Non-aqueous electrolytes and non-aqueous electrolyte batteries

Abstract

Provided are a non-aqueous electrolyte capable of suppressing the amount of gas generated during high-temperature storage of a non-aqueous electrolyte battery, a non-aqueous electrolyte battery comprising the non-aqueous electrolyte, and a compound used in the non-aqueous electrolyte. 【Solution means】A non-aqueous electrolyte for a non-aqueous electrolyte battery comprising a positive electrode and a negative electrode capable of occluding and releasing metal ions, wherein the non-aqueous electrolyte contains a compound represented by formula (1) together with an alkali metal salt and a non-aqueous solvent. TIFF2026076364000130.tif31170 In formula (1), R 1 is a hydrogen atom, a halogen atom, or a substituted / unsubstituted monovalent hydrocarbon group, R 2 is a hydrogen atom, a substituted / unsubstituted monovalent hydrocarbon group, or an alkoxy group having a substituent, X 1 is a substituted / unsubstituted divalent hydrocarbon group, n 1 is 2 or 3, p 1 is an integer from 0 to 2, q ) 1 is an integer from 1 to 3, p 1 +q 1 =2 or 3, R 1 and X 1 Two of them are bonded to each other to form a ring, and A 1 is a divalent or trivalent atomic group represented by a specific formula.

Description

[Technical Field]

[0001] The present invention relates to a non-aqueous electrolyte and a non-aqueous electrolyte battery, and more specifically to a non-aqueous electrolyte containing a specific compound in a specific amount, and a non-aqueous electrolyte battery using this non-aqueous electrolyte. [Background technology]

[0002] Non-aqueous electrolyte batteries, such as lithium-ion secondary batteries, have been put into practical use in a wide range of applications, including power supplies for so-called consumer small devices such as smartphones and laptop computers, as well as on-board power supplies for electric vehicles.

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

[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 offers 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 resistance increase rate 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 specific organosilicon compounds having organic groups such as cyano groups, isocyanate groups, or isothiocyanate groups in their structure to a non-aqueous electrolyte. Patent Document 5 discloses a study on improving the volume retention rate and resistance increase during long-term use and high-temperature storage by adding a specific fluorosilane compound to a non-aqueous electrolyte. [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 Publication No. 2018-46021 [Patent Document 5] Japanese Patent Publication No. 2009-004352 [Overview of the project] [Problems that the invention aims to solve]

[0006] In recent years, there has been an acceleration in increasing the capacity of lithium batteries for use in electric vehicles and mobile phones such as smartphones, resulting in a smaller proportion of air voids within the battery compared to conventional batteries. Consequently, the amount of gas generated when lithium batteries are exposed to high-temperature environments and the swelling of the electrodes after repeated charging and discharging become critical drawbacks.

[0007] The first objective of the present invention is to provide a non-aqueous electrolyte that can suppress the amount of gas generated when a non-aqueous electrolyte battery is stored at high temperatures, a non-aqueous electrolyte battery equipped with the non-aqueous electrolyte, and a compound used in the non-aqueous electrolyte. The amount of gas generated is the amount of gas produced by the decomposition of the solvent and additives, which are components of the electrolyte, on the electrodes. Furthermore, a second objective of the present invention is to provide a non-aqueous electrolyte battery in which battery swelling is suppressed. Battery swelling occurs when Li is added to the active material during charging and discharging. + This is an indicator that reflects the expansion of the active material itself during absorption and release. [Means for solving the problem]

[0008] As a result of diligent research to solve the above-mentioned first problem, the inventors of the present invention conceived that by using a non-aqueous electrolyte containing a compound represented by general formula (1), the amount of gas generated during high-temperature storage of a non-aqueous electrolyte battery can be suppressed, and thus completed the first aspect of the present invention. Furthermore, the inventors diligently studied to solve the second problem described above and came to the conclusion that swelling of a non-aqueous electrolyte battery can be suppressed by combining a non-aqueous electrolyte containing a compound represented by general formula (1) with a negative electrode containing a specific negative electrode active material, thereby completing a second aspect of the present invention.

[0009] In other words, the first aspect of the present invention provides the following specific embodiments. <a1>A non-aqueous electrolyte for a non-aqueous electrolyte battery comprising a positive electrode and a negative electrode capable of occluding and releasing metal ions, characterized in that the non-aqueous electrolyte contains a compound represented by the following general formula (1) together with an alkali metal salt and a non-aqueous solvent. [Chemical formula] (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, 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, q 1 represents an integer of 1 to 3, p 1 + q 1 = 2 or 3; R 1 and X 1 may be bonded to each other to form a ring; A 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).) [Chemical formula] (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 each independently represent a single bond, an oxygen atom, a sulfur atom, NR 101 ; R 101 represents a hydrogen atom or a monovalent hydrocarbon group; when R 101 is a monovalent hydrocarbon group, the R 101 may be bonded to any one of R 1 and X 1 in the general formula (1) to form a ring; r 1 is, Z 1 When is a carbon atom, it is 1, Z 1 When is a sulfur atom, it is 0, 1, or 2, and Z 1 When is a phosphorus atom, it is 0 or 1, Z 1 When it is a boron atom, it is 0; r 2 is, Z 1 When is a carbon atom or a sulfur atom, it is 0, and Z 1 When it is a phosphorus atom or a boron atom, it is 1; * represents R in the general formula (1) above. 1 or X 1 This shows the binding site. However, Z 1 is a sulfur atom, and r 1 When Y is 2, 1 and Y 2 (They can never form a single bond together.) [ka] (In general formula (3-1), Y 4 , Y 5 and Y 6 Each of these is independently an oxygen atom, a sulfur atom, or NR 201 R 201 * represents a hydrogen atom or a monovalent hydrocarbon group; * represents R in the general formula (1) above. 1 or X 1 (This indicates the binding site.) <a2>The above general formula (2-1) is the following formula (2-2), <a1>The non-aqueous electrolyte described above. [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 Each is independently either a single bond or an oxygen atom; r 3 is, Z 2 When is a carbon atom, it is 1, Z 2 When is a sulfur atom, it is 0, 1, or 2, and Z 2 When it is a phosphorus atom, it is 0 or 1; r 4 is, Z 2 When is a carbon atom or a sulfur atom, it is 0, and Z 2 The value is 1 when it is a phosphorus atom. * represents R in the general formula (1) above. 1 or X 1 This shows the binding site. However, Z 2 is a sulfur atom, and r 3 When Y is 2, 7 and Y 8 (They can never form a single bond together.) <a3>The above general formula (3-1) is the following general formula (3-2), <a1>or <a2>The non-aqueous electrolyte described above. [ka] (In general formula (3-2), * represents R in general formula (1) above.) 1 or X 1 (This indicates the binding site.) <a4>The content of the compound represented by the general formula (1) is 0.001 to 10% by mass relative to the total amount of the non-aqueous electrolyte. <a1> ~ <a3>A non-aqueous electrolyte as described in any of the following. <a5>Furthermore, it contains one or more compounds selected from the group consisting of fluorophosphates, salts having an FSO2 skeleton, and oxalates, and the total content of these compounds is 0.001 to 5% by mass relative to the total amount of the non-aqueous electrolyte. <a1> ~ <a4>A non-aqueous electrolyte as described in any of the following. <a6>A non-aqueous electrolyte battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte, wherein the non-aqueous electrolyte is <a1> ~ <a5>A non-aqueous electrolyte battery, which uses a non-aqueous electrolyte as described in any of the following. <a7>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). <a6>Non-aqueous electrolyte batteries as described above. Li a1 Ni b1 M1 c1 O2···(13) (In equation (13), a1, b1, and c1 are numerical values ​​satisfying 0.90 ≤ a1 ≤ 1.10, 0.40 ≤ b1 ≤ 0.98, and 0.00 ≤ c1 ≤ 0.50, respectively, and b1 + c1 = 1. 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 comprises a negative electrode active material capable of intercalating and releasing metal ions, and the negative electrode active material comprises a material containing a metal element and / or metalloid element that can alloy with Li. <a6>or <a7>Non-aqueous electrolyte batteries as described above. <a9>The material containing a metallic element and / or metalloid element that can be alloyed with Li is metallic Si or Si oxide. <a8>Non-aqueous electrolyte batteries as described above. <a10>Compounds represented by the following general formulas (1-4). [ka] (In general formula (1-4), R 11 R represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may have substituents; 12 X represents a hydrogen atom and a potentially substituted monovalent hydrocarbon group; X 11 This represents a divalent hydrocarbon group having 3 or more carbon atoms, which may have substituents; Y 21 and Y 22 Each of these independently consists of a single bond, an oxygen atom, a sulfur atom, or NR. 301 And; R 301 R represents a hydrogen atom or a monovalent hydrocarbon group; 301 is a monovalent hydrocarbon If it is a base, then R 301 R 11 and X 11 It may also be bonded to any of the following to form a ring; n 11 R indicates 2; 11 and X 11 Two of them may be joined together to form a ring. However, Y 21 and Y 22 is an oxygen atom, and R 11 and X 11 When they are not joined to form a ring, n 11 (It may also be 3.) <a11>The compound is selected from the group consisting of the following formulas (1-4-1) to (1-4-4). <a10>The compounds described above. [ka] <a12>A compound represented by the following general formula (1-5). [Chemical formula] (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 a monovalent hydrocarbon group which may have a substituent; X 12 represents a divalent hydrocarbon group having 3 or more carbon atoms which may have a substituent; Y 23 and Y 24 each independently represent a single bond, an oxygen atom, a sulfur atom, or NR 311 ; R 311 represents a hydrogen atom or a monovalent hydrocarbon group; when R 311 is a monovalent hydrocarbon group, the R 311 may be bonded to any one of R 13 and X 12 to form a ring; r 12 is 0, 1 or 2; n 12 represents 2 or 3; two of R 13 and X 12 may be bonded to each other to form a ring.) <a13>The compound is selected from the group consisting of the following formulas (1-5-1) and (1-5-2). <a12>The compounds described above. [ka] <a14>Compounds represented by the following general formulas (1-6). [ka] (In general formula (1-6), R 15 , and R 15 Each of the following independently represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may have substituents; R 16 X represents a hydrogen atom and a potentially substituted monovalent hydrocarbon group; X 13 This represents a divalent hydrocarbon group having 3 or more carbon atoms, which may have substituents; Y 25 , Y 25 ', and Y 26 Each of these independently consists of a single bond, an oxygen atom, a sulfur atom, or NR. 321 And; R 321 R represents a hydrogen atom or a monovalent hydrocarbon group; 321 If is a monovalent hydrocarbon group, then R 321 R 15 , R 15 ', and X 13 It may also be bonded to any of the following to form a ring; n 13 R indicates 2 or 3. 15 and X 13 Two of them may be joined together to form a ring. <a15>The compound is selected from the group consisting of the following formulas (1-6-1) to (1-6-3). <a14>The compounds described above. [ka]

[0010] Furthermore, a second aspect of the present invention provides the following specific embodiments. <b1>A non-aqueous electrolyte battery comprising a positive electrode and a negative electrode capable of intercalating and releasing metal ions, and a non-aqueous electrolyte, The negative electrode active material contained in the negative electrode contains a material that contains a metallic element and / or a metalloid element that can be alloyed with Li, A non-aqueous electrolyte battery characterized in that the non-aqueous electrolyte contains an alkali metal salt, a non-aqueous solvent, and a compound represented by the following general formula (4). [ka] (In general formula (4), R 3 R represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may have substituents; 4 X represents a hydrogen atom, a optionally substituted monovalent hydrocarbon group, or an optionally substituted alkoxy group; X 2 represents a divalent hydrocarbon group which may have substituents; n 2 represents an integer between 1 and 3; p 2 represents an integer between 0 and 2, and q 2 represents an integer between 1 and 3, and p 2 +q 2 = 2 or 3; R 3 and X 2 Two of them may be joined together to form a ring; A 2 (This refers to 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 Each of these independently consists of a single bond, an oxygen atom, a sulfur atom, or NR. 102 R 102 R represents a hydrogen atom or a monovalent hydrocarbon group; 102 If is a monovalent hydrocarbon group, then R 102 R in the general formula (2) is 3 and X 2 It may be bonded to any of the following to form a ring; r 5 is, Z 3 When is a carbon atom, it is 1, Z 3 When is a sulfur atom, it is 0, 1, or 2, and Z 3 When it is a phosphorus atom, the value is 0 or 1. r 6 is, Z 3 When is a carbon atom or a sulfur atom, it is 0, and Z 3 When it is a phosphorus atom, it is 1; * represents R in the general formula (4) above. 3 or X 2 This shows the binding site. However, Z 1 is a sulfur atom, and r 5 When Y is 2, 10 and Y 11 (They can never form a single bond together.) [ka] (In general formula (6-1), Y 13 , Y 14 and Y 15 Each of these is independently an oxygen atom, a sulfur atom, or NR 202 R 202 * represents a hydrogen atom or a monovalent hydrocarbon group; * represents R in the general formula (4) above. 3 or X 2 (This indicates the binding site.) <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 generated 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. In this specification, descriptions such as "independently" or "independently" used when explaining two or more objects together are used to mean that the 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). Although the mechanism for enhancing the suppression of the amount of gas generated during high-temperature storage of a non-aqueous electrolyte battery by using a non-aqueous electrolyte containing the compound represented by the general formula (1) 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) interacts with carbon or the like on the surface of the negative electrode active material and tends to localize in the vicinity of the surface of the negative electrode active material. Further, 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 where one F atom is bonded. As a result, the reaction activity of the Si atom of the compound represented by the general formula (1) is increased, and for example, an electrochemical reduction or a reaction with a reduction decomposition product of an 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 (1) is also concentrated on the surface of the positive electrode, reacts with an electrochemical oxidation or an oxidation decomposition product of an electrolytic solution, and forms an insulating film similarly to the negative electrode. Therefore, the inventor of the present invention believes that the compound represented by the general formula (1) contributes to suppressing the amount of gas generated during high-temperature storage. From the above, the inventor of the present invention believes that the compound represented by the general formula (1) contributes to suppressing the amount of gas generated 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 contains 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 between 0 and 2, and q 1 represents an integer between 1 and 3, and p 1 +q 1 = 2 or 3; R 1 and X 1 Two of them may be joined together to form a ring; A 1 This refers to 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 related to general formula (1) 1 This represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may have substituents. R 1 In terms of ease of industrial handling of the compound represented by general formula (1) during compound production, storage, and electrolyte production, a monovalent hydrocarbon group having 1 to 12 carbon atoms, which may have substituents, is preferred. Note that if the hydrocarbon group has substituents, the number of carbon atoms contained in the substituents is not included in this carbon number. Furthermore, from the viewpoint of suitably forming the insulating coating, R 1 It is also preferable that it be a halogen atom. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms, but fluorine atoms are preferred. Examples of monovalent hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, or aralkyl groups. Among these, alkyl groups, alkenyl groups, or alkynyl groups are preferred from the viewpoint of suppressing side reactions on the electrode of the compound represented by general formula (1), more preferably alkyl groups or alkenyl groups, and particularly preferably alkyl groups.

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

[0020] Examples of alkyl groups having a cyclic structure include alkyl groups having 3 to 12 carbon atoms, such as 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, or methylcyclohexylmethyl group. In particular, alkyl groups having a cyclic structure with 3 to 8 carbon atoms, such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclohexylmethyl group, cyclohexylethyl group, methylcyclohexyl group, dimethylcyclohexyl group, ethylcyclohexyl group, or methylcyclohexylmethyl group, are preferred, and alkyl groups having a cyclic structure with 6 to 8 carbon atoms, such as cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, methylcyclohexyl group, dimethylcyclohexyl group, ethylcyclohexyl group, or methylcyclohexylmethyl group, are especially preferred.

[0021] Among the alkyl groups mentioned above, methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, or n-hexyl groups are preferred, methyl, ethyl, n-propyl, n-butyl, or tert-butyl groups are more preferred, and methyl or ethyl groups are 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 negative electrode active material.

[0022] Specific examples of alkenyl groups include C2-C12 alkenyl groups such as vinyl group, allyl group, isopropenyl group, methallyl group, 2-butenyl group, 3-methyl2-butenyl group, 3-butenyl group, or 4-pentenyl group. Preferably, C2-C6 alkenyl groups such as vinyl group, allyl group, methallyl group, or 2-butenyl group are preferred, more preferably C2-C4 alkenyl groups such as vinyl group, allyl group, or methallyl group, and particularly preferably vinyl group or allyl group. The above-mentioned alkenyl groups are preferred because the compound represented by general formula (1) preferably forms an insulating film on the surface of the positive electrode active material and / or negative electrode active material.

