carbonate, methyl vinylene carbonate, 4,5-dimethyl vinylene carbonate, phenyl vinylene carbonate, 4,5-diphenyl vinylene carbonate, vinyl vinylene carbonate, 4,5-vinyl vinylene carbonate, allyl vinylene carbonate, and 4,5-diallyl vinylene carbonate. Examples of ethylene carbonates substituted with a substituent having an aromatic ring or a carbon-carbon double bond or a carbon-carbon triple bond include vinyl ethylene carbonate, 4,5-divinyl ethylene carbonate, 4-methyl-5-vinyl ethylene carbonate, 4-allyl-5-vinyl ethylene carbonate, ethynyl ethylene carbonate, 4,5-diethynyl ethylene carbonate, 4-methyl-5-ethynyl ethylene carbonate, 4-vinyl-5-ethynyl ethylene carbonate, 4-allyl-5-ethynyl ethylene carbonate, phenyl ethylene carbonate, 4,5-diphenyl ethylene carbonate, 4-phenyl-5-vinyl ethylene carbonate, 4-allyl-5-phenyl ethylene carbonate, allyl ethylene carbonate, 4,5-diallyl ethylene carbonate, and 4-methyl-5-allyl ethylene carbonate. Among these, vinylene carbonate, vinylethylene carbonate, and ethynylethylene carbonate are preferred because they form a more stable composite coating on the electrode, and one or more selected from vinylene carbonate and vinylethylene carbonate are more preferred, with vinylene carbonate being even more preferred. The unsaturated cyclic carbonates can be used alone or in combination of two or more kinds in any ratio.

[0082] (Fluorine atom-containing cyclic carbonate) The fluorine atom-containing cyclic carbonate is not particularly limited as long as it has a cyclic carbonate structure and contains a fluorine atom. Examples of cyclic carbonates having fluorine atoms include fluorinated cyclic carbonates having an alkylene group with 2 to 6 carbon atoms, and derivatives thereof, such as fluorinated ethylene carbonate (fluoroethylene carbonate) and derivatives thereof, and ethylene carbonate having a fluorine-containing group. Examples of derivatives of fluorinated ethylene carbonate include fluorinated ethylene carbonate substituted with an alkyl group (e.g., an alkyl group with 1 to 4 carbon atoms). Among these, fluoroethylene carbonate having 1 to 8 fluorine atoms and derivatives thereof are preferred.

[0083] Examples of fluoroethylene carbonate and derivatives thereof having 1 to 8 fluorine atoms, 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, and 4,4-difluoro-5,5-dimethylethylene carbonate. Among these, from the viewpoint of imparting high ionic conductivity to the electrolyte and facilitating the formation of a stable interface protective coating, one or more selected from monofluoroethylene carbonate, 4,4-difluoroethylene carbonate, and 4,5-difluoroethylene carbonate are preferred. The fluorine atom-containing cyclic carbonates can be used alone or in combination of two or more kinds in any ratio.

[0084] (Content of specific carbonate compounds) The content of the specific carbonate compound (total amount when two or more types are used) in the total amount of the nonaqueous electrolyte is usually 0.001 to 10 mass%, preferably 0.01 mass% or more, more preferably 0.1 mass% or more, even more preferably 0.5 mass% or more, and preferably 8.0 mass% or less, more preferably 6.0 mass% or less, even more preferably 5.0 mass% or less, preferably 0.001 to 10 mass%, more preferably 0.001 to 8.0 mass%, even more preferably 0.001 to 6.0 mass%, and most preferably 0.001 to 5.0 mass%. When the content of the specific carbonate compound is within the above range, gas generation during initial conditioning can be significantly suppressed. Although the reason for this is unclear, it is thought that the inclusion of the carbonate compound at this ratio forms a coating on the electrode, minimizing side reactions of the components of the non-aqueous electrolyte solution and thereby suppressing gas generation during initial conditioning. The identification and content of specific carbonate compounds is determined by nuclear magnetic resonance (NMR) spectroscopy.

[0085] (Mass Ratio of Compound Represented by General Formula (A) to Specific Carbonate Compound) The mass ratio of the content of the specific carbonate compound (total amount when two or more types are used) to the content of the compound represented by general formula (A) (specific carbonate compound [g] / compound represented by general formula (A) [g]) is typically 1 to 200. It is preferably 3 or more, more preferably 5 or more, and preferably 100 or less, more preferably 70 or less, and even more preferably 50 or less. It is preferably 1 to 100, more preferably 1 to 70, and even more preferably 1 to 50. When the mass ratio is within the above range, gas generation during initial conditioning can be significantly suppressed. While the reason for this is unclear, it is thought that the inclusion of the specific carbonate compound within the above mass ratio range forms a coating on the electrode, minimizing side reactions of the components of the nonaqueous electrolyte solution and thereby suppressing gas generation during initial conditioning.

[0086] (mass ratio of electrolyte to specific carbonate compound) In the nonaqueous electrolyte solution, the mass ratio (g of specific carbonate compound / g of electrolyte) of the content of the specific carbonate compound (total amount when two or more types are used) to the content of the electrolyte (preferably LiPF6) is typically 0.001 to 0.8. It is preferably 0.01 or more, more preferably 0.05 or more, and even more preferably 0.1 or more, and is preferably 0.5 or less, more preferably 0.4 or less, and even more preferably 0.35 or less. It is preferably 0.001 to 0.5, more preferably 0.001 to 0.4, and even more preferably 0.001 to 0.35. When the mass ratio is within the above range, gas generation during initial conditioning can be significantly suppressed. While the reason for this is unclear, it is thought that by including the specific carbonate compound and electrolyte within the above mass ratio range, a coating is formed on the electrode, minimizing side reactions of the electrolyte within the battery system and thereby suppressing gas generation during initial conditioning.

[0087] <1-2. Nonaqueous electrolyte battery> A nonaqueous electrolyte battery according to one embodiment of the present invention is a nonaqueous electrolyte battery comprising a positive electrode, a negative electrode, and a nonaqueous electrolyte solution, and the battery comprises the nonaqueous electrolyte solution according to the embodiment of the present invention described above. More specifically, the battery comprises a current collector and a positive electrode having a positive electrode active material layer on at least a portion of the current collector surface and capable of absorbing and releasing metal ions, a current collector and a negative electrode having a negative electrode active material layer on at least a portion of the current collector surface and capable of absorbing and releasing metal ions, and a nonaqueous electrolyte solution containing, together with an alkali metal salt and a nonaqueous solvent, at least one of the compound represented by general formula (A) and the compound represented by general formula (α) and the compound represented by general formula (β).

