Non-aqueous electrolyte and non-aqueous electrolyte battery

Abstract

This nonaqueous electrolytic solution is for a nonaqueous electrolytic solution battery provided with a negative electrode and a positive electrode capable of occluding and releasing metal ions, and is characterized by containing a compound represented by general formula (1) together with an alkali metal salt and a nonaqueous solvent. In general formula (1): R1 represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group optionally having a substituent; R2 represents a hydrogen atom, a monovalent hydrocarbon group optionally having a substituent, or an alkoxy group optionally having a substituent; X1 represents a divalent hydrocarbon group optionally having a substituent; n1represents 2 or 3; p1 represents an integer of 0-2, q1 represents an integer of 1-3, and p1+q1 equals 2 or 3; two among all R1 and all X1 optionally bind with each other to form a ring; and A1 represents a divalent or trivalent atomic group represented by general formula (2-1) or represents a trivalent atomic group represented by general formula (3-1).

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 amount of 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 active materials for positive and negative electrodes and additives for non-aqueous electrolytes.

[0004] For example, Patent Document 1 discloses a specific organosilicon compound having an organic polar group that, when used as a liquid electrolyte solvent, can provide a lithium ion battery that is endowed with effects such as improved thermal stability at high temperatures and improved safety due to an increase in the electrolyte flash point. Patent Document 2 discloses a study on improving cycle characteristics and the rate of increase in resistance by adding a monofluorosilane compound having a specific organic group. Patent Documents 3 and 4 disclose studies on improving the high-temperature cycle capacity retention rate by adding a specific organosilicon compound having an organic group such as a cyano group, an isocyanato group, or an isothiocyanato group in its structure to a non-aqueous electrolyte solution. Patent Document 5 discloses a study on improving the capacity retention rate and resistance increase during long-term use and high-temperature storage by adding a specific fluorosilane compound to a non-aqueous electrolyte solution. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Special Publication No. 2017-538667 [Patent Document 2] International Publication No. 2018 / 220997 [Patent Document 3] Special Publication No. 2016-520647 [Patent Document 4] Japanese Patent Application Publication No. 2018-46021 [Patent Document 5] Japanese Patent Application Laid-Open No. 2009-004352 Summary of the Invention [Problem to be solved by the invention]

[0006] In recent years, the capacity of lithium batteries has been increasing rapidly for use as onboard power sources for electric vehicles and mobile phones such as smartphones, and the proportion of voids within the battery has become smaller than before.As a result, the amount of gas generated when lithium batteries are placed in a high-temperature environment and the swelling of the electrodes after repeated charging and discharging are fatal drawbacks.

[0007] The present invention aims to provide a nonaqueous electrolyte solution capable of suppressing the amount of gas generated during high-temperature storage of a nonaqueous electrolyte battery, a nonaqueous electrolyte battery including the nonaqueous electrolyte solution, and compounds used in the nonaqueous electrolyte solution. The amount of gas generated is the amount of gas generated by decomposition of the solvent and additives, which are components of the electrolyte solution, on the electrodes. A second object of the present invention is to provide a non-aqueous electrolyte battery in which battery swelling is suppressed. Battery swelling occurs when Li is absorbed into the active material during charging and discharging. + is an index that reflects the expansion of the active material itself during absorption and desorption. [Means for solving the problem]

[0008] As a result of intensive research to solve the first problem, the present inventors have come up with the idea that the amount of gas generated during high-temperature storage of a nonaqueous electrolyte battery can be suppressed by using a nonaqueous electrolyte solution containing a compound represented by general formula (1), and have completed the first aspect of the present invention. Furthermore, as a result of intensive research into solving the second problem, the present inventors have come up with the idea that swelling of a nonaqueous electrolyte battery can be suppressed by combining a nonaqueous electrolyte solution containing a compound represented by general formula (1) with a negative electrode containing a specific negative electrode active material, and have thus completed the second aspect of the present invention.

[0009] That is, the first aspect of the present invention provides the following specific aspects. <a1>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 a compound represented by the following general formula (1) together with an alkali metal salt and a non-aqueous solvent: [ka] (In general formula (1), R 1 represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may have a substituent; R 2 represents a hydrogen atom, an optionally substituted monovalent hydrocarbon group, or an optionally substituted alkoxy group; X 1 represents a divalent hydrocarbon group which may have a substituent; n 1 indicates 2 or 3; p 1 represents an integer between 0 and 2, and q 1 represents an integer from 1 to 3, and p 1 +q 1 = 2 or 3; R 1 and X 1 Two of A may be bonded to each other to form a ring; 1 is a divalent or trivalent atomic group represented by the following general formula (2-1), or a trivalent atomic group represented by the following general formula (3-1). [ka] (In general formula (2-1), Z 1 represents a carbon atom, a sulfur atom, a phosphorus atom, or a boron atom; Y 101 represents an oxygen atom or a sulfur atom; Y 1 , Y 2 and Y 3 are each independently a single bond, an oxygen atom, a sulfur atom, or NR 101 indicates;R 101 represents a hydrogen atom or a monovalent hydrocarbon group; R 101 When R is a monovalent hydrocarbon group, 101 represents R in the general formula (1). 1 and X 1 may be bonded to any of the following to form a ring; r 1 is Z 1 is 1 when is a carbon atom, and Z 1 is 0, 1, or 2 when is a sulfur atom, and Z 1 is 0 or 1 when is a phosphorus atom, and Z 1 is 0 when is a boron atom; r 2 is Z 1 is 0 when is a carbon atom or a sulfur atom, and Z 1 is 1 when is a phosphorus atom or a boron atom; * represents R in the general formula (1). 1 or X 1 The binding site is shown. However, Z 1 is a sulfur atom and r 1 When is 2, Y 1 and Y 2 cannot both be single bonds.) [ka] (In general formula (3-1), Y 4 , Y 5 and Y 6 are each independently an oxygen atom, a sulfur atom, or NR 201 indicates;R 201 represents a hydrogen atom or a monovalent hydrocarbon group; * represents R in the general formula (1) 1 or X 1 The binding site is shown.) <a2>The general formula (2-1) is the following formula (2-2): <a1>The non-aqueous electrolyte solution according to claim 1. [ka] (In general formula (2-2), Z 2 represents a carbon atom, a sulfur atom, or a phosphorus atom; Y 7 , Y 8 and Y 9 are each independently a single bond or an oxygen atom; r 3 is Z 2 is 1 when is a carbon atom, and Z 2 is 0, 1, or 2 when is a sulfur atom, and Z 2 is 0 or 1 when is a phosphorus atom; r 4 is Z 2 is 0 when is a carbon atom or a sulfur atom, and Z 2 is a phosphorus atom, the value is 1. * represents R in the general formula (1). 1 or X 1 The binding site is shown. However, Z 2 is a sulfur atom and r 3 When is 2, Y 7 and Y 8 cannot both be single bonds.) <a3>The general formula (3-1) is the following general formula (3-2): <a1>or <a2> The non-aqueous electrolyte solution according to claim 1. [ka] (In the general formula (3-2), * represents R in the general formula (1) 1 or X 1 The binding site is shown.) <a4>The content of the compound represented by the general formula (1) is 0.001 to 10% by mass based on the total amount of the nonaqueous electrolyte solution. <a1> ~ <a3>The non-aqueous electrolyte solution according to any one of the preceding claims. <a5>The non-aqueous electrolyte solution further contains one or more compounds selected from the group consisting of fluorophosphates, salts having an FSO2 skeleton, and oxalates, and the total content of the compounds is 0.001 to 5 mass% based on the total amount of the non-aqueous electrolyte solution. <a1> ~ <a4>The non-aqueous electrolyte solution according to any one of the preceding claims. <a6>A non-aqueous electrolyte battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte solution, wherein the non-aqueous electrolyte solution is <a1> ~ <a5>10. A non-aqueous electrolyte battery comprising the non-aqueous electrolyte according to any one of claims 1 to 9. <a7>The positive electrode includes a positive electrode active material, and the positive electrode active material is a metal oxide represented by the following composition formula (13): <a6>The non-aqueous electrolyte battery according to claim 1. Li a1 Ni b1 M1 c1 O2···(13) (In formula (13), a1, b1, and c1 are numerical values ​​that satisfy 0.90≦a1≦1.10, 0.40≦b1≦0.98, and 0.00≦c1≦0.50, respectively, and b1+c1=1 is satisfied. M1 represents at least one element selected from the group consisting of Co, Mn, Al, Mg, Zr, Fe, Ti, and Er.) <a8>the negative electrode includes a negative electrode active material capable of absorbing and releasing metal ions, and the negative electrode active material includes a material containing a metal element and / or a metalloid element capable of alloying with Li; <a6>or <a7>The non-aqueous electrolyte battery according to claim 1. <a9>The material containing a metal element and / or a metalloid element capable of alloying with Li is metal Si or Si oxide. <a8>The non-aqueous electrolyte battery according to claim 1. <a10>A compound represented by the following general formula (1-4): [ka] (In general formula (1-4), R 11 represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may have a substituent; R 12 represents a hydrogen atom or an optionally substituted monovalent hydrocarbon group; X 11 represents a divalent hydrocarbon group having 3 or more carbon atoms which may have a substituent; Y 21 and Y 22 are each independently a single bond, an oxygen atom, a sulfur atom, or NR 301 and;R 301 represents a hydrogen atom or a monovalent hydrocarbon group; R 301 When R is a monovalent hydrocarbon group, 301 is R 11 and X 11 may be bonded to any one of the following to form a ring; 11 indicates 2; R 11 and X 11 Two of Y may be bonded to each other to form a ring. 21 and Y 22 is an oxygen atom, and R 11 and X 11 When they do not bond to form a ring, n 11 may be 3.) <a11>A compound selected from the group consisting of the following formulas (1-4-1) to (1-4-4): <a10>The compound described in [ka] <a12>A compound represented by the following general formula (1-5): [ka] (In general formula (1-5), R 13 represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may have a substituent; R 14 represents a hydrogen atom or an optionally substituted monovalent hydrocarbon group; X 12 represents a divalent hydrocarbon group having 3 or more carbon atoms which may have a substituent; Y 23 and Y 24 are each independently a single bond, an oxygen atom, a sulfur atom, or NR 311 and;R 311 represents a hydrogen atom or a monovalent hydrocarbon group; R 311 When R is a monovalent hydrocarbon group, 311 is R 13 and X 12 may be bonded to any one of the groups to form a ring; 12 is 0, 1 or 2; n 12 indicates 2 or 3; R 13 and X 1 2 Two of these may be bonded to each other to form a ring. <a13>A compound selected from the group consisting of the following formulas (1-5-1) and (1-5-2): <a12>The compound described in [ka] <a14>A compound represented by the following general formula (1-6): [ka] (In general formula (1-6), R 15 , and R 15’ each independently represents a hydrogen atom, a halogen atom, or an optionally substituted monovalent hydrocarbon group; R 16 represents a hydrogen atom or an optionally substituted monovalent hydrocarbon group; X 13 represents a divalent hydrocarbon group having 3 or more carbon atoms which may have a substituent; Y 25 , Y 25’ , and Y 26 are each independently a single bond, an oxygen atom, a sulfur atom, or NR 321 and;R 321 represents a hydrogen atom or a monovalent hydrocarbon group; R 321 When R is a monovalent hydrocarbon group, 321 is R 15 , R 15’ , and X 13 may be bonded to any one of the following to form a ring; 13 indicates 2 or 3. R 15 and X 13 Two of the groups may be bonded to each other to form a ring. A15 A compound selected from the group consisting of the following formulas (1-6-1) to (1-6-3): A14 The compound described in >. [ka]

[0010] The second aspect of the present invention also provides the following specific aspects. <b1>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, the negative electrode active material contains a material containing a metal element and / or a metalloid element that can be alloyed with Li, The nonaqueous electrolyte battery is characterized in that the nonaqueous electrolyte contains an alkali metal salt, a nonaqueous solvent, and a compound represented by the following general formula (4): [ka] (In general formula (4), R 3 represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may have a substituent; R 4 represents a hydrogen atom, an optionally substituted monovalent hydrocarbon group, or an optionally substituted alkoxy group; X 2 represents a divalent hydrocarbon group which may have a substituent; n 2 represents an integer between 1 and 3; p 2 represents an integer between 0 and 2, and q 2 represents an integer from 1 to 3, and p 2 +q 2 = 2 or 3; R 3 and X 2 Two of A may be bonded to each other to form a ring; 2 is a divalent or trivalent atomic group represented by the following general formula (5-1), or a trivalent atomic group represented by the following general formula (6-1). [ka] (In general formula (5-1), Z 3 represents a carbon atom, a sulfur atom, or a phosphorus atom; Y 102 represents an oxygen atom or a sulfur atom; Y 10 , Y 11 and Y 12 are each independently a single bond, an oxygen atom, a sulfur atom, or NR 102 indicates; R 102 represents a hydrogen atom or a monovalent hydrocarbon group; R 102 When R is a monovalent hydrocarbon group, 102 is R in the general formula (2). 3 and X 2 may be bonded to any of the following to form a ring; r 5 is Z 3 is 1 when is a carbon atom, and Z 3 is 0, 1, or 2 when is a sulfur atom, and Z 3 is 0 or 1 when is a phosphorus atom. r 6 is Z 3 is 0 when is a carbon atom or a sulfur atom, and Z 3 is 1 when is a phosphorus atom; * represents R in the general formula (4). 3 or X 2 The binding site is shown. However, Z 1 is a sulfur atom and r 5 When is 2, Y 10 and Y 11 cannot both be single bonds.) [ka] (In general formula (6-1), Y 13 , Y 14 and Y 15 are each independently an oxygen atom, a sulfur atom, or NR 202 indicates;R 202 represents a hydrogen atom or a monovalent hydrocarbon group; * represents R in the general formula (4). 3 or X 2 The binding site is shown.) <b2>n in Equation (4) 2 is 2 or 3, <b1>The non-aqueous electrolyte battery described in

Advantages of the Invention

[0011] According to the first aspect of the present invention, a non-aqueous electrolyte excellent in suppressing the amount of gas generation during high-temperature storage, a non-aqueous electrolyte battery including the non-aqueous electrolyte, and a compound used in the non-aqueous electrolyte can be obtained. Further, according to the second aspect of the present invention, a non-aqueous electrolyte battery with suppressed swelling can be obtained.

Modes for Carrying Out the Invention

[0012] 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 thereto. Further, the present invention can be arbitrarily modified and implemented without departing from the gist thereof. In this specification, the description represented by "~" represents a range including the numbers described before and after it. Also, in this specification, descriptions such as "independently" or "independently" used when explaining two or more objects together are used in the sense that these two or more objects may be the same or different.

[0013] <A. First Embodiment> <A1. Non-aqueous Electrolyte> The non-aqueous electrolyte according to the first aspect (embodiment) of the present invention contains a compound represented by the following general formula (1). By using a non-aqueous electrolyte containing a compound represented by the general formula (1), the mechanism for enhancing the suppression of the amount of gas generation during high-temperature storage of the non-aqueous electrolyte battery is not clear, but is presumed as follows. Solution Although the mechanism for enhancing the suppression of the amount of gas generation during high-temperature storage of the non-aqueous electrolyte battery is not clear, it is presumed as follows.

[0014] The compound represented by the general formula (1) has a divalent or trivalent atomic group containing at least one atom selected from an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a boron atom in the molecule. Since this atomic group is a polar group, the compound represented by the formula (1) tends to interact with carbon or the like on the surface of the negative electrode active material and localize in the vicinity of the surface of the negative electrode active material. In addition, the compound represented by the general formula (1) has a structure in which two or more fluorine (F) atoms are bonded to a silicon (Si) atom in the molecule. When two or more F atoms are bonded to the Si atom, the electron density of the Si atom is significantly reduced compared to the case of one F atom. As a result, the reaction activity of the Si atom of the compound represented by the general formula (1) is enhanced, so that, for example, electrochemical reduction and reaction with the reduction decomposition product of the electrolytic solution proceed easily. Thereby, an insulating film is formed on the negative electrode active material, and for example, when Si is used for the negative electrode active material, the surface is suitably modified. Further, it is presumed that the compound represented by the general formula (1) is also concentrated on the surface of the positive electrode, reacts with electrochemical oxidation and the oxidation decomposition product of the electrolytic solution, and forms an insulating film similarly to the negative electrode. From the above, the inventor believes that the compound represented by the general formula (1) contributes to the suppression of the gas generation amount during high-temperature storage.

[0015] <A1-1. Compound Represented by General Formula (1)> A non-aqueous electrolyte according to an embodiment of the present invention is characterized by containing a compound represented by the following general formula (1).

[0016] [Chemical Formula]

[0017] In the general formula (1), R 1 represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may have a substituent; R 2 represents a hydrogen atom, a monovalent hydrocarbon group which may have a substituent, or an alkoxy group which may have a substituent; X 1 represents a divalent hydrocarbon group which may have a substituent. n 1 represents 2 or 3; p 1 represents an integer of 0 to 2, and q 1 represents an integer from 1 to 3, and p 1 +q 1 = 2 or 3; R 1 and X 1 Two of A may be bonded to each other to form a ring; 1 is a divalent or trivalent atomic group represented by the general formula (2-1) described later, or a trivalent atomic group represented by the general formula (3-1) described later.

[0018] (R 1 ) R according to general formula (1) 1 represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may have a substituent. R 1 In terms of ease of industrial handling of the compound represented by general formula (1) during production of the compound, during storage of the compound, and during production of the electrolyte solution, a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have a substituent is preferred. When the hydrocarbon group has a substituent, the number of carbon atoms contained in the substituent is not included in the carbon number. In addition, from the viewpoint of suitably forming the insulating coating, R 1 is also preferably a halogen atom. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. Specific examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group. Among these, from the viewpoint of suppressing side reactions on the electrode of the compound represented by general formula (1), an alkyl group, an alkenyl group, or an alkynyl group is preferred, an alkyl group or an alkenyl group is more preferred, and an alkyl group is particularly preferred.

[0019] Examples of the alkyl group include a linear alkyl group, a branched alkyl group, and an alkyl group having a cyclic structure, of which the linear alkyl group is preferred from the viewpoint of favorable formation of the insulating coating. Specific examples of the linear alkyl group include linear alkyl groups having 1 to 12 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl groups. Of these, linear alkyl groups having 1 to 6 carbon atoms are preferred, and linear alkyl groups having 1 to 4 carbon atoms are particularly preferred. Specific examples of the branched alkyl group include branched alkyl groups having 1 to 12 carbon atoms, such as a methylethyl group, a methylpropyl group, a methylbutyl group, a methylpentyl group, a methylhexyl group, a methylheptyl group, a methyloctyl group, a methylnonyl group, a methyldecyl group, a methylundecyl group; a dimethylethyl group (tert-butyl group), a dimethylpropyl group, a dimethylbutyl group, a dimethylpentyl group, a dimethylhexyl group, a dimethylheptyl group, a dimethyloctyl group; a trimethylhexyl group, a trimethylheptyl group; an ethylpentyl group, an ethylhexyl group, an ethylheptyl group, an ethyloctyl group; a propylhexyl group, a propylheptyl group; and a butylhexyl group. Among these, branched alkyl groups having 1 to 6 carbon atoms, such as a methylethyl group, a methylpropyl group, a methylbutyl group, a methylpentyl group, a dimethylethyl group (tert-butyl group), a dimethylpropyl group, or a dimethylbutyl group, are preferred, and branched alkyl groups having 1 to 4 carbon atoms, such as a methylethyl group, a methylpropyl group, or a dimethylethyl group (tert-butyl group), are particularly preferred. In the examples of the branched alkyl groups, the branching position may be any position.

[0020] Specific examples of the alkyl group having a cyclic structure include alkyl groups having a cyclic structure having 3 to 12 carbon atoms, such as a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclohexylmethyl group, cyclohexylethyl group, methylcyclohexyl group, dimethylcyclohexyl group, ethylcyclohexyl group, and methylcyclohexylmethyl group. Among these, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group , Shi Preferred are alkyl groups having a cyclic structure containing 3 to 8 carbon atoms, such as a cyclohexylmethyl group, a cyclohexylethyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, an ethylcyclohexyl group, or a methylcyclohexylmethyl group, and particularly preferred are alkyl groups having a cyclic structure containing 6 to 8 carbon atoms, such as a cyclohexyl group, a cyclohexylmethyl group, a cyclohexylethyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, an ethylcyclohexyl group, or a methylcyclohexylmethyl group.

[0021] Among the alkyl groups mentioned above, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, or an n-hexyl group is preferred, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or a tert-butyl group is more preferred, and a methyl group or an ethyl group is particularly preferred. These alkyl groups are preferred because they tend to localize the compound represented by general formula (1) near the surface of the positive electrode active material and / or the negative electrode active material.

[0022] Specific examples of the alkenyl group include alkenyl groups having 2 to 12 carbon atoms, such as vinyl, allyl, isopropenyl, methallyl, 2-butenyl, 3-methyl-2-butenyl, 3-butenyl, and 4-pentenyl. Of these, preferred are alkenyl groups having 2 to 6 carbon atoms, such as vinyl, allyl, methallyl, and 2-butenyl, more preferred are alkenyl groups having 2 to 4 carbon atoms, such as vinyl, allyl, and methallyl, and particularly preferred are vinyl or allyl. The above-mentioned alkenyl groups can be used to form a positive electrode active material. and A compound represented by general formula (1) is / is preferred because it can form an insulating coating on the surface of the negative electrode active material.

[0023] Specific examples of the alkynyl group include alkynyl groups having 1 to 12 carbon atoms, such as ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, 4-pentynyl, and 5-hexynyl. Among these, preferred are alkynyl groups having 1 to 6 carbon atoms, such as ethynyl, 2-propynyl, 2-butynyl, and 3-butynyl, more preferred are alkynyl groups having 2 to 4 carbon atoms, such as 2-propynyl and 3-butynyl, and particularly preferred is 2-propynyl. The above-mentioned alkynyl groups are preferred because the compound represented by general formula (1) can suitably form an insulating coating on the surface of the positive electrode active material and / or negative electrode active material.

[0024] Specific examples of the aryl group include aryl groups having 6 to 12 carbon atoms, such as a phenyl group, a tolyl group, or a mesityl group. Among these, from the viewpoint that the compound represented by general formula (1) tends to be localized near the surface of the positive electrode active material and / or the negative electrode active material, aryl groups having 6 to 7 carbon atoms, such as a phenyl group or a tolyl group, are preferred, and a phenyl group is particularly preferred.

[0025] Examples of the aralkyl group include aralkyl groups having 7 to 12 carbon atoms, such as a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group. Among these, from the viewpoint of the tendency of the compound represented by general formula (1) to be localized near the surface of the positive electrode active material and / or the negative electrode active material, aralkyl groups having 7 to 8 carbon atoms, such as a benzyl group or a phenethyl group, are preferred, and a benzyl group is particularly preferred.