[0023] Specifically, alkynyl groups include ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, 4-pentynyl, or 5-hexynyl groups, which are alkyl groups with 1 to 12 carbon atoms. Examples include nyl groups. Preferably, these are C1-C6 alkynyl groups such as ethynyl, 2-propynyl, 2-butynyl, or 3-butynyl groups, more preferably C2-C4 alkynyl groups such as 2-propynyl or 3-butynyl groups, and particularly preferably 2-propynyl groups. The above-mentioned alkynyl groups are preferred because the compound represented by general formula (1) preferably forms an insulating film on the surface of the positive electrode active material and / or negative electrode active material.

[0024] Examples of aryl groups include phenyl groups, tolyl groups, or mesityl groups, which have 6 to 12 carbon atoms. Among these, phenyl groups or tolyl groups, which have 6 to 7 carbon atoms, are preferred, and phenyl groups are particularly preferred, from the viewpoint that the compound represented by general formula (1) tends to localize near the surface of the positive electrode active material and / or negative electrode active material.

[0025] Examples of aralkyl groups include phenylmethyl (benzyl) groups, phenylethyl (phenethyl) groups, phenylpropyl groups, phenylbutyl groups, and phenylisopropyl groups, all of which have 7 to 12 carbon atoms. Among these, aralkyl groups with 7 to 8 carbon atoms, such as benzyl or phenethyl groups, are preferred, and benzyl groups are particularly preferred, from the viewpoint that the compound represented by general formula (1) tends to localize near the surface of the positive electrode active material and / or negative electrode active material.

[0026] Examples of substituents that the hydrocarbon group may have include cyano groups, isocyanate groups, halogen atoms, or groups containing halogen atoms. Among these, isocyanate groups, halogen atoms, or groups containing halogen atoms are preferred, and halogen atoms or groups containing halogen atoms are particularly preferred. For specific and preferred examples of halogen atoms, see R 1 It is similar to what is defined in [the relevant section].

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

[0028] In this specification, R in the general formula (1) above is used. 1 is a monovalent hydrocarbon group, and R 1 and X 1 When two of these groups bond to each other to form a ring, this "monovalent" is treated as the valency of the hydrocarbon group when the bond is not formed. In other words, when a ring is formed, R 1 This becomes a divalent hydrocarbon group, but when the above bond is not formed, that is, when a ring is not formed, A 1 The monovalent hydrocarbon group bonded to R 1 Treat it as such. Similarly, X, which will be discussed later. 1 is a divalent hydrocarbon, and R 1 and X 1 Even when two of these molecules bond to each other to form a ring, this "divalent" state is treated as the valency of the hydrocarbon in the state where the bond is not formed. This treatment of "monovalent" or "divalent" states is the same for embodiments other than general formula (1).

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

[0030] Examples of alkoxy groups include alkoxy groups having 1 to 12 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, hexyloxy, octyloxy, decyloxy, or dodecyloxy groups. Among these, alkoxy groups having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, or butoxy groups, are preferred, and methoxy or ethoxy groups are particularly preferred because they have less steric hindrance to the compound represented by general formula (1) and are suitably concentrated on the active material surface.

[0031] The substituents that the alkoxy group may have are R 1 It is defined in the same way as substituents that may be present on the hydrocarbon group specified by [the relevant definition].

[0032] (X 1 ) X related to general formula (1) 1 represents a divalent hydrocarbon group which may have substituents. 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. This number of carbon atoms is preferable because it tends to localize the compound represented by general formula (1) near the surface of the positive electrode active material and / or negative electrode active material. Note that if the hydrocarbon group has substituents, the carbon atoms in the substituents are not included in this carbon number.

[0033] As the divalent hydrocarbon group, a divalent aliphatic hydrocarbon group is preferred, and specific examples include alkylene groups or alkenylene groups. Among these, alkylene groups are preferred. Substituents that the divalent hydrocarbon group may have include R 1 It is defined in the same way as substituents that may be present on the hydrocarbon group specified by [the relevant definition].

[0034] Examples of alkylene groups include linear alkylene groups, branched alkylene groups, or alkylene groups having a cyclic structure.

[0035] Specific examples of linear alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, or desilene groups.

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

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

[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 localize near the surface of the positive electrode active material and / or the negative electrode active material.

[0039] Examples of alkenylene groups include vinylene, propenylene, and 1-butenylene. Examples include the 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group, and so on.

[0040] (A 1 ) A related to general formula (1) 1 This refers to a divalent or trivalent atomic group represented by the following general formula (2-1) or the general formula (3-1) described later.

[0041] [ka]

[0042] Z 1 is a carbon atom, a sulfur atom, or a phosphorus atom or a boron atom, Y 101 is an oxygen atom or a sulfur atom, Y 1 , Y 2 and Y 3 Each of these independently consists of a single bond, an oxygen atom, a sulfur atom, or NR. 101 (-NR 101 -Base) is R 101 , a hydrogen atom, or a monovalent hydrocarbon group. 101 If is a monovalent hydrocarbon group, then R 101 R in the general formula (1) is 1 and X 1 It may be bonded to any of the following to form a ring. r 1 is, Z 1 When it is a carbon atom, it is 1, Z 1 When it is a sulfur atom, it is 0, 1, or 2, and Z 1 When it is a phosphorus atom, it is 0 or 1, Z 1 When it is a boron atom, it is 0. r 2 is, Z 1 When it is a carbon atom or a sulfur atom, it is 0, Z 1 The value is 1 when it is a phosphorus atom or a boron atom. * represents R in the general formula (1) above. 1 or X 1 This represents the connection point. However, Z 1 is a sulfur atom, and r 1 When Y is 2, 1 and Y 2 They can never be bonded together as a single bond.

[0043] (R 101 ) The above R 101 The monovalent hydrocarbon groups in each are independently R 1 This is synonymous with a monovalent hydrocarbon group as defined in [the relevant section].

[0044] Examples of divalent atomic groups represented by general formula (2-1) include oxygen atoms; sulfur atoms; divalent atomic groups consisting of oxygen atoms, carbon atoms and oxygen atoms, or hydrogen atoms, carbon atoms and oxygen atoms; or divalent atomic groups consisting of sulfur atoms, oxygen atoms and sulfur atoms, carbon atoms, oxygen atoms and sulfur atoms, or hydrogen atoms, carbon atoms, oxygen atoms and sulfur atoms.

[0045] Specific examples of divalent atomic groups consisting of an oxygen atom, a carbon atom and another oxygen atom, or a hydrogen atom, a carbon atom and another oxygen atom include divalent atomic groups having a ketone structure, a carboxylic acid ester structure, or a carbonate structure. Specifically, for example, Z 1 is a carbon atom; Y 101 is an oxygen atom; Y 1 , Y 2 , and Y 3 Examples include groups of atoms where each atom is independently bonded to a single bond or is an oxygen atom. Specific examples of divalent groups having a ketone structure include the -CO- group. Specific examples of divalent groups having a carboxylic acid ester structure include the -COO- group. ru. Specific examples of divalent groups having a carbonate structure include the -OCOO- group. Among these, the -COO- group or the -OCOO- group is particularly preferred because it produces fewer electrochemical side reactions and forms a suitable film on the active material surface.

[0046] Specific examples of divalent atomic groups consisting of a sulfur atom, an oxygen atom and another sulfur atom, a carbon atom, an oxygen atom and another sulfur atom, or a hydrogen atom, a carbon atom, an oxygen atom and another sulfur atom include divalent groups having sulfide structures, sulfone structures, sulfonic acid ester structures, sulfuric acid ester structures, sulfoxide structures, sulfite ester structures, sulfinic acid ester structures, thiocarbonyl structures, and thioester structures. Specifically, for example, Z 1 is a carbon atom; Y 101 is an oxygen atom; Y 1 , Y 2 , and Y 3 The group of atoms that is a sulfur atom, Z 1 is a carbon atom; Y 101 is a sulfur atom; Y 1 , Y 2 , and Y 3 A group of atoms that are independently single-bonded, oxygen atoms, or sulfur atoms, 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 Examples include atomic groups where each atom is independently a single bond, an oxygen atom, or a sulfur atom. Specific examples of divalent groups having a sulfide structure include the -S- group. Specific examples of divalent groups having a sulfonic acid ester structure include the -SO3- group. Specific examples of divalent groups having a sulfate ester structure include the -OSO3- group. Specific examples of divalent groups having a sulfoxide structure include the -SO- group. Specific examples of divalent groups having a sulfite ester structure include the -OSOO- group. Specific examples of divalent groups having a sulfinic acid ester structure include the -SO- group. Examples of divalent groups having a thiocarbonyl structure include the -OCSO- group or the -CSO- group. Specific examples of divalent groups having a thioester structure include -COS-, -OCOS-, and -SCOS- groups. Alternatively, divalent groups having a dithiocarboxylic acid ester structure, such as -CSS-, -OCSS-, or -SCSS- groups, may also be used. In particular, -SO3- groups, -OSO3- groups, -OSO3- groups, or -SO3- groups are preferred from the viewpoint of having fewer electrochemical side reactions and forming a suitable film on the active material surface, with -SO3- groups or -OSO3- groups being more preferred and -SO3- groups being especially preferred.

[0047] Examples of trivalent atoms or groups of atoms having at least one atom selected from oxygen, nitrogen, sulfur, phosphorus, and boron include nitrogen; phosphorus; boron; carbon, nitrogen and oxygen, or a trivalent group of atoms consisting of hydrogen, carbon, nitrogen and oxygen; carbon, nitrogen and sulfur, nitrogen, oxygen and sulfur, hydrogen, carbon, nitrogen and sulfur, or a trivalent group of atoms consisting of carbon, nitrogen, oxygen and sulfur; phosphorus, oxygen and phosphorus, or a trivalent group of atoms consisting of hydrogen, nitrogen, oxygen and phosphorus; and boron, or a trivalent group of atoms consisting of boron and oxygen; for example, Z 1 is a carbon atom; Y 101 is an oxygen atom; Y 1 , Y 2 , and Y 3 NR 101 Examples include atomic groups. Trivalent atomic groups consisting of carbon atoms, nitrogen atoms, and oxygen atoms, or hydrogen atoms, carbon atoms, nitrogen atoms, and oxygen atoms, include trivalent groups having amide, urethane, or urea structures. Specific examples of these atomic groups are shown below.

[0048] [ka]

[0049] Examples of trivalent atomic groups 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. Furthermore, trivalent groups having a dithiocarboxylic acid ester structure may also be used. Specific examples of these include the atomic groups shown below, specifically, for example, Z 1 is a carbon atom; Y 101 is a sulfur atom; Y 1 , Y 2 , and Y 3 NR 101 A manner in which Z 1 is a carbon atom; Y 101 is an oxygen atom; Y 1 , Y 2 , and Y 3 NR 101 Examples include atomic groups.

[0050] [ka]

[0051] Examples include phosphorus atoms, oxygen atoms and phosphorus atoms, or trivalent atomic groups consisting of hydrogen atoms, nitrogen atoms, oxygen atoms and phosphorus atoms, and specifically, for example, Z 1 Examples include atomic groups in which the atom is a phosphorus atom, and more specifically, trivalent groups having a phosphine oxide structure, phosphinic acid ester structure, phosphonic acid ester structure, phosphate ester structure, phosphate amide structure, phosphine structure, phosphiniate ester structure, phosphoniate ester structure, or phosphite ester structure. Specific examples of these include the atomic groups shown below.

[0052] [ka]

[0053] Among these, the following atomic groups are preferred because they have fewer electrochemical side reactions and form a suitable coating on the active material surface.

[0054] [ka]

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

[0056] [ka]

[0057] Examples include boron atoms, or trivalent atomic groups consisting of boron and oxygen atoms, and specifically, for example, Z 1 Examples include atomic groups in which the atom is boron, and more specifically, trivalent groups having a trialkylborane structure, a boric acid ester structure, a boronic acid ester structure, and a boric acid ester structure. Specific examples of these include the following atomic groups. [ka]

[0058] In particular, because it produces fewer electrochemical side reactions and forms a suitable film on the active material surface, the divalent or trivalent atomic group represented by formula (2-1) is preferably the divalent or trivalent atomic group represented by the following general formula (2-2).

[0059] [ka]

[0060] Z 2 These are carbon atoms, sulfur atoms, and phosphorus atoms, Y 7 , Y 8 and Y 9 Each of these is independently either a single bond or an oxygen atom. r 3 is, Z 2 When it is a carbon atom, it is 1, Z 2 When it is a sulfur atom, it is 0, 1, or 2. Yes, Z 2 When it is a phosphorus atom, it is 0 or 1. r 4 is, Z 2 When it is a carbon atom or a sulfur atom, it is 0, Z 2 When it is a phosphorus atom, it is 1. * represents R in the general formula (1) above. 1 or X 1 This represents the connection point. However, Z 2 is a sulfur atom, and r 3 When Y is 2, 7 and Y 8 They can never be bonded together as a single bond. Z in general formula (2-2) 2 , Y 7 , Y 8 , Y 9 , r 2 , and r 3 To the extent applicable, Z in the above general formula (2-1) 1 , Y 1 , Y 2 , Y 3 , r 0 , and r 1 Each of these conditions can be applied.

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

[0062] [ka]

[0063] Y 4 , Y 5 and Y 6 Each of these is independently an oxygen atom, a sulfur atom, or NR 201 (=NR 201 It is the basis. 201 is a hydrogen atom or a monovalent hydrocarbon group. * represents R in the general formula (1) above. 1 or X 1 This shows the binding site.

[0064] (R 201 ) The above R 201 The hydrocarbon group in R 3 It is synonymous with the hydrocarbon group defined in [the relevant section].

[0065] Among these, the atomic group represented by the following formula (3-2) is preferred because it exhibits fewer electrochemical side reactions and forms a suitable coating on the active material surface. [ka]

[0066] * represents R in the general formula (1) above. 1 or X 1 This shows the binding site.

[0067] Among the atomic groups represented by the above general formula (2-1) or general formula (3-1), Preferably, the group is 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 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 has a carbonate structure, a carboxylic acid ester structure, a sulfonic acid ester structure, 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 even 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. It is particularly preferable that the divalent group has a carbonate structure or a divalent group has a carboxylic acid ester structure.

[0068] n related to general formula (1) 1 n represents an integer between 2 and 3. n is advantageous in that it makes it easier to suppress gas generation. 1 It is preferable that it is 3.

[0069] p related to general formula (1) 1 This represents an integer between 0 and 2.

[0070] q related to general formula (1) 1 represents an integer between 1 and 3. However, p 1 +q 1 = 2 or 3 From the viewpoint of minimizing electrochemical side reactions and forming a suitable coating on the active material surface, A according to general formula (1) 1 When the structure is represented by equation (2-1) or equation (2-2), p 1 is 1 and q 1 It is preferable that p be 1 or 2. 1 is 1 and q 1 It is more preferable that it be 1. From the viewpoint of minimizing electrochemical side reactions and forming a suitable coating on the active material surface, A according to general formula (1) 1 When the structure is represented by equation (3-1) or equation (3-2), p 1 =0 and q 1 It is preferable that = 3.

[0071] R 1 and X 1 Two of these may be joined together to form a ring. That is, the manner in which a ring is formed is R 1 Allies, and also, R 1 and X 1 One example is a configuration in which the atoms are bonded together to form a ring. From the viewpoint of ease of synthesis, R 1 and X 1 A configuration in which the elements are joined to form a ring is preferred. A more preferred configuration is the following structure.

[0072] [ka]

[0073] The following are specific examples of compounds represented by the general formula (1). However, the compounds represented by general formula (1) in this embodiment are not limited in any way to the compounds represented by the following examples of formulas (F3-1) to (F3-106) and formulas (F2-1) to (F2-148).