[0088] <1-2-1. Battery configuration> The nonaqueous electrolyte battery of this embodiment is similar to conventional nonaqueous electrolyte batteries in terms of configuration other than the nonaqueous electrolyte. Typically, a positive electrode and a negative electrode are stacked via a porous membrane (separator) impregnated with the nonaqueous electrolyte, and these are housed in a case (exterior body). The shape of the nonaqueous electrolyte battery of this embodiment is not particularly limited, and may be any of cylindrical, rectangular, laminated, coin, large, and the like.

[0089] <1-2-2. Non-aqueous electrolyte> As the nonaqueous electrolyte solution, the nonaqueous electrolyte solution according to one embodiment of the present invention is used. Note that, within the scope of the present invention, other nonaqueous electrolyte solutions may be blended with the nonaqueous electrolyte solution.

[0090] <1-2-3. Positive electrode> The positive electrode has a current collector and a positive electrode active material on at least a part of the surface of the current collector. The other components can be those known in the art.

[0091] The positive electrode active material is not particularly limited as long as it can electrochemically absorb and release metal ions, but specific examples include lithium cobalt oxide and transition metal oxides containing at least Ni and Co, with Ni and Co accounting for 50 mol % or more of the transition metals, and materials capable of electrochemically absorbing and releasing lithium ions are preferred, for example, transition metal oxides containing lithium, at least Ni, and Co, with Ni and Co accounting for 60 mol % or more of the transition metals. This is because Ni and Co have oxidation-reduction potentials suitable for use as positive electrode materials for secondary batteries and are suitable for high-capacity applications.

[0092] Among the transition metal oxides, a transition metal oxide represented by the following composition formula (11) is preferred. Li a1 Ni b1 Co c1 M d1 O2···(11) In the above formula (11), a1, b1, c1, and d1 represent numerical values ​​within the range of 0.90≦a1≦1.10, 0.50≦b1≦0.98, 0.01≦c1<0.50, and 0.01≦d1<0.50, and satisfy b1+c1+d1=1. M represents at least one element selected from the group consisting of Mn, Al, Mg, Zr, Fe, Ti, and Er. In the composition formula (11), it is preferable that the value d1 satisfies 0.1≦d1<0.50. By setting the composition ratios of Ni and Co and other metal species within the above ranges, there are advantages in that transition metals are less likely to leach out of the positive electrode, and even if they do leach out, Ni and Co have little adverse effect on the non-aqueous secondary battery. A suitable example is LiNi 0.85 Co 0.10 Al 0.05 O2, LiNi 0.80 Co 0.15 Al 0.05 O2, LiNi 0.5 Co 0.2 Mn 0.3 O2, Li 1.05 Ni 0.50 Co 0.20 Mn 0.30 O2, LiNi 0.6 Co0.2 Mn 0.2 O2, LiNi 0.8 Co 0.1 Mn 0.1 Examples include O2.

[0093] <1-2-4. Negative electrode> The negative electrode has a current collector and a negative electrode active material on at least a part of the surface of the current collector. Other components may be those known in the art.

[0094] The negative electrode active material is not particularly limited as long as it can electrochemically absorb and release metal ions. Specific examples include carbon-based materials, materials containing metal elements and / or metalloid elements that can be alloyed with Li, lithium-containing metal composite oxide materials, and mixtures thereof. These materials may be used alone or in any combination of two or more. It is preferable to use a carbon-based material, a material containing metal elements and / or metalloid elements that can be alloyed with Li, or a mixture of a material containing metal elements and / or metalloid elements that can be alloyed with Li and graphite particles, in order to obtain a battery with good cycle characteristics, safety, and excellent continuous charge characteristics.

[0095] Examples of carbonaceous materials include natural graphite, artificial graphite, amorphous carbon, carbon-coated graphite, graphite-coated graphite, and resin-coated graphite, with natural graphite being preferred.

[0096] Examples of natural graphite include scaly graphite, flake graphite, and / or graphite particles obtained by spheroidizing or densifying such graphite. Among these, spherical or ellipsoidal graphite particles that have been subjected to a spheroidizing treatment are particularly preferred from the viewpoint of particle packing properties and charge / discharge rate characteristics. The average particle diameter (d50) of the graphite particles is usually 1 μm or more and 100 μm or less.

[0097] Any conventionally known material containing a metal element and / or a metalloid element that can be alloyed with Li can be used, but from the viewpoint of capacity and cycle life, it is preferable to use, for example, a simple substance or a compound of a metal element and / or a metalloid element that can be alloyed with Li selected from the group consisting of Sb, Si, Sn, Al, As, and Zn. Furthermore, when the material containing a metal element and / or a 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. Furthermore, examples of compounds containing metal elements and / or metalloid elements that can be alloyed with Li include metal oxides, metal nitrides, metal carbides, etc. The compounds may contain two or more types of metal elements and / or metalloid elements that can be alloyed with Li. Among these, metal Si (hereinafter sometimes referred to as Si) or a Si-containing compound is preferred in terms of increasing capacity.

[0098] In this specification, Si or Si-containing compounds are collectively referred to as Si compounds. Specific examples of Si compounds include SiO x , SiN x , SiC x , SiZ y O z (Z=C, N), etc. Examples of Si compounds include Si oxides (SiO x ) is preferred because it has a larger theoretical capacity than graphite, and amorphous Si or nano-sized Si crystals are preferred because they allow alkali ions such as lithium ions to easily enter and exit, making it possible to obtain a high capacity. This general formula SiO x The silicon oxide represented by the formula is obtained from silicon dioxide (SiO2) and silicon, and the value of x is usually 0. <x<2である。 When the material containing a metal element and / or a metalloid element that can be alloyed with Li is in the form of particles, the average particle size (d50) of the particles is usually 0.01 μm or more and 10 μm or less from the viewpoint of cycle life. The mixture of graphite particles and particles of a material containing a metal element and / or a metalloid element that can be alloyed with Li, which is used as the negative electrode active material, may be a mixture in which the particles of a material containing a metal element and / or a metalloid element that can be alloyed with Li and the graphite particles are mixed in the state of independent particles, or may be a composite in which particles of a material containing a metal element and / or a metalloid element that can be alloyed with Li are present on the surface or inside of graphite particles. The content of the particles of material containing a metal element and / or a metalloid element capable of being alloyed with Li relative to the total of the particles of material containing a metal element and / or a metalloid element capable of being 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 even more preferably 2.0% by mass or more. The content is usually 99% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 25% by mass or less, even more preferably 20% by mass or less, particularly preferably 15% by mass or less, and most preferably 10% by mass or less. This range allows for the control of side reactions on the Si surface, enabling a sufficient capacity to be obtained in a nonaqueous electrolyte battery.

