Non-aqueous electrolyte and non-aqueous electrolyte battery

Abstract

Provided is a nonaqueous electrolytic solution which can reduce gas evolution during the initial conditioning of nonaqueous-electrolytic-solution batteries. The nonaqueous electrolytic solution is for use in nonaqueous-electrolytic-solution batteries including a positive electrode and a negative electrode which are capable of occluding and releasing metal ions, and is characterized by comprising an alkali metal salt, a nonaqueous solvent, at least one compound represented by general formula (A) or (B) and having an Si-O structure, and a compound represented by general formula (α).

Description

[Technical field]

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

[0002] 2. Description of the Related Art Non-aqueous electrolyte batteries, such as lithium secondary batteries, have been put to practical use in a wide range of applications, such as power sources for so-called small consumer devices, such as mobile phones such as smartphones and notebook computers, and on-board power sources for driving electric vehicles and the like.

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

[0004] For example, Patent Document 1 discloses an approach to lowering the internal resistance of a battery by adding an organosilicon compound, such as 1,1,3,3,5,5-hexamethylcyclotrisilazane, to a battery that has been charged at least once, specifically, to a battery that has been conditioned. Patent Document 2 discloses a study on improving the storage stability of a silyl group-containing compound by incorporating a trialkylsilyl compound of a protonic acid, sulfonic acid, or carboxylic acid having a phosphorus atom and / or a boron atom, and a basic compound or a specific silicon compound into a non-aqueous electrolyte solution, and further improving the 4.9 V high voltage cycle capacity retention rate and the amount of gas generated during battery operation. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2003-7332 A [Patent Document 2] International Publication No. 2015 / 098471 Summary of the Invention [Problem to be solved by the invention]

[0006] In recent years, the capacity of lithium batteries has been increased for use as power sources for electric vehicles and mobile phones such as smartphones, and the proportion of voids in the battery has become smaller than before. Therefore, a large amount of gas generation during initial conditioning is a fatal drawback.

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

[0008] The present inventors have conducted extensive research to solve the above problems and have found that if the battery open circuit voltage (OCV) after electrolyte injection is high, the amount of gas generated during initial conditioning is small. In addition, it has been found that the battery OCV is high after electrolyte injection by using a non-aqueous electrolyte solution containing at least one selected from the compounds represented by general formula (A) and the compounds represented by general formula (B) and the compound represented by general formula (α). This led to the idea of ​​suppressing the amount of gas generated during initial conditioning after electrolyte injection, and invention A has been completed. Invention A provides the following specific aspects, etc.

[0009] <a1>A non-aqueous electrolyte for a non-aqueous electrolyte battery having a positive electrode and a negative electrode capable of absorbing and releasing metal ions, the non-aqueous electrolyte comprising an alkali metal salt, a non-aqueous solvent, at least one compound having a Si-O structure represented by general formula (A) or general formula (B), and a compound represented by general formula (α). [ka] (In formula (A), R 1 ~R 5 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; X represents a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR o R p R q R represents a silyl group represented by the formula: o ~R q each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; n represents an integer of 0 to 5. When n is 2 or more, multiple R 4 may be the same or different, and multiple R 5 may be the same or different.) [ka] (In formula (B), R 6 ~R 7 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; and k represents an integer of 3 to 6. 6 may be the same or different, and multiple R 7 may be the same or different.) [ka] (In formula (α), R 89 is a hydrogen atom or -SiR 8 R 9 R 10 R represents a silyl group represented by the formula: 8 ~R 10 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; R 11 represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR d R e R f R represents a silyl group represented by the formula: d ~R f each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; Y represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, -NR g -SiR h R i R j or -NR g R represents a group represented by -H; g represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent; R h ~R j R each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 11 and R g may be bonded to each other to form a ring. <a2>The content of the compound having a Si-O structure represented by the general formula (A) or (B) is 0.001% by mass to 10% by mass with respect to the total amount of the nonaqueous electrolyte solution. <a1>The non-aqueous electrolyte solution according to claim 1. <a3>The content of the compound having a Si-N structure represented by the general formula (α) is 0.01 mass ppm or more and 0.5 mass % or less with respect to the total amount of the nonaqueous electrolyte solution. <a1>or <a2>The non-aqueous electrolyte solution according to claim 1. <a4>the ratio of the content of the compound having a Si-O structure represented by the general formula (A) or the general formula (B) to the content of the compound represented by the general formula (α) in the nonaqueous electrolyte solution is 1.0 or more and 10,000 or less; <a1> ~ <a3>2. The non-aqueous electrolyte solution according to claim 1 . <a5>R 1 ~R 3 at least one of the above is a hydrocarbon group having 2 to 12 carbon atoms and a carbon-carbon unsaturated bond; <a1> ~ <a4>2. The non-aqueous electrolyte solution according to claim 1 . <a6>The non-aqueous electrolyte further contains one or more selected from the group consisting of a fluorinated salt, a fluorosilane compound, an unsaturated cyclic carbonate, a cyclic carbonate having a fluorine atom, and an oxalate salt. <a1> ~ <a5>2. The non-aqueous electrolyte solution according to claim 1 . <a7>A non-aqueous electrolyte battery comprising a positive electrode and a negative electrode capable of absorbing and releasing metal ions, and a non-aqueous electrolyte, <a1> ~ <a6>2. A non-aqueous electrolyte battery comprising the non-aqueous electrolyte according to claim 1 .

[0010] Furthermore, the present inventors have conducted extensive research to solve the above problems and have found that if the battery open circuit voltage (OCV) after electrolyte injection is high, gas generation during initial conditioning is small. In addition, it has been found that the battery OCV is high after electrolyte injection by using a non-aqueous electrolyte containing a compound represented by general formula (A2) or general formula (B2) and a compound represented by general formula (Z) or general formula (Y). This has led to the discovery that the amount of gas generation during initial conditioning after electrolyte injection can be suppressed, and has led to Invention B. Invention B provides the following specific embodiments, etc.

[0011] <b1>A non-aqueous electrolyte solution for a non-aqueous electrolyte battery having a positive electrode and a negative electrode capable of absorbing and releasing metal ions, the non-aqueous electrolyte solution comprising an alkali metal salt, a non-aqueous solvent, and at least one compound having a Si-O structure represented by general formula (A2) or general formula (B2), and at least one compound having a Si-N structure represented by general formula (Z) or general formula (Y). [ka] (In formula (A2), R 12 ~R 16 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; X' represents a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR o2 R p2 R q2 R represents a silyl group represented by the formula: o2 ~R q2 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; n' represents an integer of 0 to 5; R 12 ~R 14 At least one of R is a hydrocarbon group having 2 to 12 carbon atoms and a carbon-carbon unsaturated bond. When n' is 2 or more, multiple R 15 may be the same or different, and multiple R 16 may be the same or different.) [ka] (In formula (B2), R 17 ~R 18 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent, and k' represents an integer of 3 to 6. 17 or R 18 At least one of R is a hydrocarbon group having 2 to 12 carbon atoms and a carbon-carbon unsaturated bond. 17 may be the same or different, and multiple R 18 may be the same or different.) [ka] (In formula (Z), R 19 ~R 21 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; R 22 ~R 23 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR x R y R z R represents a silyl group represented by the formula: x ~R z R each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 22 and R 23 may be bonded to each other to form a ring. [ka] (In formula (Y), R 24 represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR a R b R c R represents a silyl group represented by the formula: a ~R c each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; R 25 ~R 26 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; and 1 represents an integer of 3 to 6. 25 may be the same or different, and multiple R 26 may be the same or different.) <b2>The content of the compound having a Si-O structure represented by the general formula (A2) or (B2) is 0.001 mass% or more and 10 mass% or less with respect to the total amount of the nonaqueous electrolyte solution. <b1>The non-aqueous electrolyte solution according to claim 1. <b3>The content of the compound having a Si-N structure represented by the general formula (Z) or the general formula (Y) is 0.01 ppm by mass or more and less than 0.5% by mass with respect to the total amount of the nonaqueous electrolyte solution. <b1>or <b2>The non-aqueous electrolyte solution according to claim 1. <b4>the ratio of the content of the compound having a Si-N structure represented by the general formula (Z) or the general formula (Y) in the nonaqueous electrolyte solution to the content of the compound represented by the general formula (A2) or the general formula (B2) is 1.0 or more and 10,000 or less; <b1> ~ <b3>2. The non-aqueous electrolyte solution according to claim 1 . <b5>The nonaqueous electrolyte solution contains a compound represented by the general formula (A2), and in the formula (A2), R 1 ~R 3 At least one of the groups is a vinyl group or an allyl group. <b1> ~ <b4>2. The non-aqueous electrolyte solution according to claim 1 . <b6>The nonaqueous electrolyte solution contains a compound represented by the general formula (B2), and in the formula (B2), R 25 or R 26 At least one of the groups is a vinyl group or an allyl group. <b1> ~ <b5>2. The non-aqueous electrolyte solution according to claim 1 . <b7>In the formula (Z), R 22 ~R 23 At least one of the groups is -SiR x R y R z is a silyl group represented by the formula: <b1> ~ <b6>2. The non-aqueous electrolyte solution according to claim 1 . <b8>The non-aqueous electrolyte further contains one or more selected from the group consisting of a fluorinated salt, a fluorosilane compound, an unsaturated cyclic carbonate, a cyclic carbonate having a fluorine atom, and an oxalate salt. <b1> ~ <b7>2. The non-aqueous electrolyte solution according to claim 1 . <b9>A non-aqueous electrolyte battery comprising a positive electrode and a negative electrode capable of absorbing and releasing metal ions, and a non-aqueous electrolyte, <b1> ~ <b8>2. A non-aqueous electrolyte battery comprising the non-aqueous electrolyte according to claim 1 . Effect of the Invention

[0012] According to the present invention, it is possible to obtain a nonaqueous electrolyte that is excellent in suppressing the amount of gas generation during initial conditioning of a nonaqueous electrolyte battery, and a nonaqueous electrolyte battery that generates a small amount of gas during initial conditioning. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Hereinafter, the embodiments of the present invention will be described in detail. The following embodiments are examples (representative examples) of the present invention, and the present invention is not limited to these. Furthermore, the present invention can be modified and carried out as desired without departing from the scope of the present invention.