[0074] [ka]

[0075] [ka]

[0076] [ka]

[0077]

change

[0078]

change

[0079]

change

[0080]

change

[0081]

change

[0082]

change

[0083]

change

[0084]

change

[0085]

change

[0086]

change

[0087]

change

[0088] [ka]

[0089] [ka]

[0090] [ka]

[0091] [ka]

[0092] Of these, from the viewpoint of ease of obtaining raw materials and ease of synthesis, A 1 This 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, X 1 Compounds in which the group is an alkylene group are preferred, and among these, the above formulas (F3-1), (F3-20), (F3- Preferably, the compound is selected from the group of compounds represented by 26), (F3-35)~(F3-37), (F3-43)~(F3-45), (F3-53)~(F3-63), (F3-67)~(F3-85), (F3-91)~(F3-99), (F3-101)~(F3-106), (F2-1), (F2-20), (F2-26), (F2-35)~(F2-37), (F2-43)~(F2-45), (F2-53)~(F2-63), (F2-67)~(F2-85), or (F2-91)~(F2-99), (F2-101)~(F2-148). A 1 This 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, X 1 Compounds in which the parent group is an alkylene group are more preferred, and among these, it is preferable that the compound is selected from the group of compounds represented by the above formulas (F3-1), (F3-20), (F3-35)~(F3-37), (F3-44)~(F3-45), (F3-53)~(F3-63), (F3-91)~(F3-99), (F2-1), (F2-20), (F2-35)~(F2-37), (F2-44)~(F2-45), (F2-53)~(F2-63), or (F2-91)~(F2-99). X 1 The propylene group is R 1 It is even more preferable that the group 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 (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) as described above. A 1 X 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 phosphate ester structure, or a trivalent atomic group having an isocyanurate structure, 1 The propylene group is R 1 Compounds in which the group is a methyl group or an ethyl group are particularly preferred, and among these, compounds 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) are particularly preferred.

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

[0094] [ka]

[0095] In general formula (1-4), R 11 R represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may have substituents; 12 This is a monovalent carbide which may have a hydrogen atom and substituents. Showing a hydrogen group; X 11 This represents a divalent hydrocarbon group having 3 or more carbon atoms, which may have substituents; Y 21 and Y 22 Each of these independently consists of a single bond, an oxygen atom, a sulfur atom, or NR. 301 (-NR 301 -Base) and;R 301 R is a hydrogen atom or a monovalent hydrocarbon group which may have substituents; 301 If is a monovalent hydrocarbon group, then R 301 R 11 and X 11 It may also be bonded to any of the following to form a ring; n 11 R indicates 2. 11 and X 11 Two of these may be joined together to form a ring. However, Y 21 and Y 22 is an oxygen atom, and R 11 and X 11 When the two are not bonded to form a ring (the compound represented by general formula (1-4) is in a chain-like state (chain carbonate)), n 11 It may also be 3. R 11 and R 12 The hydrocarbon group in the above-mentioned general formula (1) is R 1 and R 2 These are synonymous with hydrocarbon groups in each case. Also, R 301 R is a hydrogen atom or a monovalent hydrocarbon group. 301 The hydrocarbon group in R 1 It is synonymous with the hydrocarbon group defined in [the relevant section]. The conditions for the atoms constituting general formulas (1-4) can be similarly applied to the conditions for the corresponding atoms in general formula (1) described above, including preferred conditions. From the viewpoint of minimizing electrochemical side reactions and suitably forming a coating on the active material surface, A in the above-mentioned general formula (1) 1 A carbonate structure is preferred for the portion corresponding to this. Furthermore, from the perspective of achieving a balance between the resistance and insulation properties of the coating, n 11 It is preferable that it is 2. Furthermore, from the perspective of balancing the resistance and insulation properties of the coating, R 11 and X 11 It is preferable that the structure does not involve the bonding of the elements to form a ring. Furthermore, from the standpoint of high gas suppression effect during high-temperature storage, n 11 It is preferable that it is 3.

[0096] The compounds represented by the above general formula (1-4) are specifically Embodiments having a carbonate structure, in particular, Y 21 and Y 22 is an oxygen atom, n 11 If it is 2 or 3, X 11 It is preferable that is a divalent hydrocarbon group having 3 or more carbon atoms, and among these, it is preferable that it is a compound selected from the group of compounds represented by the above formulas (F3-1), (F2-1), and (F2-107) to (F2-112), and also R 11 A more preferable embodiment is one in which R 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), and also R 11 A more preferable embodiment is one in which 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 (F3-1) and (F2-1). Furthermore, embodiments having a carboxylic acid ester, in particular, Y 21 is a single bond, Y 22 is an oxygen atom, n 11 is 2 or 3, X 11 is a divalent hydrocarbon group with 3 or more carbon atoms, R 11 is a hydrogen atom or an alkyl group, and R 12 A preferred embodiment is in which is a methyl group, and among these, it is preferred 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), and also R 1 A more preferable embodiment is one in which the group 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 formula (F2-20).

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

[0098] [ka]

[0099] In general formula (1-5), R 13 R represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may have substituents; 14 X represents a hydrogen atom and a potentially substituted monovalent hydrocarbon group; X 12 This represents a divalent hydrocarbon group having 3 or more carbon atoms, which may have substituents; Y 23 and Y 24 Each of these independently consists of a single bond, an oxygen atom, a sulfur atom, or NR. 311 (-NR 311 -Base) and;R 311 R is a hydrogen atom or a monovalent hydrocarbon group which may have substituents; 311 If is a monovalent hydrocarbon group, then R 311 R 13 and X 12 It may also be bonded to any of the following to form a ring; r 12 n is 0, 1, or 2. 12 R indicates 2 or 3. 13 and X 12 Two of these may be joined together to form a ring. R 13 and R 14 The hydrocarbon group in the above-mentioned general formula (1) is R 1 and R 2 These are synonymous with hydrocarbon groups in each case. Also, R 311 R is a hydrogen atom or a hydrocarbon group. 311 The hydrocarbon group in R 1 It is synonymous with the hydrocarbon group defined in [the relevant section]. The conditions for the atoms constituting general formulas (1-5) can be similarly applied to the conditions for the corresponding atoms in general formula (1) described above, including preferred conditions. From the viewpoint of minimizing electrochemical side reactions and suitably forming a coating on the active material surface, A in the above-mentioned general formula (1) 1 The portion corresponding to this is preferably a sulfonic acid ester structure. Furthermore, from the viewpoint of ensuring that film formation proceeds smoothly and that the resistance and insulation properties of the film are balanced, it is preferable that n12 be 2. Furthermore, from the perspective of balancing the resistance and insulation properties of the coating, R 13 and X 12 It is preferable that the structure does not involve the bonding of the elements to form a ring.

[0100] The compounds represented by the above general formula (1-5) specifically have a sulfonic acid ester structure, in particular Y 23 is a single bond, and Y 24 is an oxygen atom, n 12 is 2 or 3, X 12 A preferred embodiment is an alkylene group having 3 or more carbon atoms, and among these, a preferred embodiment is a compound selected from the group of compounds represented by the above formulas (F3-35), (F2-35), (F2-119) to (F2-124), and R 13 A more preferable embodiment is one in which R 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 (F3-35) and (F2-35), and R 13 A more preferable embodiment is one in which the group 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 (F3-35) and (F2-35). Furthermore, from the standpoint of high gas suppression effect during high-temperature storage, n 12 It is preferable that it is 3.

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

[0102] [ka]

[0103] In general formula (1-6), R 15 , and R 15 Each of the following independently represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may have substituents; R 16 X represents a hydrogen atom and a potentially substituted monovalent hydrocarbon group; X 13 This represents a divalent hydrocarbon group having 3 or more carbon atoms, which may have substituents; Y 25 , Y 25 ', and Y 26 Each of these independently consists of a single bond, an oxygen atom, a sulfur atom, or NR. 321 And; R 321 R is a hydrogen atom or a monovalent hydrocarbon group which may have substituents; 321 If is a monovalent hydrocarbon group, then R 321 R 15 and X 13 It may also be bonded to any of the following to form a ring; n 13 R indicates 2 or 3. 15 and X 13 Two of these may be joined together to form a ring. R 15 and R 16 The monovalent hydrocarbon group in is R in the general formula (1) described above. 1 and R 2 These are synonymous with monovalent hydrocarbon groups in each case. Also, R 321 R is a hydrogen atom or a hydrocarbon group. 321 The hydrocarbon group in R 1 It is synonymous with the hydrocarbon group defined in [the relevant section]. The conditions for the atoms constituting general formulas (1-6) can be similarly applied to the conditions for the corresponding atoms in general formula (1) described above, including preferred conditions. From the viewpoint of minimizing electrochemical side reactions and suitably forming a coating on the active material surface, A in the above-mentioned general formula (1) 1 The portion corresponding to this is preferably a phosphate ester or phosphonic acid ester structure. From the perspective of achieving a balance between the resistance and insulation properties of the coating, n 13 It is preferable that it is 2. Furthermore, from the perspective of balancing the resistance and insulation properties of the coating, R 15 and X 13 It is preferable that the structure does not involve the bonding of the elements to form a ring. Furthermore, from the standpoint of high gas suppression effect during high-temperature storage, n 13 It is preferable that it is 3.

[0104] The compounds represented by the above general formulas (1-6) are specifically Embodiments having a phosphonic acid ester structure, particularly Y 25 and Y 25 ' is an oxygen atom, Y 26 is a single bond, n 13 Preferably, the compound is an integer from 1 to 3, and X13 is a monovalent hydrocarbon group having 3 or more carbon atoms. Among these, it is preferable that the compound is 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). 13 is 2 or 3, R 15 More preferably, is a methyl group or an ethyl group, and among these, is preferably a compound selected from the group of compounds represented by the above formulas (F3-55) to (F3-56) and (F2-55) to (F2-56), and also R 15 A more preferable embodiment is one in which is an ethyl group, and among these, it is preferable that the compound is selected from the group of compounds represented by the above formulas (F3-56) and (F2-56). Furthermore, embodiments having a phosphate ester structure, in particular, Y 25 , Y 25 ', and Y 26 is an oxygen atom, n 13 If X is an integer between 1 and 3, 13 A preferred embodiment is one in which is a hydrocarbon group having 2 or more carbon atoms, and among these, it is preferable that it be a compound selected from the group of compounds represented by the above formulas (F3-44)~(F3-45), (F2-44)~(F2-45), and (F2-125)~(F2-136), and also n 13 is 2 or 3, R 15 is a methyl group or an ethyl group A certain embodiment is more preferred, 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), and R 15 A more preferable embodiment is one in which the group is an ethyl group, and among these, the compound represented by the above formula (F2-45) is preferred.

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

[0106] [ka]

[0107] [ka]

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

[0109] [ka]

[0110] The content of the compound represented by general formula (1) in the total amount of the non-aqueous electrolyte according to this embodiment is usually 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even 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 (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 will proceed favorably, and it will be possible to manufacture a battery with less gas generation during high-temperature storage.

[0111] The compound represented by the above general formula (1) 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, a silane compound 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, a fluorosilane compound having various atomic groups can be synthesized.

[0112] <A1-2. Electrolyte> Similar to a general non-aqueous electrolyte, the non-aqueous electrolyte of the present embodiment usually contains an electrolyte as one of its components. 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 difluorooxalate borate 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 with respect to the total amount of the non-aqueous electrolyte. Also, 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, similar to a general non-aqueous electrolyte, 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. Preferably, they are saturated cyclic carbonates, linear carbonates, or carboxylic acid esters, and more preferably, saturated cyclic carbonates or linear carbonates. 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 the range where the effects of the present invention are achieved. 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, or 4,5-difluoro-4,5-dimethyl ethylene 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; trimer compounds derived from compounds having at least two isocyanate groups in the molecule, such as triallyl isocyanurate, or isocyanate compounds such as aliphatic polyisocyanates obtained by adding a polyhydric alcohol thereto; Nitrogen-containing compounds such as 1-methyl-2-pyrrolidinone; Hydrocarbon compounds such as cycloheptane; Fluorine-containing aromatic compounds such as fluorobenzene; Silane compounds such as tris(trimethylsilyl) borate; Ester compounds such as 2-propynyl 2-(methanesulfonyloxy)propionic acid; Lithium salts such as lithium ethylmethyloxycarbonylphosphonate; These are some examples. These can be used individually or in combination of two or more. By adding these additives, it is possible to suppress gas generation during initial conditioning and improve volume retention and cycle characteristics after high-temperature storage.

[0116] In particular, in the non-aqueous electrolyte according to this embodiment, using one or more selected from unsaturated cyclic carbonates and cyclic carbonates having fluorine atoms is preferable because it further suppresses gas generation during initial conditioning and results in a battery that is less prone to swelling.

[0117] Furthermore, the non-aqueous electrolyte may contain, as an auxiliary agent, phosphates having P=O and PF bonds, salts having an FSO2 skeleton, or oxalates. From the viewpoint of suitably forming a composite film with the compound represented by general formula (1), it is preferable to contain one or more compounds selected from the group consisting of phosphates having P=O and PF bonds, salts having an FSO2 skeleton, and oxalates. From the viewpoint of suppressing the amount of gas generated during charging and the increase in internal resistance, it is preferable to contain phosphates having P=O and PF bonds and / or salts having an FSO2 skeleton. The total content of compounds selected from the group consisting of phosphates having P=O and PF bonds, 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, even more preferably 0.2% by mass or more, and usually 10% by mass or less, preferably 8% by mass or less, and more preferably 5% by mass or less, in 100% by mass of the non-aqueous electrolyte (relative to the total amount of the non-aqueous electrolyte). When two or more auxiliary agents are used in combination, it is preferable that the total content satisfies the above range.

[0118] (Phosphates containing P=O and PF bonds) The phosphate containing P=O and PF bonds is not particularly limited as long as it is a phosphate containing P=O and PF bonds within the molecule. Examples of countercations of phosphates having a PF bond include alkali metals such as lithium, sodium, and potassium, with lithium being the preferred choice. Examples of fluorophosphates having a P=O bond include: Monofluorophosphates such as Li2PO3F; Difluorophosphates such as LiPO2F2, NaPO2F2, and KPO2F2; These are some examples. In particular, difluorophosphates are preferred, and lithium difluorophosphates are more preferred, in addition to their gas suppression effect during high-temperature storage, as well as their ability to further improve charge-discharge rate characteristics and impedance characteristics.

[0119] Fluorophosphates may be used individually or in any combination and ratio of two or more types. The fluorophosphate content (total amount in the case of two or more types) 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, and more preferably 3% by mass or less, based on 100% by mass of the non-aqueous electrolyte. If the fluorophosphate content is within this range, the characteristics of non-aqueous electrolyte secondary batteries, particularly the durability characteristics or continuous charging characteristics, can be significantly improved. The principle behind this is not entirely clear, but it is thought that mixing them in this ratio minimizes side reactions of the additives on the electrodes.

[0120] The mass ratio of the compound represented by the above general formula (1) to the phosphate (total amount if there are two or more types) having P=O and PF bonds is: compound represented by general formula (1) / phosphate having P=O bond The phosphate has P=O and PF bonds, and is usually 1 / 100 or more, preferably 10 / 100 or more, more preferably 20 / 100 or more, even more preferably 25 / 100 or more, usually 10000 / 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. If the mass ratio is within this range, the characteristics of non-aqueous electrolyte secondary batteries, especially the durability characteristics or continuous charging characteristics, can be significantly improved. The principle behind this is not clear, but it is thought that mixing at this ratio minimizes side reactions of the additive on the electrodes.

[0121] When LiPF6 is present in a non-aqueous electrolyte, the mass ratio of phosphates containing P=O and PF bonds (total amount if there are two or more types) to the LiPF6 content (fluorophosphate / LiPF6) is usually 0.00005 or higher, preferably 0.001 or higher, more preferably 0.01 or higher, even more preferably 0.02 or higher, particularly preferably 0.025 or higher, usually 1.0 or lower, preferably 0.5 or lower, more preferably 0.4 or lower, and even more preferably 0.35 or lower. If this mass ratio is within this range, the characteristics of non-aqueous electrolyte secondary batteries, especially durability characteristics or continuous charging characteristics, can be significantly improved. The principle behind this is not clear, but it is thought that mixing at this ratio minimizes the decomposition side reactions of LiPF6 within the non-aqueous electrolyte secondary battery. The content of phosphates containing P=O and PF bonds is determined by nuclear magnetic resonance (NMR) analysis. While NMR analysis is typically performed, ion chromatography (IC) analysis is also conducted if the assignment of other compounds is difficult due to solvent peaks.

[0122] (Salts with an FSO2 skeleton) The salt having an FSO2 skeleton used in this embodiment is not particularly limited as long as it has an FSO2 skeleton in its molecule. Examples of countercations for salts having an FSO2 skeleton include alkali metals such as lithium, sodium, and potassium, with lithium being the most preferred among them. 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); Fluorosulfonylmethide salts such as LiC(FSO2)3; These are some examples. In particular, fluorosulfonates are preferred, and lithium fluorosulfonate is more preferred, in addition to the gas suppression effect during high-temperature storage, as well as the effect of improving charge-discharge rate characteristics and impedance characteristics.