[0099] <1-2-5. Separator> A separator is usually interposed between the positive electrode and the negative electrode to prevent short circuiting. In this case, the nonaqueous electrolyte solution according to one embodiment of the present invention is usually impregnated into the separator before use. Any conventional separator can be used. [Second Invention] <2-1. Non-aqueous electrolyte> The non-aqueous electrolyte solution according to the present invention contains a compound represented by general formula (AA) and a compound represented by general formula (αα), both of which will be explained below. The mechanism by which the amount of gas generated during initial conditioning is suppressed by using a nonaqueous electrolyte solution containing a compound represented by general formula (AA) and a compound represented by general formula (αα) is not clear, but is presumed to be as follows.

[0100] Compounds represented by general formula (AA) have a cyclic structure and a polar structure (-SO2-O-) in the cyclic backbone, resulting in a higher dielectric constant than chain-like compounds. Compounds represented by general formula (α) also have a polar structure (-N-(C=O)-O) in their molecules. Therefore, these compounds tend to interact with surface functional groups of negative electrode active materials, such as carbon, and / or the surface of positive electrode active materials, such as transition metal oxides, and localize near the surface of the active materials. Furthermore, it is speculated that the interaction between the compounds localized on the active material surface (compounds represented by general formula (AA) and compounds represented by general formula (αα)) increases the amount of localized compounds adhering to the positive electrode active material and / or negative electrode active material surface. In particular, the RN-(C=O)-OR structure of compounds represented by general formula (αα) has a high adsorption property to the electrode surface, which promotes the adsorption of compounds represented by general formula (AA) to the electrode. As a result, the compound represented by general formula (αα) and the compound represented by general formula (AA), which are localized on the electrode, electrochemically decompose during the initial charge, forming a composite insulating coating. Furthermore, the ring-opening reaction of the compound represented by general formula (AA) proceeds favorably during the reaction, which is thought to facilitate efficient formation of the composite coating. It is presumed that this composite coating suppresses side reactions in the electrolyte during initial conditioning and suppresses gas generation. In addition, the compound represented by general formula (AA) has a cyclic structure and a polar structure (—SO2—O—) in the cyclic skeleton, and therefore 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 to be localized near the surface.

[0101] <2-1-1. Compounds represented by general formula (AA)> [ka] (In formula (AA), Q 31 and Q 32are each independently an alkylene group having 1 to 10 carbon atoms. The alkylene group may be substituted with a hydrocarbon group, or a hydrogen atom of the alkylene group may be substituted with a halogen atom. 31 represents an integer of 0 or 1. 31 When is 0, the sulfur atom and the oxygen atom form a direct bond.)

[0102] Q relating to general formula (AA) 31 and Q 32 each independently represents 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 As for n 31 When = 0, an alkylene group having 1 to 5 carbon atoms is preferred, an alkylene group having 1 to 3 carbon atoms is more preferred, and an alkylene group having 2 to 3 carbon atoms is particularly preferred. Also, Q 1 As for n 31 When = 1, an alkylene group having 1 to 5 carbon atoms is preferred, an alkylene group having 1 to 3 carbon atoms is more preferred, and a methylene group is particularly preferred. Q 2 As the alkylene group, an alkylene group having 1 to 5 carbon atoms is preferred, an alkylene group having 1 to 3 carbon atoms is more preferred, and a methylene group is particularly preferred. When the alkylene group has a hydrocarbon group as a substituent, the number of carbon atoms contained in the substituent is not included in the total number of carbon atoms.

[0103] Specific examples of the alkylene group include a methylene group, an ethylene group, an n-propylene group, a butylene group, and a hexylene group.

[0104] Here, examples of the substituent include a hydrocarbon group having 1 to 10 carbon atoms and a halogen atom (preferably a fluorine atom). Among these substituents, preferred are hydrocarbon groups having 1 to 8 carbon atoms and halogen atoms (preferably fluorine atoms), and particularly preferred are hydrocarbon groups having 1 to 6 carbon atoms and fluorine atoms.

[0105] Specific examples of 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, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a cyclohexyl group. Among these, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, a hexyl group, and a cyclohexyl group are preferred, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, and a cyclohexyl group are more preferred, and a methyl group, an ethyl group, an n-butyl group, a tert-butyl group, and a cyclohexyl group are particularly preferred.

[0106] Specific examples of the alkenyl group include a vinyl group, an allyl group, a methallyl group, a 2-butenyl group, a 3-methyl-2-butenyl group, a 3-butenyl group, a 4-pentenyl group, etc. Among these, a vinyl group, an allyl group, a methallyl group, and a 2-butenyl group are preferred, a vinyl group, an allyl group, and a methallyl group are more preferred, and a vinyl group or an allyl group is particularly preferred.

[0107] Specific examples of the alkynyl group include an ethynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 4-pentynyl group, a 5-hexynyl group, etc. Among these, an ethynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group are preferred, a 2-propynyl group, a 3-butynyl group are more preferred, and a 2-propynyl group is particularly preferred.

[0108] Specific examples of the aryl group include a phenyl group and a tolyl group, with the phenyl group being preferred. Specific examples of the aralkyl group include a benzyl group and a phenethyl group.

[0109] Specific examples of the compound represented by general formula (AA) include the following compounds.

[0110] [ka]

[0111] Preferred are the following compounds: [ka]

[0112] More preferably, the following compounds are used: [ka]

[0113] Particularly preferred are the following compounds: [ka]

[0114] The compound represented by general formula (AA) may be used alone or in combination of two or more kinds. The content of the compound represented by general formula (AA) (when there are two or more kinds, the total amount thereof) relative to the total amount of the nonaqueous electrolyte solution according to one embodiment of the present invention is usually 1.0 × 10 -3 % by mass or more, preferably 1.0 × 10 -2 It is usually 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1% by mass or less. When the content of the compound represented by general formula (AA) relative to the total amount of the nonaqueous electrolyte solution is within the above range, concentration of the compound in the active material proceeds more suitably, and it becomes possible to produce a battery that generates less gas during initial conditioning.

[0115] <2-1-2. Compounds represented by general formula (αα)> A non-aqueous electrolyte solution according to one embodiment of the present invention contains a compound represented by general formula (αα). [ka] (In formula (αα), R 31 and R 32 are each independently a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or -SiR 33 R 34 R 35 R represents a silyl group represented by 33 ~R 35 each independently represents a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, or an optionally substituted alkoxy group having 1 to 12 carbon atoms; Y 31 R represents an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 31 or R 32 and Y 31 may be bonded to each other to form a ring. Below, R 31 ~R 32 and Y, etc. will be explained.