[0014] [Invention A] The nonaqueous electrolyte solution according to the present invention A is a nonaqueous electrolyte solution for a nonaqueous electrolyte battery having a positive electrode and a negative electrode capable of absorbing and releasing metal ions, and is characterized in that the nonaqueous electrolyte solution contains an alkali metal salt, a nonaqueous solvent, at least one compound having a Si-O structure represented by general formula (A) or general formula (B), and a compound represented by general formula (α). [ka] (In formula (A), R 1 ~R 5 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; X represents a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR o R p R q R represents a silyl group represented by the formula: o ~R q each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; n represents an integer of 0 to 5. When n is 2 or more, multiple R 4 may be the same or different, and multiple R 5 may be the same or different.) [ka] (In formula (B), R 6 ~R 7 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; and k represents an integer of 3 to 6. 6 may be the same or different, and multiple R 7 may be the same or different.) [ka] (In formula (α), R 89 is a hydrogen atom or -SiR 8 R 9 R 10 R represents a silyl group represented by the formula: 8 ~R 10 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; R 11 represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR d R e R f R represents a silyl group represented by the formula: d ~R f each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; Y represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, -NR g -SiR h R i R j or -NR g R represents a group represented by -H; g represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent; R h ~R j R each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 11 and R g may be bonded to each other to form a ring.

[0015] <1-A. Non-aqueous electrolyte> The nonaqueous electrolyte solution according to the present invention A contains at least one compound having a Si-O structure selected from a compound represented by general formula (A) and a compound represented by general formula (B) described below (hereinafter, also referred to as a "compound represented by general formula (A) or (B)"), and a compound having a Si-N-C=O structure or a HN-C=O structure represented by general formula (α) (hereinafter, also referred to as a "compound represented by general formula (α)"). The mechanism by which the OCV during electrolyte injection is increased by using a nonaqueous electrolyte solution containing at least one compound having a Si-O structure selected from the compounds represented by general formula (A) and the compounds represented by general formula (B) and the compound represented by general formula (α) is not clear, but is presumed to be as follows.

[0016] The compound represented by the general formula (A) or (B) has a polar structure (-Si-O-) and a non-polar structure (e.g., -SiR 1 R 2 R 3 Similarly, the compound represented by the general formula (α) also has a polar structure (-N-(C=O)-) in the molecule, and a non-polar structure (-SiR 8 R 9 R 10 ) or hydrogen bond forming site (-NH). Therefore, these compounds tend to interact with the surface of the negative electrode active material such as carbon and / or the positive electrode active material such as transition metal oxide, and localize near the surface. In addition, it is speculated that the compound represented by general formula (A) or (B) and the compound represented by general formula (α) localized on the active material surface also interact with each other, thereby improving the amount of the localized compound fixed to the positive electrode active material and / or the negative electrode active material surface. In particular, since the Si-N-(C=O)-Y structure and the HN-(C=O)-Y structure of the compound represented by general formula (α) have high adsorption to the electrode surface, the fixation of the compound represented by general formula (A) or (B) to the electrode is promoted starting from the fixation of the compound represented by general formula (α) to the electrode. As a result, the compound represented by general formula (α) and the compound represented by general formula (A) or (B) localized on the electrode at the time of the first charge are electrochemically decomposed to form a composite insulating coating. It is believed that this composite coating suppresses side reactions of the electrolyte during initial conditioning and inhibits gas generation.

[0017] Here, OCV is the potential difference between the positive and negative electrodes. If the amount of the compound contained in the electrolyte adsorbed to the electrode is large, the electrode potential changes. It is considered that the OCV at the time of injection is high, which means that the amount of the compound constituting the electrolyte adsorbed to the electrode is large. Since the electrolyte according to one embodiment of the present invention has a large amount of the compound adsorbed to the electrode after injection, it is presumed that the battery OCV after injection is high. As a result, the inventor has found that the amount of gas generated during initial conditioning can be predicted by checking the OCV at the time of injection. Note that in the examples described below, the height of the OCV and the amount of gas generated do not necessarily coincide, but a correlation is observed. It is considered that the properties of the composite coating formed differ depending on the compound to be combined.

[0018] <1-A1. Compounds with Si-O structure> A nonaqueous electrolyte solution according to one embodiment of the present invention is characterized by containing at least one compound having a Si-O structure represented by the following general formula (A) or (B), i.e., at least one compound having a Si-O structure selected from the compound represented by the general formula (A) and the compound represented by the following general formula (B).

[0019] <1-A1-1. Compound represented by general formula (A)> [ka] (In formula (A), R 1 ~R 5 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; X represents a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR o R p R q R represents a silyl group represented by the formula: o ~R q each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; n represents an integer of 0 to 5. When n is 2 or more, multiple R 4 may be the same or different, and multiple R 5 may be the same or different.)

[0020] R in the general formula (A) 1 ~R 5 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. Among them, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent is preferred, and a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent is particularly preferred. In the present specification, the "hydrocarbon group" may have a branched structure and / or a cyclic structure, and may be any of a saturated hydrocarbon group, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, etc. Note that when the hydrocarbon group has a substituent, the number of carbon atoms contained in the substituent is not included in this carbon number. Also, R 1 ~R 3 At least one of the groups is preferably a hydrocarbon group having 2 to 12 carbon atoms and a carbon-carbon unsaturated bond, from the viewpoint that the compound represented by the general formula (A) tends to be suitably localized on the electrode surface. Examples of the hydrocarbon group having 2 to 12 carbon atoms and a carbon-carbon unsaturated bond include an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, which will be described later, and among them, an alkenyl group having 2 to 12 carbon atoms or an alkynyl group having 2 to 12 carbon atoms is preferred, from the viewpoint that the compound represented by the general formula (A) tends to be suitably localized on the electrode surface. An alkenyl group having 2 to 12 carbon atoms is particularly preferred. R in the general formula (A) 1 ~R 3 may be the same or different, but it is preferable that at least two or more are the same in terms of ease of synthesis of the compound, and it is more preferable that all three are the same in view of the above. R in the general formula (A) 4 and R 5 may be the same or different, but is preferably the same in terms of ease of synthesis of the compound. Also, when n is 2 or more, that is, R 4 and R 5 If there are multiple R 4 may be the same or different, but it is preferable that they are the same in terms of ease of synthesis of the compound. 5 may be the same or different, but it is preferable that they are the same in terms of ease of synthesis of the compound. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, etc. A fluorine atom is preferable because it causes fewer electrochemical side reactions. The hydrocarbon group having 1 to 12 carbon atoms is preferably a hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a hydrocarbon group having 1 to 4 carbon atoms. Specific examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, and an aryl group. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. Among them, preferred are methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, and hexyl groups, more preferred are methyl, ethyl, n-propyl, n-butyl, tert-butyl, and n-pentyl groups, and particularly preferred are methyl, ethyl, n-butyl, and tert-butyl groups. The above-mentioned alkyl groups are preferred because the compound represented by the general formula (A) tends to be localized near the surface of the positive electrode active material and / or the negative electrode active material.

[0021] Specific examples of the alkenyl group include vinyl, allyl, methallyl, 2-butenyl, 3-methyl-2-butenyl, 3-butenyl, and 4-pentenyl groups. Among these, vinyl, allyl, methallyl, and 2-butenyl groups are preferred, vinyl, allyl, and methallyl groups are more preferred, and vinyl or allyl groups are particularly preferred. The above-mentioned alkenyl groups are preferred because the compound represented by the general formula (A) tends to be localized near the surface of the positive electrode active material and / or the negative electrode active material.

[0022] Specific examples of the alkynyl group include an ethynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 4-pentynyl group, and a 5-hexynyl group. Among these, an ethynyl group, a 2-propynyl group, a 2-butynyl group, and a 3-butynyl group are preferred, a 2-propynyl group and a 3-butynyl group are more preferred, and a 2-propynyl group is particularly preferred. The above-mentioned alkynyl group is preferred because the compound represented by the general formula (A) tends to be localized near the surface of the positive electrode active material and / or the negative electrode active material.

[0023] Specific examples of the aryl group include a phenyl group, a tolyl group, etc. Among them, a phenyl group is preferred from the viewpoint that the compound represented by the general formula (A) tends to be localized near the surface of the positive electrode active material and / or the negative electrode active material. Specific examples of the aralkyl group include a benzyl group and a phenethyl group. The alkoxy group having 1 to 12 carbon atoms is preferably an alkoxy group having 1 to 6 carbon atoms, and particularly preferably an alkoxy group having 1 to 4 carbon atoms. Specific examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and an isopropoxy group, etc. Among these, a methoxy group and an ethoxy group are preferred in that they cause less steric hindrance to the compound represented by general formula (A) and are suitably concentrated on the surface of the active material.