[0123] The salts having an FSO2 skeleton may be used individually or in any combination and ratio of two or more types. The content of the salts having an FSO2 skeleton (total amount if 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, and more preferably 3% by mass or less, per 100% by mass of the non-aqueous electrolyte. If the content of the salts having an FSO2 skeleton is within this range, the characteristics of the non-aqueous electrolyte secondary battery, in particular the durability characteristics or continuous charging characteristics, can be significantly improved. The principle behind this is not clear, but it is thought that mixing them in this ratio minimizes the side reactions of the additives on the electrodes.

[0124] The mass ratio of the compound represented by the above general formula (1) to the salt having an FSO2 skeleton (total amount if there are two or more types) is, in terms of compound represented by general formula (1) / salt having an FSO2 skeleton, is usually 1 / 100 or more, preferably 10 / 100 or more, more preferably 20 / 100 or more, and further The ratio is preferably 25 / 100 or more, usually 10000 / 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. If the mass ratio is within this range, the characteristics of non-aqueous electrolyte secondary batteries, especially the durability characteristics or continuous charging characteristics, can be significantly improved. The principle behind this is not entirely clear, but it is thought that mixing at this ratio minimizes side reactions of the additives on the electrodes.

[0125] When LiPF6 is present in a non-aqueous electrolyte, the mass ratio of salts having an FSO2 skeleton (total amount if there are two or more types) to the LiPF6 content (salts having an FSO2 skeleton / LiPF6) is usually 0.00005 or higher, preferably 0.001 or higher, more preferably 0.01 or higher, even more preferably 0.02 or higher, particularly preferably 0.025 or higher, usually 1.0 or lower, preferably 0.5 or lower, more preferably 0.4 or lower, and even more preferably 0.35 or lower. If this mass ratio is within this range, the characteristics of non-aqueous electrolyte secondary batteries, especially durability characteristics or continuous charging characteristics, can be significantly improved. The principle behind this is not clear, but it is thought that mixing at this ratio minimizes the decomposition side reactions of LiPF6 within the non-aqueous electrolyte secondary battery. The content of salts containing the FSO2 skeleton is determined by nuclear magnetic resonance (NMR) analysis. While NMR analysis is usually performed, ion chromatography (IC) analysis is also performed if the assignment of other compounds is difficult due to solvent peaks.

[0126] (Oxalate) The oxalate is not particularly limited as long as it is a compound having at least one oxalic acid skeleton in its molecule. Examples of oxalate countercations include alkali metals such as lithium, sodium, and potassium, with lithium being the preferred choice. For example, oxalate borate salts such as lithium bis(oxalate)borate and lithium difluorooxalate borate; Oxalate phosphate salts such as lithium tetrafluorooxalate phosphate, lithium difluorobis(oxalate) phosphate, and lithium tris(oxalate) phosphate; These are some examples. In particular, oxalate borate salts are preferred, and lithium bis(oxalate) borate is more preferred, in addition to the gas suppression effect during high-temperature storage, as well as the improvement effect on charge-discharge rate characteristics and impedance characteristics.

[0127] Oxalates may be used individually or in any combination and ratio of two or more types. The oxalate content (total amount in the case of two or more types) 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, and more preferably 3% by mass or less, based on 100% by mass of the non-aqueous electrolyte. If the oxalate content is within this range, the characteristics of the non-aqueous electrolyte secondary battery, especially the durability characteristics or continuous charging characteristics, can be significantly improved. The principle behind this is not entirely clear, but it is thought that mixing them in this ratio minimizes side reactions of the additives on the electrodes.

[0128] The mass ratio of the compound represented by the above general formula (1) to the oxalate (total amount if there are two or more types) is, as compound represented by general formula (1) / oxalate, is usually 1 / 100 or more, preferably 10 / 100 or more, more preferably 20 / 100 or more, even more preferably 25 / 100 or more, usually 10000 / 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. If this mass ratio is within this range, the characteristics of the non-aqueous electrolyte secondary battery, particularly the durability characteristics, will be maintained. This can significantly improve charging performance or continuous charging characteristics. Although the principle behind this is not entirely clear, it is thought that mixing in this ratio minimizes side reactions of the additive on the electrodes.

[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 can be 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 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 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> A 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 a non-aqueous electrolyte including 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 the present 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 film (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 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.

[0134] <A2-2. Non-aqueous Electrolyte> As the non-aqueous electrolyte, the non-aqueous electrolyte according to the above-described embodiment of the present invention 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 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 preferable, and lithium transition metal composite oxides are more preferable. Examples of lithium transition metal composite oxides include those with a spinel structure that allows for three-dimensional diffusion, and those with a layered structure that enables two-dimensional diffusion of lithium ions. Lithium transition metal compounds having a spinel structure are generally represented by the following compositional formula (11). Li x’ M'2O4···(11) (In equation (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. Lithium transition metal compounds having a layered structure are generally represented by the following compositional formula (12). Li 1+x MO2···(12) (In equation (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, LiLiLi 0.80 Co 0.15 Al 0.05 O2, LiLiLi 0.33 Co 0.33 Mn 0.33 O2, Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O2, LiLiLi 0.5 Co 0.2 Mn 0.3 O2, Li 1.05 Ni 0.5 Co 0.2 Mn 0.3 O2, LiLiLi 0.6 Co 0.2 Mn 0.2 O2, LiLiLi 0.8 Co 0.1 Mn 0.1 Examples include O2.

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

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

[0138] In particular, an embodiment in which the transition metal oxide is represented by the following compositional formula (14) is preferred. Li a2 Ni b2 Co c2 M2 d2 O2···(14) In the above compositional formula (14), a2, b2, c2, and d2 represent numerical values of 0.90 ≤ a2 ≤ 1.10, 0.50 ≤ b2 ≤ 0.98, 0.01 ≤ c2 < 0.50, and 0.01 ≤ d2 < 0.50, and satisfy 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 E 0.2 O2, LiNi 0.8 Co 0.1 Mn 0.1 O2 and the like can be mentioned.

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

[0140] <--0001845-->The negative electrode active material is not particularly limited as long as it is capable of electrochemically intercalating and releasing metal ions. Specific examples include carbon-based materials, materials containing metal elements and / or metalloid elements that can alloy with Li, lithium-containing metal composite oxide materials, and mixtures thereof. Materials containing metal elements and / or metalloid elements that can alloy with Li are preferred because they offer high capacity per unit weight and volume of the active material, and thus increase the energy density of the battery. These may be used individually or in any combination of two or more. It is preferable to use carbon-based materials, materials containing metal elements and / or metalloid elements that can alloy with Li, or a mixture of materials containing metal elements and / or metalloid elements that can alloy with Li and carbon-based materials, as these offer good cycle characteristics, safety, and excellent continuous charging characteristics.

[0141] Examples of carbon-based materials include natural graphite, artificial graphite, amorphous carbon, carbon-coated graphite, graphite-coated graphite, and resin-coated graphite. Among these, natural graphite is preferred.

[0142] Examples of natural graphite include scaly graphite, flake graphite, and / or graphite particles obtained by processing these graphites as raw materials, such as spheroidization or densification. Among these, spherical or ellipsoidal graphite particles that have undergone spheroidization processing are particularly preferred from the viewpoint of particle packing and charge / discharge rate characteristics. The average particle size (d50) of graphite particles is typically between 1 μm and 100 μm.

[0143] Any conventionally known material containing a metallic element and / or metalloid element that can alloy with Li can be used. However, from the viewpoint of capacity and cycle life, the material containing a metallic element and / or metalloid element that can alloy with Li is preferably a metal or compound thereof selected from the group consisting of Sb, Si, Sn, Al, As, and Zn. Alternatively, an alloy made of two or more metals may be used, and the material containing a metallic element and / or metalloid element that can alloy with Li may be an alloy material formed from two or more metallic elements. Examples of metal compounds include metal oxides, metal nitrides, and metal carbides. Among these, metallic Si (hereinafter sometimes referred to as Si) or Si-containing compounds (especially Si oxides) are preferred in terms of achieving high capacity.

[0144] In this specification, Si or Si-containing compounds are collectively referred to as Si compounds. Specifically, SiO x ,SiN x SiC x SiZ x O y Examples include (Z=C, N), etc. Si compounds include Si oxide (SiO x ) is preferred because it has a larger theoretical capacity compared to graphite, or amorphous Si or nano-sized Si crystals are preferred because alkali ions such as lithium ions can easily enter and exit, making it possible to obtain high capacity. This general formula SiO x It can be obtained using silicon dioxide (SiO2) and Si as raw materials, but the value of x is usually 0 <x<2である。 As a material containing a metallic element and / or metalloid element that can be alloyed with Li, metal particles that can be alloyed with Li are preferred because they can increase the electrode density. The average particle size (d50) of metal particles that can be alloyed with Li is typically between 0.01 μm and 10 μm, from the perspective of cycle life. The mixture of a material containing a Li alloyable metal element and / or metalloid element used as a negative electrode active material and a carbon-based material may be a mixture in which the aforementioned Li alloyable metal element and / or metalloid element material and the aforementioned carbon-based material are mixed independently of each other, or it may be a composite in which the Li alloyable metal element and / or metalloid element material is present on the surface or inside the carbon-based material. 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. When within this range, it 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. When within this range, it 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 this embodiment is usually impregnated into this separator and used. 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). Although the mechanism for enhancing the suppression of gas generation amount during high-temperature storage of a non-aqueous electrolyte battery by using a non-aqueous electrolyte containing a compound represented by general formula (4) 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 in the vicinity of 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 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 (4) is increased, and thus, for example, electrochemical reduction or reaction with a reduction decomposition product of the electrolytic solution easily proceeds. Thereby, an insulating film is formed on the negative electrode active material, or the surface is preferably modified when, for example, Si is used for the negative electrode active material. Further, it is presumed that the compound represented by the general formula (4) is also concentrated on the surface of the positive electrode, reacts with electrochemical oxidation or an oxidation decomposition product of the electrolytic solution, and forms an insulating film in the same manner as 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 compound represented by the general formula (4) forms a film on the surface of the material containing the metal element and / or the metalloid element capable of alloying with Li, and a non-aqueous electrolyte battery with suppressed swelling 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 gas generation amount 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

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

[0151] (R 3 ) R related to general formula (4) 3 This represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group having 1 to 12 carbon atoms, which may have substituents. For compounds represented by general formula (4), a monovalent hydrocarbon group having 1 to 12 carbon atoms, which may have substituents, is preferred for industrial handling during compound production, storage, and electrolyte production. Note that if the hydrocarbon group has substituents, the number of carbon atoms in the substituents is not included in this carbon number. Furthermore, from the viewpoint of suitably forming the insulating coating, R 3 It is also preferable that it be a halogen atom. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms, but fluorine atoms are preferred. Examples of monovalent hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, or aralkyl groups. Among these, alkyl groups, alkenyl groups, or alkynyl groups are preferred from the viewpoint of suppressing side reactions on the electrode of the compound represented by general formula (4), more preferably alkyl groups or alkenyl groups, and particularly preferably alkynyl groups. It is a lu group. Examples of alkyl groups include linear alkyl groups, branched alkyl groups, and alkyl groups having a cyclic structure. Among these, linear alkyl groups are preferred from the viewpoint of suitably forming the insulating coating. Examples of linear alkyl groups include linear alkyl groups having 1 to 12 carbon atoms, such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, or n-dodecyl group. Among 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 branched alkyl groups include branched alkyl groups having 1 to 12 carbon atoms, such as methylethyl group, methylpropyl group, methylbutyl group, methylpentyl group, methylhexyl group, methylheptyl group, methyloctyl group, methylnonyl group, methyldecyl group, methylundecyl group; dimethylethyl group (tert-butyl group), dimethylpropyl group, dimethylbutyl group, dimethylpentyl group, dimethylhexyl group, dimethylheptyl group, dimethyloctyl group; trimethylhexyl group, trimethylheptyl group; ethylpentyl group, ethylhexyl group, ethylheptyl group, ethyloctyl group; propylhexyl group, propylheptyl group; or butylhexyl group. In particular, branched alkyl groups having 1 to 6 carbon atoms, such as methylethyl group, methylpropyl group, methylbutyl group, methylpentyl group, dimethylethyl group (tert-butyl group), dimethylpropyl group, or dimethylbutyl group, are preferred, and branched alkyl groups having 1 to 4 carbon atoms, such as methylethyl group, methylpropyl group, or dimethylethyl group (tert-butyl group), are especially preferred. In the examples of the branched alkyl groups, the position of the branching is arbitrary.

[0152] Examples of alkyl groups having a cyclic structure include alkyl groups having 3 to 12 carbon atoms, such as 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, or methylcyclohexylmethyl group. Among these, alkyl groups having a cyclic structure with 3 to 8 carbon atoms, such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclohexylmethyl group, cyclohexylethyl group, methylcyclohexyl group, dimethylcyclohexyl group, ethylcyclohexyl group, or methylcyclohexylmethyl group, are preferred, and alkyl groups having a cyclic structure with 6 to 8 carbon atoms, such as cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, methylcyclohexyl group, dimethylcyclohexyl group, ethylcyclohexyl group, or methylcyclohexylmethyl group, are particularly preferred.

[0153] Among the above, methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, or n-hexyl groups are preferred, methyl, ethyl, n-propyl, n-butyl, or tert-butyl groups are more preferred, and methyl or ethyl groups are particularly preferred. The above alkyl groups are preferred because the compound represented by general formula (4) tends to localize near the surface of the positive electrode active material and / or negative electrode active material.

[0154] Examples of alkenyl groups include C2-C12 alkenyl groups such as vinyl group, allyl group, isopropenyl group, methallyl group, 2-butenyl group, 3-methyl2-butenyl group, 3-butenyl group, or 4-pentenyl group. Preferably, C2-C6 alkenyl groups such as vinyl group, allyl group, methallyl group, or 2-butenyl group are used; more preferably, C2-C4 alkenyl groups such as vinyl group, allyl group, or methallyl group are used; and particularly preferably, vinyl group or allyl group are used. With the above-mentioned alkenyl groups, the compound represented by general formula (4) is suitably insulating on the surface of the positive electrode active material and / or negative electrode active material. It is preferable for forming a coating.

[0155] Specific examples of alkynyl groups include C1-C12 alkynyl groups such as ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, 4-pentynyl, or 5-hexynyl groups. Preferably, C1-C6 alkynyl groups such as ethynyl, 2-propynyl, 2-butynyl, or 3-butynyl groups are preferred, more preferably C2-C4 alkynyl groups such as 2-propynyl or 3-butynyl groups are preferred, and particularly preferably C2-propynyl groups are preferred. The above-mentioned alkynyl groups are preferred because the compound represented by general formula (4) preferably forms an insulating film on the surface of the positive electrode active material and / or negative electrode active material.

[0156] Examples of aryl groups include phenyl groups, tolyl groups, or mesityl groups, which have 6 to 12 carbon atoms. Among these, phenyl groups or tolyl groups, which have 6 to 7 carbon atoms, are preferred, and phenyl groups are particularly preferred, from the viewpoint that the compound represented by general formula (4) tends to localize near the surface of the positive electrode active material and / or negative electrode active material.

[0157] Examples of aralkyl groups include phenylmethyl (benzyl) groups, phenylethyl (phenethyl) groups, phenylpropyl groups, phenylbutyl groups, or phenylisopropyl groups, which have 7 to 12 carbon atoms. Among these, aralkyl groups with 7 to 8 carbon atoms, such as benzyl or phenethyl groups, are preferred, and benzyl groups are particularly preferred, from the viewpoint that the compound represented by general formula (4) tends to localize near the surface of the positive electrode active material and / or negative electrode active material.

[0158] Examples of substituents that the hydrocarbon group may have include cyano groups, isocyanate groups, halogen atoms, or groups containing halogen atoms. Among these, isocyanate groups, halogen atoms, or groups containing halogen atoms are preferred, and halogen atoms or groups containing halogen atoms are particularly preferred. For specific and preferred examples of halogen atoms, see R 1 It is similar to what is defined in [the relevant section].

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

[0160] (R 4 ) R related to general formula (4) 4 This represents a hydrogen atom, a optionally substituted monovalent hydrocarbon group, or an optionally substituted alkoxy group. Among these, an optionally substituted monovalent hydrocarbon group or an optionally substituted alkoxy group is preferred from the viewpoint of minimizing side reactions on the active material of the compound represented by general formula (1), and an optionally substituted monovalent hydrocarbon group is particularly preferred. Here, the hydrocarbon group is R 3 The hydrocarbon groups are defined similarly to those specified in [reference], and the preferred hydrocarbon groups are also defined similarly.