[0116] R according to the general formula (αα) 31 and R 32 are each independently a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or -SiR 33 R 34 R 35 R represents a silyl group represented by 33 ~R 35 each independently represents a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group of 1 to 12 carbon atoms, or an optionally substituted alkoxy group of 1 to 12 carbon atoms. Hydrocarbon groups with 1 to 12 carbon atoms are R 1 ~R 5 The same explanations as those given in R apply. 33 ~R 35The halogen atom, the hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, and the alkoxy group having 1 to 12 carbon atoms which may have a substituent are all represented by R 3 ~R 5 The same explanations as those set out in 2. above apply. Among them, R 31 and R 32 At least one of the following is -SiR 33 R 34 R 35 It is preferable that the silyl group is a silyl group represented by the following formula:

[0117] Y according to the general formula (αα) 31 represents an alkoxy group having 1 to 12 carbon atoms which may have a substituent. Among these, methoxy, ethoxy, propoxy, butoxy, and isopropoxy groups are exemplified. Among these, methoxy and ethoxy groups are preferred because they cause less steric hindrance to the compound and are suitably concentrated on the surface of the active material. Here, the substituents include a cyano group, an isocyanato group, an oxo group (=O), an acyl group (-(C=O)-R d ), acyloxy group (-O(C=O)-R d ), alkoxycarbonyl group (-(C=O)OR d ), sulfonyl group (-SO2-R d ), sulfonyloxy group (-O(SO2)-R d ), alkoxysulfonyl group (-(SO2)-OR d ), alkoxysulfonyloxy group (-O-(SO2)-OR d ), alkoxycarbonyloxy group (-O-(C=O)-OR d ), alkoxy group (-OR d ), an acrylic group, a methacrylic group, a halogen atom (preferably a fluorine atom), a trifluoromethyl group, etc. 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. d When is an alkylene group, it may be bonded to a part of the hydrocarbon group that substitutes it to form a ring. Among these substituents, a cyano group, an isocyanato group, an oxo group (=O), an acyloxy group (-O(C=O)-R d ), a halogen atom (preferably a fluorine atom), or a trifluoromethyl group, and more preferably an oxo group (=O), an isocyanato group, or an acyloxy group (-O(C=O)-R d ), a halogen atom (preferably a fluorine atom), or a trifluoromethyl group, and particularly preferably an oxo group (=O), an acyloxy group (-O(C=O)-R d ), a halogen atom (preferably a fluorine atom), or a trifluoromethyl group.

[0118] Specific examples of the compound represented by general formula (αα) include the following compounds.

[0119] [ka]

[0120] Preferred examples of the compounds include the following: [ka]

[0121] More preferred compounds include the following: [ka]

[0122] [ka] More preferred compounds include the following:

[0123] [ka] Particularly preferred are the following compounds:

[0124] The compound represented by the general formula (αα) may be used alone or in combination of two or more kinds. The content of the compound represented by general formula (αα) (when there are two or more types, the total of the compounds) relative to the total amount of the nonaqueous electrolyte solution according to one embodiment of the present invention is not particularly limited, but is preferably 0.01 mass ppm or more, more preferably 0.1 mass ppm or more, even more preferably 1.0 mass ppm or more, particularly preferably 10 mass ppm or more, and is also preferably 1.0 mass % or less, more preferably 0.75 mass % or less, even more preferably 0.5 mass % or less, and particularly preferably 0.3 mass % or less. If the content of the compound represented by general formula (αα) relative 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 smoothly, making it possible to produce a battery with less gas generation during initial conditioning.

[0125] The mass ratio of the compound represented by general formula (AA) to the content of the compound represented by general formula (αα) in the non-aqueous electrolyte solution (content of the compound represented by general formula (AA) / content of the compound represented by general formula (αα)) is not particularly limited, but is usually 1.0 or more, preferably 2.0 or more, and is usually 1.0 × 10 4 Less than or equal to 7.0 × 10 3 or less, preferably 4.0 × 10 3 or less, more preferably 2.0 × 10 3 Below, particularly preferably 1.0 × 10 3 Below 5.0 × 10, particularly preferably 2 The following is the result.

[0126] In this specification, the content of the compound means the content at the time of manufacturing the nonaqueous electrolyte solution, at the time of injecting the nonaqueous electrolyte solution into a battery, or at the time of shipping the battery. The identification and content measurement of the compound represented by general formula (αα) and the compound represented by general formula (AA) in the nonaqueous electrolyte solution are carried out by nuclear magnetic resonance (NMR) spectroscopy, gas chromatography (GC), or the like.

[0127] <2-1-3. Electrolyte> The nonaqueous electrolyte solution of this embodiment usually contains an electrolyte as a component, similar to a general nonaqueous electrolyte solution. The electrolyte used in the nonaqueous electrolyte solution of this embodiment is described in <1-1-4. Electrolyte>, and preferred embodiments are also the same.

[0128] <2-1-4. Non-aqueous solvents> The nonaqueous electrolyte solution of this embodiment, like a general nonaqueous electrolyte solution, usually contains, as its main component, a nonaqueous solvent that dissolves the above-mentioned electrolyte. The nonaqueous solvent is described in <1-1-5. Nonaqueous Solvent>, and preferred embodiments are also the same.

[0129] <2-1-5. Auxiliaries> The nonaqueous electrolyte solution of this embodiment may contain an auxiliary agent within a range that allows the effects of the present invention to be achieved. The auxiliary agent that may be used in the nonaqueous electrolyte solution of this embodiment is described in <1-1-6. Auxiliary Agent>, and preferred embodiments are also the same.

[0130] <2-2. Non-aqueous electrolyte battery> A nonaqueous electrolyte battery according to one embodiment of the present invention is a nonaqueous electrolyte battery comprising a positive electrode, a negative electrode, and a nonaqueous electrolyte solution, and the battery comprises the nonaqueous electrolyte solution according to the embodiment of the present invention described above. More specifically, the battery comprises a current collector and a positive electrode having a positive electrode active material layer on at least a portion of the current collector surface and capable of absorbing and releasing metal ions, a current collector and a negative electrode having a negative electrode active material layer on at least a portion of the current collector surface and capable of absorbing and releasing metal ions, and a nonaqueous electrolyte solution containing the compound represented by general formula (AA) and the compound represented by general formula (αα) described above together with an alkali metal salt and a nonaqueous solvent. The battery configuration, positive electrode, negative electrode, and separator are described in <1-2-1. Battery configuration>, <1-2-3. Positive electrode>, <1-2-4. Negative electrode>, and <1-2-5. Separator>, respectively, and preferred embodiments are also the same. <2-2-1. Non-aqueous electrolyte> As the nonaqueous electrolyte solution, the nonaqueous electrolyte solution according to one embodiment of the present invention is used. Note that, within the scope of the present invention, other nonaqueous electrolyte solutions may be blended with the nonaqueous electrolyte solution. [Example]

[0131] The present invention will be explained in more detail below by way of examples and comparative examples, but the present invention is not limited to these examples as long as it does not depart from the gist of the invention.