[0026] Examples of the substituent that the hydrocarbon group may have include a cyano group, an isocyanato group, a halogen atom, or a group containing a halogen atom. Among these, an isocyanato group, a halogen atom, or a group containing a halogen atom is preferred, and a halogen atom or a group containing a halogen atom is particularly preferred. Specific and preferred examples of the halogen atom are described in R 1 This is the same as that specified in

[0027] Specific examples of the group containing a halogen atom include a fluoromethyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3-tetrafluoropropyl group, a 2-fluorophenyl group, etc. Among these, from the viewpoint of suppressing electrochemical side reactions, a fluoromethyl group, a trifluoromethyl group, or a 2,2,2-trifluoroethyl group is preferred, and a trifluoromethyl group is particularly preferred.

[0028] In this specification, R in the general formula (1) 1 is a monovalent hydrocarbon group, and R 1 and X 1 When two of R are bonded to each other to form a ring, this "monovalence" is treated as the valence of the hydrocarbon group when no bond is formed. In other words, when a ring is formed, R 1 is a divalent hydrocarbon group, but when the above bond is not formed, that is, when no ring is formed, A 1 The monovalent hydrocarbon group bonded to R 1 Similarly, X, which will be described later, 1 is a divalent hydrocarbon, and R 1 and X 1 Even when two of these are bonded to each other to form a ring, this "divalent" is treated as the valence of the hydrocarbon in a state where no bond is formed. This treatment of "monovalent" or "divalent" is the same in embodiments other than general formula (1).

[0029] (R 2 ) R according to general formula (1) 2 represents a hydrogen atom, an optionally substituted monovalent hydrocarbon group, or an optionally substituted alkoxy group. Among these, from the viewpoint of minimizing side reactions on the active material of the compound represented by general formula (1), an optionally substituted monovalent hydrocarbon group or an optionally substituted alkoxy group is preferred, and an optionally substituted monovalent hydrocarbon group is particularly preferred. Here, the hydrocarbon group is R 1 The hydrocarbon groups are defined in the same manner as those defined above, and preferred hydrocarbon groups are also defined in the same manner.

[0030] Specific examples of the alkoxy group include alkoxy groups having 1 to 12 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, hexyloxy, octyloxy, decyloxy, and dodecyloxy. Of these, alkoxy groups having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, and butoxy, are preferred, with methoxy and ethoxy being particularly preferred in that they cause less steric hindrance to the compound represented by general formula (1) and are suitably concentrated on the surface of the active material.

[0031] The substituents that the alkoxy group may have are R 1 The substituents are defined in the same manner as the substituents that the hydrocarbon group defined in the above may have.

[0032] (X 1 ) X in the general formula (1) 1 represents a divalent hydrocarbon group which may have a substituent. The divalent hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms. The above carbon number is preferred because the compound represented by general formula (1) tends to be localized near the surface of the positive electrode active material and / or negative electrode active material. Note that when the hydrocarbon group has a substituent, the carbon atoms contained in the substituent are not included in this carbon number.

[0033] The divalent hydrocarbon group is preferably a divalent aliphatic hydrocarbon group, and specific examples thereof include an alkylene group or an alkenylene group. Among these, an alkylene group is preferred. Examples of the substituent that the divalent hydrocarbon group may have include R 1 The substituents are defined in the same manner as the substituents that the hydrocarbon group defined in the above may have.

[0034] Specific examples of the alkylene group include a linear alkylene group, a branched alkylene group, and an alkylene group having a cyclic structure.

[0035] Specific examples of the linear alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, and a decylene group.

[0036] Specific examples of branched alkylene groups include methylethylene, methylpropylene, methylbutylene, methylpentylene, methylhexylene, methylheptylene, methyloctylene, methylnonylene; dimethylethylene, dimethylpropylene, dimethylbutylene, dimethylpentylene, dimethylhexylene, dimethylheptylene, dimethyloctylene; trimethylhexylene, trimethylheptylene; ethylpentylene, ethylhexylene, ethylheptylene, ethyloctylene; propylhexylene, propylheptylene; butylhexylene, etc. In the examples of branched alkyl groups, the branching position may be arbitrary.

[0037] Specific examples of alkylene groups having a cyclic structure include cyclohexylene groups.

[0038] Among the above, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, methylethylene group, methylpropylene group, methylbutylene group, methylpentylene group, and cyclohexylene group are preferred, and methylene group, ethylene group, propylene group, butylene group, methylethylene group, and methylpropylene group are more preferred. The above alkylene groups are preferred because the compound represented by general formula (1) tends to be localized near the surface of the positive electrode active material and / or negative electrode active material.

[0039] Specific examples of the alkenylene group include a vinylene group, a propenylene group, a 1-butenylene group, a 2-butenylene group, a butadienylene group, a pentenylene group, a hexenylene group, a heptenylene group, and an octenylene group.

[0040] (A 1 ) A according to general formula (1) 1 represents a divalent or trivalent atomic group represented by the following general formula (2-1) or the general formula (3-1) described below.

[0041] [ka]

[0042] Z 1 is a carbon atom, a sulfur atom, a phosphorus atom, or a boron atom, and Y 101 is an oxygen atom or a sulfur atom, and Y 1 , Y 2 and Y 3 are each independently a single bond, an oxygen atom, a sulfur atom, or NR 101 (-NR 101 -group). 101 , a hydrogen atom, or a monovalent hydrocarbon group. 101 When R is a monovalent hydrocarbon group, 101 represents R in the general formula (1). 1 and X 1 may be bonded to any one of the following to form a ring. r 1 is Z 1 is a carbon atom, it is 1, and Z 1 is 0, 1, or 2 when is a sulfur atom, and Z 1 is 0 or 1 when is a phosphorus atom, and Z 1 is 0 when it is a boron atom. r 2 is Z 1 is 0 when is a carbon atom or a sulfur atom, and Z 1 is 1 when is a phosphorus atom or a boron atom. * indicates R in the above general formula (1). 1 or X 1 represents the binding site with However, Z 1 is a sulfur atom and r 1 When is 2, Y 1 and Y 2 cannot both be single bonds.

[0043] (R 101 ) The above R 101 The monovalent hydrocarbon groups in each group are independently R 1 is synonymous with the monovalent hydrocarbon group defined by

[0044] Examples of the divalent atomic group represented by general formula (2-1) include an oxygen atom; a sulfur atom; a divalent atomic group consisting of an oxygen atom, a carbon atom and an oxygen atom, or a hydrogen atom, a carbon atom and an oxygen atom; or a divalent atomic group consisting of a sulfur atom, an oxygen atom and a sulfur atom, a carbon atom, an oxygen atom and a sulfur atom, or a hydrogen atom, a carbon atom, an oxygen atom and a sulfur atom, etc.

[0045] Specific examples of the divalent atomic group consisting of an oxygen atom, a carbon atom and an oxygen atom, or a hydrogen atom, a carbon atom and an oxygen atom include divalent atomic groups having a ketone structure, a carboxylic acid ester structure, or a carbonate structure, and specific examples thereof include Z 1 is a carbon atom; Y 101 is an oxygen atom; Y 1 , Y 2 , and Y 3 are independently a single bond or an oxygen atom. Specific examples of the divalent group having a ketone structure include a -CO- group. Specific examples of the divalent group having a carboxylic acid ester structure include a -COO- group. Specific examples of the divalent group having a carbonate structure include an -OCOO- group. Among these, a -COO- group or an -OCOO- group is particularly preferred from the viewpoint of causing few electrochemical side reactions and suitably forming a coating on the surface of the active material.

[0046] Specific examples of the divalent atomic group consisting of a sulfur atom, an oxygen atom and a sulfur atom, a carbon atom, an oxygen atom and a sulfur atom, or a hydrogen atom, a carbon atom, an oxygen atom and a sulfur atom include divalent groups having a sulfide structure, a sulfone structure, a sulfonate ester structure, a sulfate ester structure, a sulfoxide structure, a sulfite ester structure, a sulfinate ester structure, a thiocarbonyl structure, and a thioester structure. Specific examples include, for example, Z 1 is a carbon atom; Y 101 is an oxygen atom; Y 1 , Y 2 , and Y 3 is a sulfur atom, Z 1 is a carbon atom; Y 101 is a sulfur atom; Y 1 , Y 2 , and Y 3 are independently a single bond, an oxygen atom, or a sulfur atom, or Z 1 is a sulfur atom; Y 101 is an oxygen atom or a sulfur atom; or Y 1 , Y 2 , and Y 3 are independently a single bond, an oxygen atom, or sulfur atom Examples of such groups include atomic groups in which Specific examples of the divalent group having a sulfide structure include an -S- group. Specific examples of divalent groups having a sulfonate structure include -SO3- groups. Specific examples of divalent groups having a sulfate ester structure include -OSO3- groups. Specific examples of divalent groups having a sulfoxide structure include -SO- groups. Specific examples of divalent groups having a sulfite ester structure include an -OSO- group. Specific examples of the divalent group having a sulfinate structure include an -SOO- group. Examples of the divalent group having a thiocarbonyl structure include an -OCSO- group and a -CSO- group. It can be obtained. Specific examples of the divalent group having a thioester structure include a -COS- group, a -OCOS- group, a -SCOS- group, etc. The divalent group may also be a dithiocarboxylic acid ester structure such as a -CSS- group, a -OCSS- group, or a -SCSS- group. Among these, from the viewpoint of reducing electrochemical side reactions and suitably forming a coating on the surface of the active material, the -SO3- group, -OSO3- group, -OSOO- group, or -SOO- group is preferred, the -SO3- group or -OSO3- group is more preferred, and the -SO3- group is particularly preferred.

[0047] Specific examples of the trivalent atom or atomic group having at least one atom selected from oxygen, nitrogen, sulfur, phosphorus, and boron atoms include a nitrogen atom; a phosphorus atom; a boron atom; a trivalent atomic group consisting of carbon, nitrogen, and oxygen atoms, or a hydrogen atom, carbon, nitrogen, and oxygen atoms; a carbon atom, nitrogen, and sulfur atoms, a nitrogen atom, oxygen, and sulfur atoms, a hydrogen atom, carbon, nitrogen, and sulfur atoms, or a trivalent atomic group consisting of carbon, nitrogen, oxygen, and sulfur atoms; a phosphorus atom, oxygen, and phosphorus atoms, or a trivalent atomic group consisting of hydrogen, nitrogen, oxygen, and phosphorus atoms; and a boron atom or a trivalent atomic group consisting of boron and oxygen atoms. Specific examples thereof include Z 1 is a carbon atom; Y 101 is an oxygen atom; Y 1 , Y 2 , and Y 3 independently NR 101 Examples of such groups include atomic groups in which The trivalent atomic group consisting of carbon, nitrogen and oxygen atoms, or hydrogen, carbon, nitrogen and oxygen atoms, includes a trivalent group having an amide structure, a urethane structure or a urea structure. Specific examples of these include the atomic groups shown below.

[0048] [ka]

[0049] Examples of the trivalent atomic group consisting of carbon atoms, nitrogen atoms and sulfur atoms, nitrogen atoms, oxygen atoms and sulfur atoms, hydrogen atoms, carbon atoms, nitrogen atoms and sulfur atoms, or carbon atoms, nitrogen atoms, oxygen atoms and sulfur atoms include trivalent groups having a thiocarbonyl structure, a thioester structure, or a sulfonamide structure. It may also be a trivalent group having a dithiocarboxylic acid ester structure. Specific examples of these include the atomic groups shown below, and specifically, for example, Z 1 is a carbon atom; Y 101 is a sulfur atom; Y 1 , Y 2 , and Y 3 independently NR 101 or Z 1 is a carbon atom; Y 101 is an oxygen atom; Y 1 , Y 2 , and Y 3 independently NR 101 Examples of such groups include atomic groups in which

[0050] [ka]

[0051] Examples include a phosphorus atom, an oxygen atom and a phosphorus atom, or a trivalent atomic group consisting of a hydrogen atom, a nitrogen atom, an oxygen atom and a phosphorus atom. Specific examples include Z 1 is a phosphorus atom, and more specifically, a trivalent group having a phosphine oxide structure, a phosphinate ester structure, a phosphonate ester structure, a phosphate ester structure, a phosphoric acid amide structure, a phosphine structure, a phosphinite ester structure, a phosphonite ester structure, or a phosphite ester structure, etc. Specific examples of these include the atomic groups shown below.

[0052] [ka]

[0053] Among these, the following atomic groups are preferred from the viewpoint of causing fewer electrochemical side reactions and favorably forming a coating on the surface of the active material.

[0054] [ka]

[0055] Among these, the following atomic groups are particularly preferred:

[0056] [ka]

[0057] Examples thereof include a boron atom, or a trivalent atomic group consisting of a boron atom and an oxygen atom. Specific examples thereof include Z 1 is a boron atom, and more specifically, trivalent groups having a trialkylborane structure, a borinic acid ester structure, a boronate ester structure, and a borate ester structure are included. Specific examples of these include the following atomic groups. [ka]

[0058] Among these, the divalent or trivalent atomic group represented by formula (2-1) is preferably a divalent or trivalent atomic group represented by the following general formula (2-2), in terms of reducing electrochemical side reactions and suitably forming a coating on the surface of the active material.

[0059] [ka]

[0060] Z 2 are carbon atoms, sulfur atoms, and phosphorus atoms, and Y 7 , Y 8 and Y 9 are each independently a single bond or an oxygen atom. r 3 is Z 2 is a carbon atom, it is 1, and Z 2 is 0, 1, or 2 when is a sulfur atom, and Z 2 is 0 or 1 when it is a phosphorus atom. r 4 is Z 2 is 0 when is a carbon atom or a sulfur atom, and Z 2 is a phosphorus atom, it is 1. * indicates R in the above general formula (1). 1 or X 1 represents the binding site with However, Z 2 is a sulfur atom and r 3 When is 2, Y 7 and Y 8 cannot both be single bonds. Z in general formula (2-2) 2 , Y 7 , Y 8 , Y 9 , r 2 , and r 3 represents, within the applicable range, Z in the above general formula (2-1). 1 , Y 1 , Y 2 , Y 3 , r 0 , and r 1 The above conditions can be applied to each of the above.

[0061] The trivalent atomic group represented by the following general formula (3-1) will be explained below.

[0062] [ka]

[0063] Y 4 , Y 5 and Y 6 are each independently an oxygen atom, a sulfur atom, or NR 201 (=NR 201 R 201 is a hydrogen atom or a monovalent hydrocarbon group. * indicates R in the above general formula (1). 1 or X 1 The binding site is shown.

[0064] (R 201 ) The above R 201 The hydrocarbon group in R 3 The hydrocarbon group has the same meaning as the hydrocarbon group defined above.

[0065] Among these, the atomic group represented by the following formula (3-2) is preferred from the viewpoint of causing fewer electrochemical side reactions and suitably forming a coating on the surface of the active material. [ka]

[0066] * indicates R in the above general formula (1). 1 or X 1 The binding site is shown.

[0067] Among the atomic groups represented by the above general formula (2-1) or general formula (3-1), It is preferably a divalent group having a ketone structure, a divalent group having a carbonate structure, a divalent group having a carboxylic acid ester structure, a divalent group having a sulfonic acid ester structure, a divalent group having a sulfate ester structure, a divalent group having a sulfite ester structure, a divalent group having a sulfinic acid structure, a trivalent group having a phosphonic acid ester structure, a trivalent group having a phosphate ester structure, or a trivalent group having an isocyanurate structure, It is more preferable that the group is a divalent group having a carbonate structure, a divalent group having a carboxylic acid ester structure, a divalent group having a sulfonic acid ester structure, a divalent group having a sulfuric acid ester structure, a trivalent group having a phosphonic acid ester structure, a trivalent group having a phosphate ester structure, or a trivalent group having an isocyanurate structure, It is more preferable that the group is a divalent group having a carbonate structure, a divalent group having a carboxylic acid ester structure, a divalent group having a sulfonic acid ester structure, a trivalent group having a phosphonic acid ester structure, a trivalent group having a phosphate ester structure, or a trivalent group having an isocyanurate structure, A divalent group having a carbonate structure or a divalent group having a carboxylic acid ester structure is particularly preferred.

[0068] n in the general formula (1) 1 represents an integer of 2 to 3. In terms of being able to easily suppress the amount of gas generation, n 1 is preferably 3.

[0069] p according to general formula (1) 1 represents an integer of 0 to 2.

[0070] q in the general formula (1) 1 represents an integer of 1 to 3, where p 1 +q 1 =2 or 3. From the viewpoint of reducing electrochemical side reactions and suitably forming a coating on the surface of the active material, A 1 When the structure is represented by formula (2-1) or formula (2-2), p 1 is 1 and q 1 is preferably 1 or 2, and p 1 is 1 and q 1 is more preferably 1. From the viewpoint of reducing electrochemical side reactions and suitably forming a coating on the surface of the active material, A 1 When the structure is represented by formula (3-1) or formula (3-2), p 1 =0 and q 1 It is preferable that =3.

[0071] R 1 and X 1 Two of these may be bonded to each other to form a ring. That is, in the embodiment of forming a ring, R 1 Comrades, as well as R 1 and X 1 In terms of ease of synthesis, R 1 and X 1 are bonded to form a ring. More preferred embodiments include the following structures:

[0072] [ka]

[0073] Specific examples of compounds represented by the general formula (1) are shown below. Note that the compounds represented by the general formula (1) according to this embodiment are not limited to the compounds represented by the following formulae (F3-1) to (F3-106) and (F2-1) to (F2-148) shown below.

[0074] [ka]

[0075]

change

[0076]

change

[0077]

change

[0078]

change

[0079]

change

[0080]

change

[0081]

change

[0082]

change

[0083]

change

[0084]

change

[0085]

change

[0086] [ka]

[0087] [ka]

[0088] [ka]

[0089] [ka]

[0090] [ka]

[0091] [ka]

[0092] Among these, from the viewpoint of ease of obtaining raw materials and ease of synthesis, A 1 is a divalent atomic group having a carbonate structure, a divalent atomic group having a carboxylic acid ester structure, a divalent atomic group having a sulfonic acid ester structure, a divalent atomic group having a phosphonic acid ester structure, a trivalent atomic group having a phosphate ester structure, or a trivalent atomic group having an isocyanurate structure; And R 1 is a hydrogen atom or an alkyl group, R 2 is an alkyl group, and X 1 is an alkylene group, and among these, compounds represented by the above formulae (F3-1), (F3-20), (F3-26), (F3-35) to (F3-37), (F3-43) to (F3-45), (F3-53) to (F3-63), (F3-67) to (F3-85), (F3-91) to (F3-99), (F3-101) to (F3-106), It is preferable that the compound is a compound selected from the group of compounds represented by (F2-1), (F2-20), (F2-26), (F2-35) to (F2-37), (F2-43) to (F2-45), (F2-53) to (F2-63), (F2-67) to (F2-85), or (F2-91) to (F2-99), (F2-101) to (F2-148), A 1 is a divalent atomic group having a carbonate structure, a divalent atomic group having a carboxylic acid ester structure, a divalent atomic group having a sulfonic acid ester structure, a divalent atomic group having a phosphonic acid ester structure, a trivalent atomic group having a phosphate ester structure, or a trivalent atomic group having an isocyanurate structure; And R 1 is a methyl group or an ethyl group, R 2 is an alkyl group, and X 1 is an alkylene group, and among these, a compound selected from the group of compounds represented by the above formulas (F3-1), (F3-20), (F3-35) to (F3-37), (F3-44) to (F3-45), (F3-53) to (F3-63), (F3-91) to (F3-99), (F2-1), (F2-20), (F2-35) to (F2-37), (F2-44) to (F2-45), (F2-53) to (F2-63), or (F2-91) to (F2-99) is preferred; X 1 is a propylene group, and R 1 is more preferably a methyl group or an ethyl group, and among these, it is preferable that it is a compound selected from the group of compounds represented by (F3-1), (F3-20), (F3-35), (F3-44), (F3-45), (F3-55), (F3-56), (F3-94), (F3-99), (F2-1), (F2-20), (F2-35), (F2-44), (F2-45), (F2-55), (F2-56), (F2-94), or (F2-99), A 1 is a divalent atomic group having a carbonate structure, a divalent atomic group having a carboxylic acid ester structure, a divalent atomic group having a phosphonic acid ester structure, a trivalent atomic group having a phosphoric acid ester structure, or a trivalent atomic group having an isocyanurate structure, and X 1 is a propylene group, and R 1 is a methyl group or an ethyl group, and among these, a compound selected from the group of compounds represented by (F3-1), (F3-20), (F3-44), (F3-45), (F3-55), (F3-56), (F3-94), (F2-1), (F2-20), (F2-44), (F2-45), (F2-55), (F2-56), or (F2-94) is particularly preferred.

[0093] Another embodiment of the present invention is a compound represented by the following general formula (1-4): The effects, uses, structural conditions, etc. obtained by this compound are similar to the effects, uses, structural conditions, etc. obtained by the compound represented by the above general formula (1), and this compound can also be used as one embodiment of the compound represented by the above general formula (1).

[0094] [ka]

[0095] In general formula (1-4), R 11 represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may have a substituent; R 12 represents a hydrogen atom or an optionally substituted monovalent hydrocarbon group; X 11 represents a divalent hydrocarbon group having 3 or more carbon atoms which may have a substituent; Y 21 and Y 22 are each independently a single bond, an oxygen atom, a sulfur atom, or NR 301 (-NR 301 -group); R 301 is a hydrogen atom or an optionally substituted monovalent hydrocarbon group; R 301 When R is a monovalent hydrocarbon group, 301 is R 11 and X 11 may be bonded to any one of the following to form a ring; 11 indicates 2. R 11 and X 11 Two of these may be bonded to each other to form a ring. However, Y 21 and Y 22 is an oxygen atom, and R 11 and X 11 When n is not bonded to form a ring (the compound represented by general formula (1-4) is a chain (a chain carbonate)), 11 may be 3. R 11 and R 12 The hydrocarbon group in the formula (1) is 1 and R 2 The hydrocarbon groups in R 301 is a hydrogen atom or a monovalent hydrocarbon group. 301 The hydrocarbon group in R 1 The hydrocarbon group has the same meaning as the hydrocarbon group defined above. The conditions for the atoms constituting the general formula (1-4) can be similarly applied to the conditions for the corresponding atoms in the general formula (1) described above, including the preferred conditions. From the viewpoint of reducing electrochemical side reactions and suitably forming a coating on the surface of the active material, A in the above general formula (1) 1 The portion corresponding to is preferably a carbonate structure. In addition, from the viewpoint of balancing the resistance and insulation of the coating, n 11 is preferably 2. In addition, from the viewpoint of balancing the resistance and insulation of the coating, R 11 and X 11 It is preferable that the structure does not form a ring by bonding with the In addition, from the viewpoint of high gas suppression effect during high temperature storage, 11 is preferably 3.

[0096] The compound represented by the above general formula (1-4) is specifically In the embodiment having a carbonate structure, particularly, Y 21 and Y 22 is an oxygen atom, n 11 is 2 or 3, and X 11 is a divalent hydrocarbon group having 3 or more carbon atoms, and among these, it is preferable that the compound is selected from the group of compounds represented by the above formulas (F3-1), (F2-1), and (F2-107) to (F2-112). 11 is a methyl group or an ethyl group, and among these, it is preferable that the compound is selected from the group of compounds represented by the above formulas (F3-1) and (F2-1). 11 is a methyl group, and among these, a compound selected from the group of compounds represented by the above formulas (F3-1) and (F2-1) is preferred, Also, in embodiments having a carboxylic acid ester, particularly Y 21 is a single bond, Y 22 is an oxygen atom, n 11 2 or 3, X 11 is a divalent hydrocarbon group having 3 or more carbon atoms, R 11 is a hydrogen atom or an alkyl group, and R 12 is a methyl group, and among these, it is preferable that the compound is selected from the group of compounds represented by the above formulas (F2-20), (F2-91) to (F2-92), and (F2-97) to (F2-98). 1 is more preferably a methyl group or an ethyl group, and among these, a compound selected from the group of compounds represented by the above formula (F2-20) is preferred.