[0161] Examples of alkoxy groups include alkoxy groups having 1 to 12 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, hexyloxy, octyloxy, decyloxy, or dodecyloxy groups. Among these, alkoxy groups having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, or butoxy groups, are preferred because they have less steric hindrance to the compound represented by general formula (4) and are suitably concentrated on the active material surface. Ethoxy groups are particularly preferred.

[0162] The substituents that the alkoxy group may have are R 3 It is defined in the same way as substituents that may be present on the hydrocarbon group specified by [the relevant definition].

[0163] (X 2 ) X related to general formula (4) 2 represents a divalent hydrocarbon group which may have substituents. 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. This number of carbon atoms is preferable because it tends to localize the compound represented by general formula (4) near the surface of the positive electrode active material and / or negative electrode active material. Note that if the hydrocarbon group has substituents, the carbon atoms in the substituents are not included in this number of carbon atoms.

[0164] Specific examples of divalent hydrocarbon groups include alkylene groups and alkenylene groups. Among these, alkylene groups are preferred. Substituents that the divalent hydrocarbon group may have include R 3 It is defined in the same way as substituents that may be present on the hydrocarbon group specified by [the relevant definition].

[0165] Examples of alkylene groups include linear alkylene groups, branched alkylene groups, or alkylene groups having a cyclic structure.

[0166] Specific examples of linear alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, or desilene groups.

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

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

[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, or methylpropylene group are more preferred. The alkylene group is preferred because the compound represented by general formula (4) tends to localize near the surface of the positive electrode active material and / or negative electrode active material.

[0170] (A 2 ) A related to general formula (4) 2 This refers to a divalent or trivalent atomic group represented by the following general formula (5-1) or the general formula (6-1) described later.

[0171] [ka]

[0172] Z 3 is a carbon atom, sulfur atom, phosphorus atom, or boron atom; Y 102 is an oxygen atom or a sulfur atom; Y 10 , Y 11 and Y 12 Each of these independently consists of a single bond, an oxygen atom, a sulfur atom, or NR. 102 (-NR 102 -Base) and;R 102 R is a hydrogen atom or a monovalent hydrocarbon group; 102 If is a monovalent hydrocarbon group, then R 102 R in the general formula (4) is 3 and X 2 It may be bonded to any of the following to form a ring. r 5 is, Z 3 When it is a carbon atom, it is 1, Z 3 When it is a sulfur atom, it is 0, 1, or 2, and Z 3 When it is a phosphorus atom, it is 0 or 1, Z 3 When it is a boron atom, it is 0. r 6 is, Z 3 When the atoms are carbon atoms and sulfur atoms, it is 0, and Z 3 The value is 1 when it is a phosphorus atom or a boron atom. * represents R in the general formula (4) above. 3 or X 2 This represents the connection point. However, Z 3 is a sulfur atom, and r 5 When Y is 2, 10 and Y 11 They can never be bonded together as a single bond.

[0173] (R 104 ) The above R 104 The monovalent hydrocarbon group in is R in the first embodiment. 1 This is synonymous with a monovalent hydrocarbon group as defined in [the relevant section].

[0174] Examples of divalent atomic groups represented by general formula (5-1) include oxygen atoms; sulfur atoms; divalent atomic groups consisting of oxygen atoms, carbon atoms and oxygen atoms, or hydrogen atoms, carbon atoms and oxygen atoms; or divalent atomic groups consisting of sulfur atoms, oxygen atoms and sulfur atoms, carbon atoms, oxygen atoms and sulfur atoms, or hydrogen atoms, carbon atoms, oxygen atoms and sulfur atoms.

[0175] Specific examples of divalent atomic groups consisting of an oxygen atom, a carbon atom and another oxygen atom, or a hydrogen atom, a carbon atom and another oxygen atom include divalent atomic groups having a ketone structure, a carboxylic acid ester structure, or a carbonate structure. Specifically, for example, Z 3 is a carbon atom; Y 102 is an oxygen atom; Y 10 , Y 11 , and Y 12 Examples include groups of atoms where each atom is independently bonded to a single bond or is an oxygen atom. Specific examples of divalent groups having a ketone structure include the -CO- group. Specific examples of divalent groups having a carboxylic acid ester structure include the -COO- group. Specific examples of divalent groups having a carbonate structure include the -OCOO- group. Among these, the -COO- group and the -OCOO- group are particularly preferred because they produce fewer electrochemical side reactions and form a suitable film on the active material surface.

[0176] Specific examples of divalent atomic groups 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 sulfide structures, sulfone structures, sulfonic acid ester structures, sulfuric acid ester structures, sulfoxide structures, and sub- Examples include divalent groups having a sulfate ester structure, a sulfinic acid ester structure, a thiocarbonyl structure, and a thioester structure. Specifically, for example, Z 3 is a carbon atom; Y 102 is an oxygen atom; Y 10 , Y 11 , and Y 12 The group of atoms that is a sulfur atom, Z 3 is a carbon atom; Y 102 is a sulfur atom; Y 10 , Y 11 , and Y 12 A group of atoms that are independently single-bonded, oxygen atoms, or sulfur atoms, 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 Examples include atomic groups where each atom is independently a single bond, an oxygen atom, or a sulfur atom. Specific examples of divalent groups having a sulfide structure include the -S- group. Specific examples of divalent groups having a sulfonic acid ester structure include the -SO3- group. Specific examples of divalent groups having a sulfate ester structure include the -OSO3- group. Specific examples of divalent groups having a sulfoxide structure include the -SO- group. Specific examples of divalent groups having a sulfite ester structure include the -OSOO- group. Specific examples of divalent groups having a sulfinic acid ester structure include the -SO- group. Examples of divalent groups having a thiocarbonyl structure include the -OCSO- group or the -CSO- group. Specific examples of divalent groups having a thioester structure include -COS-, -OCOS-, and -SCOS- groups. Alternatively, divalent groups having a dithiocarboxylic acid ester structure, such as -CSS-, -OCSS-, or -SCSS- groups, may also be used. In particular, from the viewpoint of having fewer electrochemical side reactions and forming a suitable film on the active material surface, -SO3- groups, -OSO3- groups, -OSOO- groups, or -SO- groups are preferred, -SO3- groups or -OSO3- groups are more preferred, and -SO3- groups are especially preferred.

[0177] Examples of trivalent atomic groups having at least one atom selected from oxygen, nitrogen, sulfur, phosphorus, and boron include nitrogen; phosphorus; boron; carbon, nitrogen, and oxygen; or a trivalent atomic group consisting of hydrogen, carbon, nitrogen, and oxygen; carbon, nitrogen, and sulfur; nitrogen, oxygen, and sulfur; hydrogen, carbon, nitrogen, and sulfur; or a trivalent atomic group consisting of carbon, nitrogen, oxygen, and sulfur; phosphorus, oxygen, and phosphorus; or a trivalent atomic group consisting of hydrogen, nitrogen, oxygen, and phosphorus; or boron; or a trivalent atomic group consisting of boron and oxygen; and more specifically, for example, Z 3 is a carbon atom; Y 102 is an oxygen atom; Y 10 , Y 11 , and Y 12 NR 104 Examples include atomic groups. Trivalent atomic groups consisting of carbon atoms, nitrogen atoms, and oxygen atoms, or hydrogen atoms, carbon atoms, nitrogen atoms, and oxygen atoms, include trivalent groups having amide, urethane, or urea structures. Specific examples of these atomic groups are shown below.

[0178] [ka]

[0179] As a 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, it can be a thiocarbonyl structure, a thioester structure, or a sulfonamide structure. Examples include trivalent groups having a structure. Furthermore, trivalent groups having a dithiocarboxylic acid ester structure may also be used. Specific examples of these include the atomic groups shown below, specifically, for example, Z 3 is a carbon atom; Y 102 is a sulfur atom; Y 10 , Y 11 , and Y 12 NR 104 A manner in which Z 3 is a carbon atom; Y 102 is an oxygen atom; Y 10 , Y 11 , and Y 12 NR 104 Examples include atomic groups. [ka]

[0180] Examples include phosphorus atoms, oxygen atoms and phosphorus atoms, or trivalent atomic groups consisting of hydrogen atoms, nitrogen atoms, oxygen atoms or phosphorus atoms, and specifically, for example, Z 3 Examples include atomic groups in which the atom is a phosphorus atom, and more specifically, trivalent groups having a phosphine oxide structure, phosphinic acid ester structure, phosphonic acid ester structure, phosphate ester structure, phosphate amide structure, phosphine structure, phosphiniate ester structure, phosphoniate ester structure, or phosphite ester structure. Specific examples of these include the atomic groups shown below. [ka]

[0181] Among these, the following atomic groups are preferred because they have fewer electrochemical side reactions and form a suitable coating on the active material surface. [ka]

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

[0183] [ka]

[0184] Examples of trivalent groups consisting of a boron atom or a boron atom and an oxygen atom include trivalent groups having a trialkylborane structure, a boric acid ester structure, a boronic acid ester structure, and a boric acid ester structure. Specific examples of these groups include the following: [ka]

[0185] In particular, because it produces fewer electrochemical side reactions and forms a suitable film on the active material surface, the divalent or trivalent atomic group represented by formula (5-1) is preferably the divalent or trivalent atomic group represented by the following general formula (5-2).

[0186] [ka]

[0187] Z 4 is a carbon atom, a sulfur atom, or a phosphorus atom, Y 16 , Y 17 and Y 18 Each of these is independently either a single bond or an oxygen atom. r 7 is, Z 4 When it is a carbon atom, it is 1, Z 4 When it is a sulfur atom, it is 0, 1, or 2, and Z 4 When it is a phosphorus atom, it is 0 or 1. r 8 is, Z 4 When it is a carbon atom or a sulfur atom, it is 0, Z 4 When it is a phosphorus atom, it is 1. * represents R in the general formula (4) above. 3 or X 2 This represents the connection point. However, Z 4 is a sulfur atom, and r 7 When Y is 2, 16 and Y 17 They can never be bonded together as a single bond. Z in general formula (5-2) 4 , Y 16 , Y 17 , Y 18 , r 7 , and r 8 To the extent applicable, Z in the above general formula (5-1) 3 , Y 13 , Y 14 , Y 15 , r 5 , and r 6 Each of these conditions can be applied.

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

[0189] [ka]

[0190] Y 13 , Y 14 and Y 15 Each of these is independently an oxygen atom, a sulfur atom, or NR 202 (=NR 202 It is the basis. 202 is a hydrogen atom or a monovalent hydrocarbon group. * represents R in the general formula (4) above. 3 or X 2 This represents the connection point.

[0191] (R 202 ) The above R 202 The monovalent hydrocarbon group in R 1 This is synonymous with a monovalent hydrocarbon group as defined in [the relevant section].

[0192] Among these, the atomic group represented by the following formula (6-2) is preferred because it exhibits fewer electrochemical side reactions and forms a suitable coating on the active material surface. [ka]

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

[0194] Among the atomic groups represented by the above general formula (5-1) or general formula (6-1), Preferably, the group is 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 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 has a carbonate structure, a carboxylic acid ester structure, a sulfonic acid ester structure, 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. Divalent group having a carbonate structure, divalent group having a carboxylic acid ester structure, sulfonic acid It is more preferable that the group has a divalent ester structure, a trivalent phosphonic acid ester structure, a trivalent phosphate ester structure, or a trivalent isocyanurate structure. It is particularly preferable that the divalent group has a carbonate structure or a divalent group has a carboxylic acid ester structure.

[0195] (n 2 ) n related to general formula (4) 2 n represents an integer between 1 and 3. n is chosen because it is easier to suppress battery swelling. 2 It is preferable that the number is 2 or 3.

[0196] n 2 If it is 2, R 3 is an alkyl group, R 4 is an alkyl group, X 2 is an alkylene group and A 2 R is a divalent group having a carbonate structure; 3 is an alkyl group, R 4 is an alkyl group, X 2 is an alkylene group and A 2 R is a divalent group having an ester structure; 3 is an alkyl group, R 4 is an alkyl group, 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, X 2 is an alkylene group and A 2 It is preferable that the combination of trivalent groups having an isocyanurate structure is the case.

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

[0198] (p 2 , q 2 ) p related to general formula (4) 2 This represents an integer between 0 and 2.

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

[0200] R 3 and X 2 Two of these may be joined together to form a ring. That is, the manner in which a ring is formed is R 3 Allies, and also, R 3 and X 2 One example is a configuration in which the atoms are bonded together to form a ring. From the viewpoint of ease of synthesis, R 3 and X 2 A configuration in which the elements are joined to form a ring is preferred. A more preferred configuration is the following structure.

[0201] [ka]

[0202] The following are specific examples of compounds represented by the general formula (4). However, the compounds represented by the general formula (4) in this embodiment are not limited in any way to the compounds represented by the following examples of formulas (G3-1) to (G3-106), (G2-1) to (G2-148), and (G1-1) to (G1-148).

[0203] [ka]

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[0240] [ka]

[0241] Of 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, X 2 Compounds in which the parentheses is an alkylene group are preferred, and among these, the above-mentioned formulas (G3-1), (G3-20), (G3-26), (G3-35)~(G3-37), (G3-43)~(G3-45), (G3-53)~(G3-63), (G3-67)~(G3-85), (G3-91)~(G3-99), (G3-101)~(G3-106), (G2-1), (G2-20), (G2-26), (G2-35)~(G2-37), (G2-43)~(G2-45), (G2-5 3) Preferably, the compound is selected from the group of compounds represented by (G2-63), (G2-67)~(G2-85), (G2-91)~(G2-99), (G2-101)~(G2-148), (G1-1), (G1-20), (G1-26), (G1-35)~(G1-37), (G1-43)~(G1-45), (G1-53)~(G1-63), (G1-67)~(G1-85), (G1-91)~(G1-99), and (G1-101)~(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, X 2 Compounds in which the parentheses is an alkylene group are more preferred, and among these, the above-mentioned formulas (G3-1), (G3-20), (G3-35)~(G3-37), (G3-44)~(G3-45), (G3-53)~(G3-63), (G3-91)~(G3-99), (G2-1), (G2-20), (G2-35)~(G2-37), (G2-44)~ It is preferable that the compound is selected from the group of compounds represented by (G2-45), (G2-53)~(G2-63), (G2-91)~(G2-100), (G1-1), (G1-20), (G1-35)~(G1-37), (G1-44)~(G1-45), (G1-53)~(G1-63), and (G1-91)~(G1-99). X 2 The propylene group is R 3 It is even more preferable that the group is a methyl group or an ethyl group, and among these, the above-mentioned (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) Preferably, the compound is selected from the group of compounds represented by (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 If it is 2 or 3, 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 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 X is an alkyl group having 1 to 6 carbon atoms. 2 Compounds in which the group is a propylene group are particularly preferred, and among these, it is preferable that the compound is 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), (G2-94) above. It is particularly preferable that the compound is 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 It is a divalent group of atoms having a carbonate structure, R 3 is an alkyl group, n 2 =2, R 4 is an alkyl group, and X 2 A form in which is an alkylene group; or R 3 is an alkyl group, n 2 is 3 and X 2 The aspect in which the group is an alkylene group; A 2 It is a divalent group having a carboxylic acid ester structure, R 3 is an alkyl group, n 2 =2, R 4 is an alkyl group, and X 2 The aspect in which the group is an alkylene group; A 2 It is a divalent group having a sulfonic acid ester structure, R 3 is an alkyl group, n 2 =2, R 4 is an alkyl group, and X 2 A form in which is an alkylene group; or R 3 is an alkyl group, n 2 is 3 and X 2 The aspect in which the group is an alkylene group; A 2 It is a divalent group having a phosphonic acid ester structure, R 3 is an alkyl group, n 2 =2, R 4 is an alkyl group, and X 2 A form in which is an alkylene group; or R 3 is an alkyl group, n 2 is 3 and X 2 The aspect in which the group is an alkylene group; A 2 It is a trivalent group having a phosphate ester structure, R 3 is an alkyl group, n 2 =2, R 4 is an alkyl group, and X 2 A form in which is an alkylene group; or R 1 is an alkyl group, n 2 is 3 and X 2 In the embodiment where is an alkylene group, the following compounds are preferred.