[0024] Here, the substituent is a cyano group, an isocyanato group, an acyl group (-(C=O)-R r ), acyloxy group (-O(C=O)-R r ), alkoxycarbonyl group (-(C=O)OR r ), sulfonyl group (-SO2-R r ), sulfonyloxy group (-O(SO2)-R r ), alkoxysulfonyl group (-(SO2)-OR r ), alkoxysulfonyloxy group (-O-(SO2)-OR r ), alkoxycarbonyloxy group (-O-(C=O)-OR r ), ether group (-OR r ), a halogen atom (preferably a fluorine atom), a trifluoromethyl group, etc. r R represents an alkyl group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms. r When is an alkylene group, it may be bonded to a part of the hydrocarbon group which substitutes it to form a ring. Among these substituents, a cyano group, an isocyanato group, an acyloxy group (-O(C=O)-R r ), halogen (preferably, a fluorine atom), or a trifluoromethyl group, and more preferably, an isocyanato group, or an acyloxy group (-O(C=O)-R r ), a halogen atom (preferably a fluorine atom), a trifluoromethyl group, and particularly preferably an acyloxy group (-O(C=O)-R r ), a halogen atom (preferably a fluorine atom), or a trifluoromethyl group. In the general formula (A), X is a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR o R p R q The silyl group is represented by the following formula: Here, the hydrocarbon group having 1 to 12 carbon atoms is R 1 ~R 5 Examples of the above include those described above. -SiR o R p R q R in the silyl group represented by o ~R q each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. Of these, preferred are a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent, and particularly preferred are a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent. Here, R is any of a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, and an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 1 ~R 5 The preferred embodiments are also the same. -SiR o R p R q Specific examples of the silyl group represented by the formula are -Si(CH3)3, -Si(CH3)2(C2H5), -Si(CH3)2(CH=CH2), -Si(CH3)2(CH2CH2CH3), -Si(CH3)2(CH2CH=CH2), -Si(CH3)2[CH(CH3)2], -Si(CH3)2[(CH2)3CH3)], -Si(CH3)2[CH2CH(CH3)2], -Si(CH3)2[C( CH3)3], -Si(CH3)2(C6H5), -Si(CH3)(C6H5)2, -Si(C6H5)3, -Si(C2H5)3, -Si(CH=CH2)3, -Si(CH2CH2CH3)3, Examples include -Si[CH(CH3)2]3, -Si(CH2CH=CH2)3, -Si(CH3)(C6H5)(CH=CH2), -Si(C6H5)2(CH=CH2), and -Si(CF3)3. Of these, -Si(CH3)3, -Si(CH3)2(CH=CH2), -Si(CH3)2(CH2CH=CH2), -Si(C2H5)3, -Si(CH3)(C6H5)(CH=CH2), and -Si(C6H5)2(CH=CH2) are preferred, and -Si(CH3)2(CH=CH2) and -Si(CH3)2(CH2CH=CH2) are particularly preferred.

[0025] In the general formula (A), n represents an integer of 0 to 5. In terms of ease of synthesis of the compound, n is preferably 0 to 2. Among them, a compound represented by the general formula (A1) in which n=0 or a compound in which n=1 is preferred. The compound represented by general formula (A1), in which n=0 in general formula (A), is preferred because it has an excellent effect of suppressing gas generation during initial conditioning. [ka] (In formula (A), R 1 ~R 3 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; X represents a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR o R p R q R represents a silyl group represented by the formula: o ~R q each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. Above R 1 ~R 3 and X is R of general formula (A) 1 ~R 3 and X, respectively. Moreover, in the general formula (A), a compound in which n=1 is preferred since it has an excellent effect of suppressing gas generation during initial conditioning.

[0026] <1-A1-2. Compound represented by general formula (B)> [ka] (In formula (B), R 6 ~R 7 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; and k represents an integer of 3 to 6. 6 may be the same or different, and multiple R 7 may be the same or different.)

[0027] R in the general formula (B) 6 ~R 7 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 6 may be the same or different, and multiple R 7 may be the same or different. R in the general formula (B) 6 ~R 7 may be the same or different, but it is preferable that they are the same in terms of ease of synthesis of the compound. Multiple R 6 (R present in the repeating unit 6 ) may be the same or different, but 3 to 6 R 6 It is preferable that all R are the same in terms of ease of compound synthesis. 7 (R present in the repeating unit 7 ) may be the same or different, but 3 to 6 R 7 are preferably all the same in terms of ease of compound synthesis. Here, R is any of a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, and an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 1 ~R 5 This has the same meaning as that specified in.

[0028] In formula (B), k is usually an integer of 3 to 6, with 3 or 4 being preferable.

[0029] In one embodiment of the present invention, at least one compound selected from the compounds represented by general formula (A) and the compounds represented by general formula (B) is used. Specific examples of the compounds represented by general formula (A) or general formula (B) include compounds having the following structures.

[0030] (Specific examples of the compound represented by formula (A)) [ka] [ka] [ka]

[0031] (Specific examples of the compound represented by formula (B)) [ka] [ka]

[0032] Preferred examples of the compound represented by general formula (A) or (B) include the following compounds. [ka] [ka] [ka] [ka]

[0033] More preferred examples of the compound represented by formula (A) or (B) include the following compounds. [ka] [ka]

[0034] Particularly preferred examples of the compound represented by formula (A) or (B) include the following compounds. [ka]

[0035] The nonaqueous electrolyte solution according to one embodiment of the present invention may contain one or more of the compounds having a Si-O structure represented by general formula (A) or general formula (B). The total content of the compounds having a Si-O structure represented by general formula (A) or (B) relative to the total amount of the nonaqueous electrolyte solution according to one embodiment of the present invention is usually 0.001 mass% or more, preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and even more preferably 0.2 mass% or more, and is usually 10 mass% or less, preferably 8 mass% or less, more preferably 6.0 mass% or less, even more preferably 4.0 mass% or less, especially preferably 3.0 mass% or less, particularly preferably 2.5 mass% or less, and most preferably 2.0 mass% or less. When the total content of the compounds having a Si-O structure represented by general formula (A) or (B) relative to the total amount of the nonaqueous electrolyte solution is within the above-mentioned range, the concentration of the compounds in the active material proceeds favorably, and it becomes possible to prepare a battery that generates less gas during initial conditioning. The compound having a Si-O structure represented by general formula (A) or (B) in the nonaqueous electrolyte solution is identified and its content is measured by nuclear magnetic resonance (NMR) spectroscopy.

[0036] <1-A2. Compound represented by general formula (α)> A nonaqueous electrolyte solution according to one embodiment of the present invention is characterized by containing a compound having a Si-NC=O structure or a HNC=O structure, which is represented by general formula (α). [ka] (In formula (α), R 89 is a hydrogen atom or -SiR 8 R 9 R 10 R represents a silyl group represented by the formula: 8 ~R 10 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; R 11 represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR d R e R f R represents a silyl group represented by the formula: d ~R f each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; Y represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, -NR g -SiR h R i R j or -NR g R represents a group represented by -H; g represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent; R h ~R j R each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 11 and R g may be bonded to each other to form a ring. Below, R 89 , R 8 ~R 11 , R g , and Y, etc. will be explained.

[0037] R relating to general formula (α) 89 is a hydrogen atom or -SiR 8 R 9 R 10 R represents a silyl group represented by the formula: 8 ~R 10 each independently represents a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, or an optionally substituted alkoxy group having 1 to 12 carbon atoms. -SiR 8 R 9 R 10 In the silyl group represented by the formula 8 ~R 10 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. Of these, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent and an alkoxy group having 1 to 12 carbon atoms which may have a substituent are preferred, and a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent is particularly preferred. When the hydrocarbon group has a substituent, the number of carbon atoms contained in the substituent is not included in this carbon number. Also, R 8 ~R 10 At least one of R is preferably an alkyl group having 1 to 12 carbon atoms, from the viewpoint that the compound according to the general formula (α) tends to be suitably localized on the electrode surface. 8 ~R 10 All of the groups are alkyl groups having 1 to 12 carbon atoms. R relating to general formula (α) 8 ~R 10 may be the same or different, but it is preferable that at least two or more are the same in terms of ease of synthesis of the compound, and it is even more preferable that all three are the same in view of the above.

[0038] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, etc. A fluorine atom is preferable because it causes fewer electrochemical side reactions. The hydrocarbon group having 1 to 12 carbon atoms is preferably a hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a hydrocarbon group having 1 to 4 carbon atoms.

[0039] Specific examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, and an aryl group. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. Among them, preferred are methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, and hexyl groups, more preferred are methyl, ethyl, n-propyl, n-butyl, tert-butyl, and n-pentyl groups, and particularly preferred are methyl, ethyl, n-butyl, and tert-butyl groups. The above-mentioned alkyl groups are preferred because the compound represented by the general formula (α) tends to be localized near the surface of the positive electrode active material and / or the negative electrode active material.

[0040] Specific examples of the alkenyl group include vinyl, allyl, methallyl, 2-butenyl, 3-methyl-2-butenyl, 3-butenyl, and 4-pentenyl groups. Among these, vinyl, allyl, methallyl, and 2-butenyl groups are preferred, vinyl, allyl, and methallyl groups are more preferred, and vinyl or allyl groups are particularly preferred. The above-mentioned alkenyl groups are preferred because the compound represented by the general formula (α) tends to be localized near the surface of the positive electrode active material and / or the negative electrode active material.

[0041] Specific examples of the alkynyl group include an ethynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 4-pentynyl group, and a 5-hexynyl group. Among these, an ethynyl group, a 2-propynyl group, a 2-butynyl group, and a 3-butynyl group are preferred, a 2-propynyl group and a 3-butynyl group are more preferred, and a 2-propynyl group is particularly preferred. The above-mentioned alkynyl group is preferred because the compound represented by the general formula (α) tends to be localized near the surface of the positive electrode active material and / or the negative electrode active material.

[0042] Specific examples of the aryl group include a phenyl group, a tolyl group, etc. Among them, a phenyl group is preferred from the viewpoint that the compound represented by the general formula (α) tends to be localized near the surface of the positive electrode active material and / or the negative electrode active material. Specific examples of the aralkyl group include a benzyl group and a phenethyl group. The alkoxy group having 1 to 12 carbon atoms is preferably an alkoxy group having 1 to 6 carbon atoms, and particularly preferably an alkoxy group having 1 to 4 carbon atoms. Specific examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and an isopropoxy group, etc. Among these, a methoxy group and an ethoxy group are preferred in that they cause less steric hindrance to the compound and are suitably concentrated on the surface of the active material. Here, the substituent is a cyano group, an isocyanato group, an acyl group (-(C=O)-R s ), acyloxy group (-O(C=O)-R s ), alkoxycarbonyl group (-(C=O)OR s ), sulfonyl group (-SO2-R s ), sulfonyloxy group (-O(SO2)-R s ), alkoxysulfonyl group (-(SO2)-OR s ), alkoxysulfonyloxy group (-O-(SO2)-OR s ), alkoxycarbonyloxy group (-O-(C=O)-OR s ), ether group (-OR s ), an acrylic group, a methacrylic group, a halogen atom (preferably a fluorine atom), a trifluoromethyl group, etc. s R represents an alkyl group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms. s When is an alkylene group, it may be bonded to a part of the hydrocarbon group which substitutes it to form a ring. Among these substituents, a cyano group, an isocyanato group, an acyloxy group (-O(C=O)-R s ), a halogen atom (preferably a fluorine atom), or a trifluoromethyl group, and more preferably an isocyanato group or an acyloxy group (-O(C=O)-R s ), a halogen atom (preferably a fluorine atom), a trifluoromethyl group, and particularly preferably an acyloxy group (-O(C=O)-R s ), a halogen atom (preferably a fluorine atom), or a trifluoromethyl group.