[0097] Another embodiment of the present invention is a compound represented by the following general formula (1-5): The effects, uses, structural conditions, etc. obtained by this compound are similar to the effects, uses, structural conditions, etc. obtained by the compound represented by the above general formula (1), and this compound can also be used as one aspect of the compound represented by the above general formula (1).

[0098] [ka]

[0099] In general formula (1-5), R 13 represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may have a substituent; R 14 represents a hydrogen atom or an optionally substituted monovalent hydrocarbon group; X 12 represents a divalent hydrocarbon group having 3 or more carbon atoms which may have a substituent; Y 23 and Y 24 are each independently a single bond, an oxygen atom, a sulfur atom, or NR 311 (-NR 311 -group); R 311 is a hydrogen atom or an optionally substituted monovalent hydrocarbon group; R 311 When R is a monovalent hydrocarbon group, 311 is R 13 and X 12 may be bonded to any one of the groups to form a ring; 12 is 0, 1 or 2. 12 indicates 2 or 3. R 13 and X 12 Two of these may be bonded to each other to form a ring. R 13 and R 14 The hydrocarbon group in the formula (1) is 1 and R 2 The hydrocarbon groups in R 311 is a hydrogen atom or a hydrocarbon group. 311 The hydrocarbon group in R 1 The hydrocarbon group has the same meaning as the hydrocarbon group defined above. The conditions for the atoms constituting the general formula (1-5) can be similarly applied to the conditions for the corresponding atoms in the general formula (1) described above, including the preferred conditions. From the viewpoint of reducing electrochemical side reactions and suitably forming a coating on the surface of the active material, A in the above general formula (1) 1 The portion corresponding to the formula (I) preferably has a sulfonate ester structure. Furthermore, n12 is preferably 2 from the viewpoint of ensuring that film formation proceeds smoothly and achieving a balance between the resistance and insulating properties of the film. In addition, from the viewpoint of balancing the resistance and insulation of the coating, R 13 and X 12 It is preferable that the structure does not form a ring by bonding with the

[0100] The compound represented by the above general formula (1-5) specifically has a sulfonate structure, particularly, Y 23 is a single bond, and Y 24 is an oxygen atom, n 12 2 or 3, X 12 is an alkylene group having 3 or more carbon atoms, and among these, it is preferable that the compound is selected from the group of compounds represented by the above formulas (F3-35), (F2-35), (F2-119) to (F2-124). 13 is a methyl group or an ethyl group, and among these, it is preferable that the compound is a compound selected from the group of compounds represented by the above formulas (F3-35) and (F2-35). 13 is a methyl group, and among these, a compound selected from the group of compounds represented by the above formulas (F3-35) and (F2-35) is preferred. In addition, from the viewpoint of high gas suppression effect during high temperature storage, 12 is preferably 3.

[0101] Another embodiment of the present invention is a compound represented by the following general formula (1-6): The effects, uses, structural conditions, etc. obtained by this compound are similar to the effects, uses, structural conditions, etc. obtained by the compound represented by the above general formula (1), and this compound can also be used as one embodiment of the compound represented by the above general formula (1).

[0102] [ka]

[0103] In general formula (1-6), R 15 , and R 15 R ′ each independently represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may have a substituent; 16 represents a hydrogen atom or an optionally substituted monovalent hydrocarbon group; X 13 represents a divalent hydrocarbon group having 3 or more carbon atoms which may have a substituent; Y 25 , Y 25 ', and Y 26 are each independently a single bond, an oxygen atom, a sulfur atom, or NR 321 and;R 321 is a hydrogen atom or an optionally substituted monovalent hydrocarbon group; R 321 When R is a monovalent hydrocarbon group, 321 is R 15 and X 13 may be bonded to any one of the following to form a ring; 13 indicates 2 or 3. R 15 and X 13 Two of these may be bonded to each other to form a ring. R 15 and R 16 The monovalent hydrocarbon group in the formula (1) is R 1 and R 2 Each of these has the same meaning as the monovalent hydrocarbon group in the above formula. 321 is a hydrogen atom or a hydrocarbon group. 321 The hydrocarbon group in R 1 The hydrocarbon group has the same meaning as the hydrocarbon group defined above. The conditions for the atoms constituting the general formula (1-6) can be similarly applied to the conditions for the corresponding atoms in the general formula (1) described above, including the preferred conditions. From the viewpoint of reducing electrochemical side reactions and suitably forming a coating on the surface of the active material, A in the above general formula (1) 1 The portion corresponding to the formula (I) preferably has a phosphate ester or phosphonate ester structure. From the viewpoint of balancing the resistance and insulation of the coating, n 13 is preferably 2. In addition, from the viewpoint of balancing the resistance and insulation of the coating, R 15 and X 13 It is preferable that the structure does not form a ring by bonding with the In addition, from the viewpoint of high gas suppression effect during high temperature storage, 13 is preferably 3.

[0104] The compound represented by the above general formula (1-6) is specifically In the embodiment having a phosphonate ester structure, particularly, Y 25 and Y 25 ' is an oxygen atom, Y 26 is a single bond, n 13 is an integer of 1 to 3, and X13 is a monovalent hydrocarbon group having 3 or more carbon atoms. Among these, compounds selected from the group of compounds represented by the above formulas (F3-55) to (F2-57), (F2-55) to (F2-57), and (F2-137) to (F2-148) are preferred. 13 is 2 or 3, R 15 is a methyl group or an ethyl group, and among these, it is preferable that the compound is selected from the group of compounds represented by the above formulas (F3-55) to (F3-56) and (F2-55) to (F2-56). 15 is an ethyl group, and among these, a compound selected from the group of compounds represented by the above formulas (F3-56) and (F2-56) is preferred, In addition, in an embodiment having a phosphate ester structure, particularly, Y 25 , Y 25 ', and Y 26 is an oxygen atom, n 13 is an integer between 1 and 3, X 13 is a hydrocarbon group having 2 or more carbon atoms, and among these, it is preferable that the compound is selected from the group of compounds represented by the above formulas (F3-44) to (F3-45), (F2-44) to (F2-45), and (F2-125) to (F2-136). 13 is 2 or 3, R 15 is a methyl group or an ethyl group, and among these, it is preferable that the compound is selected from the group of compounds represented by the above formulas (F3-44) to (F3-45) and (F2-44) to (F2-45). 15 is an ethyl group, and among these, the compound represented by the above formula (F2-45) is preferred.

[0105] From the viewpoint of a high effect of suppressing gas generation during high-temperature storage and a high effect of improving the rate of increase in resistance, the compounds represented by general formula (1-4) or general formula (1-6) are preferred. Among the compounds represented by the above general formulas (1-4) to (1-6), when a compound is selected from the viewpoint of achieving a balance between the resistance and insulating properties of the coating, the compounds represented by the following formula are preferred.

[0106] [ka]

[0107] [ka]

[0108] Among these, compounds represented by the following formula (1-4-1) or (1-4-2) are particularly preferred from the viewpoint of favorably forming the insulating coating.

[0109] [ka]

[0110] The content of the compound represented by the general formula (1) with respect to the total amount of the non-aqueous electrolyte according to the present embodiment is usually 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and is usually 10% by mass or less, preferably 5.0% by mass or less, more preferably 3.0% by mass or less, particularly preferably 2.0% by mass or less, and most preferably 1.0% by mass or less. If the content of the compound represented by the general formula (1) with respect to the total amount of the non-aqueous electrolyte is within the above range, the concentration of the compound represented by the general formula (1) in the active material proceeds preferably, and it becomes possible to produce a battery with less gas generation during high-temperature storage.

[0111] The compound represented by the general formula (1) above can be produced by the following known methods and by combining the following known methods. However, it is not limited to the following methods. Using an olefin and a hydrosilane compound as raw materials, silane compounds having various atomic groups can be synthesized by a hydrosilylation reaction using a platinum catalyst. A fluorosilane compound can be synthesized by fluorinating a chlorosilane compound or an alkoxysilane compound with a metal fluoride, boron trifluoride, or a boron trifluoride complex. By combining the hydrosilylation reaction and the fluorination reaction, fluorosilane compounds having various atomic groups can be synthesized.

[0112] <A1-2. Electrolyte> The non-aqueous electrolyte of the present embodiment usually contains an electrolyte as its component, similar to a general non-aqueous electrolyte. The electrolyte used in the non-aqueous electrolyte of the present embodiment is not particularly limited as long as it is an alkali metal salt, and lithium salts such as LiBF4, LiPF6, LiN(FSO2)2, LiN(CF3SO2)2, or lithium difluorooxalatoborate can be preferably used. Also, these lithium salts can be used alone or in combination of two or more.

[0113] The total concentration of the alkali metal salt in the non-aqueous electrolyte is not particularly limited, but is usually 8% by mass or more, preferably 8.5% by mass or more, more preferably 9% by mass or more, based on the total amount of the non-aqueous electrolyte. The upper limit 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 salt as the electrolyte is within the above range, the electrical conductivity becomes appropriate for battery operation, and sufficient output characteristics tend to be obtained.

[0114] <A1-3. Non-aqueous solvent> The non-aqueous electrolyte of this embodiment contains, as a main component, a non-aqueous solvent that dissolves the above-described electrolyte, as in a general non-aqueous electrolyte. There is no particular limitation on the non-aqueous solvent, and known organic solvents can be used. Examples of the organic solvent include saturated cyclic carbonates such as ethylene carbonate, propylene carbonate, or butylene carbonate; linear carbonates such as dimethyl carbonate, diethyl carbonate, or ethyl methyl carbonate; carboxylic acid esters such as methyl acetate, ethyl acetate, propyl acetate, or butyl acetate; ether compounds such as dimethoxymethane, diethoxymethane, ethoxymethoxymethane, tetrahydrofuran, 1,3-dioxane, or 1,4-dioxane; sulfone compounds such as 2-methylsulfolane, 3-methylsulfolane, 2-fluorosulfolane, 3-fluorosulfolane, dimethyl sulfone, ethyl methyl sulfone, or monofluoromethyl methyl sulfone; and the like. Saturated cyclic carbonates, linear carbonates, or carboxylic acid esters are preferred, and saturated cyclic carbonates or linear carbonates are more preferred. These non-aqueous solvents can be used alone or in combination of two or more.

[0115] <A1-4. Auxiliary agent> In the non-aqueous electrolyte of this embodiment, an auxiliary agent may be contained within a range in which the effects of the present invention are exhibited. Examples of the auxiliary agent include unsaturated cyclic carbonates such as vinylene carbonate, vinyl ethylene carbonate, or ethynyl ethylene 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; Sulfur-containing compounds such as ethylene sulfite; 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; silane compounds such as tris(trimethylsilyl) borate; 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.

[0116] In particular, in the nonaqueous electrolyte solution according to this embodiment, the use of one or more selected from unsaturated cyclic carbonates and cyclic carbonates having fluorine atoms is preferred in that gas generation during initial conditioning is further suppressed, resulting in a battery that is less prone to swelling.

[0117] The nonaqueous electrolyte may also contain, as an auxiliary agent, a phosphate having a P=O bond and a PF bond, a salt having an FSO2 skeleton, or an oxalate. From the viewpoint of favorably forming a composite coating together with the compound represented by general formula (1), it is preferable for the electrolyte to contain one or more compounds selected from the group consisting of a phosphate having a P=O bond and a PF bond, a salt having an FSO2 skeleton, and an oxalate. From the viewpoint of suppressing the amount of gas generation during storage at charge and an increase in internal resistance, it is preferable for the electrolyte to contain a phosphate having a P=O bond and a PF bond and / or a salt having an FSO2 skeleton. The total content of compounds selected from the group consisting of phosphates having a P=O bond and a PF bond, salts having an FSO2 skeleton, and oxalates 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, in 100% by mass of the non-aqueous electrolyte (relative to the total amount of the non-aqueous electrolyte), 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 types of auxiliary agents are used in combination, it is preferable that the total content satisfies the above range.

[0118] (phosphate salts with P=O and PF bonds) The phosphate having a P=O bond and a PF bond is not particularly limited as long as it has a P=O bond and a PF bond in the molecule. Counter cations of phosphate salts having a PF bond include alkali metals such as lithium, sodium, and potassium, with lithium being preferred. Fluorophosphates having a P=O bond include: Monofluorophosphates such as Li2PO3F; Difluorophosphates such as LiPO2F2, NaPO2F2, KPO2F2; etc. In particular, difluorophosphates are preferred, and lithium difluorophosphate is more preferred, from the viewpoint of further enhancing the effects of suppressing gas generation during high-temperature storage and further improving the charge / discharge rate characteristics and impedance characteristics.

[0119] The fluorophosphate may be used alone or in any combination and ratio of two or more. The content of the fluorophosphate (total amount when two or more types are used) can be 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and can be 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, based on 100% by mass of the non-aqueous electrolyte solution. If the fluorophosphate content is within this range, the characteristics of the non-aqueous electrolyte secondary battery, particularly the durability characteristics or continuous charging characteristics, can be significantly improved. Although the mechanism behind this is unclear, it is thought that mixing at this ratio minimizes side reactions of the additive on the electrode.

[0120] The mass ratio of the compound represented by the general formula (1) to the phosphate having a P=O bond and a PF bond (total amount when two or more types are used) is typically 1 / 100 or more, preferably 10 / 100 or more, more preferably 20 / 100 or more, and even more preferably 25 / 100 or more, and typically 10,000 / 100 or less, preferably 500 / 100 or less, more preferably 100 / 100, particularly preferably 80 / 100 or less, and most preferably 40 / 100 or less. This mass ratio range significantly improves the characteristics of nonaqueous electrolyte secondary batteries, particularly their durability and continuous charging characteristics. While the underlying mechanism is unclear, it is believed that mixing at this ratio minimizes side reactions of the additives on the electrode.

[0121] When LiPF6 is contained in a non-aqueous electrolyte, the mass ratio of the phosphate having a P=O bond and a PF bond (total amount if two or more types are present) to the LiPF6 content (fluorophosphate / LiPF6) is typically 0.00005 or more, preferably 0.001 or more, more preferably 0.01 or more, even more preferably 0.02 or more, and particularly preferably 0.025 or more, and typically 1.0 or less, preferably 0.5 or less, more preferably 0.4 or less, and even more preferably 0.35 or less. This mass ratio range significantly improves the characteristics of non-aqueous electrolyte secondary batteries, particularly their durability and continuous charge characteristics. While the underlying mechanism is unclear, it is believed that mixing at this ratio minimizes the decomposition side reaction of LiPF6 in non-aqueous electrolyte secondary batteries. The content of phosphates with P=O and PF bonds is measured by nuclear magnetic resonance (NMR) analysis. NMR analysis is usually performed, but when the solvent peaks make it difficult to identify other compounds, ion chromatography (IC) analysis is also performed.

[0122] (Salt with FSO2 skeleton) The salt having an FSO2 skeleton used in this embodiment is not particularly limited as long as it is a salt having an FSO2 skeleton in the molecule. Counter cations of salts having an FSO2 skeleton include alkali metals such as lithium, sodium, and potassium, with lithium being preferred. For example, fluorosulfonates such as FSO3Li, FSO3Na, FSO3K, FSO3(CH3)4N, FSO3(C2H5)4N, and FSO3(n-C4H9)4N; Fluorosulfonylimide salts such as LiN(FSO2)2, LiN(FSO2)(CF3SO2), etc.; Fluorosulfonylmethide salts such as LiC(FSO2)3; etc. In particular, fluorosulfonates are preferred, and lithium fluorosulfonate is more preferred, from the viewpoint of further enhancing the effects of improving charge / discharge rate characteristics and impedance characteristics in addition to the effect of suppressing gas generation during high-temperature storage.

[0123] The salt having an FSO2 skeleton may be used singly or in any combination and ratio of two or more. The content of the salt having an FSO2 skeleton (total amount when two or more types are used) can be 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and can be 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, based on 100% by mass of the nonaqueous electrolyte. If the content of the salt having an FSO2 skeleton is within this range, the characteristics of the nonaqueous electrolyte secondary battery, particularly its durability and continuous charging characteristics, can be significantly improved. Although the mechanism behind this is unclear, it is thought that mixing at this ratio minimizes side reactions of the additive on the electrode.

[0124] The mass ratio of the compound represented by general formula (1) to the salt having an FSO2 skeleton (total amount when two or more types are used) is typically 1 / 100 or more, preferably 10 / 100 or more, more preferably 20 / 100 or more, and even more preferably 25 / 100 or more, and typically 10,000 / 100 or less, preferably 500 / 100 or less, more preferably 100 / 100, particularly preferably 80 / 100 or less, and most preferably 40 / 100 or less. This mass ratio range significantly improves the characteristics of nonaqueous electrolyte secondary batteries, particularly their durability and continuous charge characteristics. While the underlying mechanism is unclear, it is believed that mixing at this ratio minimizes side reactions of the additives on the electrode.

[0125] When LiPF6 is contained in a non-aqueous electrolyte, the mass ratio of the salt having an FSO2 skeleton (total amount when two or more types are used) to the content of LiPF6 (salt having an FSO2 skeleton / LiPF6) is typically 0.00005 or more, preferably 0.001 or more, more preferably 0.01 or more, even more preferably 0.02 or more, and particularly preferably 0.025 or more, and typically 1.0 or less, preferably 0.5 or less, more preferably 0.4 or less, and even more preferably 0.35 or less. This mass ratio range significantly improves the characteristics of non-aqueous electrolyte secondary batteries, particularly their durability and continuous charge characteristics. While the underlying mechanism is unclear, it is believed that mixing at this ratio minimizes the decomposition side reaction of LiPF6 in non-aqueous electrolyte secondary batteries. The content of salts with an FSO2 skeleton is measured by nuclear magnetic resonance (NMR) analysis. NMR analysis is usually performed, but when the solvent peak makes it difficult to identify other compounds, ion chromatography (IC) analysis is also performed.

[0126] (oxalate) The oxalate is not particularly limited as long as it is a compound having at least one oxalic acid skeleton in the molecule. Counter cations of the oxalate include alkali metals such as lithium, sodium, and potassium, with lithium being preferred. For example, oxalatoborate salts such as lithium bis(oxalato)borate and lithium difluorooxalatoborate; oxalate phosphate salts such as lithium tetrafluorooxalate phosphate, lithium difluorobis(oxalate)phosphate, and lithium tris(oxalate)phosphate; etc. In particular, from the viewpoint of further enhancing the effects of suppressing gas generation during high-temperature storage as well as improving charge / discharge rate characteristics and impedance characteristics, oxalatoborate salts are preferred, and lithium bis(oxalato)borate is more preferred.

[0127] One type of oxalate may be used alone, or two or more types may be used in any combination and ratio. The content of the oxalate (total amount when two or more types are used) can be 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and can be 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, based on 100% by mass of the non-aqueous electrolyte solution. If the content of the oxalate is within this range, the characteristics of the non-aqueous electrolyte secondary battery, particularly the durability characteristics or continuous charging characteristics, can be significantly improved. Although the mechanism behind this is unclear, it is thought that by mixing at this ratio, side reactions of the additive on the electrode can be minimized.

[0128] The mass ratio of the compound represented by the general formula (1) to the oxalate (total amount when two or more types are present) is typically 1 / 100 or more, preferably 10 / 100 or more, more preferably 20 / 100 or more, and even more preferably 25 / 100 or more, and typically 10,000 / 100 or less, preferably 500 / 100 or less, more preferably 100 / 100, particularly preferably 80 / 100 or less, and most preferably 40 / 100 or less. This mass ratio range significantly improves the characteristics of non-aqueous electrolyte secondary batteries, particularly their durability and continuous charging characteristics. While the underlying mechanism is unclear, it is believed that mixing at this ratio minimizes side reactions of the additives on the electrode.

[0129] When LiPF6 is present in a non-aqueous electrolyte, the mass ratio of the oxalate (total amount in the case of two or more kinds) to the content of LiPF6 (oxalate / LiPF6) is usually 0.00005 or more, preferably 0.001 or more, more preferably 0.01 or more, still more preferably 0.02 or more, particularly preferably 0.025 or more, and usually 1.0 or less, preferably 0.5 or less, more preferably 0.4 or less, still more preferably 0.35 or less. If the mass ratio is within this range, the characteristics of the non-aqueous electrolyte secondary battery, particularly the durability characteristics or continuous charging characteristics, can be significantly improved. Although the principle is not clear, it is considered that by mixing at this ratio, the decomposition side reaction of LiPF6 in the non-aqueous electrolyte secondary battery is minimized.

[0130] The content of the oxalate is determined by nuclear magnetic resonance (NMR) analysis. Usually, NMR analysis is performed. However, when it is difficult to assign other compounds due to the peak of the solvent, ion chromatography (IC) analysis is also performed. Among the additives, some can be listed as salts as electrolytes. In that case, it is discriminated by the concentration range. For example, when a certain fluorinated inorganic salt is contained at 10% by mass in the non-aqueous electrolyte, it is discriminated as an electrolyte, and when a certain salt having an oxalic acid skeleton is contained at 0.5% by mass, it can be discriminated as an additive.

[0131] The total content of the auxiliary agents is usually 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and also usually 10% by mass or less, preferably 8% by mass or less, more preferably 5% by mass or less in 100% by mass of the non-aqueous electrolyte (with respect to the total amount of the non-aqueous electrolyte). When two or more kinds of auxiliary agents are used in combination, it is preferable that the total content satisfies the above range.

[0132] <A2. Non-aqueous electrolyte battery> The non-aqueous electrolyte battery according to an embodiment of the present invention is a non-aqueous electrolyte battery including a positive electrode, a negative electrode, and a non-aqueous electrolyte, and includes the non-aqueous electrolyte according to the above-described embodiment. More specifically, a positive electrode having a current collector and a positive electrode active material layer on at least a part of the surface of the current collector and capable of occluding and releasing metal ions, a negative electrode having a current collector and a negative electrode active material layer on at least a part of the surface of the current collector and capable of occluding and releasing metal ions, and the non-aqueous electrolyte includes a non-aqueous electrolyte containing a compound represented by the above general formula (1) together with an alkali metal salt and a non-aqueous solvent.

[0133] <A2-1. Battery Configuration> For the non-aqueous electrolyte battery of this embodiment, with respect to the configuration other than the above non-aqueous electrolyte, it is the same as a conventionally known non-aqueous electrolyte battery. Usually, the positive electrode and the negative electrode are laminated through a porous membrane (separator) impregnated with the above non-aqueous electrolyte, and they are in a form housed in a case (outer package). The shape of the non-aqueous electrolyte battery of this embodiment is not particularly limited, and it may be any of a cylindrical shape, a rectangular shape, a laminate shape, a coin shape, a large size, etc.