[0132] [Example 1] The compounds used in the present examples and comparative examples are shown below.

[0133] [ka] Compound 1-1

[0134] [ka] Compound 1-2

[0135] [ka] Compound 1-3

[0136] [ka] Compound 1-4

[0137] [ka] Compound 1-5

[0138] [ka] Compound 1-6

[0139] [ka] Compounds 1-7

[0140]

change

[0141]

change

[0142]

change

[0143]

change

[0144]

change

[0145]

change

[0146]

change

[0147]

change

[0148]

change

[0149]

change

[0150] [ka] Compound 1-18

[0151] [ka] Compound 1-19

[0152] [ka] Compound 1-20

[0153] [ka] Compound 1-21

[0154] [ka] Compound 1-22

[0155] [ka] Compound 1-23

[0156] <Examples 1-1 to 1-27 and Comparative Examples 1-1 to 1-26> [Preparation of positive electrode] The positive electrode active material was lithium-nickel-cobalt-manganese composite oxide (Li 1.0 Ni 0.5 Co 0.2 Mn 0.3 90 parts by mass of O2), 7 parts by mass of acetylene black as a conductive material, and 3 parts by mass of polyvinylidene fluoride (PVdF) as a binder were mixed in N-methylpyrrolidone solvent using a disperser to form a slurry. This slurry was evenly applied to both sides of a 15 μm thick aluminum foil, dried, and then pressed to form a positive electrode.

[0157] [Preparation of negative electrode] 98 parts by mass of natural graphite was mixed with 1 part by mass of an aqueous dispersion of sodium carboxymethylcellulose (concentration of sodium carboxymethylcellulose: 1% by mass) as a thickener and 1 part by mass of an aqueous dispersion of styrene-butadiene rubber (concentration of styrene-butadiene rubber: 50% by mass) as a binder, and the mixture was mixed in a disperser to form a slurry. The resulting slurry was applied to one side of a 10 μm thick copper foil, dried, and then pressed to form a negative electrode.

[0158] [Preparation of non-aqueous electrolyte] Under a dry argon atmosphere, 1.2 mol / L (14.8 mass%, as the concentration in the non-aqueous electrolyte) of thoroughly dried LiPF6 was dissolved as an electrolyte in a mixture of ethylene carbonate (EC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC) (volume ratio EC:DEC:EMC = 3:3:4). Furthermore, 2.0 mass% each of vinylene carbonate (VC) and fluoroethylene carbonate (FEC) (as the concentration in the non-aqueous electrolyte) was added (hereinafter referred to as reference electrolyte 1). Compounds 1-1 to 1-23 were added to reference electrolyte 1 in the amounts listed in Table 1 below to prepare the non-aqueous electrolytes of Examples 1-1 to 1-27 and Comparative Examples 1-2 to 1-26. The "content (mass%)" in the table refers to the content when the total non-aqueous electrolyte is taken as 100 mass%. The non-aqueous electrolyte solution of Comparative Example 1-1 is Reference Electrolyte Solution 1.

[0159] [Manufacturing non-aqueous electrolyte batteries] The positive electrode, negative electrode, and polyethylene separator were stacked in this order to prepare a battery element. This battery element was inserted into a bag made of a laminate film of aluminum (40 μm thick) coated on both sides with a resin layer so that the positive and negative electrode terminals protruded. The prepared nonaqueous electrolyte solution was then poured into the bag, which was then vacuum-sealed to prepare a laminated nonaqueous electrolyte battery.

[0160] <Evaluation of non-aqueous electrolyte batteries> [Initial conditioning] The battery was charged at a constant current of 0.05 C for 6 hours in a 25°C thermostatic chamber, then discharged at 0.2 C to 3.0 V. CC-CV charging was performed at 0.2 C to 4.1 V. Aging was then performed at 45°C for 72 hours. The battery was then discharged at 0.2 C to 3.0 V to stabilize the laminated battery. CC-CV charging was then performed at 0.2 C to 4.2 V, followed by discharging at 0.2 C to 3.0 V for initial conditioning. [Initial gas volume measurement] Before and after the initial conditioning, the battery was immersed in an ethanol bath and the volume was measured. The amount of gas generated was calculated from the change in volume before and after the initial conditioning, and this was designated as the "initial gas amount." The initial gas amount values ​​for each Example and Comparative Example, when the initial gas amount for Comparative Example 1-1 was set to 100, are shown in Table 1 as "initial gas." In addition, in Table 1, "compound (A)" refers to the "compound represented by formula (A)," and "compound (α)" refers to the "compound represented by formula (α)."

[0161] [Table 1]