[0043] R relating to general formula (α) 11 represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR d R e R f Among them, a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR d R e R f A silyl group represented by the following formula is preferred. Here, the hydrocarbon group having 1 to 12 carbon atoms which may have a substituent is R 8 ~R 10 This has the same meaning as specified in. In addition, -SiR d R e R f R in the silyl group represented by d ~R f each independently represents a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, or an optionally substituted alkoxy group having 1 to 12 carbon atoms. Here, R is any of a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, and an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 8 ~R 10 This has the same meaning as that specified in. When the hydrocarbon group has a substituent, the number of carbon atoms contained in the substituent is not included in the number of carbon atoms.

[0044] Y in the general formula (α) is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, -NR g -SiR h R i R j or a group represented by -NR g R represents a group represented by -H. g represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent; R h ~R j each independently represents a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, or an optionally substituted alkoxy group having 1 to 12 carbon atoms. Here, the halogen atom, the hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, and the alkoxy group having 1 to 12 carbon atoms which may have a substituent are all represented by R 8 ~R 10 This has the same meaning as specified in. -NR g -SiR h R i R j In the group represented by the formula g is R 11 In addition, -SiR h R i R j The group represented by is -SiR d R e R f It has the same meaning as the group represented by the following formula: -NR g In the group represented by -H, R g is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent. Here, the hydrocarbon group having 1 to 12 carbon atoms which may have a substituent is R 11 Among these, a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent is preferred, a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms is more preferred, a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms is even more preferred, and a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms is particularly preferred.

[0045] Moreover, the compound represented by general formula (α) is preferably a compound represented by general formula (α1) or a compound represented by general formula (α2) described below.

[0046] (Compound represented by general formula (α1)) [ka] (In formula (α1), R 8 ~R 10 R each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 11 represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR d R e R f R represents a silyl group represented by the formula: d ~R f each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. Y' represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, or -NR g -SiR h R i R j R represents a group represented by the formula: g R represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent. h ~R j R each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 11 and R g may be bonded to each other to form a ring. In the above formula, R 8 ~R 11 , and R g ~R j is the R of formula (α) 8 ~R 11 , R g ~R j and Y' corresponds to, among Y in formula (α), a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, or -NR g -SiR h R i R j The compound corresponds to a group represented by the formula:

[0047] Specific examples of the compound having the Si-N structure represented by the general formula (α1) include compounds having the following structures.

[0048] [ka]

[0049] Preferred examples of the compounds include the following: [ka]

[0050] More preferred examples of the compounds include the following: [ka]

[0051] Particularly preferred are the following compounds: [ka]

[0052] (Compound represented by general formula (α2)) [ka] (In formula (α2), R 111 represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent. Y″ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, or —NR g R represents a group represented by -H. g represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent. In the above formula, R 111 is the R of formula (α) 11 R is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent. g is the R of formula (α) g and Y″ is, among the Y in formula (α), a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, or —NR g R in the general formula (α2) corresponds to a group represented by —H. 111 is preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, more preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, still more preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

[0053] Specific examples of the compound represented by the general formula (α2) include compounds having the following structures.

[0054] [ka]

[0055] Preferred examples of the compound represented by general formula (α2) include the following compounds. [ka]

[0056] More preferred examples of the compound represented by general formula (α2) include the following compounds. [ka]

[0057] Particularly preferred examples of the compound represented by the general formula (α2) include the following compounds. [ka]

[0058] The compound represented by the general formula (α) may be used alone or in combination with two or more kinds. When using two or more kinds, it is preferable to use one or more kinds of each of the compound represented by the general formula (α1) and the compound represented by the general formula (α2) in terms of increasing the adhesion rate to the electrode. The ratio of the content (mass) of the compound represented by the general formula (α1) and the compound represented by the general formula (α2) is not particularly limited, but is usually in the range of 10000:1 to 1:10000. The total content of the compounds represented by general formula (α) relative to the total amount of the nonaqueous electrolyte solution according to one embodiment of the present invention is not particularly limited, but is preferably 0.01 ppm by mass or more, more preferably 0.1 ppm by mass or more, even more preferably 1.0 ppm by mass or more, and particularly preferably 10 ppm by mass or more, and is also preferably 0.5% by mass or less, more preferably less than 0.5% by mass, more preferably 0.4% by mass or less, more preferably 0.3% by mass or less, more preferably 0.2% by mass or less, more preferably 0.1% by mass or less, more preferably 0.05% by mass or less, and more preferably 0.03% by mass or less. When the total content of the compound represented by general formula (α) relative to the total amount of the nonaqueous electrolyte is within the above range, the concentration of the compound represented by general formula (α) in the active material proceeds smoothly, and it becomes possible to produce a battery that generates less gas during initial conditioning. When two or more kinds of the compound represented by general formula (α) are used, the total amount of them is regarded as the content of the compound represented by general formula (α). The mass ratio of the content of the compound represented by general formula (A) or general formula (B) to the content of the compound represented by general formula (α) in the nonaqueous electrolyte is not particularly limited, but is usually 1.0 or more, preferably 2.0 or more, particularly preferably 3.0 or more, while it is usually 10000 or less, preferably 7000 or less, more preferably 4000 or less, even more preferably 2000 or less, particularly preferably 1000 or less, particularly preferably 500 or less. In addition, when both the compound represented by general formula (A) and the compound represented by general formula (B) are included, the above ratio indicates the ratio of the total content of the compound represented by general formula (A) and the compound represented by general formula (B) to the content of the compound represented by general formula (α) (total content of the compound represented by general formula (A) and the compound represented by general formula (B) / total content of the compound represented by general formula (α)).

[0059] The total content of the compounds represented by general formula (α1) relative to the total amount of the nonaqueous electrolyte according to one embodiment of the present invention is not particularly limited, but is preferably 0.01 ppm by mass or more, more preferably 0.1 ppm by mass or more, even more preferably 1.0 ppm by mass or more, and particularly preferably 10 ppm by mass or more, and is usually 0.5% by mass or less, preferably less than 0.5% by mass, more preferably 0.4% by mass or less, even more preferably 0.3% by mass or less, especially preferably 0.2% by mass or less, and particularly preferably 0.1% by mass or less. When the total content of the compound represented by general formula (α1) relative to the total amount of the nonaqueous electrolyte is within the above range, the concentration of the compound represented by general formula (α1) in the active material proceeds smoothly, making it possible to produce a battery that generates less gas during initial conditioning. The mass ratio of the content of the compound represented by general formula (A) or general formula (B) to the content of the compound represented by general formula (α1) in the non-aqueous electrolyte is not particularly limited, but is usually 1.0 or more, preferably 2.0 or more, particularly preferably 3.0 or more, while it is usually 10000 or less, preferably 7000 or less, more preferably 4000 or less, even more preferably 2000 or less, particularly preferably 1000 or less, particularly preferably 500 or less. In addition, when both compounds represented by general formula (A) and general formula (B) are included, the above ratio indicates the ratio of the total content of the compound represented by general formula (A) and the compound represented by general formula (B) to the content of the compound represented by general formula (α1) (total content of the compound represented by general formula (A) and the compound represented by general formula (B) / total content of the compound represented by general formula (α1)).

[0060] The total content of the compounds represented by general formula (α2) relative to the total amount of the nonaqueous electrolyte according to one embodiment of the present invention is not particularly limited, but is preferably 0.01 ppm by mass or more, more preferably 0.1 ppm by mass or more, even more preferably 1.0 ppm by mass or more, particularly preferably 10 ppm by mass or more, and is preferably 0.50% by mass or less, more preferably 0.2% by mass or less, even more preferably 0.1% by mass or less, especially preferably 0.05% by mass or less, and particularly preferably 0.03% by mass or less. When the total content of the compound represented by general formula (α2) relative to the total amount of the nonaqueous electrolyte is within the above range, the concentration of the compound represented by general formula (α2) in the active material proceeds smoothly, and it becomes possible to produce a battery that generates less gas during initial conditioning. The mass ratio of the content of the compound represented by general formula (A) or general formula (B) to the content of the compound represented by general formula (α2) in the nonaqueous electrolyte solution is not particularly limited, but is usually 1.0 or more, preferably 2.0 or more, and particularly preferably 3.0 or more, while it is usually 10,000 or less, preferably 7,000 or less, more preferably 4,000 or less, even more preferably 2,000 or less, particularly preferably 1,000 or less, and particularly preferably 500 or less. In addition, when both compounds represented by general formula (A) and general formula (B) are contained, the above ratio indicates the ratio of the total content of the compound represented by general formula (A) and the compound represented by general formula (B) to the content of the compound represented by general formula (α2) (total content of the compound represented by general formula (A) and the compound represented by general formula (B) / total content of the compound represented by general formula (α2)).

[0061] The compound represented by general formula (α) in the nonaqueous electrolyte solution is identified and its content is measured by nuclear magnetic resonance (NMR) spectroscopy. The method of adding the compound represented by the general formula (α) and the compound represented by the general formula (A) or (B) to the electrolyte is not particularly limited. In addition to the method of directly adding the compound to the electrolyte, the compound may be generated in the battery or in the electrolyte.

[0062] In this specification, the content of the compound means the content at the time of production of the nonaqueous electrolyte solution, at the time of injection of the nonaqueous electrolyte solution into a battery, or at the time of shipment of the battery.