[0243] [ka]

[0244] Also, A 2 It is a divalent group of atoms having a carbonate structure, R 3 is an alkyl group, n 2 =2, R 4 is an alkyl group, and X 3 A form in which is an alkylene group; or R 3 is an alkyl group, n 2 is 3 and X 2 The aspect in which the group is an alkylene group; A 2 It is a divalent group having a carboxylic acid ester structure, R 3 is an alkyl group, n 2 =2, R 4 is an alkyl group, and X 2 The aspect in which the group is an alkylene group; A 2 It is a divalent group having a phosphonic acid ester structure, R 3 is an alkyl group, n 2 =2, R 4 is an alkyl group, and X 2 A form in which is an alkylene group; or R 3 is an alkyl group, n 2 is 3 and X 2 The aspect in which the group is an alkylene group; A 2 It is a trivalent group having a phosphate ester structure, R 3 is an alkyl group, n 2 =2, R 4 is an alkyl group, and X 2 A form in which is an alkylene group; or R 1 is an alkyl group, n 2 is 3 and X 2 In the embodiment where is an alkylene group, the following compounds are preferred.

[0245] [ka]

[0246] Among the compounds represented by the above general formula (4), the compounds represented by the following formula are preferable from the viewpoint of achieving a balance between the resistance of the film and the suppression of gas generation due to insulation.

[0247]

Chemical formula

[0248] Among them, the compounds represented by the following formula (4-a1) or (4-a2) are 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 layer provided on at least a part of the surface of the current collector. Other configurations can be those known in the art.

[0252] The negative electrode active material is not particularly limited as long as it is electrochemically capable of intercalating and releasing metal ions and contains a metallic element and / or metalloid element that can alloy with Li. Specific examples include carbon-based materials, materials containing a metallic element and / or metalloid element that can alloy with Li, lithium-containing metal composite oxide materials, and mixtures thereof. The material containing a metallic element and / or metalloid element that can alloy with Li may be used alone, or a material containing a metallic element and / or metalloid element that can alloy with Li may be used in combination with a carbon-based material or a lithium-containing metal composite oxide material as desired. It is preferable to use a material containing a metallic element and / or metalloid element that can alloy with Li, or a mixture of a material containing a metallic element and / or metalloid element that can alloy with Li and a carbon-based material, as these offer good cycle characteristics, safety, and excellent continuous charging characteristics.

[0253] Examples of carbon-based materials include natural graphite, artificial graphite, amorphous carbon, carbon-coated graphite, graphite-coated graphite, and resin-coated graphite. Among these, natural graphite is preferred.

[0254] Examples of natural graphite include scaly graphite, flake graphite, and / or graphite particles obtained by processing these graphites as raw materials, such as spheroidization or densification. Among these, spherical or ellipsoidal graphite particles that have undergone spheroidization processing are particularly preferred from the viewpoint of particle packing and charge / discharge rate characteristics. The average particle size (d50) of graphite particles is typically between 1 μm and 100 μm.

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

[0256] In this specification, Si or Si-containing compounds are collectively referred to as Si compounds. Specifically, Si compounds include SiO x ,SiN x SiC x SiZ x O y Examples include (Z=C, N), etc. Si metal oxides (SiO x ) is preferred because it has a larger theoretical capacity compared to graphite, or amorphous Si or nano-sized Si crystals are preferred because alkali ions such as lithium ions can easily enter and exit, making it possible to obtain high capacity. This general formula SiO x It can be obtained using silicon dioxide (SiO2) and Si as raw materials, but the value of x is usually 0 <x<2である。 As a material containing a metallic element and / or metalloid element that can be alloyed with Li, metal particles that can be alloyed with Li are preferred because they can increase the electrode density. The average particle size (d50) of metal particles that can be alloyed with Li is typically between 0.01 μm and 10 μm, from the perspective of cycle life. The mixture of the material containing a metal element and / or a metalloid element capable of alloying with Li used as the negative electrode active material and the graphite particles may be a mixture in which the material containing a metal element and / or a metalloid element capable of alloying with Li and the aforementioned graphite particles are mixed in a state independent of each other, or may be a composite in which the material containing a metal element and / or a metalloid element capable of alloying with Li is present on the surface or inside of the 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 containing a metal element and / or a metalloid element capable of alloying with Li 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 it is within this range, it is preferable in that the side reaction on the Si surface can be controlled and the expansion 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 it is 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> 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 this embodiment is usually used by impregnating this separator. A conventionally known separator can be used.

[0258] <B1-2. Electrolyte> The non-aqueous electrolyte of this embodiment contains an electrolyte as its component, similar to a general non-aqueous electrolyte. 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 difluorooxalate borate can be preferably used. These lithium salts can also 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> The non-aqueous electrolyte of this embodiment, like a general non-aqueous electrolyte, 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 this embodiment, an auxiliary agent may be contained within the range where the effects of the present invention are achieved. 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, or 4,5-difluoro-4,5-dimethyl ethylene 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; trimer compounds derived from compounds having at least two isocyanate groups in the molecule, such as triallyl isocyanurate, or isocyanate compounds such as aliphatic polyisocyanates obtained by adding a polyhydric alcohol thereto; Nitrogen-containing compounds such as 1-methyl-2-pyrrolidinone; Hydrocarbon compounds such as cycloheptane; Fluorine-containing aromatic compounds such as fluorobenzene; Silane compounds such as tris(trimethylsilyl) borate; Ester compounds such as 2-propynyl 2-(methanesulfonyloxy)propionic acid; Lithium salts such as lithium ethylmethyloxycarbonylphosphonate; These are some examples. These can be used individually or in combination of two or more. By adding these additives, it is possible to suppress gas generation during initial conditioning and improve volume retention and cycle characteristics after high-temperature storage.

[0262] In particular, in the non-aqueous electrolyte according to this embodiment, using one or more selected from unsaturated cyclic carbonates and cyclic carbonates having fluorine atoms is preferable because it further suppresses gas generation during initial conditioning and results in a battery that is less prone to swelling.

[0263] Furthermore, the non-aqueous electrolyte 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 film with the compound represented by general formula (4), it is preferable to contain one or more compounds selected from the group consisting of phosphates 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 generated during charging and the 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. Phosphates having P=O and PF bonds, salts having an FSO2 skeleton, and oxalic acid The total content of compounds selected from the group consisting of salts is usually 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, and usually 10% by mass or less, preferably 8% by mass or less, and more preferably 5% by mass or less, in 100% by mass of the non-aqueous electrolyte (relative to the total amount of the non-aqueous electrolyte). When two or more auxiliary agents are used in combination, it is preferable that the total content satisfies the above range.

[0264] (Phosphates containing P=O and PF bonds) The phosphate containing P=O and PF bonds is not particularly limited as long as it is a phosphate containing P=O and PF bonds within the molecule. Examples of countercations of phosphates having a PF bond include alkali metals such as lithium, sodium, and potassium, with lithium being the preferred choice. Examples of fluorophosphates having a P=O bond include: Monofluorophosphates such as Li2PO3F; Difluorophosphates such as LiPO2F2, NaPO2F2, and KPO2F2; These are some examples. In particular, difluorophosphates are preferred, and lithium difluorophosphates are more preferred, in addition to their gas suppression effect during high-temperature storage, as well as their ability to further improve charge-discharge rate characteristics and impedance characteristics.

[0265] Fluorophosphates may be used individually or in any combination and ratio of two or more types. The fluorophosphate content (total amount in the case of two or more types) 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, and more preferably 3% by mass or less, based on 100% by mass of the non-aqueous electrolyte. If the fluorophosphate content is within this range, the characteristics of non-aqueous electrolyte secondary batteries, particularly the durability characteristics or continuous charging characteristics, can be significantly improved. The principle behind this is not entirely clear, but it is thought that mixing them in this ratio minimizes side reactions of the additives on the electrodes.

[0266] The mass ratio of the compound represented by the above general formula (1) to the phosphate having P=O and PF bonds (total amount if there are two or more types) is usually 1 / 100 or more, preferably 10 / 100 or more, more preferably 20 / 100 or more, even more preferably 25 / 100 or more, usually 10000 / 100 or less, preferably 500 / 100 or less, more preferably 100 / 100 or less, particularly preferably 80 / 100 or less, and most preferably 40 / 100 or less. If the mass ratio is within this range, the characteristics of non-aqueous electrolyte secondary batteries, especially durability characteristics or continuous charging characteristics, can be significantly improved. The principle behind this is not clear, but it is thought that mixing at this ratio minimizes side reactions of the additive on the electrodes.

[0267] When LiPF6 is present in a non-aqueous electrolyte, the mass ratio of phosphates containing P=O and PF bonds (total amount if there are two or more types) to the LiPF6 content (fluorophosphate / LiPF6) is usually 0.00005 or higher, preferably 0.001 or higher, more preferably 0.01 or higher, even more preferably 0.02 or higher, particularly preferably 0.025 or higher, usually 1.0 or lower, preferably 0.5 or lower, more preferably 0.4 or lower, and even more preferably 0.35 or lower. If this mass ratio is within this range, the characteristics of non-aqueous electrolyte secondary batteries, especially durability characteristics or continuous charging characteristics, can be significantly improved. The principle behind this is not clear, but it is thought that mixing at this ratio minimizes the decomposition side reactions of LiPF6 within the non-aqueous electrolyte secondary battery. The content of phosphates containing P=O and PF bonds is determined by nuclear magnetic resonance (NMR). Analysis is performed. Typically, NMR analysis is used, but if the assignment of other compounds is difficult due to solvent peaks, ion chromatography (IC) analysis is also performed.

[0268] (Salts with an FSO2 skeleton) The salt having an FSO2 skeleton used in this embodiment is not particularly limited as long as it has an FSO2 skeleton in its molecule. Examples of countercations for salts having an FSO2 skeleton include alkali metals such as lithium, sodium, and potassium, with lithium being the most preferred among them. 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); Fluorosulfonylmethide salts such as LiC(FSO2)3; These are some examples. In particular, fluorosulfonates are preferred, and lithium fluorosulfonate is more preferred, in addition to the gas suppression effect during high-temperature storage, as well as the effect of improving charge-discharge rate characteristics and impedance characteristics.

[0269] The salts having an FSO2 skeleton may be used individually or in any combination and ratio of two or more types. The content of the salts having an FSO2 skeleton (total amount if 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, and more preferably 3% by mass or less, per 100% by mass of the non-aqueous electrolyte. If the content of the salts having an FSO2 skeleton is within this range, the characteristics of the non-aqueous electrolyte secondary battery, in particular the durability characteristics or continuous charging characteristics, can be significantly improved. The principle behind this is not clear, but it is thought that mixing them in this ratio minimizes the side reactions of the additives on the electrodes.

[0270] The mass ratio of the compound represented by the above general formula (1) to the salt having an FSO2 skeleton (total amount if there are two or more types) is usually 1 / 100 or more, preferably 10 / 100 or more, more preferably 20 / 100 or more, even more preferably 25 / 100 or more, usually 10000 / 100 or less, preferably 500 / 100 or less, more preferably 100 / 100 or less, particularly preferably 80 / 100 or less, and most preferably 40 / 100 or less. If the mass ratio is within this range, the characteristics of non-aqueous electrolyte secondary batteries, especially durability characteristics or continuous charging characteristics, can be significantly improved. The principle behind this is not clear, but it is thought that mixing at this ratio minimizes side reactions of the additive on the electrodes.

[0271] When LiPF6 is present in a non-aqueous electrolyte, the mass ratio of salts having an FSO2 skeleton (total amount if there are two or more types) to the LiPF6 content (salts having an FSO2 skeleton / LiPF6) is usually 0.00005 or higher, preferably 0.001 or higher, more preferably 0.01 or higher, even more preferably 0.02 or higher, particularly preferably 0.025 or higher, usually 1.0 or lower, preferably 0.5 or lower, more preferably 0.4 or lower, and even more preferably 0.35 or lower. If this mass ratio is within this range, the characteristics of non-aqueous electrolyte secondary batteries, especially durability characteristics or continuous charging characteristics, can be significantly improved. The principle behind this is not clear, but it is thought that mixing at this ratio minimizes the decomposition side reactions of LiPF6 within the non-aqueous electrolyte secondary battery. The content of salts containing the FSO2 skeleton is determined by nuclear magnetic resonance (NMR) analysis. While NMR analysis is usually performed, ion chromatography (IC) analysis is also performed if the assignment of other compounds is difficult due to solvent peaks.

[0272] (Oxalate) The oxalate is not particularly limited as long as it is a compound having at least one oxalic acid skeleton in its molecule. Examples of oxalate countercations include alkali metals such as lithium, sodium, and potassium, with lithium being the preferred choice. For example, oxalate borate salts such as lithium bis(oxalate)borate and lithium difluorooxalate borate; Oxalate phosphate salts such as lithium tetrafluorooxalate phosphate, lithium difluorobis(oxalate) phosphate, and lithium tris(oxalate) phosphate; These are some examples. In particular, oxalate borate salts are preferred, and lithium bis(oxalate) borate is more preferred, in addition to the gas suppression effect during high-temperature storage, as well as the improvement effect on charge-discharge rate characteristics and impedance characteristics.

[0273] Oxalates may be used individually or in any combination and ratio of two or more types. The oxalate content (total amount in the case of two or more types) 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, and more preferably 3% by mass or less, based on 100% by mass of the non-aqueous electrolyte. If the oxalate content is within this range, the characteristics of the non-aqueous electrolyte secondary battery, especially the durability characteristics or continuous charging characteristics, can be significantly improved. The principle behind this is not entirely clear, but it is thought that mixing them in this ratio minimizes side reactions of the additives on the electrodes.

[0274] The mass ratio of the compound represented by the above general formula (1) to the oxalate (total amount if there are two or more types) is usually 1 / 100 or more, preferably 10 / 100 or more, more preferably 20 / 100 or more, even more preferably 25 / 100 or more, usually 10000 / 100 or less, preferably 500 / 100 or less, more preferably 100 / 100 or less, particularly preferably 80 / 100 or less, and most preferably 40 / 100 or less. If the mass ratio is within this range, the characteristics of non-aqueous electrolyte secondary batteries, especially the durability characteristics or continuous charging characteristics, can be significantly improved. The principle behind this is not clear, but it is thought that mixing at this ratio minimizes side reactions of the additive on the electrodes.

[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, 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 the 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 solvent peak, 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 in the non-aqueous electrolyte at 10% by mass, it is discriminated as an electrolyte, and when a salt having an oxalic acid 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 capable of occluding and releasing metal ions, a negative electrode, and the above-described non-aqueous electrolyte, The non-aqueous electrolyte battery is characterized in that the negative electrode active material included in the negative electrode contains a material containing a metal element and / or a metalloid element that can be alloyed 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 the non-aqueous electrolyte includes 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 included in the negative electrode contains a material containing a metal element and / or a metalloid element that can be alloyed 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 a conventionally known non-aqueous electrolyte battery. Usually, the positive electrode and the negative electrode are laminated via 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 embodiment of the present invention 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 adopt conventionally known ones. Lithium transition metal compounds are compounds having a structure that allows for the removal and insertion of lithium ions. Examples include sulfides, phosphate compounds, silicate compounds, borate compounds, and lithium transition metal composite oxides. 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 with a spinel structure that allows for three-dimensional diffusion, and those with a layered structure that enables two-dimensional diffusion of lithium ions. Lithium transition metal compounds having a spinel structure are generally represented by the following compositional formula (11-2). Li x2’ M3'2O4···(11-2) (In equation (11-2), x2' is 1 ≤ x2' ≤ 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. Lithium transition metal compounds having a layered structure are generally represented by the following compositional formula (12-2). Li 1+x3 M3O2···(12-2) (In equation (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, LiLiLi 0.80 Co 0.15 Al 0.05 O2, LiLiLi 0.33 Co 0.33 Mn 0.33 O2, Li 1.05 Ni 0.33 Co 0.33 Mn 0.33 O2, LiLiLi 0.5 Co 0.2 Mn 0.3 O2, Li 1.05 Ni 0.5 Co 0.2 Mn 0.3 O2, LiLiLi 0.6 Co 0.2 Mn 0.2 O2, LiLiLi 0.8 Co 0.1 Mn 0.1 Examples include O2.

[0282] In particular, from the viewpoint of improving battery capacity, lithium transition metal composite oxides having a layered structure are preferred, and lithium transition metal composite oxides represented by the following compositional formula (13-2) are more preferred. Li a13 Ni b13 M13 c13 O2···(13-2) (In equation (13-2), a13, b13, and c13 are numerical values ​​satisfying 0.90 ≤ a13 ≤ 1.10, 0.40 ≤ b13 ≤ 0.98, and 0.00 ≤ c13 ≤ 0.50, respectively, and satisfying b13 + c13 = 1. 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 higher, more preferably 0.60 or higher, even more preferably 0.65 or higher, particularly preferably 0.70 or higher, more preferably 0.75 or higher, more preferably 0.80 or higher, and more preferably 0.90 or higher. Furthermore, c13 is preferably 0.01 or higher.