[0134] <A2-2. Non-aqueous Electrolyte> As the non-aqueous electrolyte, the non-aqueous electrolyte according to the above-described embodiment is used. In addition, within a range not departing from the gist of the present invention, it is also possible to blend and use other non-aqueous electrolytes with the above non-aqueous electrolyte.

[0135] <A2-3. Positive Electrode> The positive electrode refers to one having a current collector and a positive electrode active material layer on at least a part of the surface of the current collector. Other configurations can adopt conventionally known ones. The lithium transition metal-based compound is a compound having a structure capable of desorbing and inserting lithium ions, and examples thereof include sulfides, phosphate compounds, silicate compounds, borate compounds, lithium transition metal composite oxides, etc. Among them, phosphate compounds or lithium transition metal composite oxides are preferred, and lithium transition metal composite oxides are more preferred. Examples of lithium transition metal composite oxides include those having a spinel structure that allows three-dimensional diffusion and those having a layered structure that allows two-dimensional diffusion of lithium ions. A lithium transition metal compound having a spinel structure is generally represented by the following composition formula (11). Li x’ M'2O4···(11) (In formula (11), x' is 1≦x'≦1.5, and M' represents at least one transition metal element.) Specifically, LiMn2O4, LiCoMnO4, LiNi 0.5 Mn 1.5 Examples include O4 and LiCoVO4. The lithium transition metal compound having a layered structure is generally represented by the following composition formula (12). Li 1+x MO2···(12) (In formula (12), x is −0.1≦x≦0.5, and M represents at least one transition metal element.) Specifically, LiCoO2, LiNiO2, LiNi 0.85 Co 0.10 Al 0.05 O2, LiNi 0.80 Co 0.15 Al 0.05 O2, LiNi 0.33 Co 0.33 Mn 0.33 O2, Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O2, LiNi 0.5 Co 0.2 Mn 0.3 O2, Li 1.05 Ni 0.5 Co 0.2 Mn 0.3 O2, LiNi 0.6 Co 0.2 Mn 0.2 O2, LiNi 0.8 Co 0.1 Mn 0.1 Examples include O2.

[0136] Among these, from the viewpoint of improving the battery capacity, a lithium transition metal composite oxide having a layered structure is preferred, and a lithium transition metal composite oxide represented by the following composition formula (13) is more preferred. Li a1 Ni b1 M c1 O2···(13) (In formula (13), a1, b1, and c1 are numerical values ​​that satisfy 0.90≦a1≦1.10, 0.40≦b1≦0.98, and 0.00≦c1≦0.50, respectively, and b1+c1=1 is satisfied. M represents at least one element selected from the group consisting of Co, Mn, Al, Mg, Zr, Fe, Ti, and Er.) In the composition formula (13), b1 is preferably 0.55 or more, more preferably 0.60 or more, even more preferably 0.65 or more, particularly preferably 0.70 or more, more preferably 0.75 or more, more preferably 0.80 or more, and even more preferably 0.90 or more. Also, c1 is preferably 0.01 or more.

[0137] The positive electrode active material is not particularly limited as long as it is a lithium cobalt oxide or a transition metal oxide containing at least Ni and Co, with 50 mol % or more of the transition metals being Ni and Co, and capable of electrochemically absorbing and desorbing metal ions, but for example, a material capable of electrochemically absorbing and desorbing lithium ions is preferred, and a transition metal oxide containing lithium, at least Ni, and Co, with 60 mol % or more of the transition metals being Ni and Co is preferred. This is because Ni and Co have oxidation-reduction potentials suitable for use as positive electrode materials in secondary batteries and are suitable for high-capacity applications.

[0138] Among these, a preferred embodiment is a transition metal oxide represented by the following composition formula (14). Li a2 Ni b2 Co c2 M2 d2 O2···(14) In the above compositional formula (14), a2, b2, c2, and d2 represent numerical values where 0.90 ≤ a2 ≤ 1.10, 0.50 ≤ b2 ≤ 0.98, 0.01 ≤ c2 < 0.50, 0.01 ≤ d2 < 0.50, and b2 + c2 + d2 = 1. M2 represents at least one element selected from the group consisting of Mn, Al, Mg, Zr, Fe, Ti, and Er. In the compositional formula ( 14 ), it is preferable that the numerical value of 0.1 ≤ d2 < 0.5 is shown. By setting the composition ratios of Ni and Co and the composition ratios of other metal species within the above ranges, transition metals are less likely to elute from the positive electrode, and even if they elute, Ni and Co have the advantage of having little adverse effect in the non-aqueous secondary battery. As a preferred specific example, for example, 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 Co 0.2 Mn 0.2 O2, LiNi 0.8 Co 0.1 Mn 0.1 O2, etc. can be mentioned.

[0139] <A2-4. Negative Electrode> The negative electrode refers to a current collector and a negative electrode active material on at least a part of the surface of the current collector. layer Other configurations can adopt those known in the art.

[0140] 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. Materials containing metal elements and / or metalloid elements that can be alloyed with Li are preferred because they provide a high capacity per weight and volume of the active material and an increased energy density of the battery. These materials may be used alone or in any combination of two or more. In terms of good cycle characteristics, safety, and excellent continuous charge characteristics, it is preferred to use carbon-based materials, materials containing metal elements and / or metalloid elements that can be alloyed with Li, or mixtures of materials containing metal elements and / or metalloid elements that can be alloyed with Li and carbon-based materials.

[0141] 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.

[0142] Examples of natural graphite include scaly graphite, scaly graphite, and / or graphite particles obtained by treating such graphite as a raw material with treatments such as spheroidization and densification. Among these, spherical or ellipsoidal graphite particles that have been subjected to a spheroidization treatment are particularly preferred from the viewpoints of particle packing properties and charge / discharge rate characteristics. The average particle size (d50) of the graphite particles is usually 1 μm or more and usually 100 μm or less.

[0143] 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, the material containing a metal element and / or a metalloid element that can be alloyed with Li is preferably a metal selected from the group consisting of Sb, Si, Sn, Al, As, and Zn, or a compound thereof. Furthermore, an alloy consisting of two or more metals may be used, and the material containing a metal element and / or a metalloid element that can be alloyed with Li may be an alloy material formed from two or more metal elements. Examples of metal compounds include metal oxides, metal nitrides, metal carbides, etc. Among these, metal Si (hereinafter sometimes referred to as Si) or Si-containing compounds (particularly Si oxides) are preferred in terms of increasing capacity.

[0144] 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 x O y (Z=C, N), etc. 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 can absorb lithium ions and the like. This is preferable in that alkali ions can easily enter and exit the material, and a high capacity can be obtained. This general formula SiO x is obtained from silicon dioxide (SiO2) and Si as raw materials, and the value of x is usually 0 <x<2である。 As the material containing a metal element and / or a metalloid element that can be alloyed with Li, metal particles that can be alloyed with Li are preferred in terms of increasing the electrode density. The average particle size (d50) of metal particles that can be alloyed with Li is usually 0.01 μm or more and usually 10 μm or less from the viewpoint of cycle life. The mixture of a material containing a metal element and / or a metalloid element that can be alloyed with Li and a carbon-based material used as the negative electrode active material may be a mixture in which the material containing a metal element and / or a metalloid element that can be alloyed with Li and the carbon-based material are mixed independently of each other, or a mixture in which the material containing a metal element and / or a metalloid element that can be alloyed with Li and the carbon-based material are mixed independently of each other. carbon-based materials The complex may be present on the surface or inside of the substrate. The content ratio of the material containing a metal element and / or a metalloid element capable of alloying with Li to the total of the material and the graphite particles is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more. Also, it is usually 99% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, particularly preferably 25% by mass or less. Being within this range is preferable in that side reactions on the Si surface can be controlled and swelling of the negative electrode can be suitably controlled in a non-aqueous electrolyte battery. The content ratio of the metal particles capable of alloying with Li to the total of the metal particles capable of alloying 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, still more preferably 2.0% by mass or more. Also, it is usually 99% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, still 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, most preferably 10% by mass or less. Being within this range is preferable in that side reactions on the Si surface can be controlled and sufficient capacity can be obtained in a non-aqueous electrolyte battery.

[0145] <A2-5. Separator> A separator is usually interposed between the positive electrode and the negative electrode to prevent short circuit. In this case, the non-aqueous electrolyte according to the present embodiment is usually used by impregnating this separator. A conventionally known separator can be used.

[0146] <B. Second Embodiment> Another embodiment of the present invention is a non-aqueous electrolyte battery, and the non-aqueous electrolyte according to the non-aqueous electrolyte battery contains a compound represented by the following general formula (4). By using a non-aqueous electrolyte containing the compound represented by the general formula (4), the non-aqueous Solution Although the mechanism for enhancing the suppression of gas generation amount during high-temperature storage of the electrolyte battery is not clear, it is presumed as follows.

[0147] <B1. Non-aqueous electrolyte> The compound represented by the general formula (4) has a divalent or trivalent atomic group having at least one atom selected from an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a boron atom in the molecule. Since this atomic group is a polar group, the compound represented by the formula (4) interacts with carbon or the like on the surface of the negative electrode active material and tends to localize near the surface of the negative electrode active material. Further, the compound represented by the general formula (4) has a structure in which two or more fluorine (F) atoms are bonded to a silicon (Si) atom in the molecule. When two or more F atoms are bonded to the Si atom, the electron density of the Si atom is significantly lower than in the case of one F atom. As a result, the reaction activity of the Si atom of the compound represented by the general formula (4) increases, and thus, for example, an electrochemical reduction or a reaction with a reduction decomposition product of the electrolytic solution easily proceeds. Thereby, an insulating film is formed on the negative electrode active material, and for example, when Si is used for the negative electrode active material, the surface is suitably modified. Further, it is presumed that the compound represented by the general formula (4) is also concentrated on the positive electrode surface, reacts with an electrochemical oxidation or an oxidation decomposition product of the electrolytic solution, and forms an insulating film similarly to the negative electrode. Furthermore, by combining a non-aqueous electrolyte containing the compound represented by the general formula (4) with a negative electrode including a negative electrode active material containing a metal element and / or a metalloid element capable of alloying with Li, a non-aqueous electrolyte battery in which a film of the compound represented by the general formula (4) is formed on the surface of the material containing the metal element and / or the metalloid element capable of alloying with Li and swelling is suppressed can be obtained. From the above, the inventor of the present invention believes that the compound represented by the general formula (4) contributes to the suppression of the amount of gas generated during high-temperature storage.

[0148] <B1-1-1. Compound represented by general formula (4)> The non-aqueous electrolyte according to the present embodiment is characterized by containing a compound represented by the following general formula (4).

[0149] [Chemical formula] [[ID=②]]

[0150] In the general formula (4), R 3 represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may have a substituent; R 4 represents a hydrogen atom, an optionally substituted monovalent hydrocarbon group, or an optionally substituted alkoxy group; X 2 represents a divalent hydrocarbon group which may have a substituent. 2 represents an integer from 1 to 3. 2 represents an integer between 0 and 2, and q 2 represents an integer from 1 to 3, and p 2 +q 2 = 2 or 3. R 3 and X 2 Two of the groups may be bonded to each other to form a ring. 2 is a divalent or trivalent atomic group represented by general formula (5-1) described later, or a trivalent atomic group represented by general formula (6-1) described later.

[0151] (R 3 ) R according to general formula (4) 3 represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have a substituent. A monovalent hydrocarbon group having 1 to 12 carbon atoms, which may have a substituent, is preferred in terms of ease of industrial handling of the compound represented by general formula (4) during production of the compound, storage of the compound, and production of an electrolyte solution. When the hydrocarbon group has a substituent, the number of carbon atoms contained in the substituent is not included in the carbon number. In addition, from the viewpoint of suitably forming the insulating coating, R 3 is also preferably a halogen atom. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. Specific examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group. Among these, from the viewpoint of suppressing side reactions on the electrode of the compound represented by general formula (4), an alkyl group, an alkenyl group, or an alkynyl group is preferred, an alkyl group or an alkenyl group is more preferred, and an alkyl group is particularly preferred. Examples of the alkyl group include a linear alkyl group, a branched alkyl group, and an alkyl group having a cyclic structure, etc. Among these, a linear alkyl group is preferred from the viewpoint of favorable formation of the insulating coating. Specific examples of the linear alkyl group include linear alkyl groups having 1 to 12 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl groups. Of these, linear alkyl groups having 1 to 6 carbon atoms are preferred, and linear alkyl groups having 1 to 4 carbon atoms are particularly preferred. Specific examples of the branched alkyl group include branched alkyl groups having 1 to 12 carbon atoms, such as a methylethyl group, a methylpropyl group, a methylbutyl group, a methylpentyl group, a methylhexyl group, a methylheptyl group, a methyloctyl group, a methylnonyl group, a methyldecyl group, a methylundecyl group; a dimethylethyl group (tert-butyl group), a dimethylpropyl group, a dimethylbutyl group, a dimethylpentyl group, a dimethylhexyl group, a dimethylheptyl group, a dimethyloctyl group; a trimethylhexyl group, a trimethylheptyl group; an ethylpentyl group, an ethylhexyl group, an ethylheptyl group, an ethyloctyl group; a propylhexyl group, a propylheptyl group; and a butylhexyl group. Among these, branched alkyl groups having 1 to 6 carbon atoms, such as a methylethyl group, a methylpropyl group, a methylbutyl group, a methylpentyl group, a dimethylethyl group (tert-butyl group), a dimethylpropyl group, or a dimethylbutyl group, are preferred, and branched alkyl groups having 1 to 4 carbon atoms, such as a methylethyl group, a methylpropyl group, or a dimethylethyl group (tert-butyl group), are particularly preferred. In the examples of the branched alkyl groups, the branching position may be any position.

[0152] Specific examples of the alkyl group having a cyclic structure include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclohexylmethyl group, a cyclohexylethyl group, a methyl Examples of the alkyl group include alkyl groups having a cyclic structure having 3 to 12 carbon atoms, such as an ethylcyclohexyl group, a dimethylcyclohexyl group, an ethylcyclohexyl group, and a methylcyclohexylmethyl group. Among these, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, S Preferred are alkyl groups having a cyclic structure of 3 to 8 carbon atoms, such as cyclohexylmethyl, cyclohexylethyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, and methylcyclohexylmethyl groups, and particularly preferred are alkyl groups having a cyclic structure of 6 to 8 carbon atoms, such as cyclohexyl, cyclohexylmethyl, cyclohexylethyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, and methylcyclohexylmethyl groups.

[0153] Among the above, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, or an n-hexyl group is preferred, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or a tert-butyl group is more preferred, and a methyl group or an ethyl group is particularly preferred. When the alkyl group is one of the above, a group represented by the general formula ( 4 ) is preferred because it tends to be localized.

[0154] Specific examples of the alkenyl group include alkenyl groups having 2 to 12 carbon atoms, such as vinyl, allyl, isopropenyl, methallyl, 2-butenyl, 3-methyl-2-butenyl, 3-butenyl, and 4-pentenyl. Of these, preferred are alkenyl groups having 2 to 6 carbon atoms, such as vinyl, allyl, methallyl, and 2-butenyl, more preferred are alkenyl groups having 2 to 4 carbon atoms, such as vinyl, allyl, and methallyl, and particularly preferred are vinyl or allyl. The above-mentioned alkenyl groups can be applied to the surface of the positive electrode active material and / or negative electrode active material, whereby a compound represented by the general formula ( 4 ) is preferred because it can form an insulating coating film suitably.

[0155] Specific examples of the alkynyl group include alkynyl groups having 1 to 12 carbon atoms, such as ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, 4-pentynyl, and 5-hexynyl. Among these, preferred are alkynyl groups having 1 to 6 carbon atoms, such as ethynyl, 2-propynyl, 2-butynyl, and 3-butynyl, more preferred are alkynyl groups having 2 to 4 carbon atoms, such as 2-propynyl and 3-butynyl, and particularly preferred is 2-propynyl. The above-mentioned alkynyl groups are preferred because the compound represented by general formula (4) can suitably form an insulating coating on the surface of the positive electrode active material and / or negative electrode active material.

[0156] Specific examples of the aryl group include aryl groups having 6 to 12 carbon atoms, such as a phenyl group, a tolyl group, or a mesityl group. Among these, a group represented by the general formula ( 4 ) tends to be localized, an aryl group having 6 to 7 carbon atoms such as a phenyl group or a tolyl group is preferred, and a phenyl group is particularly preferred.

[0157] Examples of the aralkyl group include aralkyl groups having 7 to 12 carbon atoms, such as a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, or a phenylisopropyl group. Among these, from the viewpoint of the tendency of the compound represented by general formula (4) to be localized near the surface of the positive electrode active material and / or the negative electrode active material, aralkyl groups having 7 to 8 carbon atoms, such as a benzyl group or a phenethyl group, are preferred, and a benzyl group is particularly preferred.

[0158] Examples of the substituent that the hydrocarbon group may have include a cyano group, an isocyanato group, a halogen atom, or a group containing a halogen atom. Among these, an isocyanato group, a halogen atom, or a group containing a halogen atom is preferred, and a halogen atom or a group containing a halogen atom is particularly preferred. Specific and preferred examples of the halogen atom are described in R 1 This is the same as that specified in

[0159] Specific examples of the group containing a halogen atom include a fluoromethyl group, a chloromethyl group, a bromomethyl group, an iodomethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3-tetrafluoropropyl group, a 2-fluorophenyl group, etc. Among these, from the viewpoint of suppressing electrochemical side reactions, a fluoromethyl group, a trifluoromethyl group, and a 2,2,2-trifluoroethyl group are preferred, and a trifluoromethyl group is particularly preferred.

[0160] (R 4 ) General formula ( 4 ) related to R 4 represents a hydrogen atom, a monovalent hydrocarbon group which may have a substituent, or an alkoxy group which may have a substituent. Among these, the general formula ( 4 ) is preferably a monovalent hydrocarbon group which may have a substituent or an alkoxy group which may have a substituent, and particularly preferably a monovalent hydrocarbon group which may have a substituent, from the viewpoint of minimizing side reactions on the active material of the compound represented by the formula (I). Here, the hydrocarbon group is R 3 The hydrocarbon groups are defined in the same manner as those defined above, and preferred hydrocarbon groups are also defined in the same manner.

[0161] Specific examples of the alkoxy group include alkoxy groups having 1 to 12 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, an octyloxy group, a decyloxy group, or a dodecyloxy group. Among these, alkoxy groups having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group, are preferred, and examples of the alkoxy group represented by the general formula ( 4 A methoxy group or an ethoxy group is particularly preferred in that the compound represented by the formula (1) has little steric hindrance and is suitably concentrated on the surface of the active material.

[0162] The substituents that the alkoxy group may have are R 3 The substituents are defined in the same manner as the substituents that the hydrocarbon group defined in the above may have.

[0163] (X 2 ) General formula ( 4 ) related to X 2 represents a divalent hydrocarbon group which may have a substituent. The number of carbon atoms in the divalent hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. By having the above number of carbon atoms, it is possible to attach a group represented by the general formula ( 4 ) is preferred because it tends to be localized. When the hydrocarbon group has a substituent, the carbon atoms contained in the substituent are not included in this carbon number.

[0164] Specific examples of the divalent hydrocarbon group include an alkylene group and an alkenylene group. Among these, an alkylene group is preferred. Examples of the substituent that the divalent hydrocarbon group may have include R 3 The substituents are defined in the same manner as the substituents that the hydrocarbon group defined in the above may have.

[0165] Specific examples of the alkylene group include a linear alkylene group, a branched alkylene group, and an alkylene group having a cyclic structure.

[0166] Specific examples of the linear alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, and a decylene group.

[0167] Specific examples of branched alkylene groups include methylethylene, methylpropylene, methylbutylene, methylpentylene, methylhexylene, methylheptylene, methyloctylene, methylnonylene; dimethylethylene, dimethylpropylene, dimethylbutylene, dimethylpentylene, dimethylhexylene, dimethylheptylene, dimethyloctylene; trimethylhexylene, trimethylheptylene; ethylpentylene, ethylhexylene, ethylheptylene, ethyloctylene; propylhexylene, propylheptylene; and butylhexylene. In the examples of branched alkyl groups, the branching position is optional.

[0168] Specific examples of alkylene groups having a cyclic structure include cyclohexylene groups.

[0169] Among the above, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, methylethylene group, methylpropylene group, methylbutylene group, methylpentylene group, and cyclohexylene group are preferred, and methylene group, ethylene group, propylene group, butylene group, methylethylene group, and methylpropylene group are more preferred. The above alkylene groups are preferred because the compound represented by general formula (4) tends to be localized near the surface of the positive electrode active material and / or negative electrode active material.

[0170] (A 2 ) A according to general formula (4) 2 is represented by the following general formula (5-1) or the general formula ( 6-1) represents a divalent or trivalent atomic group.

[0171] [ka]

[0172] Z 3 is a carbon atom, a sulfur atom, a phosphorus atom, or a boron atom; Y 102 is an oxygen atom or a sulfur atom; Y 10 , Y 11 and Y 12 are each independently a single bond, an oxygen atom, a sulfur atom, or N R 102 (-N R 102 - group); R 102 is a hydrogen atom or a monovalent hydrocarbon group; R 102 When is a monovalent hydrocarbon group, R 102 is represented by the general formula ( 4) R in 3 and X 2 may be bonded to any one of the following to form a ring. r 5 is Z 3 is a carbon atom, it is 1, and Z 3 is 0, 1, or 2 when is a sulfur atom, and Z 3 is 0 or 1 when is a phosphorus atom, and Z 3 is 0 when it is a boron atom. r 6 is Z 3 is 0 when it is a carbon atom or sulfur atom, and Z 3 is 1 when is a phosphorus atom or a boron atom. * represents R in the above general formula (4). 3 or X 2 represents the binding site with However, Z 3 is a sulfur atom and r 5 When is 2, Y 10 and Y 11 cannot both be single bonds.

[0173] (R 104 ) The above R 104 The monovalent hydrocarbon group in 1 is synonymous with the monovalent hydrocarbon group defined by

[0174] General formula ( 5-1 ) includes, for example, an oxygen atom; a sulfur atom; a divalent atomic group consisting of an oxygen atom, a carbon atom and an oxygen atom, or a hydrogen atom, a carbon atom and an oxygen atom; or a divalent atomic group consisting of a sulfur atom, an oxygen atom and a sulfur atom, a carbon atom, an oxygen atom and a sulfur atom, or a hydrogen atom, a carbon atom, an oxygen atom and a sulfur atom, or a hydrogen atom, a carbon atom, an oxygen atom and a sulfur atom.

[0175] Specific examples of the divalent atomic group consisting of an oxygen atom, a carbon atom and an oxygen atom, or a hydrogen atom, a carbon atom and an oxygen atom include divalent atomic groups having a ketone structure, a carboxylic acid ester structure, or a carbonate structure, and specific examples thereof include Z 3 is a carbon atom; Y 102 is an oxygen atom; Y 10 , Y 11 , and Y 12 are independently a single bond or an oxygen atom. Specific examples of the divalent group having a ketone structure include a -CO- group. Specific examples of the divalent group having a carboxylic acid ester structure include a -COO- group. Specific examples of the divalent group having a carbonate structure include an -OCOO- group. Among these, the —COO— group and —OCOO— group are particularly preferred from the viewpoint of causing few electrochemical side reactions and suitably forming a coating on the surface of the active material.