[0063] [Invention B] The nonaqueous electrolyte solution according to present invention B is a nonaqueous electrolyte solution for a nonaqueous electrolyte battery having a positive electrode and a negative electrode capable of absorbing and releasing metal ions, characterized in that the nonaqueous electrolyte solution contains an alkali metal salt, a nonaqueous solvent, and at least one compound having a Si-O structure represented by general formula (A2) or general formula (B2), and contains at least one compound having a Si-N structure represented by general formula (Z) or general formula (Y). [ka] (In formula (A2), R 12 ~R 16 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; X' represents a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR o2 R p2 R q2 R represents a silyl group represented by the formula: o2 ~R q2 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; n' represents an integer of 0 to 5; R 12 ~R 14 At least one of R is a hydrocarbon group having 2 to 12 carbon atoms and a carbon-carbon unsaturated bond. When n' is 2 or more, multiple R 15 may be the same or different, and multiple R 16 may be the same or different.) [ka] (In formula (B2), R 17 ~R 18 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; k' represents an integer of 3 to 6; R 17 or R 18 At least one of R is a hydrocarbon group having 2 to 12 carbon atoms and a carbon-carbon unsaturated bond. 17 may be the same or different, and multiple R 18 may be the same or different.) [ka] (In formula (Z), R 19 ~R 21 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; R 22 ~R 23 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR x R y R z R represents a silyl group represented by the formula: x ~R z R each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 22 and R 23 may be bonded to each other to form a ring. [ka] (In formula (Y), R 24 represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR a R b R c R represents a silyl group represented by the formula: a ~R c R each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 25 ~R 26 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent, and 1 represents an integer of 3 to 6. 25 may be the same or different, and multiple R 26 may be the same or different.)

[0064] <1-B. Nonaqueous electrolyte> The nonaqueous electrolyte solution according to the present invention B contains at least one compound having a Si-O structure represented by general formula (A2) or general formula (B2) described below, and at least one compound having a Si-N structure represented by general formula (Z) or general formula (Y). The mechanism by which the OCV during electrolyte injection is increased by using a nonaqueous electrolyte solution containing a compound having a Si-O structure represented by general formula (A2) or general formula (B2) and a compound having a Si-N structure represented by general formula (Z) or general formula (Y) is not clear, but is presumed to be as follows.

[0065] The compound represented by the general formula (A2) or (B2) has a polar structure (-Si-O-) and a non-polar structure (e.g., -SiR 12 R 13 R 14 In addition, the compound represented by the general formula (Z) or (Y) also has a polar structure (-Si-N-) and a non-polar structure (e.g., -SiR 19 R 20 R 21 , -Si(R 25 R 26 )-). Therefore, these compounds tend to interact with the surface of the negative electrode active material such as carbon and / or the surface of the positive electrode active material such as transition metal oxide, and are localized near the surface. In addition, it is speculated that the amount of the localized compound fixed to the surface of the positive electrode active material and / or the negative electrode active material is improved by the interaction between the compound represented by general formula (A2) or general formula (B2) and the compound represented by general formula (Z) or general formula (Y) localized on the active material surface. In particular, since the nitrogen atom of the compound represented by general formula (Z) or general formula (Y) has high adsorption to the electrode surface, the fixation of the compound represented by general formula (A2) or general formula (B2) to the electrode is promoted starting from the fixation of the compound represented by general formula (Z) or general formula (Y) to the electrode. As a result, the compound represented by general formula (Z) or general formula (Y) and the compound represented by general formula (A2) or general formula (B2) localized on the electrode at the time of the first charge are electrochemically decomposed to form a composite insulating coating. It is presumed that this composite coating suppresses side reactions of the electrolyte during initial conditioning and suppresses gas generation.

[0066] Here, OCV is the potential difference between the positive and negative electrodes. If the amount of the compound contained in the electrolyte adsorbed to the electrode is large, the electrode potential changes. It is considered that the OCV at the time of injection is high, which means that the amount of the compound constituting the electrolyte adsorbed to the electrode is large. Since the electrolyte according to one embodiment of the present invention has a large amount of the compound adsorbed to the electrode after injection, it is presumed that the battery OCV after injection is high. As a result, the inventor has found that the amount of gas generated during initial conditioning can be predicted by checking the OCV at the time of injection. Note that in the examples described below, the height of the OCV and the amount of gas generated do not necessarily coincide, but a correlation is observed. It is considered that the properties of the composite coating formed differ depending on the compound to be combined.

[0067] <1-B1. Compounds with Si-O structure> The nonaqueous electrolyte solution of the present invention is characterized by containing a compound having a Si—O structure represented by the following general formula (A2) or (B2).

[0068] <1-B1-1. Compound represented by general formula (A2)> [ka] (In formula (A2), R 12 ~R 16 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; X' represents a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR o2 R p2 R q2 R represents a silyl group represented by the formula: o2 ~R q2 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; n' represents an integer of 0 to 5; R 12 ~R 14 At least one of R is a hydrocarbon group having 2 to 12 carbon atoms and a carbon-carbon unsaturated bond. When n' is 2 or more, multiple R 15 may be the same or different, and multiple R 16 may be the same or different.)

[0069] R in the general formula (A2) 12 ~R 16 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. Among these, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, and an alkoxy group having 1 to 12 carbon atoms which may have a substituent are preferred, and a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent or an alkoxy group having 1 to 12 carbon atoms which may have a substituent are particularly preferred. When the hydrocarbon group has a substituent, the number of carbon atoms contained in the substituent is not included in this carbon number. R 12 ~R 14 At least one of the groups is preferably a hydrocarbon group having 2 to 12 carbon atoms and a carbon-carbon unsaturated bond, from the viewpoint that the compound according to the general formula (A2) tends to be suitably localized on the electrode surface. Examples of the hydrocarbon group having 2 to 12 carbon atoms and a carbon-carbon unsaturated bond include an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, which will be described later, and among them, an alkenyl group having 2 to 12 carbon atoms or an alkynyl group having 2 to 12 carbon atoms is preferred, from the viewpoint that the compound according to the general formula (A2) tends to be suitably localized on the electrode surface. An alkenyl group having 2 to 12 carbon atoms is particularly preferred. R in the general formula (A2) 12 ~R 14 may be the same or different, but it is preferable that at least two or more are the same in terms of ease of synthesis of the compound, and it is more preferable that all three are the same in terms of the above-mentioned viewpoint. R in the general formula (A2) 15 ~R 16 may be the same or different, but it is preferable that they are the same in terms of ease of synthesis of the compound. Also, when n' is 2 or more, that is, R 15 and R 16 If there are multiple R 15 may be the same or different, but it is preferable that they are the same in terms of ease of compound synthesis. 16 may be the same or different, but it is preferable that they are the same in terms of ease of synthesis of the compound. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, etc. A fluorine atom is preferable because it causes fewer electrochemical side reactions. The hydrocarbon group having 1 to 12 carbon atoms is preferably a hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a hydrocarbon group having 1 to 4 carbon atoms. Specific examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, and an aryl group. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. Among them, preferred are methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, and hexyl groups, more preferred are methyl, ethyl, n-propyl, n-butyl, tert-butyl, and n-pentyl groups, and particularly preferred are methyl, ethyl, n-butyl, and tert-butyl groups. The above-mentioned alkyl groups are preferred because the compound represented by the general formula (A2) tends to be localized near the surface of the positive electrode active material and / or the negative electrode active material.

[0070] Specific examples of the alkenyl group include vinyl, allyl, methallyl, 2-butenyl, 3-methyl-2-butenyl, 3-butenyl, and 4-pentenyl groups. Among them, vinyl, allyl, methallyl, and 2-butenyl groups are preferred, vinyl, allyl, and methallyl groups are more preferred, and vinyl or allyl groups are particularly preferred. The above-mentioned alkenyl groups are preferred because the compound represented by general formula (A2) tends to be localized near the surface of the positive electrode active material and / or the negative electrode active material.

[0071] Specific examples of the alkynyl group include an ethynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 4-pentynyl group, and a 5-hexynyl group. Among these, an ethynyl group, a 2-propynyl group, a 2-butynyl group, and a 3-butynyl group are preferred, a 2-propynyl group and a 3-butynyl group are more preferred, and a 2-propynyl group is particularly preferred. The above-mentioned alkynyl group is preferred because the compound represented by the general formula (A2) tends to be localized near the surface of the positive electrode active material and / or the negative electrode active material.

[0072] Specific examples of the aryl group include a phenyl group and a tolyl group, etc. Among them, a phenyl group is preferred from the viewpoint that the compound according to the general formula (A2) tends to be localized near the surface of the positive electrode active material and / or the negative electrode active material. Specific examples of the aralkyl group include a benzyl group and a phenethyl group. The alkoxy group having 1 to 12 carbon atoms is preferably an alkoxy group having 1 to 6 carbon atoms, and more preferably an alkoxy group having 1 to 4 carbon atoms. Specific examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and an isopropoxy group, etc. Among them, a methoxy group and an ethoxy group are preferred in that they cause less steric hindrance to the compound represented by the general formula (A2) and are suitably concentrated on the surface of the active material.