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

[0284] In particular, an embodiment in which the transition metal oxide is represented by the following compositional formula (14-2) is preferred. Li a23 Ni b23 Co c23 M23 d23 O2···(14-2) In the above compositional formula (14-2), a23, b23, c23, and d23 represent values ​​such as 0.90 ≤ a23 ≤ 1.10, 0.50 ≤ b23 ≤ 0.98, 0.01 ≤ c23 < 0.50, and 0.01 ≤ d23 < 0.50, satisfying 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 the value is 0.1 ≤ d23 < 0.5. By setting the composition ratios of Ni, Co, and other metal species within the above range, transition metals are less likely to leach from the positive electrode, and even if they do leach, Ni and Co have the advantage of having little adverse effect within a non-aqueous secondary battery. A suitable example is LiNi 0.85 Co 0.10 Al 0.05 O2, LiLiLi 0.80 Co 0.15 Al 0.05 O2, LiLiLi 0.5 Co 0.2 Mn 0.3 O2, Li 1.05 Ni 0.50 Co 0.20 Mn 0.30 O2, LiLiLi 0.6 Co 0.2 Mn 0.2 O2, LiLiLi 0.8 Co 0.1 Mn 0.1 Examples include O2.

[0285] <B2-5.セパレータ> A separator is usually placed between the positive and negative electrodes to prevent short circuits. In this case, the non-aqueous electrolyte according to this embodiment is usually used by impregnating this separator. Conventional separators can be used. [Examples]

[0286] The present invention will be described in more detail below with reference to examples and reference examples, but the present invention is not limited to these examples unless it exceeds the gist of the invention.

[0287] The compounds used in this example and comparative example 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] <Example of synthesis> In the following synthesis examples, the Karrstedt catalyst used was a 2 wt% xylene solution of a Sigma-Aldrich platinum(0)-1,3-divinyltetramethyldisiloxane complex. Furthermore, the various 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 using a Bruker 400 Ultrashield at 400, 101, and 376 MHz, respectively. The samples were dissolved in deuterated chloroform (CDCl3) before measurement. [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). The conditions were as follows: Column: DB-1 (Length 30m, Inner diameter 0.32mm, Film thickness 0.25μm, manufactured by Agilent Technologies) Detector: FID Temperature: The temperature was increased from 40°C to 280°C at a rate of 10°C / min. Purity was determined from the peak area percentage.

[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 while stirring under ice cooling. By heating and stirring at 70°C for 15 minutes, a toluene solution of 3-(chlorodimethylsilyl)propylmethyl carbonate was obtained. 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. Under ice cooling and stirring, a toluene solution of 3-(chlorodimethylsilyl)propylmethyl carbonate was added dropwise, and the mixture was heated under reflux for 3 hours. The reaction mixture was filtered, and after solvent concentration, 3-(fluorodimethylsilyl)propylmethyl carbonate (0.185 g, 0.952 mmol) was obtained by silica gel column chromatography. The estimated purity by GC analysis was 99%. 1 H-NMR, 13 C-NMR, 19 The results of the 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, CDCl3): 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. By heating and stirring at 80°C for 15 minutes, a toluene solution of 3-(dichloromethylsilyl)propylmethyl carbonate was obtained. 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. Under ice cooling and stirring, a toluene solution of 3-(dichloromethylsilyl)propylmethyl carbonate was added dropwise. After heating under reflux for 3 hours, the mixture was allowed to cool to room temperature. The reaction mixture was filtered, the solvent was removed by distillation, and 3-(difluoromethylsilyl)propylmethyl carbonate (80.0 mg, 0.404 mmol) was obtained by distillation. The estimated purity by GC analysis was 99%. 1 H-NMR, 19 The results of the 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 (376MHz, CDCl3): 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. By distillation of the solvent, 3-(trimethoxysilyl)propylmethyl carbonate (12.3 g, 51.5 mmol) was obtained. 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 solvent were removed by distillation. Purification was performed using a Kugellohr distillation apparatus to obtain carbonate. 3-(trifluorosilyl)propylmethyl (1.26 g, 6.23 mmol) was obtained. The purity estimated by GC analysis was 97%. 1 H-NMR, 13 C-NMR, 19 The results of the 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 (376MHz, CDCl3): δ = -137.1

[0310] <Synthesis Example 4> Synthesis of compound 4 (4-[2-(difluoromethylsilyl)ethyl]-1,3-dioxolan-2-one) Vinylethylene carbonate (6.00 g, 52.6 mmol) was dissolved in toluene (80 mL), and 60 μL of Karstedt's catalyst was added. While stirring under ice cooling, dichloromethylsilane (6.72 mL, 63.1 mmol) was added dropwise, 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 charged, and potassium fluoride (12.2 g, 210 mmol) was added in small amounts. After heating under reflux for 4 hours, the mixture was cooled to room temperature, and the inorganic salt was 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 estimated purity by GC analysis was 87%. 1 H-NMR, 13 C-NMR, 19 The results of the 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, CDCl3): δ = -135.2

[0311] <Synthesis Example 5> Synthesis of compound 5 (4-(2-trifluorosilylethyl)-1,3-dioxolan-2-one) Vinylethylene 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 while stirring under ice cooling, and the mixture was heated and stirred at 50°C for 2 hours. By distillation of the solvent, 4-(2-trimethoxysilylethyl)-1,3-dioxolan-2-one (23.8 g, 101 mmol) was obtained. 4-(2-trimethoxysilylethyl)-1,3-dioxolan-2-one (15.0 g, 63.5 mmol) was dissolved in diethyl ether (70 mL), and boron trifluoride diethyl ether complex (7.97 mL, 63.5 mmol) was added dropwise under ice cooling. After heating under reflux for 5 hours, low-boiling by-products and solvent were removed by distillation. 3 g of the crude product was purified by distillation to obtain 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 the 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, CDCl3): 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 charged, and potassium fluoride (6.96 g, 120 mmol) was added in small amounts. After heating under reflux for 3 hours, the mixture was allowed to cool to room temperature. The reaction mixture was filtered, the filtrate was concentrated, and then purified by distillation to obtain 3-(difluoromethylsilyl)propyl acetate (1.10 g, 6.04 mmol). The estimated purity by GC analysis was 95%. 1 H-NMR, 13 C-NMR, 19 The results of the 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 (376MHz, CDCl3): δ = -135.4

[0313] <Synthesis Example 7> Synthesis of compound 7 (3-trifluorosilylpropyl acetate) 34.5 g, 155.2 mmol of 3-trimethoxysilylpropyl acetate was dissolved in toluene (345 mL), and 38.3 mL, 310.4 mmol of boron trifluoride diethyl ether complex was added dropwise under ice cooling. After stirring at 80°C for 2 hours, low-boiling by-products and solvent were removed by distillation. 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 13C-NMR 19 The analysis results of 19F-NMR were as follows. 1 1H-NMR (400 MHz, CDCl3): δ = 4.18 (t, J = 6.1 Hz, 2H), 2.21 (s, 3H), 1.91 - 1.98 (m, 2H), 1.11 - 1.07 (m, 2H) 13 13C-NMR (101 MHz, CDCl3): δ = 173.6, 66.8, 20.6, 20.4, 3.9 19 19F-NMR (376 MHz, CDCl3): 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 salts were 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 solution was filtered, and the filtrate was concentrated. Toluene was added and the precipitate was filtered off. Then, the filtrate was 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 thereto under ice cooling. After heating under reflux for 5 hours, low-boiling by-products and the solvent were distilled off, and 3-(Difluoromethylsilyl)propyl methanesulfonate (0.21 g, 0.962 mmol) was obtained by distillation purification. The purity estimated by GC analysis was 86%. 1 1H-NMR, 13 13C-NMR, 19 The analysis results of 19F-NMR were as follows. 1 1H-NMR (400 MHz, CDCl3): δ = 4.22 (t, J = 6.4 Hz, 2H), 3.03 (s, 3H), 1.96 - 1.88 (m, 2H), 0.92 - 0.88 (m, 2H), 0.39 (t, J H-F = 6.3 Hz, 3H) 13 13C-NMR (101 MHz, CDCl3): δ = 71.0, 37.3, 21.6, 9.4, - 4.4 19 19F-NMR (376 MHz, CDCl3): δ = - 135.2

[0315] <Synthesis Example 9> Synthesis of Compound 9 (3-(Trifluoromethylsilyl)propyl 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. The mixture was stirred at room temperature for 1 hour, then heated under reflux for 4 hours. The reaction mixture was filtered, and the filtrate was concentrated. Toluene was added to separate the precipitate, and the filtrate was 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 solvent were removed by distillation, and 3-trifluorosilylpropyl methanesulfonic acid (0.15 g, 0.675 mmol) was obtained by distillation. The purity estimated by GC analysis was 97%. 1 H-NMR, 13 C-NMR, 19 The results of the 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, CDCl3): δ = -136.7

[0316] <Synthesis Example 10> Synthesis of compound 10 (3-diethoxyphosphorylpropyl-difluoromethylsilane) 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 while stirring under ice cooling, and the mixture was heated and stirred at 90°C for 3 hours. By removing the solvent, 3-diethoxyphosphorylpropyl-dimethoxy-methylsilane (4.79 g, 16.8 mmol) was obtained. 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 solvent were removed by distillation. By distillation purification, 3-Diethoxyphosphorylpropyl-difluoromethylsilane (1.87 g, 7.18 mmol) was obtained. 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 (376MHz, CDCl3): δ = -135.3 31 P-NMR (162 MHz, CDCl3): 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 while stirring under ice cooling, and the mixture was heated and stirred at room temperature for 30 minutes. By distillation of the solvent, 3-diethoxyphosphorylpropyl(trimethoxy)silane (1.69 g, 5.61 mmol) was obtained. 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 solvent were removed by distillation. By distillation purification, 3-Diethoxyphosphorylpropyl(trifluoro)silane (0.35 g, 1.32 mmol) was obtained. 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, CDCl3): δ = -136.8 31 P-NMR (162 MHz, CDCl3): δ = 29.9

[0318] <Synthesis Example 12> Synthesis of compound 12 (3-[difluoro(methyl)silyl]propyldiethyl phosphate) Allyl diethyl 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 while stirring under ice cooling, and the mixture was stirred at room temperature for 30 minutes. By distillation of the solvent, 3-[methyl(dimethoxy)silyl]propyldiethyl phosphate (4.45 g, 14.8 mmol) was obtained. 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 solvent were removed by distillation. By distillation purification, 3-[difluoro(methyl)silyl]propyldiethyl phosphate (0.62 g, 2.24 mmol) was obtained. 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 (376MHz, CDCl3): δ = -135.4 31 P-NMR (162 MHz, CDCl3): 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 solvent were removed by distillation to obtain a crude product (2.90 g) containing 3.2 wt% diethyl ether. 1 H-NMR, 19 The results of the 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, CDCl3): 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 charged, and potassium fluoride (8.66 g, 149 mmol) was added in small amounts. The mixture was heated under reflux for 7 hours, and then cooled to room temperature. The reaction mixture was filtered, the filtrate was concentrated, and then purified by distillation to obtain 4-(difluoromethylsilyl)butanenitrile (0.77 g, 5.16 mmol). 1 H-NMR, 13 C-NMR, 19 The results of the 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, CDCl3): δ = -135.2

[0321] Compound 14 was synthesized using the synthesis method described in Patent Document 1. Furthermore, commercially available compounds 16, 17, and 18 were used.

[0322] <Examples A1-1 to A1-23, Comparative Examples A1-1 to A1-6> [Fabrication of the positive electrode] Lithium nickel cobalt manganese composite oxide (Li) is used as the positive electrode active material. 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 an N-methylpyrrolidone solvent using a disperser to form a slurry. This slurry was uniformly applied to both sides of a 15 μm thick aluminum foil, dried, and then pressed to form the positive electrode.

[0323] [Fabrication of the negative electrode] 98 parts by mass of natural graphite, with an aqueous dispersion of sodium carboxymethylcellulose (1% by mass concentration of sodium carboxymethylcellulose) as a thickening agent and binder. One part by mass of the solution and one part by mass of an aqueous styrene-butadiene rubber dispersion (styrene-butadiene rubber concentration 50% by mass) were added and 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 the negative electrode.

[0324] [Preparation of non-aqueous electrolytes] Under a dry argon atmosphere, a mixture of ethylene carbonate (EC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC) (volume ratio EC:DEC:EMC = 3:3:4) was dissolved with 1.2 mol / L (14.8% by mass; as concentration in the non-aqueous electrolyte) of thoroughly dried LiPF6 as the electrolyte. Furthermore, vinylene carbonate (VC) and fluoroethylene carbonate (FEC) were added at 2.0% by mass each (as concentration in the non-aqueous electrolyte) (hereinafter referred to as standard electrolyte 1). Non-aqueous electrolytes were prepared by adding compounds 1-7 and 9-13 to standard electrolyte 1 in the amounts listed in Table 1 below. Note that the "Content (mass%)" in the table represents the content when the total amount of each non-aqueous electrolyte is considered as 100% by mass.

[0325] [Manufacturing of non-aqueous electrolyte batteries] The positive electrode, negative electrode, and polyethylene separator described above were stacked in the order of negative electrode, separator, and positive electrode to create a battery element. This battery element was inserted into a bag made of laminate film, which consists of aluminum (40 μm thick) coated on both sides with a resin layer, so that the terminals of the positive and negative electrodes protruded from the bag. Then, the prepared non-aqueous electrolyte was injected into the bag, and it was vacuum-sealed to create a laminate-type non-aqueous electrolyte battery.

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

[0327] [Charge and storage test] After initial conditioning, non-aqueous electrolyte batteries were recharged to 4.2V at 0.2C using CC-CV charging, and then stored at high temperature for two weeks at 60°C. After the non-aqueous electrolyte batteries were sufficiently cooled, their volume was measured by immersion in an ethanol bath, and the amount of gas generated was determined from the volume change before and after the storage test. This was defined as the "charge storage gas amount." Table 1 below shows the charge storage gas amount values, with the charge storage gas amount of Comparative Example A1-1 set to 100.

[0328] [Table 1]

[0329] The results from Examples A1-1 to A1-24 and Comparative Examples A1-2 to A1-4 show that non-aqueous electrolyte batteries manufactured using a non-aqueous electrolyte containing a compound having a polar group according to the present invention can suppress gas generation more effectively than non-aqueous electrolyte batteries manufactured using a non-aqueous electrolyte containing a conventional compound. Furthermore, the results from Examples A1-1 to A1-19 indicate an increase in the number of SiF bonds in the compound. Consequently, it was found that this tends to reduce the amount of gas generated. Furthermore, the results from Examples A1-9, A1-10, A1-13, A1-15, A1-20 to A1-24, Comparative Example A1-5, and Comparative Example A1-6 show that when a 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 compared to when each is used alone. Furthermore, from the results of Examples A1-1 to A1-19, the Z of the compound in each of the above embodiments was found to be 1 ~Z 4 When comparing the configurations in which the resulting atom is a carbon atom, a sulfur atom, and a phosphorus atom, it was found that the configuration in which the atom is a carbon atom tends to suppress the amount of gas generated.

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

[0331] [Fabrication of the negative electrode] A negative electrode similar to that used in Example A1-1 was fabricated and used.

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

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

[0334] <Evaluation of non-aqueous electrolyte batteries> [Initial Conditioning] In a constant temperature bath at 25°C, the non-aqueous electrolyte battery prepared using the above method was charged with a constant current equivalent to 0.05C (1C refers to the current value that takes 1 hour to charge or discharge; the same applies hereinafter) for 6 hours, and then discharged to 3.0V at 0.2C. Subsequently, constant current-constant voltage charging (hereinafter referred to as CC-CV charging) was performed at 0.2C to 4.1V. After that, aging was performed by holding the battery at 45°C for 72 hours. After that, the non-aqueous electrolyte battery was discharged to 3.0V at 0.2C to stabilize it. Furthermore, CC-CV charging was performed at 0.2C to 4.2V, and then discharged to 3.0V at 0.2C to perform initial conditioning. After initial conditioning, the batteries were charged using CC-CV charging at 0.2C to half of their initial discharge capacity. These batteries were then discharged at 1.0C, 2.0C, and 3.0C at 25°C, and the voltage was measured after 5 seconds. The average of the slopes of the current-voltage lines obtained at 1.0C, 2.0C, and 3.0C was defined as the battery's internal resistance.