[0176] Specific examples of the divalent atomic group consisting of a sulfur atom, an oxygen atom and a sulfur atom, a carbon atom, an oxygen atom and a sulfur atom, or a hydrogen atom, a carbon atom, an oxygen atom and a sulfur atom include divalent groups having a sulfide structure, a sulfone structure, a sulfonate ester structure, a sulfate ester structure, a sulfoxide structure, a sulfite ester structure, a sulfinate ester structure, a thiocarbonyl structure, and a thioester structure. Specific examples include, for example, Z 3 is a carbon atom; Y 102 is an oxygen atom; Y 10 , Y 11 , and Y 12 is a sulfur atom, Z 3 is a carbon atom; Y 102 is a sulfur atom; Y 10 , Y 11 , and Y 12 are independently a single bond, an oxygen atom, or a sulfur atom, or Z 3 is a sulfur atom; Y 102 is an oxygen atom or a sulfur atom; or Y 10 , Y 11 , and Y 12 are independently a single bond, an oxygen atom, or sulfur atom Examples of such groups include atomic groups in which Specific examples of the divalent group having a sulfide structure include an -S- group. Specific examples of divalent groups having a sulfonate structure include -SO3- groups. Specific examples of divalent groups having a sulfate ester structure include -OSO3- groups. Specific examples of divalent groups having a sulfoxide structure include -SO- groups. Specific examples of divalent groups having a sulfite ester structure include an -OSO- group. Specific examples of the divalent group having a sulfinate structure include an -SOO- group. Examples of the divalent group having a thiocarbonyl structure include an -OCSO- group and an -CSO- group. Specific examples of the divalent group having a thioester structure include a -COS- group, a -OCOS- group, a -SCOS- group, etc. The divalent group may also be a dithiocarboxylic acid ester structure such as a -CSS- group, a -OCSS- group, or a -SCSS- group. Among these, from the viewpoint of reducing electrochemical side reactions and suitably forming a coating on the surface of the active material, a -SO3- group, or a -OSO3- group, or a -OSOO- group, or a -SOO- group is preferred, a -SO3- group or a -OSO3- group is more preferred, and a -SO3- group is particularly preferred.

[0177] Specific examples of the trivalent atomic group having at least one atom selected from oxygen, nitrogen, sulfur, phosphorus, and boron atoms include a nitrogen atom; a phosphorus atom; a boron atom; a trivalent atomic group consisting of carbon, nitrogen, and oxygen atoms, or a hydrogen atom, carbon, nitrogen, and oxygen atoms; a trivalent atomic group consisting of carbon, nitrogen, and sulfur atoms, nitrogen, oxygen, and sulfur atoms, hydrogen atoms, carbon, nitrogen, and sulfur atoms, or a trivalent atomic group consisting of carbon, nitrogen, oxygen, and sulfur atoms; a phosphorus atom, oxygen, and phosphorus atoms, or a trivalent atomic group consisting of hydrogen, nitrogen, oxygen, and phosphorus atoms; or a boron atom, or a trivalent atomic group consisting of boron and oxygen atoms; and specific examples thereof include Z 3 is a carbon atom; Y 102 is an oxygen atom; Y 10 , Y 11 , and Y 12 independently NR 104 Examples of such groups include atomic groups in which The trivalent atomic group consisting of carbon, nitrogen and oxygen atoms, or hydrogen, carbon, nitrogen and oxygen atoms, includes a trivalent group having an amide structure, a urethane structure or a urea structure. Specific examples of these include the atomic groups shown below.

[0178] [ka]

[0179] Examples of the trivalent atomic group consisting of carbon atoms, nitrogen atoms and sulfur atoms, nitrogen atoms, oxygen atoms and sulfur atoms, hydrogen atoms, carbon atoms, nitrogen atoms and sulfur atoms, or carbon atoms, nitrogen atoms, oxygen atoms and sulfur atoms include trivalent groups having a thiocarbonyl structure, a thioester structure, or a sulfonamide structure. It may also be a trivalent group having a dithiocarboxylic acid ester structure. Specific examples of these include the atomic groups shown below, and specifically, for example, Z 3 is a carbon atom; Y 102 is a sulfur atom; Y 10 , Y 11 , and Y 12 independently NR 104 or Z 3 is a carbon atom; Y 102 is an oxygen atom; Y 10 , Y 11 , and Y 12 independently NR 104 Examples of such groups include atomic groups in which [ka]

[0180] Examples include a phosphorus atom, an oxygen atom and a phosphorus atom, or a trivalent atomic group consisting of a hydrogen atom, a nitrogen atom, an oxygen atom, or a phosphorus atom. Specific examples include Z 3 is a phosphorus atom, and more specifically, a trivalent group having a phosphine oxide structure, a phosphinate ester structure, a phosphonate ester structure, a phosphate ester structure, a phosphoric acid amide structure, a phosphine structure, a phosphinite ester structure, a phosphonite ester structure, or a phosphite ester structure, etc. Specific examples of these include the atomic groups shown below. [ka]

[0181] Among these, the following atomic groups are preferred from the viewpoint of causing fewer electrochemical side reactions and favorably forming a coating on the surface of the active material. [ka]

[0182] Among these, the following atomic groups are particularly preferred:

[0183] [ka]

[0184] Examples of the trivalent atomic group consisting of a boron atom or a boron atom and an oxygen atom include a trivalent group having a trialkylborane structure, a borinic acid ester structure, a boronate ester structure, and a borate ester structure. Specific examples of these include the following atomic groups. [ka]

[0185] Among these, the divalent or trivalent atomic group represented by formula (5-1) is preferably a divalent or trivalent atomic group represented by the following general formula (5-2), in terms of reducing electrochemical side reactions and favorably forming a coating on the surface of the active material.

[0186] [ka]

[0187] Z4 is a carbon atom, a sulfur atom, or a phosphorus atom; Y 16 , Y 17 and Y 18 are each independently a single bond or an oxygen atom. r 7 is Z 4 is a carbon atom, it is 1, and Z 4 is 0, 1, or 2 when is a sulfur atom, and Z 4 is 0 or 1 when it is a phosphorus atom. r 8 is Z 4 is 0 when is a carbon atom or a sulfur atom, and Z 4 is a phosphorus atom, it is 1. * represents R in the above general formula (4). 3 or X 2 represents the binding site with However, Z 4 is a sulfur atom and r 7 When is 2, Y 16 and Y 17 cannot both be single bonds. General formula ( 5-2 ) in Z 4 , Y 16 , Y 17 , Y 18 , r 7 , and r 8 is, to the extent applicable, the general formula ( 5-1 ) in Z 3 , Y 13 , Y 14 , Y 15 , r 5 , and r 6 The above conditions can be applied to each of the above.

[0188] The trivalent atomic group represented by the following general formula (6-1) will be explained below.

[0189] [ka]

[0190] Y 13 , Y 14 and Y 15 are each independently an oxygen atom, a sulfur atom, or NR 202 (=NR 202 R 202 is a hydrogen atom or a monovalent hydrocarbon group. * represents R in the above general formula (4). 3 or X 2 represents the binding site with

[0191] (R 202 ) The above R 202 The monovalent hydrocarbon group in R 1 is synonymous with the monovalent hydrocarbon group defined by

[0192] Among these, the atomic group represented by the following formula (6-2) is preferred from the viewpoint of causing few electrochemical side reactions and suitably forming a coating on the surface of the active material. [ka]

[0193] * represents R in the above general formula (4). 3 or X 2 The binding site is shown.

[0194] Among the atomic groups represented by the general formula (5-1) or (6-1), It is preferably a divalent group having a ketone structure, a divalent group having a carbonate structure, a divalent group having a carboxylic acid ester structure, a divalent group having a sulfonic acid ester structure, a divalent group having a sulfate ester structure, a divalent group having a sulfite ester structure, a divalent group having a sulfinic acid structure, a trivalent group having a phosphonic acid ester structure, a trivalent group having a phosphate ester structure, or a trivalent group having an isocyanurate structure, It is more preferable that the group is a divalent group having a carbonate structure, a divalent group having a carboxylic acid ester structure, a divalent group having a sulfonic acid ester structure, a divalent group having a sulfuric acid ester structure, a trivalent group having a phosphonic acid ester structure, a trivalent group having a phosphate ester structure, or a trivalent group having an isocyanurate structure, It is more preferable that the group is a divalent group having a carbonate structure, a divalent group having a carboxylic acid ester structure, a divalent group having a sulfonic acid ester structure, a trivalent group having a phosphonic acid ester structure, a trivalent group having a phosphate ester structure, or a trivalent group having an isocyanurate structure, A divalent group having a carbonate structure or a divalent group having a carboxylic acid ester structure is particularly preferred.

[0195] (n 2 ) n in the general formula (4) 2 represents an integer of 1 to 3. n 2 is preferably 2 or 3.

[0196] n 2 If is 2, R 3 is an alkyl group, R 4 is an alkyl group, and X 2 is an alkylene group and A 2 is a divalent group having a carbonate structure; R 3 is an alkyl group, R 4 is an alkyl group, and X 2 is an alkylene group and A 2 is a divalent group having an ester structure; R 3 is an alkyl group, R 4 is an alkyl group, and X 2 is an alkylene group and A 2 is a divalent group having a sulfone structure; or R 3 is an alkyl group, R 4 is an alkyl group, and X 2 is an alkylene group and A 2 is preferably a combination of trivalent groups having an isocyanurate structure.

[0197] n 2 If is 3, R 3 is an alkyl group, and X 2 is an alkylene group and A 2 is a divalent group having a carbonate structure; R 3 is an alkyl group, and X 2 is an alkylene group and A 2 is a divalent group having an ester structure; R 3 is an alkyl group, and X 2 is an alkylene group and A 2 is a divalent group having a sulfone structure; or R 3 is an alkyl group, and X 2 is an alkylene group and A 2 is preferably a combination of trivalent groups having an isocyanurate structure.

[0198] (p 2 , q 2 ) p according to general formula (4) 2 represents an integer of 0 to 2.

[0199] q relating to general formula (4) 2 represents an integer of 1 to 3, where p 2 +q 2 =2 or 3. From the viewpoint of reducing electrochemical side reactions and suitably forming a coating on the surface of the active material, A 2 When the structure is represented by formula (5-1) or formula (5-2), p 2 is 1 and q 2 is preferably 1 or 2, and p 2 is 1 and q 2 is more preferably 1. From the viewpoint of reducing electrochemical side reactions and suitably forming a coating on the surface of the active material, A 2 When the structure is represented by formula (6-1) or formula (6-2), p 2 =0 and q 2 It is preferable that =3.

[0200] R 3 and X 2 Two of these may be bonded to each other to form a ring. That is, in the embodiment of forming a ring, R 3 Comrades, as well as R 3 and X 2 In terms of ease of synthesis, R 3 and X 2 are bonded to form a ring. More preferred embodiments include the following structures:

[0201] [ka]

[0202] Specific examples of compounds represented by general formula (4) are shown below. Note that the compounds represented by general formula (4) according to this embodiment are not limited to the compounds represented by formulae (G3-1) to (G3-106), (G2-1) to (G2-148), and (G1-1) to (G1-148) shown below.

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[0239] [ka]

[0240] [ka]

[0241] Among these, from the viewpoint of ease of obtaining raw materials and ease of synthesis, A 2 is a divalent atomic group having a carbonate structure, a divalent atomic group having a carboxylic acid ester structure, a divalent atomic group having a sulfonic acid ester structure, a divalent atomic group having a phosphonic acid ester structure, a trivalent atomic group having a phosphate ester structure, or a trivalent atomic group having an isocyanurate structure, and R 3 is a hydrogen atom or an alkyl group, R 4 is an alkyl group, and X 2 is an alkylene group, and among these, compounds of the above formulae (G3-1), (G3-20), (G3-26), (G3-35) to (G3-37), (G3-43) to (G3-45), (G3-53) to (G3-63), (G3-67) to (G3-85), (G3-91) to (G3-99), (G3-101) to (G3-106), (G2-1), (G2-20), (G2-26), (G2-35) to (G2-37), (G2-43) to (G2-45), (G2-5 and the compound is preferably a compound selected from the group of compounds represented by (G1-3) to (G2-63), (G2-67) to (G2-85), (G2-91) to (G2-99), (G2-101) to (G2-148), (G1-1), (G1-20), (G1-26), (G1-35) to (G1-37), (G1-43) to (G1-45), (G1-53) to (G1-63), (G1-67) to (G1-85), (G1-91) to (G1-99), and (G1-101) to (G1-148), Also, A 2 is a divalent atomic group having a carbonate structure, a divalent atomic group having a carboxylic acid ester structure, a divalent atomic group having a sulfonic acid ester structure, a divalent atomic group having a phosphonic acid ester structure, a trivalent atomic group having a phosphate ester structure, or a trivalent atomic group having an isocyanurate structure, and R 3 is a methyl group or an ethyl group, R 4 is an alkyl group, and X 2 is an alkylene group, and among these, the compounds represented by the above formulae (G3-1), (G3-20), (G3-35) to (G3-37), (G3-44) to (G3-45), (G3-53) to (G3-63), (G3-91) to (G3-99), (G2-1), (G2-20), (G2-35) to (G2-37), (G2-44) to (G2-45) are more preferred. It is preferable that the compound is a compound selected from the group of compounds represented by (G2-45), (G2-53) to (G2-63), (G2-91) to (G2-100), (G1-1), (G1-20), (G1-35) to (G1-37), (G1-44) to (G1-45), (G1-53) to (G1-63), and (G1-91) to (G1-99), X 2 is a propylene group, and R 3 is more preferably a methyl group or an ethyl group, and among these, it is preferable that the compound is a compound selected from the group of compounds represented by (G3-1), (G3-20), (G3-35), (G3-44), (G3-45), (G3-55), (G3-56), (G3-94), (G2-1), (G2-20), (G2-35), (G2-44), (G2-45), (G2-55), (G2-56), (G2-94), (G2-100), (G1-1), (G1-20), (G1-35), (G1-44), (G1-45), (G1-55), (G1-56), and (G1-94), n 2 is 2 or 3, and A 2 is a divalent atomic group having a carbonate structure, a divalent atomic group having a carboxylic acid ester structure, a divalent atomic group having a phosphonic acid ester structure, a trivalent atomic group having a phosphoric acid ester structure, or a trivalent atomic group having an isocyanurate structure, and R 3 is a methyl group or an ethyl group, R 4 is an alkyl group having 1 to 6 carbon atoms, and X 2 is a propylene group, and among these, a compound selected from the group of compounds represented by (G3-1), (G3-20), (G3-44), (G3-45), (G3-55), (G3-56), (G3-94), (G2-1), (G2-20), (G2-44), (G2-45), (G2-55), (G2-56), and (G2-94) is preferred; Particularly preferred is a compound selected from the group of compounds represented by (G3-1), (G3-20), (G3-44), (G3-45), (G3-55), (G3-56), (G3-94), (G2-1), (G2-20), (G2-44), (G2-45), (G2-55), (G2-56), and (G2-94).

[0242] Also, A 2 is a divalent atomic group having a carbonate structure, and R 3 is an alkyl group, n 2 =2, R 4 is an alkyl group, and X 2 is an alkylene group; or R 3 is an alkyl group, n 2 is 3 and X 2 is an alkylene group; A 2 is a divalent group having a carboxylic acid ester structure, and R 3 is an alkyl group, n 2 =2, R 4 is an alkyl group, and X 2 is an alkylene group; A 2 is a divalent group having a sulfonate ester structure, and R 3 is an alkyl group, n 2 =2, R 4 is an alkyl group, and X 2 is an alkylene group; or R 3 is an alkyl group, n 2 is 3 and X 2 is an alkylene group; A 2 is a divalent group having a phosphonate ester structure, and R 3 is an alkyl group, n 2 =2, R 4 is an alkyl group, and X 2 is an alkylene group; or R 3 is an alkyl group, n 2 is 3 and X 2 is an alkylene group; A 2 is a trivalent group having a phosphate ester structure, and R 3 is an alkyl group, n 2 =2, R 4 is an alkyl group, and X 2 is an alkylene group; or R 1 is an alkyl group, n 2 is 3 and X 2 is an alkylene group; In this case, the following compounds are preferred:

[0243] [ka]

[0244] Also, A 2 is a divalent atomic group having a carbonate structure, and R 3 is an alkyl group, n 2 =2, R 4 is an alkyl group, and X 3 is an alkylene group; or R 3 is an alkyl group, n 2 is 3 and X 2 is an alkylene group; A 2 is a divalent group having a carboxylic acid ester structure, and R 3 is an alkyl group, n 2 =2, R 4 is an alkyl group, and X 2 is an alkylene group; A 2 is a divalent group having a phosphonate ester structure, and R 3 is an alkyl group, n 2 =2, R 4 is an alkyl group, and X 2 is an alkylene group; or R 3 is an alkyl group, n 2 is 3 and X 2 is an alkylene group; A 2 is a trivalent group having a phosphate ester structure, and R 3 is an alkyl group, n 2 =2, R 4 is an alkyl group, and X 2 is an alkylene group; or R 1 is an alkyl group, n 2 is 3 and X 2 is an alkylene group; in this embodiment, the following compound is preferable.

[0245] [ka]

[0246] Among the compounds represented by the above general formula (4), the compounds represented by the following formula are preferred from the viewpoint of achieving a balance between the resistance of the coating and the inhibition of gas generation due to the insulating properties.

[0247] [Chemical formula]

[0248] Among these, the compound represented by the following formula (4-a1) or (4-a2) is particularly preferable from the viewpoint of preferably forming the insulating film.

[0249] [Chemical formula]

[0250] (Content) The content of the compound represented by the general formula (4) with respect to the total amount of the non-aqueous electrolyte according to the present embodiment is usually 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and usually 10% by mass or less, preferably 5.0% by mass or less, more preferably 3.0% by mass or less, particularly preferably 2.0% by mass or less, and most preferably 1.0% by mass or less. If the content of the compound represented by the general formula (4) with respect to the total amount of the non-aqueous electrolyte is within the above range, the concentration of the compound represented by the general formula (4) in the active material proceeds preferably, and it becomes possible to produce a battery with less gas generation during high-temperature storage.

[0251] <B1-1-2. Negative electrode> The negative electrode refers to a current collector and a negative electrode active material on at least a part of the surface of the current collector. layer Other configurations can adopt those known in the art.

[0252] The negative electrode active material is not particularly limited as long as it is capable of electrochemically absorbing and releasing metal ions and contains a metal element and / or a metalloid element capable of alloying with Li. Specific examples include carbon-based materials, materials containing a metal element and / or a metalloid element capable of alloying with Li, lithium-containing metal composite oxide materials, and mixtures thereof. A material containing a metal element and / or a metalloid element capable of alloying with Li may be used alone, or a material containing a metal element and / or a metalloid element capable of alloying with Li may be used in any combination with a carbon-based material or a lithium-containing metal composite oxide material. In terms of excellent cycle characteristics, safety, and continuous charge characteristics, it is preferable to use a material containing a metal element and / or a metalloid element capable of alloying with Li, or a mixture of a material containing a metal element and / or a metalloid element capable of alloying with Li and a carbon-based material, and more preferably a mixture of a material containing a metal element and / or a metalloid element capable of alloying with Li and a carbon-based material.

[0253] 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.

[0254] Examples of natural graphite include scaly graphite, scaly graphite, and / or graphite particles obtained by treating such graphite as a raw material with treatments such as spheroidization and densification. Among these, spherical or ellipsoidal graphite particles that have been subjected to a spheroidization treatment are particularly preferred from the viewpoints of particle packing properties and charge / discharge rate characteristics. The average particle size (d50) of the graphite particles is usually 1 μm or more and usually 100 μm or less.

[0255] Any conventionally known material containing a metallic element and / or a semi-metallic element that can be alloyed with Li can be used. However, from the viewpoint of capacity and cycle life, Can be alloyed with Li The material containing a metal element and / or a metalloid element is preferably a metal selected from the group consisting of Sb, Si, Sn, Al, As, and Zn, or a compound thereof. Alternatively, an alloy consisting of two or more metals may be used. Can be alloyed with Li The material containing a metal element and / or a metalloid element may be an alloy material formed from two or more kinds of metal elements. Examples of the metal compound include metal oxides, metal nitrides, metal carbides, etc. Among them, metal Si (hereinafter sometimes referred to as Si) or Si-containing compounds are preferred in terms of increasing capacity.

[0256] 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 x O y (Z=C, N), etc. Si compounds include Si metal 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 is obtained from silicon dioxide (SiO2) and Si as raw materials, and the value of x is usually 0 <x<2である。 As the material containing a metal element and / or a metalloid element that can be alloyed with Li, metal particles that can be alloyed with Li are preferred in terms of increasing the electrode density. The average particle size (d50) of metal particles that can be alloyed with Li is usually 0.01 μm or more and usually 10 μm or less from the viewpoint of cycle life. The mixture of graphite particles and 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 material containing a metal element and / or a metalloid element that can be alloyed with Li and the graphite particles are mixed independently of each other, or may be a composite in which the material containing a metal element and / or a metalloid element that can be alloyed with Li is present on the surface or inside of graphite particles. The content ratio of the material containing a metal element and / or a metalloid element capable of alloying with Li to the total of the material and the graphite particles is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more. Also, it is usually 99% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less. When within this range, it is preferable in that the side reaction on the Si surface can be controlled and the swelling of the negative electrode can be suitably controlled in a non-aqueous electrolyte battery. The content ratio of the metal particles capable of alloying with Li to the total of the metal particles capable of alloying 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, still more preferably 2.0% by mass or more. Also, it is usually 99% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, still 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. When within this range, it is preferable in that the side reaction on the Si surface can be controlled and a sufficient capacity can be obtained in a non-aqueous electrolyte battery.

[0257] <B2-5. Separator> Normally, a separator is interposed between the positive electrode and the negative electrode to prevent short circuit. In this case, the non-aqueous electrolyte according to this embodiment is usually impregnated into this separator and used. A conventionally known separator can be used.

[0258] <B1-2. Electrolyte> Similar to a general non-aqueous electrolyte, the non-aqueous electrolyte of this embodiment usually contains an electrolyte as its component. The electrolyte used in the non-aqueous electrolyte of this embodiment is not particularly limited as long as it is an alkali metal salt, and lithium salts such as LiBF4, LiPF6, LiN(FSO2)2, LiN(CF3SO2)2, or lithium difluorooxalatoborate can be preferably used. Also, these lithium salts can be used alone or in combination of two or more.

[0259] The total concentration of the alkali metal salt in the non-aqueous electrolyte is not particularly limited, but is usually 8% by mass or more, preferably 8.5% by mass or more, more preferably 9% by mass or more, based on the total amount of the non-aqueous electrolyte. The upper limit 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 salt as the electrolyte is within the above range, the electrical conductivity becomes appropriate for battery operation, and sufficient output characteristics tend to be obtained.