[0073] Here, the substituent is a cyano group, an isocyanato group, an acyl group (-(C=O)-R t ), acyloxy group (-O(C=O)-R t ), alkoxycarbonyl group (-(C=O)OR t ), sulfonyl group (-SO2-R t ), sulfonyloxy group (-O(SO2)-R t ), alkoxysulfonyl group (-(SO2)-OR t ), alkoxysulfonyloxy group (-O-(SO2)-OR t ), alkoxycarbonyloxy group (-O-(C=O)-OR t ), ether group (-OR t ), an acrylic group, a methacrylic group, a halogen atom (preferably a fluorine atom), a trifluoromethyl group, etc. t R represents an alkyl group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms. t When is an alkylene group, it may be bonded to a part of the hydrocarbon group which substitutes it to form a ring. Among these substituents, a cyano group, an isocyanato group, an acyloxy group (-O(C=O)-R t ), a halogen atom (preferably a fluorine atom), or a trifluoromethyl group, and more preferably an isocyanato group or an acyloxy group (-O(C=O)-R t ), a halogen atom (preferably a fluorine atom), a trifluoromethyl group, and particularly preferably an acyloxy group (-O(C=O)-R t ), a halogen atom (preferably a fluorine atom), or a trifluoromethyl group. In the general formula (A2), X' is a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR o2 R p2 R q2 The silyl group is represented by the following formula: Here, the hydrocarbon group having 1 to 12 carbon atoms and the alkoxy group having 1 to 12 carbon atoms include R 1 ~R 3 Examples of the above include those described above. -SiR o2 R p2 R q2 R in the silyl group represented by o2 ~R q2 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. Of these, preferred are a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent, and particularly preferred are a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent. Here, R represents any of a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, and an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 12 ~R 14 The preferred embodiments are also the same. -SiR o R p R q Specific examples of the silyl group represented by the formula are -Si(CH3)3, -Si(CH3)2(C2H5), -Si(CH3)2(CH=CH2), -Si(CH3)2(CH2CH2CH3), -Si(CH3)2(CH2CH=CH2), -Si(CH3)2[CH(CH3)2], -Si(CH3)2[(CH2)3CH3)], -Si(CH3)2[CH2CH(CH3)2], -Si(CH3)2[C( CH3)3], -Si(CH3)2(C6H5), -Si(CH3)(C6H5)2, -Si(C6H5)3, -Si(C2H5)3, -Si(CH=CH2)3, -Si(CH2CH2CH3)3, Examples include -Si[CH(CH3)2]3, -Si(CH2CH=CH2)3, -Si(CH3)(C6H5)(CH=CH2), -Si(C6H5)2(CH=CH2), and -Si(CF3)3. Of these, -Si(CH3)3, -Si(CH3)2(CH=CH2), -Si(CH3)2(CH2CH=CH2), -Si(C2H5)3, -Si(CH3)(C6H5)(CH=CH2), and -Si(C6H5)2(CH=CH2) are preferred, and -Si(CH3)2(CH=CH2) and -Si(CH3)2(CH2CH=CH2) are particularly preferred.

[0074] In the general formula (A2), n' represents an integer of 0 to 5. In terms of ease of synthesis of the compound, it is preferably an integer of 0 to 2. Among these, the compound represented by general formula (A3), in which n'=0 in general formula (A2), is preferred because it has an excellent effect of suppressing gas generation during initial conditioning. [ka] (In formula (A3), R 12 ~R 14 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; X' represents a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR o2 R p2 R q2 R o2 ~R q2 R each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 12 ~R 14 At least one of the groups is a hydrocarbon group having 2 to 12 carbon atoms and a carbon-carbon unsaturated bond.) In general formula (A3), R 12 ~R 14 , X' and R o2 ~R q2 is R in general formula (A2). 12 ~R 14 , X' and R o2 ~R q2 correspond to the following: Moreover, the compound of general formula (A2) where n'=1 is also preferred because it has an excellent effect of suppressing gas generation during initial conditioning.

[0075] <1-B1-2. Compound represented by general formula (B2)> [ka] (In formula (B2), R 17 ~R 5 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent, and k' represents an integer of 3 to 6. 17 or R 18 At least one of R is a hydrocarbon group having 2 to 12 carbon atoms and a carbon-carbon unsaturated bond. 17 may be the same or different, and multiple R 18 may be the same or different.)

[0076] R according to general formula (B2) 17 ~R 18 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 17 (R present in the repeating unit 17 ) may be the same or different, and multiple R 18 (R present in the repeating unit 18 ) may be the same or different. That is, 3 to 6 R 17 may be the same or different, and 3 to 6 R 18 may be the same or different from each other. R according to general formula (B2) 17 ~R 18 may be the same or different, but it is preferable that they are the same in terms of ease of synthesis of the compound. Here, R represents any of a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, and an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 12 ~R 14 This has the same meaning as that specified in. R 17 ~R 5 At least one of the groups is preferably a hydrocarbon group having 2 to 12 carbon atoms and a carbon-carbon unsaturated bond, from the viewpoint that the compound according to the general formula (A2) tends to be suitably localized on the electrode surface. Examples of the hydrocarbon group having 2 to 12 carbon atoms and a carbon-carbon unsaturated bond include an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, which will be described later, and among them, an alkenyl group having 2 to 12 carbon atoms and an alkynyl group having 2 to 12 carbon atoms are preferred, from the viewpoint that the compound according to the general formula (A2) tends to be suitably localized on the electrode surface. An alkenyl group having 2 to 12 carbon atoms is particularly preferred.

[0077] In formula (B2), k' is usually an integer of 3 to 6, and among these, k is preferably 3 or 4.

[0078] Specific examples of the compound represented by formula (A2) or (B2) preferably include compounds having the following structures. [ka] [ka] [ka]

[0079] More preferred examples of the compound represented by formula (A2) or (B2) include the following compounds. [ka] [ka]

[0080] Particularly preferred examples of the compound represented by formula (A2) or (B2) include the following compounds. [ka]

[0081] The total content of the compounds represented by general formula (A2) or (B2) relative to the total amount of the nonaqueous electrolyte solution of the present invention is usually 0.001 mass% or more, preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and even more preferably 0.2 mass% or more, and is usually 10 mass% or less, preferably 8 mass% or less, more preferably 6.0 mass% or less, even more preferably 4.0 mass% or less, especially preferably 3.0 mass% or less, particularly preferably 2.5 mass% or less, and most preferably 2.0 mass% or less. When the total content of the compounds represented by general formula (A2) or (B2) relative to the total amount of the nonaqueous electrolyte solution is within the above-mentioned range, concentration of the compounds in the active material proceeds favorably, and it becomes possible to prepare a battery with less gas generation during initial conditioning. The compound represented by general formula (A2) or (B2) in the nonaqueous electrolyte solution is identified and its content is measured by nuclear magnetic resonance (NMR) spectroscopy.

[0082] <1-B2. Compounds with Si-N structure> <1-B2-1. Compound represented by general formula (Z)> [ka] (In formula (Z), R 19 ~R 21 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; R 22 ~R 23 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, or -SiR x R y R z R represents a silyl group represented by the formula: x ~R z R each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 22 and R 23 may be bonded to each other to form a ring.

[0083] R in the general formula (Z) 19 ~R 21 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. Of these, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent and an alkoxy group having 1 to 12 carbon atoms which may have a substituent are preferred, and a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent is particularly preferred. Also, R 19 ~R 21 At least one of these is preferably an alkyl group having 1 to 12 carbon atoms, from the viewpoint of enabling the compound represented by general formula (Z) to be suitably adsorbed onto the electrode surface. R in the general formula (Z) 19 ~R 21 may be the same or different, but preferably at least two or more are the same in terms of ease of compound synthesis, and more preferably all three are the same from the above-mentioned viewpoint. Examples of halogen atoms include fluorine atoms, chlorine atoms, and bromine atoms. Preferably, fluorine atoms are used in terms of fewer electrochemical side reactions. The hydrocarbon group having 1 to 12 carbon atoms is preferably a hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a hydrocarbon group having 1 to 4 carbon atoms.

[0084] Specific examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, and an aryl group. Among these, an alkyl group, an alkenyl group, or an alkynyl group is preferred, and an alkyl group or an alkenyl group is particularly preferred. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. Among them, preferred are methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, and hexyl groups, more preferred are methyl, ethyl, n-propyl, n-butyl, tert-butyl, and n-pentyl groups, and particularly preferred are methyl, ethyl, n-butyl, and tert-butyl groups. The above-mentioned alkyl groups are preferred because the compound represented by the general formula (Z) tends to be localized near the surface of the positive electrode and / or negative electrode active material.

[0085] Specific examples of the alkenyl group include vinyl, allyl, methallyl, 2-butenyl, 3-methyl-2-butenyl, 3-butenyl, and 4-pentenyl groups. Among these, vinyl, allyl, methallyl, and 2-butenyl groups are preferred, vinyl, allyl, and methallyl groups are more preferred, and vinyl groups are particularly preferred. The above-mentioned alkenyl groups are preferred because the compound represented by general formula (Z) tends to be localized near the surface of the positive electrode and / or negative electrode active material.

[0086] Specific examples of the alkynyl group include an ethynyl group, a 2-propynyl group, a 2-butynyl group, a 3-butynyl group, a 4-pentynyl group, and a 5-hexynyl group. Among these, an ethynyl group, a 2-propynyl group, a 2-butynyl group, and a 3-butynyl group are preferred, a 2-propynyl group and a 3-butynyl group are more preferred, and a 2-propynyl group is particularly preferred. This is preferred because the compound represented by the general formula (Z) tends to be localized near the surface of the positive electrode and / or negative electrode active material.

[0087] Specific examples of the aryl group include a phenyl group, a tolyl group, etc. Among them, a phenyl group is preferred from the viewpoint that the compound represented by the general formula (Z) tends to be localized near the surface of the positive electrode and / or negative electrode active material. Specific examples of the aralkyl group include a benzyl group and a phenethyl group. The alkoxy group having 1 to 12 carbon atoms is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and even more preferably an alkoxy group having 1 to 2 carbon atoms. Specific examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and an isopropoxy group, etc. Among them, a methoxy group and an ethoxy group are preferred in that they cause less steric hindrance to the compound represented by general formula (Z) and are suitably concentrated on the surface of the active material. Here, the substituent is a cyano group, an isocyanato group, an acyl group (-(C=O)-R u ), acyloxy group (-O(C=O)-R u ), alkoxycarbonyl group (-(C=O)OR u ), sulfonyl group (-SO2-R u ), sulfonyloxy group (-O(SO2)-R u ), alkoxysulfonyl group (-(SO2)-OR u ), alkoxysulfonyloxy group (-O-(SO2)-OR u ), alkoxycarbonyloxy group (-O-(C=O)-OR u ), ether group (-OR u ), an acrylic group, a methacrylic group, a halogen atom (preferably a fluorine atom), a trifluoromethyl group, etc. u R represents an alkyl group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms. u When is an alkylene group, it may be bonded to a part of the hydrocarbon group which substitutes it to form a ring. R in the general formula (Z) 22 ~R 23 represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR x R y R z In particular, a silyl group represented by the formula: x R y R z A silyl group represented by the following formula is preferred. Also, R 22 ~R 23 At least one of the following is -SiR x R y R z The silyl group represented by the following formula (1) is preferred in that it reduces the polarity of the compound represented by general formula (Z). Here, the hydrocarbon group having 1 to 12 carbon atoms which may have a substituent is R 19 ~R 21 This has the same meaning as specified in. In addition, -SiR x R y R z R in the silyl group represented by x ~R z each independently represents a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, or an optionally substituted alkoxy group having 1 to 12 carbon atoms. Here, R is any of a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, and an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 19 ~R 21 This has the same meaning as that specified in.