[0162] As is clear from Table 1, the batteries produced in Examples 1-1 to 1-27 had smaller initial gas amounts than the batteries produced in Comparative Examples 1-1 to 1-26. A comparison of Comparative Example 1-1 with Comparative Examples 1-2, 1-25, and 1-26 reveals that when a nonaqueous electrolyte solution containing only the compound represented by formula (A) without containing the compound represented by formula (α) is used, the initial gas amount tends to be larger than that of Comparative Example 1. Similarly, a comparison of Comparative Example 1-1 with Comparative Examples 1-3, 1-4, 1-6, and 1-10 to 1-23 reveals that when a nonaqueous electrolyte solution containing only the compound represented by formula (α) without containing the compound represented by formula (A) is used, the initial gas amount tends to be larger than that of Comparative Example 1-1. From the results of Comparative Examples 1-1 to 1-3, it was predicted that the amount of initial gas would be greater in the battery using an electrolyte solution containing the compound combination of Example 1-1 than in Comparative Example 1-1, but the amount of initial gas generation in the battery of Example 1-1 was significantly reduced compared to Comparative Example 1-1. From the results of Comparative Examples 1-1, 1-2, and 1-4, it was predicted that the amount of initial gas would be significantly increased in the battery using an electrolyte solution containing the compound combination of Example 1-2 compared to Comparative Example 1-1, but the amount of initial gas generation in the battery of Example 1-2 was significantly suppressed compared to Comparative Example 1-1. From the results of Comparative Examples 1-1, 1-2, and 1-10, it was predicted that the amount of initial gas would be significantly increased in the battery using an electrolyte solution containing the compound combination of Example 1-5 compared to Comparative Example 1-1, but the amount of initial gas generation in the battery of Example 1-5 was significantly reduced compared to Comparative Example 1-1. From the results of Comparative Examples 1-1, 1-2, and 1-11, it was predicted that the amount of initial gas would be greater in the battery using an electrolyte solution containing the compound combination of Example 1-6 than in Comparative Example 1-1, but the amount of initial gas generation in the battery of Example 1-6 was significantly reduced compared to Comparative Example 1-1. From the results of Comparative Examples 1-1, 1-2, and 1-12, it was predicted that the amount of initial gas would be significantly increased in the battery using an electrolyte solution containing the compound combination of Example 1-7 compared to Comparative Example 1-1, but the amount of initial gas generation in the battery of Example 1-7 was significantly reduced compared to Comparative Example 1-1. From the results of Comparative Examples 1-1, 1-2, and 1-13, it was predicted that the amount of initial gas would be greater in the battery using an electrolyte solution containing the compound combination of Example 1-8 than in Comparative Example 1-1, but the amount of initial gas generation in the battery of Example 1-8 was suppressed more than in Comparative Example 1-1. From the results of Comparative Examples 1-1, 1-2, and 1-15, it was predicted that the amount of initial gas would be greater in the battery using an electrolyte solution containing the compound combination of Example 1-10 than in Comparative Example 1-1, but the amount of initial gas generation in the battery of Example 1-10 was significantly reduced compared to Comparative Example 1-1. From the results of Comparative Examples 1-1, 1-2, and 1-18, it was predicted that the amount of initial gas generated in the battery using the electrolyte solution containing the compound combination of Example 1-13 would be significantly larger than that of Comparative Example 1-1. However, the amount of initial gas generated in the battery of Example 1-13 was significantly reduced compared to that of Comparative Example 1-1. From the results of Comparative Examples 1-1, 1-2, and 1-19, it was predicted that the amount of initial gas would be greater in the battery using an electrolyte solution containing the compound combination of Example 1-14 than in Comparative Example 1-1, but the amount of initial gas generation in the battery of Example 1-14 was suppressed more than in Comparative Example 1-1. From the results of Comparative Examples 1-1, 1-2, and 1-20, it was predicted that the amount of initial gas would be significantly increased in the battery using an electrolyte solution containing the compound combination of Example 1-15 compared to Comparative Example 1-1, but the amount of initial gas generation in the battery of Example 1-15 was significantly suppressed compared to Comparative Example 1-1. From the results of Comparative Examples 1-1, 1-2, and 1-21, it was predicted that the amount of initial gas would be significantly increased in the battery using an electrolyte solution containing the compound combination of Example 1-19 compared to Comparative Example 1-1, but the amount of initial gas generation in the battery of Example 1-19 was significantly suppressed compared to Comparative Example 1-1. From the results of Comparative Examples 1-1, 1-2, and 1-22, it was predicted that the amount of initial gas would be significantly increased in the battery using the electrolyte solution containing the compound combination of Example 1-20 compared to Comparative Example 1-1, but the amount of initial gas generation in the battery of Example 1-20 was significantly suppressed compared to Comparative Example 1-1. From the results of Comparative Examples 1-1, 1-2, and 1-23, it was predicted that the amount of initial gas would be significantly increased in the battery using an electrolyte solution containing the compound combination of Example 1-24 compared to Comparative Example 1-1, but the amount of initial gas generation in the battery of Example 1-24 was significantly suppressed compared to Comparative Example 1-1. From the results of Comparative Examples 1-1, 1-4, and 1-25, it was predicted that the amount of initial gas generated in the battery using the electrolyte solution containing the compound combination of Example 1-16 would be significantly larger than that of Comparative Example 1-1, but the amount of initial gas generated in the battery of Example 1-16 was suppressed more than that of Comparative Example 1-1. From the results of Comparative Examples 1-1, 1-4, and 1-26, it was predicted that the amount of initial gas would be significantly increased in the battery using an electrolyte solution containing the compound combination of Example 1-17 compared to Comparative Example 1-1, but the amount of initial gas generation in the battery of Example 1-17 was significantly suppressed compared to Comparative Example 1-1. Furthermore, a comparison of Examples 1-21, 1-23, and 1-24 with Examples 1-25, 1-26, and 1-27 revealed that the effect of suppressing the generation of initial gas was further improved by further including lithium difluorophosphate, a specific anion-containing compound. Furthermore, in Comparative Examples 1-5, 1-7 to 1-9, which used a compound represented by formula (α) in combination with a compound other than the compound represented by formula (A), the amount of initial gas was increased compared to Comparative Example 1-1, unlike the battery using an electrolyte solution which used a compound represented by formula (α) in combination with the compound represented by formula (A). Furthermore, in Comparative Example 1-24, in which a compound represented by formula (A) and a compound other than the compound represented by formula (α) were used in combination, the amount of initial gas was increased compared to Comparative Example 1-1, unlike the battery using an electrolyte solution in which a compound represented by formula (α) and a compound represented by formula (A) were used in combination. It is presumed that in the batteries of Examples 1-1 to 1-27, the compound represented by general formula (α) and the compound represented by general formula (A) were suitably adsorbed to the positive electrode active material and / or the negative electrode active material, and the compounds localized on the electrodes during the initial charge were electrochemically decomposed to form a composite insulating coating on the surface of the positive electrode active material and / or the negative electrode active material. As shown by these results, by combining the compound represented by general formula (α) with the compound represented by general formula (A), the adsorption of the compounds onto the electrode can be controlled, and the amount of initial gas generation can be suitably suppressed.

[0163] [Example 2] The compounds used in the present examples and comparative examples are shown below.

[0164] [ka] Compound 2-1

[0165] [ka] Compound 2-2

[0166] [ka] Compound 2-3

[0167] [ka] Compound 2-4

[0168] [ka] Compound 2-5

[0169] <Example 2-1, Comparative Examples 2-1 to 2-6> [Preparation of positive electrode] The positive electrode active material was lithium-nickel-cobalt-manganese composite oxide (Li 1.0 Ni 0.5 Co 0.2 Mn 0.3 90 parts by mass of O2), 7 parts by mass of acetylene black as a conductive material, and 3 parts by mass of polyvinylidene fluoride (PVdF) as a binder were mixed in N-methylpyrrolidone solvent using a disperser to form a slurry. This slurry was evenly applied to both sides of a 15 μm thick aluminum foil, dried, and then pressed to form a positive electrode.