[0260] <B1-3. Non-aqueous solvent> Similar to a general non-aqueous electrolyte, the non-aqueous electrolyte of the present embodiment usually contains, as its main component, a non-aqueous solvent that dissolves the above-described electrolyte. There is no particular limitation on the non-aqueous solvent, and known organic solvents can be used. Examples of the organic solvent include saturated cyclic carbonates such as ethylene carbonate, propylene carbonate, or butylene carbonate; linear carbonates such as dimethyl carbonate, diethyl carbonate, or ethyl methyl carbonate; carboxylic acid esters such as methyl acetate, ethyl acetate, propyl acetate, or butyl acetate; ether compounds such as dimethoxymethane, diethoxymethane, ethoxymethoxymethane, tetrahydrofuran, 1,3-dioxane, or 1,4-dioxane; sulfone compounds such as 2-methylsulfolane, 3-methylsulfolane, 2-fluorosulfolane, 3-fluorosulfolane, dimethyl sulfone, ethyl methyl sulfone, or monofluoromethyl methyl sulfone; and the like. Saturated cyclic carbonates, linear carbonates, or carboxylic acid esters are preferred, and saturated cyclic carbonates or linear carbonates are more preferred. These non-aqueous solvents can be used alone or in combination of two or more.

[0261] <B1-4. Auxiliary agent> In the non-aqueous electrolyte of the present embodiment, an auxiliary agent may be contained within a range in which the effects of the present invention are exhibited. Examples of the auxiliary agent include unsaturated cyclic carbonates such as vinylene carbonate, vinyl ethylene carbonate, or ethynyl ethylene 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; Sulfur-containing compounds such as ethylene sulfite; 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; silane compounds such as tris(trimethylsilyl) borate; 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.

[0262] In particular, in the nonaqueous electrolyte solution according to this embodiment, the use of one or more selected from unsaturated cyclic carbonates and cyclic carbonates having fluorine atoms is preferred in that gas generation during initial conditioning is further suppressed, resulting in a battery that is less prone to swelling.

[0263] The nonaqueous electrolyte solution may contain, as an auxiliary agent, a phosphate having a P=O bond and a PF bond, a salt having an FSO2 skeleton, or an oxalate. From the viewpoint of suitably forming a composite coating together with the compound represented by general formula (4), it is preferable to contain one or more compounds selected from the group consisting of a phosphate having a P=O bond and a PF bond, a salt having an FSO2 skeleton, and an oxalate. From the viewpoint of suppressing the amount of gas generation during storage at charge and an increase in internal resistance, it is preferable to contain a phosphate having a P=O bond and a PF bond and / or a salt having an FSO2 skeleton. The total content of compounds selected from the group consisting of phosphates having a P=O bond and a PF bond, salts having an FSO2 skeleton, and oxalates 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, in 100% by mass of the non-aqueous electrolyte (relative to the total amount of the non-aqueous electrolyte), 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 types of auxiliary agents are used in combination, it is preferable that the total content satisfies the above range.

[0264] (phosphate salts with P=O and PF bonds) The phosphate having a P=O bond and a PF bond is not particularly limited as long as it has a P=O bond and a PF bond in the molecule. Counter cations of phosphate salts having a PF bond include alkali metals such as lithium, sodium, and potassium, with lithium being preferred. Fluorophosphates having a P=O bond include: Monofluorophosphates such as Li2PO3F; Difluorophosphates such as LiPO2F2, NaPO2F2, KPO2F2; etc. In particular, difluorophosphates are preferred, and lithium difluorophosphate is more preferred, from the viewpoint of further enhancing the effects of suppressing gas generation during high-temperature storage and further improving the charge / discharge rate characteristics and impedance characteristics.

[0265] The fluorophosphate may be used alone or in any combination and ratio of two or more. The content of the fluorophosphate (total amount when two or more types are used) can be 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and can be 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, based on 100% by mass of the non-aqueous electrolyte solution. If the fluorophosphate content is within this range, the characteristics of the non-aqueous electrolyte secondary battery, particularly the durability characteristics or continuous charging characteristics, can be significantly improved. Although the mechanism behind this is unclear, it is thought that mixing at this ratio minimizes side reactions of the additive on the electrode.

[0266] The mass ratio of the compound represented by the general formula (1) to the phosphate having a P=O bond and a PF bond (total amount when there are two or more types) is usually 1 / 100 or more, preferably 10 / 100 or more, more preferably 20 / 100 or more, and even more preferably 25 / 100 or more, and is usually 10000 / 100 or less, preferably 500 / 100 or less, and more preferably 100 / 100. below , particularly preferably 80 / 100 or less, and most preferably 40 / 100 or less. When the mass ratio is within this range, the characteristics of the nonaqueous electrolyte secondary battery, particularly the durability characteristics and continuous charging characteristics, can be significantly improved. Although the mechanism behind this is unclear, it is thought that mixing at this ratio minimizes side reactions of the additives on the electrode.

[0267] When LiPF6 is contained in a non-aqueous electrolyte, the mass ratio of the phosphate having a P=O bond and a PF bond (total amount if two or more types are present) to the LiPF6 content (fluorophosphate / LiPF6) is typically 0.00005 or more, preferably 0.001 or more, more preferably 0.01 or more, even more preferably 0.02 or more, and particularly preferably 0.025 or more, and typically 1.0 or less, preferably 0.5 or less, more preferably 0.4 or less, and even more preferably 0.35 or less. This mass ratio range significantly improves the characteristics of non-aqueous electrolyte secondary batteries, particularly their durability and continuous charge characteristics. While the underlying mechanism is unclear, it is believed that mixing at this ratio minimizes the decomposition side reaction of LiPF6 in non-aqueous electrolyte secondary batteries. The content of phosphates with P=O and PF bonds is measured by nuclear magnetic resonance (NMR) analysis. NMR analysis is usually performed, but when the solvent peaks make it difficult to identify other compounds, ion chromatography (IC) analysis is also performed.

[0268] (Salt with FSO2 skeleton) The salt having an FSO2 skeleton used in this embodiment is not particularly limited as long as it is a salt having an FSO2 skeleton in the molecule. Counter cations of salts having an FSO2 skeleton include alkali metals such as lithium, sodium, and potassium, with lithium being preferred. For example, fluorosulfonates such as FSO3Li, FSO3Na, FSO3K, FSO3(CH3)4N, FSO3(C2H5)4N, and FSO3(n-C4H9)4N; Fluorosulfonylimide salts such as LiN(FSO2)2, LiN(FSO2)(CF3SO2), etc.; Fluorosulfonylmethide salts such as LiC(FSO2)3; etc. In particular, fluorosulfonates are preferred, and lithium fluorosulfonate is more preferred, from the viewpoint of further enhancing the effects of improving charge / discharge rate characteristics and impedance characteristics in addition to the effect of suppressing gas generation during high-temperature storage.

[0269] The salt having an FSO2 skeleton may be used singly or in any combination and ratio of two or more. The content of the salt having an FSO2 skeleton (total amount when two or more types are used) can be 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and can be 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, based on 100% by mass of the nonaqueous electrolyte. If the content of the salt having an FSO2 skeleton is within this range, the characteristics of the nonaqueous electrolyte secondary battery, particularly its durability and continuous charging characteristics, can be significantly improved. Although the mechanism behind this is unclear, it is thought that mixing at this ratio minimizes side reactions of the additive on the electrode.

[0270] The mass ratio of the compound represented by the general formula (1) to the salt having an FSO2 skeleton (total amount when two or more types are used) is usually 1 / 100 or more, preferably 10 / 100 or more, more preferably 20 / 100 or more, and even more preferably 25 / 100 or more, and is usually 10000 / 100 or less, preferably 500 / 100 or less, and more preferably 100 / 100. below , particularly preferably 80 / 100 or less, and most preferably 40 / 100 or less. When the mass ratio is within this range, the characteristics of the nonaqueous electrolyte secondary battery, particularly the durability characteristics and continuous charging characteristics, can be significantly improved. Although the mechanism behind this is unclear, it is thought that mixing at this ratio minimizes side reactions of the additives on the electrode.

[0271] When LiPF6 is contained in a non-aqueous electrolyte, the mass ratio of the salt having an FSO2 skeleton (total amount when two or more types are used) to the content of LiPF6 (salt having an FSO2 skeleton / LiPF6) is typically 0.00005 or more, preferably 0.001 or more, more preferably 0.01 or more, even more preferably 0.02 or more, and particularly preferably 0.025 or more, and typically 1.0 or less, preferably 0.5 or less, more preferably 0.4 or less, and even more preferably 0.35 or less. This mass ratio range significantly improves the characteristics of non-aqueous electrolyte secondary batteries, particularly their durability and continuous charge characteristics. While the underlying mechanism is unclear, it is believed that mixing at this ratio minimizes the decomposition side reaction of LiPF6 in non-aqueous electrolyte secondary batteries. The content of salts with an FSO2 skeleton is measured by nuclear magnetic resonance (NMR) analysis. NMR analysis is usually performed, but when the solvent peak makes it difficult to identify other compounds, ion chromatography (IC) analysis is also performed.

[0272] (oxalate) The oxalate is not particularly limited as long as it is a compound having at least one oxalic acid skeleton in the molecule. Counter cations of the oxalate include alkali metals such as lithium, sodium, and potassium, with lithium being preferred. For example, oxalatoborate salts such as lithium bis(oxalato)borate and lithium difluorooxalatoborate; oxalate phosphate salts such as lithium tetrafluorooxalate phosphate, lithium difluorobis(oxalate)phosphate, and lithium tris(oxalate)phosphate; etc. In particular, from the viewpoint of further enhancing the effects of suppressing gas generation during high-temperature storage as well as improving charge / discharge rate characteristics and impedance characteristics, oxalatoborate salts are preferred, and lithium bis(oxalato)borate is more preferred.

[0273] One type of oxalate may be used alone, or two or more types may be used in any combination and ratio. The content of the oxalate (total amount when two or more types are used) can be 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and can be 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, based on 100% by mass of the non-aqueous electrolyte solution. If the content of the oxalate is within this range, the characteristics of the non-aqueous electrolyte secondary battery, particularly the durability characteristics or continuous charging characteristics, can be significantly improved. Although the mechanism behind this is unclear, it is thought that by mixing at this ratio, side reactions of the additive on the electrode can be minimized.

[0274] The mass ratio of the compound represented by the general formula (1) to the oxalate (total amount when two or more types are used) is usually 1 / 100 or more, preferably 10 / 100 or more, more preferably 20 / 100 or more, and even more preferably 25 / 100 or more, and is usually 10000 / 100 or less, preferably 500 / 100 or less, and more preferably 100 / 100. below , particularly preferably 80 / 100 or less, and most preferably 40 / 100 or less. When the mass ratio is within this range, the characteristics of the nonaqueous electrolyte secondary battery, particularly the durability characteristics and continuous charging characteristics, can be significantly improved. Although the mechanism behind this is unclear, it is thought that mixing at this ratio minimizes side reactions of the additives on the electrode.

[0275] When LiPF6 is present in a non-aqueous electrolyte, the mass ratio of the oxalate (total amount in the case of two or more kinds) to the content of LiPF6 (oxalate / LiPF6) is usually 0.00005 or more, preferably 0.001 or more, more preferably 0.01 or more, still more preferably 0.02 or more, particularly preferably 0.025 or more, and usually 1.0 or less, preferably 0.5 or less, more preferably 0.4 or less, still more preferably 0.35 or less. If the mass ratio is within this range, the characteristics of the non-aqueous electrolyte secondary battery, particularly the durability characteristics or continuous charging characteristics, can be significantly improved. Although the principle is not clear, it is considered that by mixing at this ratio, the decomposition side reaction of LiPF6 in the non-aqueous electrolyte secondary battery can be minimized.

[0276] The content of the oxalate is determined by nuclear magnetic resonance (NMR) analysis. Usually, NMR analysis is performed. However, when it is difficult to assign other compounds due to the peaks of the solvent, ion chromatography (IC) analysis is also performed. Among the additives, some can be listed as salts as electrolytes. In that case, it is discriminated by the concentration range. For example, when a certain fluorinated inorganic salt is contained at 10% by mass in the non-aqueous electrolyte, it is discriminated as an electrolyte, and when a certain salt having an oxalate skeleton is contained at 0.5% by mass, it can be discriminated as an additive.

[0277] The total content of the auxiliary agents is usually 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and also usually 10% by mass or less, preferably 8% by mass or less, more preferably 5% by mass or less, in 100% by mass of the non-aqueous electrolyte (with respect to the total amount of the non-aqueous electrolyte). When two or more kinds of auxiliary agents are used in combination, it is preferable that the total content satisfies the above range.

[0278] <B2. Non-aqueous electrolyte battery> The non-aqueous electrolyte battery according to an embodiment of the present invention is a non-aqueous electrolyte battery including a positive electrode and a negative electrode capable of occluding and releasing metal ions, and the above-described non-aqueous electrolyte. The non-aqueous electrolyte battery is characterized in that the negative electrode active material contained in the negative electrode contains a material containing a metal element and / or a semi-metal element capable of alloying with Li. More specifically, a positive electrode having a current collector and a positive electrode active material layer on at least a part of the surface of the current collector and capable of occluding and releasing metal ions, a negative electrode having a current collector and a negative electrode active material layer on at least a part of the surface of the current collector and capable of occluding and releasing metal ions, and a non-aqueous electrolyte containing a compound represented by the above general formula (4) together with an alkali metal salt and a non-aqueous solvent, and the negative electrode active material contained in the negative electrode contains a material containing a metal element and / or a semi-metal element capable of alloying with Li.

[0279] <B2-1. Battery Configuration> Regarding the configuration other than the above non-aqueous electrolyte and negative electrode, the non-aqueous electrolyte battery of the present embodiment is the same as the conventionally known non-aqueous electrolyte battery. Usually, the positive electrode and the negative electrode are laminated through a porous film (separator) impregnated with the above non-aqueous electrolyte, and they are housed in a case (outer package). The shape of the non-aqueous electrolyte battery of the present embodiment is not particularly limited, and it may be any of a cylindrical shape, a rectangular shape, a laminate shape, a coin shape, a large size, etc.

[0280] <B2-2. Non-aqueous Electrolyte> As the non-aqueous electrolyte, the non-aqueous electrolyte according to the above-described present embodiment is used. In addition, within a range not departing from the gist of the present invention, it is also possible to blend and use other non-aqueous electrolytes with the above non-aqueous electrolyte.

[0281] <B2-3. Positive Electrode> The positive electrode refers to one having a current collector and a positive electrode active material layer on at least a part of the surface of the current collector. Other configurations can employ conventionally known ones. The lithium transition metal compound is a compound having a structure capable of desorbing and inserting lithium ions, and examples thereof include sulfides, phosphate compounds, silicate compounds, borate compounds, lithium transition metal composite oxides, etc. Among these, phosphate compounds or lithium transition metal composite oxides are preferred, and lithium transition metal composite oxides are more preferred. Examples of lithium transition metal composite oxides include those having a spinel structure that allows three-dimensional diffusion and those having a layered structure that allows two-dimensional diffusion of lithium ions. The lithium transition metal compound having a spinel structure is generally represented by the following composition formula (11-2). Li x2’ M3'2O4···(11-2) (In formula (11-2), x 2’ is 1≦x 2’ ≦1.5, and M3′ represents at least one transition metal element. Specifically, LiMn2O4, LiCoMnO4, LiNi 0.5 Mn 1.5 Examples include O4 and LiCoVO4. The lithium transition metal compound having a layered structure is generally represented by the following composition formula (12-2). Li 1+x3 M3O2···(12-2) (In formula (12-2), x3 is −0.1≦x3≦0.5, and M3 represents at least one transition metal element.) Specifically, LiCoO2, LiNiO2, LiNi 0.85 Co 0.10 Al 0.05 O2, LiNi 0.80 Co 0.15 Al 0.05 O2, LiNi 0.33 Co 0.33 Mn 0.33 O2, Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O2, LiNi 0.5 Co 0.2 Mn 0.3 O2, Li 1.05 Ni 0.5 Co 0.2 Mn 0.3 O2, LiNi 0.6 Co 0.2 Mn 0.2 O2, LiNi 0.8 Co 0.1 Mn 0.1 Examples include O2.

[0282] Among these, from the viewpoint of improving the battery capacity, a lithium transition metal composite oxide having a layered structure is preferred, and a lithium transition metal composite oxide represented by the following composition formula (13-2) is more preferred. Li a13 Ni b13 M13 c13 O2···(13-2) (In formula (13-2), a13, b13, and c13 are numerical values ​​that satisfy 0.90≦a13≦1.10, 0.40≦b13≦0.98, and 0.00≦c13≦0.50, respectively, and b13+c13=1 is satisfied. M13 represents at least one element selected from the group consisting of Co, Mn, Al, Mg, Zr, Fe, Ti, and Er.) In the composition formula (13-2), b13 is preferably 0.55 or more, more preferably 0.60 or more, even more preferably 0.65 or more, particularly preferably 0.70 or more, more preferably 0.75 or more, more preferably 0.80 or more, and even more preferably 0.90 or more. Also, c13 is preferably 0.01 or more.

[0283] The positive electrode active material is not particularly limited as long as it is a lithium cobalt oxide or a transition metal oxide containing at least Ni and Co, with 50 mol % or more of the transition metals being Ni and Co, and capable of electrochemically absorbing and desorbing metal ions, but for example, a material capable of electrochemically absorbing and desorbing lithium ions is preferred, and a transition metal oxide containing lithium, at least Ni, and Co, with 60 mol % or more of the transition metals being Ni and Co is preferred. This is because Ni and Co have oxidation-reduction potentials suitable for use as positive electrode materials in secondary batteries and are suitable for high-capacity applications.

[0284] Among these, a transition metal oxide represented by the following composition formula (14-2) is preferred. Li a23 Ni b23 Co c23 M23 d23 O2···(14-2) The above composition formula ( 14-2 In the formula (I), a23, b23, c23, and d23 are numerical values ​​within the range of 0.90≦a23≦1.10, 0.50≦b23≦0.98, 0.01≦c23<0.50, and 0.01≦d23<0.50, and satisfy b23+c23+d23=1. M23 represents at least one element selected from the group consisting of Mn, Al, Mg, Zr, Fe, Ti, and Er. In the composition formula (14-2), it is preferable that d23 satisfies the numerical value 0.1≦d23<0.5. 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 specific example of a suitable material 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 Co 0.2 Mn 0.2 O2, LiNi 0.8 Co 0.1 Mn 0.1 Examples include O2.

[0285] <B2-5.セパレータ> 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 the present embodiment is usually impregnated into the separator. Any conventional separator can be used. [Example]

[0286] The present invention will be explained in more detail below by way of examples and reference examples, but the present invention is not limited to these examples as long as it does not depart from the gist of the invention.

[0287] The compounds used in the present examples and comparative examples are shown below.

[0288] [ka]

[0289] [ka]

[0290] [ka]

[0291] [ka]

[0292] [ka]

[0293] [ka]

[0294] [ka]

[0295] [ka]

[0296] [ka]

[0297] [ka]

[0298] [ka]

[0299] [ka]

[0300] [ka]

[0301] [ka]

[0302] [ka]

[0303] [ka]

[0304] compound 17 Lithium difluorophosphate (LiPO2F2)

[0305] compound 18 Lithium fluorosulfonate (LiSO3F)

[0306] <Synthesis example> In the following synthesis examples, the Karstedt catalyst used was a 2 wt % xylene solution of platinum(0)-1,3-divinyltetramethyldisiloxane complex manufactured by Sigma-Aldrich. The analytical methods used in the following synthesis examples are as follows. [Nuclear magnetic resonance (NMR) analysis] 1 H, 13 C. 19 F-NMR was measured at 400, 101, and 376 MHz using a Bruker 400 Ultrashield. The sample was dissolved in deuterated chloroform (CDCl3) and measured. [Gas Chromatography (GC) Analysis] 100 μL of the sample was dissolved in 1 mL of hexane. The resulting solution was analyzed using a GC analyzer (Shimadzu GC-2010) under the following conditions. Column: DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm, manufactured by Agilent Technologies) Detector: FID Temperature: 40°C → 280°C, increased at 10°C / min. The purity was determined from the peak area %.

[0307] <Synthesis Example 1> Synthesis of Compound 1 (3-(fluorodimethylsilyl)propylmethyl carbonate) Allyl methyl carbonate (2.00 g, 17.2 mmol) was dissolved in toluene (20 mL) and 20 μL of Karstedt's catalyst was added. Chlorodimethylsilane (2.25 mL, 20.7 mmol) was added dropwise with stirring under ice cooling. The mixture was heated and stirred at 70°C for 15 minutes to obtain a toluene solution of 3-(chlorodimethylsilyl)propylmethyl carbonate. In a separate reactor, potassium fluoride (2.00 g, 34.5 mmol), 18-crown-6-ether (0.911 g, 3.44 mmol), and acetonitrile (40 mL) were charged, and a toluene solution of 3-(chlorodimethylsilyl)propylmethyl carbonate was added dropwise with stirring under ice cooling, followed by heating under reflux for 3 hours. The reaction mixture was filtered, the solvent was concentrated, and then silica gel column chromatography was used to obtain 3-(fluorodimethylsilyl)propylmethyl carbonate (0.185 g, 0.952 mmol). GC analysis estimated the purity to be 99%. 1 H-NMR, 13 C-NMR, 19 The results of F-NMR analysis were as follows: 1 H-NMR (400MHz, CDCl3): δ=4.12(t,J=6.8Hz,2H),3.78(s,3H),1.80-1.73(m,2H),0.75-0.69(m,2H),0.24(s,6H) 13 C-NMR(101MHz,CDCl3):δ=155.8,70.0,54.7,22.0,12.4,-1.6 19 F-NMR (376 MHz, CDCl): δ = -162.2

[0308] <Synthesis Example 2> Synthesis of Compound 2 (3-(difluoromethylsilyl)propylmethyl carbonate) Allyl methyl carbonate (6.50 g, 56.0 mmol) was dissolved in toluene (65 mL), and 70 μL of Karstedt's catalyst was added. Dichloromethylsilane (6.90 mL, 67.2 mmol) was added dropwise while stirring under ice cooling. The mixture was heated and stirred at 80°C for 15 minutes to obtain a toluene solution of 3-(dichloromethylsilyl)propylmethyl carbonate. In a separate reactor, potassium fluoride (13.0 g, 224 mmol), 18-crown-6-ether (2.96 g, 11.2 mmol), and acetonitrile (130 mL) were charged, and a toluene solution of 3-(dichloromethylsilyl)propylmethyl carbonate was added dropwise while stirring under ice cooling. The mixture was heated under reflux for 3 hours and then allowed to cool to room temperature. The reaction mixture was filtered, the solvent was distilled off, and the product was purified by distillation to obtain 3-(difluoromethylsilyl)propylmethyl carbonate (80.0 mg, 0.404 mmol). GC analysis indicated an estimated purity of 99%. 1 H-NMR, 19 The results of F-NMR analysis were as follows: 1 H-NMR (400MHz, CDCl3): δ=4.13(t,J=6.5Hz,2H),3.79(s,3H),1.87-1.79(m,2H),0.89-0.82(m,2H), 0.38-0.35(m,3H) 19 F-NMR (376 MHz, CDCl): δ = -135.5