[0088] Specific examples of the compound having the Si-N structure represented by general formula (Z) include compounds having the following structures.

[0089] [ka]

[0090] Preferred examples of the compound represented by general formula (Z) include the following compounds. [ka]

[0091] More preferred examples of the compound represented by formula (Z) include the following compounds. [ka]

[0092] Particularly preferred examples of the compound represented by formula (Z) include the following compounds. [ka]

[0093] <1-B2-2. Compound represented by general formula (Y)> [ka] (In formula (Y), R 24 represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR a R b R c R represents a silyl group represented by the formula: a ~R c each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; R 25 ~R 26 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; and 1 represents an integer of 3 to 6. 25 may be the same or different, and multiple R 26 may be the same or different.)

[0094] R 24 represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR a R b R c The silyl group is represented by the following formula: Here, the hydrocarbon group having 1 to 12 carbon atoms which may have a substituent is R 22 ~R 23 This has the same meaning as that specified in. -SiR a R b R c The silyl group represented by the above-mentioned -SiR x R y R z This has the same meaning as the silyl group represented by the following formula: R 25 ~R 26 each independently represents a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, or an optionally substituted alkoxy group having 1 to 12 carbon atoms. Here, R represents any of a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, and an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 19 ~R 21 This has the same meaning as that specified in. Also, multiple R 25 (R present in the repeating unit 25 ) may be the same or different, and multiple R 26 (R present in the repeating unit 26 ) may be the same or different. That is, 3 to 6 R 25 may be the same or different, and 3 to 6 R 26 may be the same or different from each other. R in the general formula (Y) 25 ~R 26 may be the same or different, but it is preferable that they are the same in terms of facilitating the synthesis of the compound. l represents an integer of 3 to 6. l is preferably 3 or 4. Specific examples of the compound having the Si-N structure represented by general formula (Y) include compounds having the following structures.

[0095] [ka]

[0096] Preferred examples of the compounds include the following: [ka]

[0097] More preferred examples of the compounds include the following: [ka]

[0098] The total content of the compounds having a Si-N structure represented by general formula (Z) or general formula (Y) relative to the total amount of the nonaqueous electrolyte solution of the present invention is not particularly limited, but is preferably 0.01 ppm by mass or more, more preferably 0.1 ppm by mass or more, even more preferably 1.0 ppm by mass or more, particularly preferably 10 ppm by mass or more, and is preferably less than 0.5% by mass, more preferably 0.4% by mass or less, even more preferably 0.3% by mass or less, especially preferably 0.2% by mass or less, and particularly preferably 0.1% by mass or less. When the total content of the compounds having a Si-N structure represented by general formula (Z) or general formula (Y) relative to the total amount of the nonaqueous electrolyte is within the above-mentioned range, the concentration of the compounds in the active material proceeds favorably, and it becomes possible to prepare a battery with less gas generation during initial conditioning. The identification and content of the compound represented by general formula (Z) or general formula (Y) in the nonaqueous electrolyte solution are carried out by nuclear magnetic resonance (NMR) spectroscopy.

[0099] The mass ratio of the content of the compound represented by general formula (A2) or general formula (B2) to the content having a Si-N structure represented by general formula (Z) or general formula (Y) in the nonaqueous electrolyte is not particularly limited, but is usually 1.0 or more, preferably 2.0 or more, more preferably 3.0 or more, and is usually 10000 or less, preferably 7000 or less, more preferably 4000 or less, even more preferably 2000 or less, especially preferably 1000 or less, and particularly preferably 500 or less. In addition, when both compounds represented by general formula (A2) and general formula (B2) are included, the above ratio indicates the ratio of the total content of the compounds represented by general formula (A2) and general formula (B2) to the content of the compound having a Si-N structure represented by general formula (Z) or general formula (Y). In the case where both the compounds represented by general formula (Z) and general formula (Y) are contained, the above ratio indicates the ratio of the content of the compound represented by general formula (A2) or general formula (B2) to the total content of the compounds having a Si-N structure represented by general formula (Z) and general formula (Y). The method of adding a compound having a Si-N structure represented by general formula (Z) or general formula (Y) or a compound having a Si-O structure represented by general formula (A2) or (B2) to the electrolyte of the present invention is not particularly limited. In addition to the method of directly adding the compound to the electrolyte, a method of generating the compound in a battery or in the electrolyte can be mentioned.

[0100] In this specification, the content of the compound means the content at the time of production of the nonaqueous electrolyte solution, at the time of injection of the nonaqueous electrolyte solution into a battery, or at the time of shipment of the battery.

[0101] [Invention C] The nonaqueous electrolyte solution according to present invention C is a nonaqueous electrolyte solution for a nonaqueous electrolyte battery having a positive electrode and a negative electrode capable of absorbing and releasing metal ions, characterized in that the nonaqueous electrolyte solution contains at least one kind of an alkali metal salt, a nonaqueous solvent, and a compound having a Si-O structure represented by general formula (A2) or general formula (B2), and contains at least one kind selected from the group consisting of a compound represented by general formula (α), a compound represented by general formula (Z), and a compound represented by general formula (Y).

[0102] [ka] (In formula (A2), R 12 ~R 16 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; X represents a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR o R p R q R represents a silyl group represented by the formula: o ~R q each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; n represents an integer of 0 to 5; R 12 ~R 14 At least one of R is a hydrocarbon group having 2 to 12 carbon atoms and a carbon-carbon unsaturated bond. When n' is 2 or more, multiple R 15 may be the same or different, and multiple R 16 may be the same or different.)

[0103] [ka] (In formula (B), R 17 ~R 18 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; k' represents an integer of 3 to 6; R 17 or R 18 At least one of R is a hydrocarbon group having 2 to 12 carbon atoms and a carbon-carbon unsaturated bond. 17 may be the same or different, and multiple R 18 may be the same or different.)

[0104] [ka] (In formula (α), R 89 is a hydrogen atom or -SiR 8 R 9 R 10 R represents a silyl group represented by the formula: 8 ~R 10 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; R 11 represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR d R e R f R represents a silyl group represented by the formula: d ~R f each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; Y represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, -NR g -SiR h R i R j or -NR g R represents a group represented by -H; g represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent; R h ~R j R each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 11 and R g may be bonded to each other to form a ring.

[0105] [ka] (In formula (Z), R 19 ~R 21 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; R 22 ~R 23 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR x R y R z R represents a silyl group represented by the formula: x ~R z R each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. 22 and R 23 may be bonded to each other to form a ring.

[0106] [ka] (In formula (Y), R 24 represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR a R b R c R represents a silyl group represented by the formula: a ~R c each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; R 25 ~R 26 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; and 1 represents an integer of 3 to 6. 25 may be the same or different, and multiple R 26 may be the same or different.)

[0107] The above description of <1-B1. Compound having Si-O structure> is applied to the compound having the Si-O structure represented by general formula (A2) or general formula (B2). The explanation of <1-A2. Compounds represented by general formula (α)> applies to the compounds represented by general formula (α). The explanation of <1-B2-1. Compounds represented by general formula (Z)> applies to the compounds represented by general formula (Z). The explanation of <1-B2-2. Compounds represented by general formula (Y)> applies to the compounds represented by general formula (Y).

[0108] <1-3. Electrolytes> The non-aqueous electrolyte solution of the present invention A to C usually contains an electrolyte as a component, similar to a general non-aqueous electrolyte solution. The electrolyte used in the non-aqueous electrolyte solution of the present embodiment is not particularly limited, and any known electrolyte can be used. Specific examples of the electrolyte will be described in detail below.

[0109] <1-3-1. Alkali metal salts> As the electrolyte in the nonaqueous electrolyte solution of the present embodiment, an alkali metal salt such as a lithium salt is usually used. The lithium salt is not particularly limited as long as it is known to be used for this purpose, and any one or more kinds of lithium salts can be used.

[0110] Specific examples of the lithium salt include: Inorganic lithium salts such as LiBF4, LiClO4, LiAlF4, LiSbF6, LiTaF6, LiWF7; Lithium fluorophosphates such as LiPF6; Lithium tungstate salts such as LiWOF5; Lithium carboxylates such as CF3CO2Li; Lithium sulfonate salts such as CH3SO3Li; Lithium imide salts such as LiN(FSO2)2, LiN(CF3SO2)2; Lithium methide salts such as LiC(FSO2)3; Other fluorine-containing organic lithium salts such as LiPF4(CF3)2; etc.

[0111] In order to further enhance the effects of improving the charge / discharge rate characteristics and impedance characteristics in addition to improving the charge storage characteristics under high temperature environments obtained by the present invention, it is preferable to use a material selected from inorganic lithium salts, lithium fluorophosphates, lithium sulfonate salts, lithium imide salts, and lithium oxalate salts, and in order to improve the charge / discharge characteristics, lithium fluorophosphates, inorganic lithium salts, and lithium imide salts are more preferable, lithium fluorophosphates or lithium imide salts are even more preferable, LiPF6 or LiN(FSO2)2 are particularly preferable, and LiPF6 is particularly preferable.