[0335] <Evaluation of non-aqueous electrolyte batteries> [Charge and storage test] After initial conditioning, laminated batteries were recharged to 4.2V at 0.2C using CC-CV charging, and then stored at high temperature for 168 hours at 60°C. After the batteries had cooled sufficiently, the cells after the storage test were discharged to 2.5V at 0.2C, and then recharged using CC-CV charging at 0.2C to half of the initial discharge capacity. The internal resistance of the batteries after the storage test was then determined. The "increase in internal resistance" was calculated using the following formula (X). Internal resistance increase rate = [(Internal resistance after storage test) / (Internal resistance after initial conditioning)] × 100%(X) Table 2 below shows the ratio of the internal resistance increase rates when the internal resistance increase rate of Comparative Example B1-1 is set to 100.

[0336] [Table 2]

[0337] The results from Examples B1-1 to B1-11 and Comparative Example B1-2 show that non-aqueous electrolyte batteries manufactured using a non-aqueous electrolyte containing a compound having a polar group according to the present embodiment can suppress the increase in resistance during high-temperature storage more effectively than non-aqueous electrolyte batteries manufactured using a non-aqueous electrolyte containing a conventional compound. Furthermore, from the results of Examples B1-1 to B1-11, the Z of the compound in each of the above embodiments was found to be 1 ~Z 4 When comparing the configurations in which the resulting atom is a carbon atom, a sulfur atom, and a phosphorus atom, it was found that the configuration in which the atom is a carbon atom tends to suppress the increase in resistance during high-temperature storage. Furthermore, the results from Examples B1-3 to B1-5, Examples B1-7 to B1-11, Comparative Example B1-3, and Comparative Example B1-4 show that when a 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 is used individually. Furthermore, from the results of Examples A1-1 to 1-12 in Table 1 and Examples B1-1 to 1-3 in Table 2, the Z of the compound in each of the above embodiments can be seen. 1 ~Z 4 When comparing the configurations in which the resulting atom is a carbon atom, a sulfur atom, and a phosphorus atom, it was found that the configuration in which the atom is a carbon atom tends to suppress gas generation and the rate of increase in internal resistance.

[0338] <Examples 2-1 to 2-9, Comparative Examples 2-1 and 2-2> [Fabrication of the positive electrode] Lithium nickel manganese cobalt composite oxide (Li) is used as the positive electrode active material. 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 an N-methylpyrrolidone solvent using a disperser to form a slurry. This slurry was then made to a thickness of 2 A 1 μm thick aluminum foil was uniformly coated on both sides, dried, and then pressed to form the positive electrode.

[0339] [Fabrication of the negative electrode] Si nanoparticles with an average particle size of 50 nm were dispersed in flaky graphite with an average particle size of 35 μm. This was placed in a hybridization system (manufactured by Nara Machine Works Co., Ltd.) and processed by circulating or retaining the mixture in the apparatus at a rotor speed of 7000 rpm for 180 seconds to obtain a composite of Si and graphite particles. The obtained composite was mixed with coal tar pitch as an organic compound that would become a carbon-based substance so that the coverage rate after calcination would be 16.8%, and then kneaded and dispersed using a twin-screw kneader. The resulting dispersion was introduced into a calcination furnace and calcined at 1000°C for 3 hours under a nitrogen atmosphere. The resulting calcined material was further pulverized with a hammer mill and then sieved (45 μm) to produce a negative electrode active material. The silicon element content measured by the above measurement method was 14.0 mass%.

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

[0341] [Preparation of non-aqueous electrolytes] Under a dry argon atmosphere, 1.2 mol / L of thoroughly dried LiPF6 (as a concentration in the non-aqueous electrolyte) was dissolved in a mixture of ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) (volume ratio 3:4:3). To this mixture, 2.0% by mass of vinylene carbonate (VC) was added (this is called standard electrolyte 2). In Examples 2-1 to 2-9 and Comparative Examples 2-1 to 2-3, non-aqueous electrolytes were prepared by adding each compound to standard electrolyte 2 so that the adjusted content was as shown in Table 3 below. However, Comparative Example 2-1 is standard electrolyte 2 itself. Note that "Content (mass%)" in the table is the concentration in 100% by mass of the non-aqueous electrolyte.

[0342] [Manufacturing of non-aqueous electrolyte secondary batteries] The positive electrode, negative electrode, and polyethylene separator described above were stacked in the order of negative electrode, separator, and positive electrode to create a battery element. This battery element was inserted into a bag made of laminate film, which consisted of aluminum (40 μm thick) coated on both sides with a resin layer, with the terminals of the positive and negative electrodes protruding from the bag. Then, the electrolyte was injected into the bag, and it was vacuum sealed to create a laminate-type cell non-aqueous electrolyte secondary battery.

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

[0344] [High-temperature cycling test] After the initial conditioning is complete, use a micrometer (Mitutoyo, model number: I After measuring the battery thickness using D-C112XB), the cells were CC-CV charged to 4.2V at 0.5C in a constant temperature bath at 45°C, and then discharged to 2.5V at a constant current of 0.5C. This process was performed 100 times, with each cycle being considered one unit. After that, the battery thickness was measured again, as in the initial conditioning stage, to determine the change in battery thickness associated with the cycle charging and discharging. Table 3 below shows the percentage change in battery thickness in each example, with the change in battery thickness in Comparative Example 2-1 set to 100, as "battery swelling." That is, if "battery swelling" is less than 100, it indicates that the change in battery thickness is less than in Comparative Example 2-1, and if it is greater than 100, it indicates that the change in battery thickness is greater than in Comparative Example 2-1.

[0345] [Table 3]

[0346] From the results of Examples 2-1 to 2-9 and Comparative Example 2-2, it was found that non-aqueous electrolyte batteries manufactured using a non-aqueous electrolyte containing a compound having a polar group according to the present embodiment can suppress battery swelling more effectively than non-aqueous electrolyte batteries manufactured using a non-aqueous electrolyte containing a conventional compound. Furthermore, from the results of Examples 2-1 to 2-7, the Z of the compound in each of the above embodiments was found to be 1 ~Z 4 When comparing the configurations in which the resulting atom is a carbon atom, a sulfur atom, and a phosphorus atom, it was found that the configuration in which the atom is a carbon atom tends to suppress battery swelling.

[0347] <Examples 3-1 to 3-4, Comparative Example 3-1> [Fabrication of the positive electrode] Lithium nickel cobalt manganese composite oxide (Li) is used as the positive electrode active material. 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 an N-methylpyrrolidone solvent using a disperser to form a slurry. This slurry was uniformly applied to both sides of a 15 μm thick aluminum foil, dried, and then pressed to form the positive electrode.

[0348] [Fabrication of the negative electrode] 97 parts by mass of natural graphite, with an aqueous dispersion of sodium carboxymethylcellulose (concentration of sodium carboxymethylcellulose 1.5 parts by mass) as a thickener and binder. %) 1 part by mass and 1.5 parts by mass of aqueous styrene-butadiene rubber dispersion (styrene-butadiene rubber concentration 50% by mass) were added and mixed in a disperser to form a slurry. The obtained slurry was applied to one side of a 10 μm thick copper foil, dried, and then pressed to form the negative electrode.

[0349] [Preparation of non-aqueous electrolytes] Under a dry argon atmosphere, a mixture of ethylene carbonate (EC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC) (volume ratio EC:EMC:DEC = 3:4:3) was dissolved with 1.2 mol / L (14.8% by mass; as concentration in the non-aqueous electrolyte) of thoroughly dried LiPF6 as the electrolyte. Furthermore, vinylene carbonate (VC) and fluoroethylene carbonate (FEC) were added at 2.0% by mass each (as concentration in the non-aqueous electrolyte) (hereinafter referred to as standard electrolyte 1). Compounds 4 to 8 were added to standard electrolyte 1 in the amounts listed in Table 4 below to prepare non-aqueous electrolytes. Note that the "Content (mass%)" in the table refers to the content when the total amount of each non-aqueous electrolyte is considered as 100% by mass.

[0350] [Manufacturing of non-aqueous electrolyte batteries] The positive electrode, negative electrode, and polyethylene separator described above were stacked in the order of negative electrode, separator, and positive electrode to create a battery element. This battery element was inserted into a bag made of laminate film, which consists of aluminum (40 μm thick) coated on both sides with a resin layer, so that the terminals of the positive and negative electrodes protruded from the bag. Then, the prepared non-aqueous electrolyte was injected into the bag, and it was vacuum-sealed to create a laminate-type non-aqueous electrolyte battery.

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

[0352] [Charge and storage test] After subjecting the non-aqueous electrolyte battery after initial conditioning to CC-CV charging up to 4.2 V at 0.2C again, high-temperature storage was carried out under the conditions of 60°C for 2 weeks. After that, after sufficiently cooling the non-aqueous electrolyte battery, it was immersed in an ethanol bath to measure the volume, and the amount of gas generated was determined from the volume change before and after the storage test, and this was defined as the "gas amount during charge storage". Table 3 below shows the values of the gas amount during charge storage when the gas amount during charge storage of Comparative Example 3-1 was set to 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 non-aqueous electrolyte battery manufactured using the non-aqueous electrolyte containing the compound according to the embodiment of the present application can suppress the gas amount during charge storage more than the non-aqueous electrolyte battery manufactured using the non-aqueous electrolyte containing the conventional compound. Also, from the results of Examples 3-1 to 3-4, it was found that the compound having a carboxylic acid ester structure tends to be able to suppress the amount of charge storage residue.

[0355] <Examples 4-1 to 4-4, Comparative Example 4-1> [Fabrication of positive electrode] As a positive electrode active material, 95 parts by mass of lithium nickel cobalt manganese composite oxide (Li 1.0 Ni 0.9 Co 0.06 Mn 0.04 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 an N-methylpyrrolidone solvent using a disperser to form a slurry. This was uniformly applied to both sides of an aluminum foil with a thickness of 15 μm, dried, and then pressed to obtain a positive electrode.

[0356] [Fabrication of negative electrode] 97 parts by mass of natural graphite were mixed with 1 part by mass of aqueous carboxymethylcellulose sodium dispersion (carboxymethylcellulose sodium concentration 1.5% by mass) and 1.5 parts by mass of aqueous styrene-butadiene rubber dispersion (styrene-butadiene rubber concentration 50% by mass) as thickeners and binders, and the mixture was prepared by mixing 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 the negative electrode.

[0357] [Preparation of non-aqueous electrolytes] Under a dry argon atmosphere, a mixture of ethylene carbonate (EC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC) (volume ratio EC:EMC:DEC = 3:4:3) was dissolved with 1.2 mol / L (14.8 mass%; concentration in the non-aqueous electrolyte) of thoroughly dried LiPF6 as the electrolyte. Furthermore, vinylene carbonate (VC) and fluoroethylene carbonate (FEC) were added at 2.0 mass% each (concentration in the non-aqueous electrolyte) (hereinafter referred to as standard electrolyte 1). Compounds 4 to 8 were added to standard electrolyte 1 in the amounts listed in Table 5 below to prepare non-aqueous electrolytes. Note that the "Content (mass%)" in the table represents the content when the total amount of each non-aqueous electrolyte is considered as 100 mass%.

[0358] [Manufacturing of non-aqueous electrolyte batteries] The positive electrode, negative electrode, and polyethylene separator described above are arranged in the order of negative electrode, separator, and positive electrode. Battery elements were fabricated by lamination. These battery elements were inserted into a bag made of laminate film, which consisted of aluminum (40 μm thick) coated on both sides with resin layers, so that the positive and negative electrode terminals protruded from the bag. Then, the prepared non-aqueous electrolyte was injected into the bag, and it was vacuum-sealed to produce a laminate-type non-aqueous electrolyte battery.

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

[0360] [Charge and storage test] After initial conditioning, non-aqueous electrolyte batteries were recharged to 4.2V at 0.2C using CC-CV charging, and then stored at high temperature for two weeks at 60°C. After the non-aqueous electrolyte batteries were sufficiently cooled, their volume was measured by immersion in an ethanol bath, and the amount of gas generated was determined from the volume change before and after the storage test. This was defined as the "charge storage gas amount." Table 5 below shows the charge storage gas amount values ​​when the charge storage gas amount of Comparative Example 4-1 is set to 100.

[0361] [Table 5]

[0362] From the results of Examples 4-1 to 4-4 and Comparative Example 4-1, it was found that non-aqueous electrolyte batteries manufactured using a non-aqueous electrolyte containing a compound having a polar group according to the present invention can suppress the amount of gas used during charging and storage more effectively than non-aqueous electrolyte batteries manufactured using a non-aqueous electrolyte containing a conventional compound. Furthermore, the results from Examples 4-1 to 4-4 showed that compounds having a carboxylic acid ester structure tended to suppress the amount of charge storage residue.

[0363] Although the present invention has been described above with reference to specific embodiments, each embodiment is presented as an example and does not limit the scope of the present invention. Each embodiment described herein 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 that is feasible. < / a1> < / a1> < / a1>

Claims

1. A non-aqueous electrolyte battery comprising a positive electrode and a negative electrode capable of intercalating and releasing metal ions, and a non-aqueous electrolyte, The negative electrode contains a negative electrode active material which contains a material that contains a metallic element and / or a metalloid element that can be alloyed with Li, The negative electrode further contains a carbon-based material, wherein the carbon-based material is graphite particles. The material containing a metallic element and / or metalloid element that can be alloyed with Li is a metallic particle that can be alloyed with Li, The ratio of metal particles that can be alloyed with Li to the total of metal particles that can be alloyed with Li and graphite particles is 0.1% by mass or more and 99% by mass or less. A non-aqueous electrolyte battery characterized in that the non-aqueous electrolyte contains an alkali metal salt, a non-aqueous solvent, and a compound represented by the following general formula (4). 【Chemistry 1】 (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, a monovalent hydrocarbon group which may have a substituent, or an alkoxy group which may have a substituent; X ２ represents a divalent hydrocarbon group which may have a substituent; n ２ represents an integer of 1 to 3; p ２ represents an integer of 0 to 2, q ２ represents an integer of 1 to 3, p ２ + q ２ = 2 or 3; two of R ３ and X ２ may be bonded to each other to form a ring; A 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). ) 【Chemistry 2】 (In general formula (5-1), Z ３ represents a carbon atom, sulfur atom, phosphorus atom, or boron atom; Y １０２ represents an oxygen atom or a sulfur atom; Y １０ , Y １１ and Y １２ Each is independently a single bond, an oxygen atom, a sulfur atom, or NR １０２ R １０２ represents a hydrogen atom or a monovalent hydrocarbon group; r ５ is, Z ３ When is a carbon atom, it is 1, Z ３ When is a sulfur atom, it is 0, 1, or 2, and Z ３ When is a phosphorus atom, it is 0 or 1, Z ３ When it is a boron atom, it is 0. r ６ is, Z ３ When is a carbon atom or a sulfur atom, it is 0, and Z ３ When it is a phosphorus atom or a boron atom, it is 1; * represents R in the general formula (4) above. ３ or X ２ This shows the binding site. However, Z ３ The sulfur atom is good, and r ５ When Y is 2, １０ and Y １１ (They can never form a single bond together.) 【Transformation 3】 (In general formula (6-1), Y １３ , Y １４ and Y １５ Each is independently an oxygen atom, a sulfur atom, or NR ２０２ R ２０２ represents a hydrogen atom or a monovalent hydrocarbon group; * represents R in the general formula (4) above. ３ or X ２ (This indicates the binding site.)

2. A in formula (4) ２ The non-aqueous electrolyte battery according to claim 1, wherein the atom is a divalent or trivalent group represented by formula (5-1).

3. The non-aqueous electrolyte battery according to claim 1, wherein the divalent or trivalent atomic group represented by the general formula (5-1) is 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 sulfite ester structure, a divalent group having a sulfinic acid ester structure, a trivalent group having a phosphonic acid ester structure, or a trivalent group having a phosphate ester structure.

4. Z in the general formula (5-1) above ３ A non-aqueous electrolyte battery according to claim 1, wherein is a carbon atom.

5. The non-aqueous electrolyte battery according to claim 1, wherein the compound represented by formula (4) is one of the following compounds: compound 1, compound 2, compound 3, compound 4, compound 5, compound 6, compound 7, compound 9, or compound 13. 【Chemistry 4】

6. The non-aqueous electrolyte battery according to claim 1 or 2, wherein the ratio of metal particles that can be alloyed with Li to the total of metal particles that can be alloyed with Li and graphite particles is 0.1% by mass or more and 50% by mass or less.

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