[0170] [Preparation of negative electrode] 98 parts by mass of natural graphite was mixed with 1 part by mass of an aqueous dispersion of sodium carboxymethylcellulose (concentration of sodium carboxymethylcellulose: 1% by mass) as a thickener and 1 part by mass of an aqueous dispersion of styrene-butadiene rubber (concentration of styrene-butadiene rubber: 50% by mass) as a binder, and the mixture was mixed in a disperser to form a slurry. The resulting slurry was applied to one side of a 10 μm thick copper foil, dried, and then pressed to form a negative electrode.

[0171] [Preparation of non-aqueous electrolyte] Under a dry argon atmosphere, thoroughly dried LiPF was dissolved as an electrolyte at 1.2 mol / L (14.8% by mass, as the concentration in the non-aqueous electrolyte solution) in a mixture of ethylene carbonate (EC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC) (volume ratio EC:DEC:EMC = 3:3:4). Furthermore, vinylene carbonate (VC) and fluoroethylene carbonate (FEC) were each added at 2.0% by mass (as the concentration in the non-aqueous electrolyte solution) (hereinafter, this will be referred to as reference electrolyte solution 2). Compounds 2-1 to 2-5 were added to reference electrolyte solution 2 in the amounts listed in Table 2 below to prepare the non-aqueous electrolyte solutions of Example 2-1 and Comparative Examples 2-1 to 2-6. The "content (% by mass)" in the table refers to the content when the total amount of each non-aqueous electrolyte solution is taken as 100% by mass. The non-aqueous electrolyte solution of Comparative Example 2-1 is reference electrolyte solution 2.

[0172] [Manufacturing non-aqueous electrolyte batteries] The positive electrode, negative electrode, and polyethylene separator were stacked in this order to prepare a battery element. This battery element was inserted into a bag made of a laminate film of aluminum (40 μm thick) coated on both sides with a resin layer so that the positive and negative electrode terminals protruded. The prepared nonaqueous electrolyte solution was then poured into the bag, which was then vacuum-sealed to prepare a laminated nonaqueous electrolyte battery.

[0173] <Evaluation of non-aqueous electrolyte batteries> [Initial conditioning] The battery was charged at a constant current of 0.05 C for 6 hours in a 25°C thermostatic chamber, then discharged at 0.2 C to 3.0 V. CC-CV charging was performed at 0.2 C to 4.1 V. Aging was then performed at 45°C for 72 hours. The battery was then discharged at 0.2 C to 3.0 V to stabilize the laminated battery. CC-CV charging was then performed at 0.2 C to 4.2 V, followed by discharging at 0.2 C to 3.0 V for initial conditioning. [Initial gas volume measurement] Before and after the initial conditioning, the battery was immersed in an ethanol bath and the volume was measured, and the amount of gas generated was calculated from the change in volume before and after the initial conditioning, and this was designated as the "initial gas amount." The initial gas amount values ​​for each Example and Comparative Example, when the initial gas amount for Comparative Example 2-1 was set to 100, are shown as "initial gas" in Table 2. In Table 2, "compound (A)" refers to the "compound represented by formula (A)," and "compound (β)" refers to the "compound represented by formula (β)."

[0174] [Table 2]

[0175] As is clear from Table 2, the battery produced in Example 2-1 had a smaller initial gas amount than the batteries produced in Comparative Examples 2-1 to 2-6. As shown by these results, by combining the compound represented by general formula (β) with the compound represented by general formula (A), the adsorption of the compound onto the electrode can be controlled, and the amount of initial gas generation can be suitably suppressed.

[0176] [Example 3] The compounds used in the present examples and comparative examples are shown below.

[0177] [ka] Compound 3-1

[0178] [ka] Compound 3-2

[0179] [ka] Compound 3-3

[0180] [ka] Compound 3-4

[0181] [ka] Compound 3-5

[0182] <Examples 3-1 to 3-3 and Comparative Examples 3-1 to 3-6> [Preparation of positive electrode] The positive electrode active material was lithium-nickel-cobalt-manganese composite oxide (Li 1.0 Ni 0.5 Co 0.2 Mn 0.3 90 parts by mass of O2), 7 parts by mass of acetylene black as a conductive material, and 3 parts by mass of polyvinylidene fluoride (PVdF) as a binder were mixed in N-methylpyrrolidone solvent using a disperser to form a slurry. This slurry was evenly applied to both sides of a 15 μm thick aluminum foil, dried, and then pressed to form a positive electrode.

[0183] [Preparation of negative electrode] 98 parts by mass of natural graphite was mixed with 1 part by mass of an aqueous dispersion of sodium carboxymethylcellulose (concentration of sodium carboxymethylcellulose: 1% by mass) as a thickener and 1 part by mass of an aqueous dispersion of styrene-butadiene rubber (concentration of styrene-butadiene rubber: 50% by mass) as a binder, and the mixture was mixed in a disperser to form a slurry. The resulting slurry was applied to one side of a 10 μm thick copper foil, dried, and then pressed to form a negative electrode.

[0184] [Preparation of non-aqueous electrolyte] Under a dry argon atmosphere, thoroughly dried LiPF was dissolved as an electrolyte at 1.2 mol / L (14.8% by mass, as the concentration in the non-aqueous electrolyte solution) in a mixture of ethylene carbonate (EC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC) (volume ratio EC:DEC:EMC = 3:3:4). Furthermore, vinylene carbonate (VC) and fluoroethylene carbonate (FEC) were each added at 2.0% by mass (as the concentration in the non-aqueous electrolyte solution) (hereinafter, this will be referred to as reference electrolyte solution 3). Compounds 3-1 to 3-5 were added to reference electrolyte solution 3 in the amounts listed in Table 3 below to prepare the non-aqueous electrolyte solutions of Examples 3-1 to 3-3 and Comparative Examples 3-1 to 3-6. The "content (% by mass)" in the table refers to the content when the total amount of each non-aqueous electrolyte solution is taken as 100% by mass. The non-aqueous electrolyte solution of Comparative Example 3-1 is reference electrolyte solution 3.

[0185] [Manufacturing non-aqueous electrolyte batteries] The positive electrode, negative electrode, and polyethylene separator were stacked in this order to prepare a battery element. This battery element was inserted into a bag made of a laminate film of aluminum (40 μm thick) coated on both sides with a resin layer so that the positive and negative electrode terminals protruded. The prepared nonaqueous electrolyte solution was then poured into the bag, which was then vacuum-sealed to prepare a laminated nonaqueous electrolyte battery.