[0309] <Synthesis Example 3> Synthesis of Compound 3 (3-(trifluorosilyl)propylmethyl carbonate) Allyl methyl carbonate (7.50 g, 64.6 mmol) was dissolved in toluene (110 mL) and 75 μL of Karstedt's catalyst was added. Trimethoxysilane (9.87 mL, 77.5 mmol) was added dropwise while stirring under ice cooling. The mixture was heated and stirred at 50°C for 15 minutes. The solvent was distilled off to obtain 3-(trimethoxysilyl)propylmethyl carbonate (12.3 g, 51.5 mmol). 3-(Trimethoxysilyl)propylmethyl carbonate (12.3 g, 51.5 mmol) was dissolved in diethyl ether (180 mL) and boron trifluoride diethyl ether complex (6.46 mL, 51.5 mmol) was added dropwise under ice cooling. After heating under reflux for 6 hours, low-boiling by-products and the solvent were distilled off. 3-(Trifluorosilyl)propylmethyl carbonate (1.26 g, 6.23 mmol) was obtained by purifying using a Kugelrohr distillation apparatus. The purity estimated by GC analysis was 97%. 1 H-NMR, 13 C-NMR, 19 The results of F-NMR analysis were as follows: 1 H-NMR (400MHz, CDCl3): δ=4.17(t,J=6.3Hz,2H), 3.80(s,3H),1.96-1.89(m,2H),1.12-1.07(m,2H) 13 C-NMR(101MHz,CDCl3):δ=155.8,68.6,55.0,20.6,3.4 19 F-NMR (376 MHz, CDCl): δ = -137.1

[0310] <Synthesis Example 4> Synthesis of Compound 4 (4-[2-(difluoromethylsilyl)ethyl]-1,3-dioxolan-2-one) Vinyl ethylene carbonate (6.00 g, 52.6 mmol) was dissolved in toluene (80 mL) and 60 μL of Karstedt's catalyst was added. Dichloromethylsilane (6.72 mL, 63.1 mmol) was added dropwise with stirring under ice cooling, and the mixture was heated and stirred at 100 °C for 2 hours. After cooling to room temperature, acetonitrile (160 mL) and 18-crown-6-ether (2.78 g, 10.5 mmol) were added, and potassium fluoride (12.2 g, 210 mmol) was added in small portions. After heating and refluxing for 4 hours, the mixture was cooled to room temperature and the inorganic salts were filtered off. The filtrate was concentrated and purified by distillation to obtain 4-[2-(difluoromethylsilyl)ethyl]-1,3-dioxolan-2-one (0.300 g, 1.53 mmol). The purity was estimated to be 87% by GC analysis. 1 H-NMR, 13 C-NMR, 19 The results of F-NMR analysis were as follows: 1 H-NMR (400MHz, CDCl3): δ=4.68-4.74(m,1H),4.56(dd,J=8.6,7.9Hz,1H),4.10(dd,J =8.6,6.8 Hz,1H),1.94-1.87(m,2H),1.03-0.85(m,2H),0.42(t,J H-F =6.3Hz,3H) 13 C-NMR (101MHz, CDCl3): δ=154.6,77.5,68.7,26.1,8.3,-4.3 19 F-NMR (376 MHz, CDCl): δ = -135.2

[0311] <Synthesis Example 5> Synthesis of Compound 5 (4-(2-trifluorosilylethyl)-1,3-dioxolan-2-one) Vinyl ethylene carbonate (12.0 g, 105 mmol) was dissolved in toluene (120 mL) and 100 μL of Karstedt's catalyst was added. Trimethoxysilane (16.1 mL, 126 mmol) was added dropwise with stirring under ice cooling, and the mixture was heated and stirred at 50°C for 2 hours. The solvent was distilled off to obtain 4-(2-trimethoxysilylethyl)-1,3-dioxolan-2-one (23.8 g, 101 mmol). 4-(2-Trimethoxysilylethyl)-1,3-dioxolan-2-one (15.0 g, 63.5 mmol) was dissolved in diethyl ether (70 mL) and added dropwise with ice-cooling to boron trifluoride diethyl etherate (7.97 mL, 63.5 mmol). After heating under reflux for 5 hours, low-boiling by-products and the solvent were distilled off. 3 g of the crude product was purified by distillation to give 4-(2-trifluorosilylethyl)-1,3-dioxolan-2-one (0.88 g, 4.40 mmol). The purity estimated by GC analysis was 99%. 1 H-NMR, 13 C-NMR, 19 The results of F-NMR analysis were as follows: 1 H-NMR (400MHz, CDCl3): δ=4.68-4.75(m,1H),4.60-4.55(m,1H),4.10(dd,J=8.6,6.6 Hz,1H),2.01-1.95(m,2H),1.30-1.21(m,1H),1.16-1.07(m,1H) 13 C-NMR(101MHz,CDCl3):δ=154.2,76.9,68.6, 25.8,2.4 19 F-NMR (376 MHz, CDCl): δ = -136.7

[0312] <Synthesis Example 6> Synthesis of Compound 6 (3-(difluoromethylsilyl)propyl acetate) Allyl acetate (3.00 g, 30.0 mmol) was dissolved in toluene (40 mL) and 30 μL of Karstedt's catalyst was added. While stirring under ice cooling, dichloromethylsilane (3.83 mL, 36.0 mmol) was added dropwise, and the mixture was heated and stirred at 80°C for 15 minutes. After cooling to room temperature, acetonitrile (80 mL) and 18-crown-6-ether (1.58 g, 5.99 mmol) were added, and potassium fluoride (6.96 g, 120 mmol) was added in small portions. The mixture was heated under reflux for 3 hours and then cooled to room temperature. The reaction mixture was filtered, and the filtrate was concentrated and purified by distillation to obtain 3-(difluoromethylsilyl)propyl acetate (1.10 g, 6.04 mmol). The purity was estimated to be 95% by GC analysis. 1 H-NMR, 13 C-NMR, 19 The results of F-NMR analysis were as follows: 1 H-NMR (400MHz, CDCl3): δ=4.06(t,J=6.5Hz,2H), 2.12(s,3H),1.83-1.76(m,2H),0.87-0.81(m,2H),0.37(t,J H-F =6.4Hz,3H) 13 C-NMR(101MHz,CDCl3):δ=171.0,65.7,20.9, 20.8,9.9,-4.3 19 F-NMR (376 MHz, CDCl): δ = -135.4

[0313] <Synthesis Example 7> Synthesis of Compound 7 (3-trifluorosilylpropyl acetate) 3-Trimethoxysilylpropyl acetate (34.5 g, 155.2 mmol) was dissolved in toluene (345 mL) and boron trifluoride diethyl ether complex (38.3 mL, 310.4 mmol) was added dropwise under ice cooling. After stirring at 80 °C for 2 hours, low-boiling by-products and the solvent were distilled off. 3 g of the crude product was purified by distillation to obtain 3-trifluorosilylpropyl acetate (0.90 g, 4.83 mmol). The purity estimated by GC analysis was 92%. 1 H-NMR, 13 C-NMR, 19 The results of F-NMR analysis were as follows: 1 H-NMR(400MHz, CDCl3):δ=4.18(t,J=6.1Hz,2H), 2.21(s,3H),1.91-1.98(m,2H),1.11-1.07(m,2H) 13 C-NMR(101MHz,CDCl3):δ=173.6,66.8,20.6, 20.4,3.9 19 F-NMR (376 MHz, CDCl): δ = -136.8

[0314] <Synthesis Example 8> Synthesis of Compound 8 (3-(difluoromethylsilyl)propyl methanesulfonate) 3-Chloropropyl-dimethoxy-methylsilane (5.00 g, 27.4 mmol) was dissolved in acetone (30 mL), sodium iodide (6.15 g, 41.0 mmol) was added, and the mixture was heated under reflux for 16 hours. After distilling off the solvent, dichloromethane was added, and the precipitated inorganic salt was filtered off. The filtrate was concentrated to obtain 3-iodopropyl-dimethoxy-methylsilane (6.37 g, 23.2 mmol). Silver methanesulfonate (2.89 g, 14.2 mmol) was dissolved in acetonitrile (50 mL), and 3-iodopropyl-dimethoxy-methylsilane (3.00 g, 10.9 mmol) was added. The mixture was heated under reflux for 2 hours. The reaction mixture was filtered, and the filtrate was concentrated. Toluene was added, and the precipitate was filtered off. The filtrate was then concentrated to obtain 3-(dimethoxymethylsilyl)propyl methanesulfonate (2.30 g, 9.49 mmol). 3-(Dimethoxymethylsilyl)propyl methanesulfonate (2.30 g, 9.49 mmol) was dissolved in diethyl ether (30 mL) and boron trifluoride diethyl ether complex (0.795 mL, 6.33 mmol) was added dropwise under ice cooling. After heating under reflux for 5 hours, low-boiling by-products and the solvent were removed by distillation, and the resulting product was purified by distillation to obtain 3-(difluoromethylsilyl)propyl methanesulfonate (0.21 g, 0.962 mmol). The purity estimated by GC analysis was 86%. 1 H-NMR, 13 C-NMR, 19 The results of F-NMR analysis were as follows: 1 H-NMR (400MHz, CDCl3): δ=4.22(t,J=6.4Hz,2H),3.03(s,3H),1.96-1.88(m,2H),0.92-0.88(m,2H),0.39(t,J H-F =6.3Hz,3H) 13 C-NMR(101MHz,CDCl3):δ=71.0,37.3,21.6,9.4, -4.4 19 F-NMR (376 MHz, CDCl): δ = -135.2

[0315] <Synthesis Example 9> Synthesis of Compound 9 (3-Trifluorosilylpropyl methanesulfonate) Silver methanesulfonate (1.23 g, 6.04 mmol) was dissolved in acetonitrile (15 mL), and 3-iodopropyl(trimethoxy)silane (1.46 g, 5.03 mmol) was added. After stirring at room temperature for 1 hour, the mixture was heated to reflux for 4 hours. The reaction solution was filtered, and the filtrate was concentrated. Toluene was added, and the precipitate was filtered off. The filtrate was then concentrated to obtain 3-trimethoxysilylpropyl methanesulfonate (1.02 g, 3.95 mmol). 3-Trimethoxysilylpropyl methanesulfonate (1.00 g, 3.87 mmol) was dissolved in diethyl ether (15 mL) and boron trifluoride diethyl ether complex (0.486 mL, 3.87 mmol) was added dropwise under ice cooling. After heating under reflux for 9 hours, low-boiling by-products and the solvent were removed by distillation, and the resulting product was purified by distillation to obtain 3-trifluorosilylpropyl methanesulfonate (0.15 g, 0.675 mmol). The purity estimated by GC analysis was 97%. 1 H-NMR, 13 C-NMR, 19 The results of F-NMR analysis were as follows: 1 H-NMR (400MHz, CDCl3): δ=4.26(t,J=6.1Hz,2H),3.06(s,3H),2.05-1.98(m,2H),1.18-1.11(m,2H) 13 C-NMR (101MHz, CDCl3): δ=69.9,37.4,21.2,3.3 19 F-NMR (376 MHz, CDCl): δ = -136.7

[0316] <Synthesis Example 10> Synthesis of Compound 10 (3-diethoxyphosphorylpropyl-difluoro-methylsilane) Diethyl allylphosphonate (3.00 g, 16.8 mmol) was dissolved in toluene (30 mL) and 90 μL of Karstedt's catalyst was added. Methyl(dimethoxy)silane (3.12 mL, 25.3 mmol) was added dropwise with stirring under ice cooling, and the mixture was heated and stirred at 90°C for 3 hours. The solvent was distilled off to obtain 3-diethoxyphosphorylpropyl-dimethoxy-methylsilane (4.79 g, 16.8 mmol). 3-Diethoxyphosphorylpropyl-dimethoxymethylsilane (4.79 g, 16.8 mmol) was dissolved in diethyl ether (30 mL) and boron trifluoride diethyl ether complex (1.41 mL, 11.2 mmol) was added dropwise under ice cooling. After heating under reflux for 1.5 hours, low-boiling by-products and the solvent were distilled off. 3-Diethoxyphosphorylpropyl-difluoromethylsilane (1.87 g, 7.18 mmol) was obtained by distillation purification. The purity estimated by GC analysis was 76%. 1 H-NMR, 13 C-NMR, 19 F-NMR, 31 The P-NMR analysis results were as follows: 1 H-NMR (400MHz, CDCl3): δ=4.15-4.05(m,4H),1.82-1.75(m,4H),1.35-1.22(m,6H),0.93(m,0.96-0.90,2H),0.40-0.34(m,3H) 13 C-NMR (101MHz, CDCl3): δ=61.5,29.2,27.8,16.4,14.6,-4.3 19 F-NMR (376 MHz, CDCl): δ = -135.3 31 P-NMR (162 MHz, CDCl): δ = 30.7

[0317] <Synthesis Example 11> Synthesis of Compound 11 (3-diethoxyphosphorylpropyl(trifluoro)silane) Diethyl allylphosphonate (1.00 g, 5.61 mmol) was dissolved in toluene (10 mL) and 10 μL of Karstedt's catalyst was added. Trimethoxysilane (0.857 mL, 6.74 mmol) was added dropwise with stirring under ice cooling, and the mixture was heated and stirred at room temperature for 30 minutes. The solvent was evaporated to give 3-diethoxyphosphorylpropyl(trimethoxy)silane (1.69 g, 5.61 mmol). 3-Diethoxyphosphorylpropyl(trimethoxy)silane (1.69 g, 5.63 mmol) was dissolved in diethyl ether (20 mL) and boron trifluoride diethyl ether complex (0.707 mL, 5.63 mmol) was added dropwise under ice cooling. After heating under reflux for 5 hours, low-boiling by-products and the solvent were distilled off. 3-Diethoxyphosphorylpropyl(trifluoro)silane (0.35 g, 1.32 mmol) was obtained by distillation purification. The purity estimated by GC analysis was 90%. 1 H-NMR, 13 C-NMR, 19 F-NMR, 31 The P-NMR analysis results were as follows: 1 H-NMR (400MHz, CDCl3): δ=4.16-4.06(m,4H),1.90-1.80(m,4H),1.36-1.31(m,6H),1.17-1.14(m,2H) 13 C-NMR (101MHz, CDCl3): δ=61.7,28.7,27.3,16.4,14.8 19 F-NMR (376 MHz, CDCl): δ = -136.8 31 P-NMR (162 MHz, CDCl): δ = 29.9

[0318] <Synthesis Example 12> Synthesis of Compound 12 (3-[difluoro(methyl)silyl]propyldiethyl phosphate) Allyldiethyl phosphate (3.00 g, 15.5 mmol) was dissolved in toluene (30 mL) and 30 μL of Karstedt's catalyst was added. Methyl(dimethoxy)silane (2.29 mL, 18.5 mmol) was added dropwise with stirring under ice cooling, and the mixture was stirred at room temperature for 30 minutes. The solvent was evaporated to give 3-[methyl(dimethoxy)silyl]propyldiethyl phosphate (4.45 g, 14.8 mmol). 3-[methyl(dimethoxy)silyl]propyldiethyl phosphate (4.45 g, 14.8 mmol) was dissolved in diethyl ether (30 mL) and boron trifluoride diethyl ether complex (1.24 mL, 9.88 mmol) was added dropwise under ice cooling. After heating under reflux for 1.5 hours, low-boiling by-products and the solvent were distilled off. 3-[difluoro(methyl)silyl]propyldiethyl phosphate (0.62 g, 2.24 mmol) was obtained by distillation and purification. The purity estimated by GC analysis was 92%. 1 H-NMR, 13 C-NMR, 19 F-NMR, 31 The P-NMR analysis results were as follows: 1 H-NMR (400MHz, CDCl3): δ=4.16-4.08(m,4H),4.02(m,4.05-4.00,2H),1.86-1.81(m,2H),1.34(t,J=7.1Hz,6H),0.91-0.85(m,2H),0.37(t,J H-F =6.4Hz,3H) 13 C-NMR (101MHz, CDCl3): δ=68.7,63.8,22.5,16.1,9.4,-4.3 19 F-NMR (376 MHz, CDCl): δ = -135.4 31 P-NMR (162 MHz, CDCl): δ = -0.9

[0319] <Synthesis Example 13> Synthesis of Compound 13 (Tris(3-trifluorosilylpropyl)isocyanurate) Tris(3-trimethoxysilylpropyl)isocyanurate (5.00 g, 8.12 mmol) was dissolved in diethyl ether (80 mL), and boron trifluoride diethyl ether complex (3.06 mL, 24.4 mmol) was added dropwise under ice cooling. After heating under reflux for 17 hours, low-boiling by-products and the solvent were distilled off to obtain a crude product (2.90 g) containing 3.2 wt% diethyl ether. 1 H-NMR, 19 The results of F-NMR analysis were as follows: 1 H-NMR(400MHz, CDCl3):δ=3.94(t,J=7.4Hz,6H), 1.95-1.87(m,6H),1.08-1.03(m,6H) 19 F-NMR (376 MHz, CDCl): δ = -137.0

[0320] <Synthesis Example 15> Synthesis of Compound 15 (4-(difluoromethylsilyl)butanenitrile) Allyl cyanide (2.50 g, 37.3 mmol) was dissolved in toluene (40 mL) and 40 μL of Karstedt's catalyst was added. Dichloromethylsilane (4.76 mL, 44.7 mmol) was added dropwise while stirring under ice cooling. The mixture was heated and stirred at 70°C for 15 minutes. After cooling to room temperature, acetonitrile (80 mL) and 18-crown-6-ether (1.97 g, 7.45 mmol) were added, and potassium fluoride (8.66 g, 149 mmol) was added in small portions. The mixture was heated under reflux for 7 hours and then cooled to room temperature. The reaction mixture was filtered, and the filtrate was concentrated and purified by distillation to obtain 4-(difluoromethylsilyl)butanenitrile (0.77 g, 5.16 mmol). 1 H-NMR, 13 C-NMR, 19 The results of F-NMR analysis were as follows: 1 H-NMR(400MHz, CDCl3):δ=2.42(t,J=7.0Hz,2H), 1.88-1.80(m,2H),0.99-0.95(m,2H),0.39(s,3H) 13 C-NMR(101MHz,CDCl3):δ=118.9,19.9,18.2, 12.8,-4.3 19 F-NMR (376 MHz, CDCl): δ = -135.2

[0321] Compound 14 was synthesized by the synthesis method described in Patent Document 1. Compounds 16, 17, and 18 were commercially available products.

[0322] <Examples A1-1 to A1-23, Comparative Examples A1-1 to A1-6> [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.

[0323] [Preparation of negative electrode] To 98 parts by mass of natural graphite, 1 part by mass of an aqueous dispersion of sodium carboxymethylcellulose (concentration of sodium carboxymethylcellulose: 1% by mass) and 1 part by mass of an aqueous dispersion of styrene-butadiene rubber (concentration of styrene-butadiene rubber: 50% by mass) were added as thickeners and binders, 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.

[0324] [Preparation of non-aqueous electrolyte] Under a dry argon atmosphere, 1.2 mol / L (14.8% by mass; 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% by mass of vinylene carbonate (VC) and fluoroethylene carbonate (FEC) were added (hereinafter referred to as reference electrolyte 1). Compounds 1 to 7 and 9 to 13 were added to reference electrolyte 1 in the amounts listed in Table 1 below to prepare non-aqueous electrolytes. The "content (mass%)" in the table is the content when the total non-aqueous electrolyte is taken as 100% by mass.

[0325] [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.

[0326] <Evaluation of non-aqueous electrolyte batteries> [Initial conditioning] The nonaqueous electrolyte battery prepared by the above method was charged at a constant current of 0.05 C (1 C refers to the current value required for charging or discharging in 1 hour; the same applies below) for 6 hours in a constant temperature bath at 25°C, and then discharged at 0.2 C to 3.0 V. Subsequently, constant current-constant voltage charging (hereinafter referred to as CC-CV charging) was performed at 0.2 C to 4.1 V. After that, the battery was held at 45°C for 72 hours for aging. The battery was then discharged at 0.2 C to 3.0 V to stabilize the nonaqueous electrolyte battery. Furthermore, CC-CV charging was performed at 0.2 C to 4.2 V, and then discharged at 0.2 C to 3.0 V for initial conditioning.

[0327] [Charged storage test] After initial conditioning, the nonaqueous electrolyte battery was again subjected to CC-CV charging at 0.2 C to 4.2 V, followed by high-temperature storage at 60°C for two weeks. After cooling sufficiently, the nonaqueous electrolyte battery was immersed in an ethanol bath and its volume was measured. The amount of gas generated was calculated from the change in volume before and after the storage test, and this was recorded as the "amount of gas generated during storage during charging." Table 1 below shows the amount of gas generated during storage during charging, assuming the amount of gas generated during storage during charging for Comparative Example A1-1 as 100.

[0328] [Table 1]

[0329] From the results of Examples A1-1 to A1-24 and Comparative Examples A1-2 to A1-4, it was found that the amount of gas generated was more suppressed in the nonaqueous electrolyte battery manufactured using the nonaqueous electrolyte solution containing the compound having a polar group according to the present invention than in the nonaqueous electrolyte battery manufactured using the nonaqueous electrolyte solution containing the conventional compound. Furthermore, the results of Examples A1-1 to A1-19 reveal that the amount of gas generated tends to be suppressed as the number of SiF bonds in the compound increases. Furthermore, from the results of Examples A1-9, A1-10, A1-13, A1-15, A1-20 to A1-24, Comparative Examples A1-5 and A1-6, it was found that when the compound having a polar group according to the present invention is used in combination with LiPO2F2 or LiSO3F, the amount of gas generated can be suppressed more than when each compound is used alone. Furthermore, from the results of Examples A1-1 to A1-19, Z in the compounds in each of the above-mentioned embodiments 1 ~Z 4 When comparing the embodiments in which the atom considered to be the carbon atom, the sulfur atom, and the phosphorus atom, it was found that the amount of gas generated tends to be more suppressed in the embodiment in which the atom considered to be the carbon atom.

[0330] <Examples B1-1 to B1-11, Comparative Examples B1-1 to B1-4> [Preparation of positive electrode] A positive electrode similar to that in Example A1-1 was prepared.

[0331] [Preparation of negative electrode] A negative electrode similar to that of Example A1-1 was prepared and used.

[0332] [Preparation of non-aqueous electrolyte] A reference electrolyte 1 similar to that in Example A1-1 was prepared.

[0333] [Manufacturing non-aqueous electrolyte batteries] It was prepared in the same manner as in Example A1-1.

[0334] <Evaluation of non-aqueous electrolyte batteries> [Initial conditioning] The nonaqueous electrolyte battery prepared by the above method was charged at a constant current of 0.05 C (1 C refers to the current value required for charging or discharging in 1 hour; the same applies below) for 6 hours in a constant temperature bath at 25°C, and then discharged at 0.2 C to 3.0 V. Subsequently, constant current-constant voltage charging (hereinafter referred to as CC-CV charging) was performed at 0.2 C to 4.1 V. After that, the battery was held at 45°C for 72 hours for aging. The battery was then discharged at 0.2 C to 3.0 V to stabilize the nonaqueous electrolyte battery. Furthermore, CC-CV charging was performed at 0.2 C to 4.2 V, and then discharged at 0.2 C to 3.0 V for initial conditioning. After initial conditioning, the batteries were CC-CV charged at 0.2 C to half the initial discharge capacity. They were then discharged at 1.0 C, 2.0 C, and 3.0 C at 25°C, and the voltage was measured after 5 seconds. The average slope of the current-voltage curves at 1.0 C, 2.0 C, and 3.0 C was used as the battery internal resistance.