[0186] <Evaluation of non-aqueous electrolyte batteries> [Initial conditioning] The battery was charged at a constant current of 0.05 C for 6 hours in a 25°C thermostatic chamber, then discharged at 0.2 C to 3.0 V. CC-CV charging was performed at 0.2 C to 4.1 V. Aging was then performed at 45°C for 72 hours. The battery was then discharged at 0.2 C to 3.0 V to stabilize the laminated battery. CC-CV charging was then performed at 0.2 C to 4.2 V, followed by discharging at 0.2 C to 3.0 V for initial conditioning. [Initial gas volume measurement] Before and after the initial conditioning, the battery was immersed in an ethanol bath and the volume was measured. The amount of gas generated was calculated from the change in volume before and after the initial conditioning, and this was designated as the "initial gas amount." The initial gas amount values ​​for each Example and Comparative Example, when the initial gas amount for Comparative Example 3-1 was set to 100, are shown as "initial gas" in Table 3. In Table 3, "compound (AA)" refers to the "compound represented by formula (AA)," and "compound (αα)" refers to the "compound represented by formula (αα)."

[0187] [Table 3]

[0188] As is clear from Table 3, the batteries produced in Examples 3-1 to 3-3 had smaller initial gas amounts than the batteries produced in Comparative Examples 3-1 to 3-6. As shown by these results, by combining a compound represented by general formula (αα) with a compound represented by general formula (AA), the adsorption of the compounds onto the electrode can be controlled, and the amount of initial gas generation can be suitably suppressed. [Industrial Applicability]

[0189] The nonaqueous electrolyte of the present invention is useful because it can suppress the amount of gas generated during initial conditioning of a nonaqueous electrolyte battery and improve the deterioration of high-capacity batteries. The nonaqueous electrolyte of the present invention and the nonaqueous electrolyte battery using the same can be used in various known applications for nonaqueous electrolyte batteries. Specific examples include notebook computers, pen-input personal computers, mobile personal computers, electronic book players, mobile phones, mobile fax machines, mobile copiers, mobile printers, headphone stereos, video movie players, LCD televisions, handheld vacuum cleaners, portable CD players, minidiscs, transceivers, electronic organizers, calculators, memory cards, portable tape recorders, radios, backup power supplies, motors, motorcycles, mopeds, bicycles, lighting equipment, toys, game consoles, clocks, power tools, flash devices, cameras, home backup power supplies, business backup power supplies, load-leveling power supplies, and natural energy storage power supplies.

Claims

1. A non-aqueous electrolyte solution for a non-aqueous electrolyte battery having a positive electrode and a negative electrode capable of absorbing and releasing metal ions, the non-aqueous electrolyte solution containing an alkali metal salt, a non-aqueous solvent, a compound represented by general formula (A), and at least one of a compound represented by general formula (α) and a compound represented by general formula (β), wherein the compound represented by general formula (α) is at least one selected from the following formulas (α1) to (α15): 【Chemistry 1】 (In formula (A), Q １ and Q ２ n each independently represents an alkylene group having 1 to 10 carbon atoms which may have a substituent. １ represents an integer of 0 or 1. １ When is 0, the sulfur atom and the oxygen atom form a direct bond.) 【Chemistry 2】 (In formula (α), R １ and R ２ are each independently a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or —SiR ３ R ４ R ５ represents a silyl group represented by the formula: ３ ~R ５ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; Y represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, -NR ６ -SiR ７ R ８ R ９ or a group represented by —NR １０ -R １１ R represents a group represented by ６ , R １０ and R １１ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent; R ７ ~R ９ R each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. １ or R ２ and Y may be bonded to each other to form a ring. 【Transformation 3】 (In formula (β), R ２１ ~R ２３ each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 18 carbon atoms, or an optionally substituted aralkyl group having 7 to 18 carbon atoms; and Z represents an optionally substituted alkenyl group or alkynyl group having 2 to 10 carbon atoms. 【Transformation 6】

2. The content of the compound represented by the general formula (A) is 1.0 × 10 －３ The nonaqueous electrolyte solution according to claim 1 , wherein the content of the nonaqueous electrolyte is from 1% by mass to 10% by mass.

3. The nonaqueous electrolyte solution according to claim 1 or 2, wherein the content of the compound represented by the general formula (α) or the compound represented by the general formula (β) is 0.01 mass ppm or more and 0.5 mass% or less with respect to the total amount of the nonaqueous electrolyte solution.

4. The mass ratio of the content of the compound represented by the general formula (A) to the content of the compound represented by the general formula (α) or the compound represented by the general formula (β) in the nonaqueous electrolyte solution is 1.0 or more and 1.0 × 10 ４ The non-aqueous electrolyte solution according to any one of claims 1 to 3, wherein:

5. A non-aqueous electrolyte solution for a non-aqueous electrolyte battery having a positive electrode and a negative electrode capable of absorbing and releasing metal ions, the non-aqueous electrolyte solution comprising an alkali metal salt, a non-aqueous solvent, a compound represented by general formula (AA), and a compound represented by general formula (αα). 【Chemistry 4】 (In formula (AA), Q ３１ and Q ３２ are each independently an alkylene group having 1 to 10 carbon atoms. The alkylene group may be substituted with a hydrocarbon group, or a hydrogen atom of the alkylene group may be substituted with a halogen atom. ３１ represents an integer of 0 or 1. ３１ When is 0, the sulfur atom and the oxygen atom form a direct bond.) 【Transformation 5】 (In formula (αα), R ３１ and R ３２ are each independently a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or —SiR ３３ R ３４ R ３５ represents a silyl group represented by the formula: ３３ ~R ３５ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; Y ３１ represents an alkoxy group having 1 to 12 carbon atoms which may have a substituent. ３１ or R ３２ and Y ３１ may be bonded to each other to form a ring.)

6. The content of the compound represented by the general formula (AA) is 1.0 × 10 －３ The nonaqueous electrolyte solution according to claim 5 , wherein the content of the nonaqueous electrolyte is from 1% by mass to 10% by mass.

7. The non-aqueous electrolyte solution according to claim 5 or 6, wherein the content of the compound represented by the general formula (αα) is 0.01 mass ppm or more and 0.5 mass% or less with respect to the total amount of the non-aqueous electrolyte solution.

8. 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 (αα) in the nonaqueous electrolyte solution is 1.0 or more and 1.0 × 10 ４ The nonaqueous electrolyte solution according to any one of claims 5 to 7, wherein:

9. 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 solution, wherein the non-aqueous electrolyte solution is the non-aqueous electrolyte solution according to any one of claims 1 to 8.

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