[0335] <Evaluation of non-aqueous electrolyte batteries> [Charged storage test] After initial conditioning, the laminated battery was again subjected to CC-CV charging at 0.2C to 4.2V, followed by high-temperature storage at 60°C for 168 hours. After the battery was cooled sufficiently, the post-storage test cell was discharged to 2.5V at 0.2C and CC-CV charged at 0.2C to half the initial discharge capacity, and the battery internal resistance after the storage test was determined. The "internal resistance increase rate" was calculated using the following formula (X): Internal resistance increase rate = [(internal resistance after storage test) / (internal resistance after initial conditioning)] x 100% (X) Table 2 below shows the ratio of the internal resistance increase rate when the internal resistance increase rate of Comparative Example B1-1 is set to 100.

[0336] [Table 2]

[0337] From the results of Examples B1-1 to B1-11 and Comparative Example B1-2, it was found that the nonaqueous electrolyte battery manufactured using the nonaqueous electrolyte containing the compound having a polar group according to the present invention can suppress the increase in resistance during high-temperature storage more effectively than the nonaqueous electrolyte battery manufactured using the nonaqueous electrolyte containing the conventional compound. Furthermore, from the results of Examples B1-1 to B1-11, Z in the compounds in each of the above-mentioned embodiments 1 ~Z 4 When comparing the embodiments in which the atom is a carbon atom, a sulfur atom, and a phosphorus atom, it was found that the embodiment in which the atom is a carbon atom tends to be able to suppress an increase in resistance during high-temperature storage. Furthermore, from the results of Examples B1-3 to B1-5, Examples B1-7 to B1-11, Comparative Example B1-3, and Comparative Example B1-4, it was found that when the compound having a polar group according to the present invention is used in combination with LiPO2F2 or LiSO3F, the increase in resistance during high-temperature storage can be suppressed more effectively than when each compound is used alone. Furthermore, from the results of Examples A1-1 to 1-12 in Table 1 and Examples B1-1 to 1-3 in Table 2, it is clear that Z in the compounds in each of the above-mentioned embodiments 1 ~Z 4 When comparing the embodiments in which the atom is a carbon atom, a sulfur atom, and a phosphorus atom, it was found that the embodiment in which the atom is a carbon atom tends to be able to suppress the amount of gas generation and also the rate of increase in internal resistance.

[0338] <Examples 2-1 to 2-9, Comparative Examples 2-1 and 2-2> [Preparation of positive electrode] The positive electrode active material was lithium nickel manganese cobalt composite oxide (Li 1.00 Ni 0.34 Co 0.33 Mn 0.33 85% by mass of O2, 10% by mass of acetylene black as a conductive material, and 5% 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 21 μm thick aluminum foil, dried, and pressed to form a positive electrode.

[0339] [Preparation of negative electrode] Si microparticles with an average particle size of 50 nm were dispersed in flake graphite with an average particle size of 35 μm, and then placed in a hybridization system (manufactured by Nara Machinery Works, Ltd.). The mixture was circulated or retained within the system at a rotor rotation speed of 7000 rpm for 180 seconds to obtain a composite of Si and graphite particles. The resulting composite was mixed with coal tar pitch as an organic compound to form a carbonaceous material, so that the coverage after firing would be 16.8%, and the mixture was kneaded and dispersed using a twin-screw kneader. The resulting dispersion was introduced into a firing furnace and fired at 1000°C for 3 hours under a nitrogen atmosphere. The resulting fired material was further pulverized in a hammer mill and sieved (45 μm) to produce a negative electrode active material. The silicon content measured using the above-mentioned method was 14.0% by mass.

[0340] To the negative electrode active material (above negative electrode active material:graphite = 35:65 weight ratio), an aqueous dispersion of sodium carboxymethylcellulose (concentration of sodium carboxymethylcellulose: 1% by mass) and an aqueous dispersion of styrene-butadiene rubber (concentration of styrene-butadiene rubber: 50% by mass) were added as a thickener and binder, respectively, and mixed in a disperser to form a slurry. This slurry was evenly applied to one side of a 10 μm thick copper foil, dried, and then pressed to form a negative electrode. Note that the negative electrode was prepared so that the mass ratio of negative electrode active material:sodium carboxymethylcellulose:styrene-butadiene rubber after drying was 97.5:1.5:1.

[0341] [Preparation of non-aqueous electrolyte] In a dry argon atmosphere, 1.2 mol / L (as the concentration in the non-aqueous electrolyte) of thoroughly dried LiPF6 was dissolved in a mixture of ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) (volume ratio: 3:4:3), and 2.0 mass% of vinylene carbonate (VC) was added to the solution (referred to as reference electrolyte 2). In Examples 2-1 to 2-9 and Comparative Examples 2-1 to 2-3, the reference electrolyte was adjusted to have the contents shown in Table 3 below. 2 Each compound was added to prepare a non-aqueous electrolyte solution. However, Comparative Example 2-1 is the same as Reference Electrolyte Solution 2. In the table, the "content (mass %)" is the concentration in 100 mass % of the non-aqueous electrolyte solution.

[0342] [Manufacturing of non-aqueous electrolyte secondary 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, with the positive and negative electrode terminals protruding, and the electrolyte solution was then poured into the bag, which was then vacuum-sealed to prepare a laminated cell nonaqueous electrolyte secondary battery.

[0343] <Evaluation of non-aqueous electrolyte secondary batteries> [Initial conditioning] The nonaqueous electrolyte battery prepared by the above method was charged at a constant current of 0.05 C (1 C refers to the current value required for charging or discharging in 1 hour; the same applies below) for 6 hours in a constant temperature bath at 25°C, and then discharged at 0.2 C to 3.0 V. Subsequently, constant current-constant voltage charging (hereinafter referred to as CC-CV charging) was performed at 0.2 C to 4.1 V. After that, the battery was held at 45°C for 72 hours for aging. The battery was then discharged at 0.2 C to 3.0 V to stabilize the nonaqueous electrolyte battery. Furthermore, CC-CV charging was performed at 0.2 C to 4.2 V, and then discharged at 0.2 C to 3.0 V for initial conditioning.

[0344] [High temperature cycle test] After the initial conditioning, the battery thickness was measured using a micrometer (Mitutoyo, model ID-C112XB). The cells were then subjected to CC-CV charging at 0.5 C to 4.2 V in a 45°C thermostatic chamber, followed by discharging at a constant current of 0.5 C to 2.5 V. This cycle was repeated 100 times. The battery thickness was then measured in the same manner as after the initial conditioning, and the change in battery thickness due to cycle charging and discharging was determined. Table 3 below shows the percentage change in battery thickness for each example, expressed as "battery swelling," relative to the change in battery thickness for Comparative Example 2-1, which is set to 100. In other words, a "battery swelling" value below 100 indicates a smaller change in battery thickness compared to Comparative Example 2-1, while a value above 100 indicates a larger change in battery thickness compared to Comparative Example 2-1.

[0345] [Table 3]

[0346] The results of Examples 2-1 to 2-9 and Comparative Example 2-2 show that the nonaqueous electrolyte battery manufactured using the nonaqueous electrolyte solution containing the compound having a polar group according to the present invention can suppress battery swelling more effectively than the nonaqueous electrolyte battery manufactured using the nonaqueous electrolyte solution containing a conventional compound. Furthermore, from the results of Examples 2-1 to 2-7, Z in the compounds in each of the above-mentioned embodiments 1 ~Z 4 When comparing the embodiments in which the atom leading to the above is a carbon atom, a sulfur atom, and a phosphorus atom, it was found that the embodiment in which the atom leading to the above is a carbon atom tends to be more effective in suppressing battery swelling.

[0347] <Examples 3-1 to 3-4, Comparative Example 3-1> [Preparation of positive electrode] The positive electrode active material was lithium-nickel-cobalt-manganese composite oxide (Li 1.0 Ni 0.82 Co 0.11 Mn 0.07 95 parts by mass of O2, 3 parts by mass of acetylene black as a conductive material, and 2 parts by mass of polyvinylidene fluoride (PVdF) as a binder were mixed in N-methylpyrrolidone solvent using a disperser to form a slurry, which was then uniformly applied to both sides of a 15 μm thick aluminum foil, dried, and pressed to form a positive electrode.

[0348] [Preparation of negative electrode] To 97 parts by mass of natural graphite, 1 part by mass of an aqueous dispersion of sodium carboxymethylcellulose (concentration of sodium carboxymethylcellulose: 1.5% by mass) and 1.5 parts by mass of an aqueous dispersion of styrene-butadiene rubber (concentration of styrene-butadiene rubber: 50% by mass) were added as thickeners and binders, 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.

[0349] [Preparation of non-aqueous electrolyte] In a dry argon atmosphere, 1.2 mol / L (14.8 mass%; concentration in non-aqueous electrolyte) of LiPF6 was dissolved as an electrolyte in a mixture of ethylene carbonate (EC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC) (volume ratio EC:EMC:DEC = 3:4:3). Furthermore, 2.0 mass% each of vinylene carbonate (VC) and fluoroethylene carbonate (FEC) were added (non-aqueous electrolyte). (Hereinafter, this will be referred to as Reference Electrolyte 1). 4 The compound at the content described in 4~8 The "content (mass %)" in the table is the content when the total amount of each nonaqueous electrolyte solution is taken as 100 mass %.

[0350] [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.

[0351] <Evaluation of non-aqueous electrolyte batteries> [Initial conditioning] The nonaqueous electrolyte battery prepared by the above method was charged at a constant current of 0.05 C (1 C refers to the current value required for charging or discharging in 1 hour; the same applies below) for 6 hours in a constant temperature bath at 25°C, and then discharged at 0.2 C to 3.0 V. Subsequently, constant current-constant voltage charging (hereinafter referred to as CC-CV charging) was performed at 0.2 C to 4.1 V. After that, the battery was held at 45°C for 72 hours for aging. The battery was then discharged at 0.2 C to 3.0 V to stabilize the nonaqueous electrolyte battery. Furthermore, CC-CV charging was performed at 0.2 C to 4.2 V, and then discharged at 0.2 C to 3.0 V for initial conditioning.

[0352] [Charged storage test] After initial conditioning, the nonaqueous electrolyte battery was again subjected to CC-CV charging at 0.2 C to 4.2 V, and then stored at high temperature at 60°C for two weeks. After that, the nonaqueous electrolyte battery was allowed to cool sufficiently, 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 storage test, and this was recorded as the "amount of gas generated during storage during charging." Table 3 below shows the values ​​of the amount of gas generated during storage during charging, assuming the amount of gas generated during storage during charging in Comparative Example 3-1 as 100.

[0353] [Table 4]

[0354] From the results of Examples 3-1 to 3-4 and Comparative Example 3-1, it was found that the amount of gas stored during charging can be reduced more effectively in a nonaqueous electrolyte battery manufactured using a nonaqueous electrolyte solution containing a compound having a polar group according to an embodiment of the present application than in a nonaqueous electrolyte battery manufactured using a nonaqueous electrolyte solution containing a conventional compound. Furthermore, the results of Examples 3-1 to 3-4 reveal that compounds having a carboxylic acid ester structure tend to be more effective in suppressing the amount of residue generated during storage under charge.

[0355] <Examples 4-1 to 4-4, Comparative Example 4-1> [Preparation of positive electrode] The positive electrode active material was lithium-nickel-cobalt-manganese composite oxide (Li 1.0 Ni 0.9 Co 0.06 Mn 0.04 95 parts by mass of O2, 3 parts by mass of acetylene black as a conductive material, and 2 parts by mass of polyvinylidene fluoride (PVdF) as a binder were mixed in N-methylpyrrolidone solvent using a disperser to form a slurry, which was then uniformly applied to both sides of a 15 μm thick aluminum foil, dried, and pressed to form a positive electrode.

[0356] [Preparation of negative electrode] To 97 parts by mass of natural graphite, 1 part by mass of an aqueous dispersion of sodium carboxymethylcellulose (concentration of sodium carboxymethylcellulose: 1.5% by mass) and 1.5 parts by mass of an aqueous dispersion of styrene-butadiene rubber (concentration of styrene-butadiene rubber: 50% by mass) were added as thickeners and binders, 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.

[0357] [Preparation of non-aqueous electrolyte] In a dry argon atmosphere, 1.2 mol / L (14.8 mass%; concentration in 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:EMC:DEC = 3:4:3), and then 2.0 mass% each of vinylene carbonate (VC) and fluoroethylene carbonate (FEC) (concentration in non-aqueous electrolyte) was added (hereinafter referred to as Reference Electrolyte 1). 5 The compound at the content described in 4~8 The "content (mass %)" in the table is the content when the total amount of each nonaqueous electrolyte solution is taken as 100 mass %.

[0358] [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.

[0359] <Evaluation of non-aqueous electrolyte batteries> [Initial conditioning] The nonaqueous electrolyte battery prepared by the above method was charged at a constant current of 0.05 C (1 C refers to the current value required for charging or discharging in 1 hour; the same applies below) for 6 hours in a constant temperature bath at 25°C, and then discharged at 0.2 C to 3.0 V. Subsequently, constant current-constant voltage charging (hereinafter referred to as CC-CV charging) was performed at 0.2 C to 4.1 V. After that, the battery was held at 45°C for 72 hours for aging. The battery was then discharged at 0.2 C to 3.0 V to stabilize the nonaqueous electrolyte battery. Furthermore, CC-CV charging was performed at 0.2 C to 4.2 V, and then discharged at 0.2 C to 3.0 V for initial conditioning.

[0360] [Charged storage test] After initial conditioning, the non-aqueous electrolyte battery was again CC-CV charged at 0.2C to 4.2V, and then stored at high temperature at 60°C for 2 weeks. After that, the non-aqueous electrolyte battery was allowed to cool sufficiently, and then immersed in an ethanol bath to measure the volume. The amount of gas generated was calculated from the change in volume before and after the storage test, and this was taken as the "amount of gas generated during storage after charging." 5 4 shows the amount of gas stored in the battery when the amount of gas stored in the battery in Comparative Example 4-1 is set to 100.

[0361] [Table 5]

[0362] The results of Examples 4-1 to 4-4 and Comparative Example 4-1 show that the amount of gas stored during charging can be reduced more effectively in a nonaqueous electrolyte battery manufactured using a nonaqueous electrolyte solution containing a compound having a polar group according to an embodiment of the present application than in a nonaqueous electrolyte battery manufactured using a nonaqueous electrolyte solution containing a conventional compound. Furthermore, the results of Examples 4-1 to 4-4 reveal that compounds having a carboxylic acid ester structure tend to be more effective in suppressing the amount of residue generated during storage under charge.

[0363] While the present invention has been described above with reference to specific embodiments, these embodiments are presented as examples and do not limit the scope of the present invention. Each embodiment described in this specification can be modified in various ways without departing from the spirit of the invention, and can be combined with features described in other embodiments to the extent possible. < / a1> < / a1> < / a1>

Claims

1. A nonaqueous electrolyte solution for a nonaqueous electrolyte battery having a positive electrode and a negative electrode capable of absorbing and releasing metal ions, the nonaqueous electrolyte solution containing a compound represented by the following general formula (1) together with an alkali metal salt and a nonaqueous solvent: 【Chemistry 1】 (In general formula (1), R １ represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may have a substituent; R ２ represents a hydrogen atom, an optionally substituted monovalent hydrocarbon group, or an optionally substituted alkoxy group; X １ represents a divalent hydrocarbon group which may have a substituent; n １ represents 2 or 3; １ represents an integer of 0 to 2, and q １ represents an integer of 1 to 3, and p １ +q １ = 2 or 3; R １ and X １ two of A may be bonded to each other to form a ring; １ is a divalent or trivalent atomic group represented by the following general formula (2-1), or a trivalent atomic group represented by the following general formula (3-1): 【Chemistry 2】 (In general formula (2-1), Z １ represents a carbon atom, a sulfur atom, a phosphorus atom, or a boron atom; Y １０１ represents an oxygen atom or a sulfur atom; Y １ , Y ２ and Y ３ are each independently a single bond, an oxygen atom, a sulfur atom, or NR １０１ represents a group; R １０１ represents a hydrogen atom or a monovalent hydrocarbon group; R １０１ When R is a monovalent hydrocarbon group, １０１ represents R in the general formula (1). １ and X １ may be bonded to any of the following to form a ring; r １ Is Z １ is 1 when Z is a carbon atom; １ is 0, 1, or 2 when is a sulfur atom; １ is 0 or 1 when it is a phosphorus atom, and Z １ is 0 when is a boron atom; r ２ Is Z １ is 0 when Z is a carbon atom or a sulfur atom; １ is 1 when is a phosphorus atom or a boron atom; * represents R in the general formula (1) １ or X １ The binding site is shown. However, Z １ is a sulfur atom, and r １ When is 2, Y １ and Y ２ cannot both be single bonds.) 【Transformation 3】 (In general formula (3-1), Y ４ , Y ５ and Y ６ are each independently an oxygen atom, a sulfur atom, or NR ２０１ indicates; R ２０１ represents a hydrogen atom or a monovalent hydrocarbon group; * represents a group represented by the general formula R in (1) １ or X １ The binding site is shown.) (However, when Z 1 in the general formula (2-1) is a carbon atom, the compound represented by the general formula (1) is a compound represented by the following general formula (1-4): 【Chemistry 4】 (In general formula (1-4), R 11 represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may have a substituent; R 12 represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent; X 11 represents a divalent hydrocarbon group having 3 or more carbon atoms which may have a substituent; Y 21 and Y 22 each independently represent a single bond, an oxygen atom, a sulfur atom, or NR 301 ; when R 301 is a monovalent hydrocarbon group, R 301 may be bonded to either R 11 or X 11 to form a ring; n 11 represents 2; are not bonded to form a ring. However, when Y 21 and Y 22 are oxygen atoms, n 11 may be 3.

2. The nonaqueous electrolyte solution according to claim 1, wherein the general formula (2-1) is the following formula (2-2): 【Transformation 5】 (In general formula (2-2), Z ２ represents a carbon atom, a sulfur atom, or a phosphorus atom; Y ７ , Y ８ and Y ９ are each independently a single bond or an oxygen atom; r ３ Is Z ２ is 1 when Z is a carbon atom; ２ is 0, 1, or 2 when is a sulfur atom; ２ is 0 or 1 when is a phosphorus atom; r ４ Is Z ２ is 0 when Z is a carbon atom or a sulfur atom; ２ is a phosphorus atom, the value is 1. * indicates the bonding site with R1 or X1 in the general formula (1). However, Z ２ is a sulfur atom, and r ３ When is 2, Y ７ and Y ８ are never both single bonds.)

3. The nonaqueous electrolyte solution according to claim 1 or 2, wherein the general formula (3-1) is the following general formula (3-2): 【Transformation 6】 (In the general formula (3-2), * represents R in the general formula (1) １ or X １ The binding site is shown.)

4. The non-aqueous electrolyte solution according to any one of claims 1 to 3, wherein the content of the compound represented by the general formula (1) is 0.001 to 10 mass% based on the total amount of the non-aqueous electrolyte solution.

5. Furthermore, fluorophosphates, FSO ２ The non-aqueous electrolyte solution according to any one of claims 1 to 4, comprising one or more compounds selected from the group consisting of salts having a skeletal structure and oxalates, and the total content of the compounds is 0.001 to 5 mass% with respect to the total amount of the non-aqueous electrolyte solution.

6. The nonaqueous electrolyte solution according to claim 1, wherein X 11 in the general formula (1-4) is an alkylene group.

7. A non-aqueous electrolyte battery comprising a positive electrode, a negative electrode, 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 6.

8. 8. The nonaqueous electrolyte battery according to claim 7, wherein the positive electrode contains a positive electrode active material, and the positive electrode active material is a metal oxide represented by the following composition formula (13): Li ａ１ Ni ｂ１ M1 ｃ１ O ２ ・・・(13) (In formula (13), a1, b1, and c1 are numerical values ​​that satisfy 0.90≦a1≦1.10, 0.40≦b1≦0.98, and 0.00≦c1≦0.50, respectively, and b1+c1=1 is satisfied. M1 represents at least one element selected from the group consisting of Co, Mn, Al, Mg, Zr, Fe, Ti, and Er.)

9. 9. The nonaqueous electrolyte battery according to claim 7, wherein the negative electrode comprises a negative electrode active material capable of absorbing and releasing metal ions, and the negative electrode active material comprises a material containing a metal element and / or a metalloid element capable of alloying with Li.

10. 10. The nonaqueous electrolyte battery according to claim 9, wherein the material containing a metal element and / or a metalloid element capable of alloying with Li is metallic Si or a Si oxide.

11. A compound represented by the following general formula (1-4): 【Chemistry 11】 (In general formula (1-4), R １１ represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may have a substituent; R １２ represents a hydrogen atom or an optionally substituted monovalent hydrocarbon group; X １１ represents a divalent hydrocarbon group having 3 or more carbon atoms which may have a substituent; Y 21 represents a single bond, an oxygen atom, a sulfur atom, or NR ３０１ Y 22 is an oxygen atom; R ３０１ When R is a monovalent hydrocarbon group, ３０１ is R １１ and X １１ may be bonded to any one of the following to form a ring; １１ represents 2; R 11 and X 11 do not combine to form a ring. However, when Y 21 and Y 22 are oxygen atoms, n １１ may be 3.) 12. The compound according to claim 11, wherein in the general formula (1-4), Y 21 is an oxygen atom.

13. A compound selected from the group consisting of the following formulas (1-4-1) to (1-4-4): 【Chemistry 12】

14. A compound represented by the following general formula (1-5): 【Chemistry 13】 (In general formula (1-5), R １３ represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may have a substituent; R １４ represents a hydrogen atom or an optionally substituted monovalent hydrocarbon group; X represents an optionally substituted divalent hydrocarbon group having 3 or more carbon atoms; Y ２３ and Y ２４ are each independently a single bond, an oxygen atom, a sulfur atom, or NR ３１１ and R ３１１ When R is a monovalent hydrocarbon group, ３１１ is R １３ and X １２ may be bonded to any one of the groups to form a ring; １２ is 0, 1 or 2; n １２ represents 2 or 3; R １３ and X １２ Two of these may be bonded to each other to form a ring.

15. The compound according to claim 14, which is a compound selected from the group consisting of the following formulas (1-5-1) and (1-5-2): 【Chemistry 14】

16. A compound represented by the following general formula (1-6): 【Chemistry 15】 (In general formula (1-6), R １５ , and R １５’ each independently represents a hydrogen atom, a halogen atom, or an optionally substituted monovalent hydrocarbon group; R represents a hydrogen atom or an optionally substituted monovalent hydrocarbon group; X １３ represents a divalent hydrocarbon group having 3 or more carbon atoms which may have a substituent; Y ２５ , Y ２５’ , and Y ２６ are each independently a single bond, an oxygen atom, a sulfur atom, or NR ３２１ and R ３２１ represents a hydrogen atom or a monovalent hydrocarbon group; R ３２１ When R is a monovalent hydrocarbon group, ３２１ is R １５ , R １５’ , and X １３ may be bonded to any one of the following to form a ring; １３ represents 2 or 3; R １５ and X １３ Two of these may be bonded to each other to form a ring.

17. The compound according to claim 16, which is a compound selected from the group consisting of the following formulas (1-6-1) to (1-6-3): 【Chemistry 16】

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