[0112] The total concentration of these electrolytes 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 electrolytes is within the above range, the electrical conductivity is appropriate for the battery operation, so that sufficient output characteristics tend to be obtained. The mass ratio of the compound having the Si-O structure represented by general formula (A) or general formula (B) to the lithium salt in the non-aqueous electrolyte is not particularly limited as long as it does not significantly impair the effects of the present invention, but is preferably 0.0001 or more, more preferably 0.001 or more, and particularly preferably 0.01 or more. The upper limit is preferably 0.5 or less, more preferably 0.25 or less, and particularly preferably 0.1 or less. If the mass ratio of these compounds is within the above preferred range, it is preferable in that the compound having the Si-O structure represented by general formula (A) or general formula (B) is suitably adsorbed to the electrode active material. The mass ratio of the compound represented by the general formula (α) to the lithium salt in the non-aqueous electrolyte is not particularly limited as long as it does not significantly impair the effects of the present invention, but is preferably 0.0001 or more, more preferably 0.001 or more, and particularly preferably 0.01 or more. The upper limit is preferably 0.5 or less, more preferably 0.25 or less, and particularly preferably 0.1 or less. If the mass ratio of these compounds is within the above preferred range, it is preferable in that the compound represented by the general formula (α) is suitably adsorbed to the electrode active material. The mass ratio of the compound having the Si-O structure represented by general formula (A2) or general formula (B2) to the lithium salt in the non-aqueous electrolyte is not particularly limited as long as it does not significantly impair the effects of the present invention, but is preferably 0.0001 or more, more preferably 0.001 or more, and particularly preferably 0.01 or more. The upper limit is preferably 0.5 or less, more preferably 0.25 or less, and particularly preferably 0.1 or less. If the mass ratio of these compounds is within the above preferred range, it is preferable in that the compound having the Si-O structure represented by general formula (A2) or general formula (B2) is suitably adsorbed to the electrode active material. The mass ratio of the compound having the Si-N structure represented by general formula (Z) or general formula (Y) to the lithium salt in the non-aqueous electrolyte is not particularly limited as long as it does not significantly impair the effects of the present invention, but is preferably 0.0001 or more, more preferably 0.001 or more, and particularly preferably 0.01 or more. The upper limit is preferably 0.5 or less, more preferably 0.25 or less, and particularly preferably 0.1 or less. If the mass ratio of these compounds is within the above preferred range, it is preferable in that the compound having the Si-N structure represented by general formula (Z) or general formula (Y) is suitably adsorbed to the electrode active material.

[0113] <1-4.Non-aqueous solvents> The non-aqueous electrolyte of the present embodiment, like a general non-aqueous electrolyte, usually contains a non-aqueous solvent that dissolves the above-mentioned electrolyte as its main component. There is no particular limitation on the non-aqueous solvent, and a known organic solvent can be used. Examples of the organic solvent include saturated cyclic carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate; chain carbonates such as dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate; carboxylic acid esters such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; ether compounds such as dimethoxymethane, diethoxymethane, ethoxymethoxymethane, tetrahydrofuran, 1,3-dioxane, and 1,4-dioxane; and sulfone compounds such as 2-methylsulfolane, 3-methylsulfolane, 2-fluorosulfolane, 3-fluorosulfolane, dimethylsulfone, ethylmethylsulfone, and monofluoromethylmethylsulfone. Preferred are saturated cyclic carbonates, chain carbonates or carboxylates, more preferred are saturated cyclic carbonates or chain carbonates. These non-aqueous solvents can be used alone or in combination of two or more. As a combination of two or more non-aqueous solvents, a combination of two or more selected from the group consisting of saturated cyclic carbonates, chain carbonates and carboxylates is preferred, and a combination of saturated cyclic carbonates and chain carbonates is more preferred.

[0114] <1-5. Auxiliaries> The nonaqueous electrolyte solution of the present embodiment may contain an auxiliary agent within a range in which the effects of the present invention can be achieved. As an auxiliary, Fluorinated salts such as difluorophosphates, fluorosulfonates, fluoroboron salts and fluoroimide salts; Unsaturated cyclic carbonates such as vinylene carbonate, vinyl ethylene carbonate, and ethynyl ethylene carbonate; Fluorinated cyclic carbonates such as monofluoroethylene carbonate, 4,4-difluoroethylene carbonate, 4,5-difluoroethylene carbonate, and 4,5-difluoro-4,5-dimethylethylene carbonate; oxalate salts such as lithium bis(oxalato)borate, lithium tetrafluorooxalatophosphate, lithium difluorobis(oxalato)phosphate, and lithium tris(oxalato)phosphate; Carbonate compounds such as methoxyethyl-methyl carbonate; Spiro compounds such as methyl-2-propynyl oxalate; Sulfur-containing compounds such as ethylene sulfite; isocyanate compounds such as 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, and aliphatic polyisocyanates obtained by adding polyhydric alcohols to the trimer compounds; Nitrogen-containing compounds such as 1-methyl-2-pyrrolidinone; Hydrocarbon compounds such as cycloheptane; Fluorinated aromatic compounds such as fluorobenzene; Fluorosilane compounds such as fluorotrimethylsilane, fluorodimethylvinylsilane, difluorodimethylsilane, and difluorovinylmethylsilane; 2-(methanesulfonyloxy)propionic acid 2-propynyl ester compounds; Lithium salts such as lithium ethylmethyloxycarbonylphosphonate; These may be used alone or in combination of two or more. By adding these auxiliary agents, not only can gas generation during initial conditioning be suppressed, but also the initial resistance can be reduced, and the battery characteristics can be improved overall.

[0115] Among them, in the non-aqueous electrolyte according to one embodiment of the present invention, by containing one or more selected from fluorinated salts, fluorosilane compounds, unsaturated cyclic carbonates, cyclic carbonates having fluorine atoms, and oxalate salts, gas generation during initial conditioning is further suppressed, and not only is a battery that is less likely to swell obtained, but also the initial resistance of the battery is low, which is preferable. More preferably, the electrolyte contains at least an unsaturated cyclic carbonate or a cyclic carbonate having fluorine atoms, and even more preferably, the electrolyte contains an unsaturated cyclic carbonate and a cyclic carbonate having fluorine atoms. In addition, it is also preferable to contain at least an unsaturated cyclic carbonate or a cyclic carbonate having a fluorine atom, and one or more selected from a fluorinated salt, a fluorosilane compound, and an oxalate salt, because gas generation during initial conditioning is further suppressed, a battery that is less likely to swell is obtained, and the initial resistance of the battery is also low. In addition, it is more preferable to contain an unsaturated cyclic carbonate and a cyclic carbonate having a fluorine atom, and one or more selected from a fluorinated salt, a fluorosilane compound, and an oxalate salt. The "fluorinated salts", "fluorosilane compounds", "unsaturated cyclic carbonates", "fluorinated cyclic carbonates" and "oxalate salts" will be described in detail below.

[0116] (Fluorinated salts) The non-aqueous electrolyte according to this embodiment may contain a fluorinated salt. There is no particular limitation on the fluorinated salt, but since it has a highly detachable fluorine atom in the structure, it can react favorably with the decomposition product of the compound represented by the general formula (A), (B), (α), (Y), or (Z) to form a composite coating, and the initial battery resistance can be reduced, difluorophosphate, fluorosulfonate, fluoroboron salt, and fluoroimide salt are preferred. Since the elimination of fluorine atoms is particularly high and the reaction with nucleophiles proceeds favorably, fluoroboron salt, fluorosulfonate, and difluorophosphate are more preferred, fluorosulfonate and difluorophosphate are particularly preferred, and fluorosulfonate is most preferred because of its high elimination of fluorine. In addition, as the fluorinated salt, a fluorinated lithium salt is preferred. The fluorinated salt may be used alone or in any combination and ratio of two or more.The content of the fluorinated salt relative to the total amount of the non-aqueous electrolyte is not particularly limited and is any content as long as it does not significantly impair the effect of the present invention, but is usually 0.001 mass% or more, preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and is usually less than 8 mass%, preferably 5 mass% or less, more preferably 3 mass% or less, even more preferably 2 mass% or less, and most preferably 1 mass% or less. These various salts are described below.

[0117] <Difluorophosphate> The counter cation of the difluorophosphate is not particularly limited, but may be lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, or NR 27 R 28 R 29 R 30 (In the formula, R 27 ~R 30 each independently represents a hydrogen atom or an organic group having 1 to 12 carbon atoms. Examples thereof include ammonium represented by the following formula: Of these, lithium is preferred.

[0118] The above ammonium R 27 ~R 30 The organic group having 1 to 12 carbon atoms represented by the formula (I) is not particularly limited, but examples thereof include an alkyl group which may be substituted with a halogen atom, a cycloalkyl group which may be substituted with a halogen atom or an alkyl group, an aryl group which may be substituted with a halogen atom or an alkyl group, and a nitrogen atom-containing heterocyclic group which may have a substituent. 27 ~R 30 are each preferably independently a hydrogen atom, an alkyl group, a cycloalkyl group, or a nitrogen atom-containing heterocyclic group.

[0119] Specific examples of difluorophosphates include lithium difluorophosphate, sodium difluorophosphate, potassium difluorophosphate, etc., with lithium difluorophosphate being preferred. Difluorophosphate may be used alone or in any combination and ratio of two or more.The content of difluorophosphate relative to the total amount of non-aqueous electrolyte is not particularly limited and is optional as long as it does not significantly impair the effect of the present invention, but is usually 0.001 mass% or more, preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and is usually less than 8 mass%, preferably 5 mass% or less, more preferably 3 mass% or less, even more preferably 2 mass% or less, and most preferably 1 mass% or less. When the content of the difluorophosphate is within this range, the nonaqueous electrolyte secondary battery is likely to exhibit a sufficient effect of improving the cycle characteristics, and it is also likely to avoid situations in which the high-temperature storage characteristics are deteriorated, the amount of gas generated is increased, and the discharge capacity retention rate is reduced.

[0120] <Fluorosulfonate> The counter cation of the fluorosulfonate is not particularly limited, but may be lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, or NR 17 R 18 R 19 R 20 (In the formula, R 17 ~R 20 each independently represents a hydrogen atom or an organic group having 1 to 12 carbon atoms. Examples thereof include ammonium represented by the following formula: Of these, lithium is preferred.

[0121] The above ammonium R 17 ~R 20 The organic group having 1 to 12 carbon atoms represented by the formula (I) is not particularly limited, but examples thereof include an alkyl group which may be substituted with a halogen atom, a cycloalkyl group which may be substituted with a halogen atom or an alkyl group, an aryl group which may be substituted with a halogen atom or an alkyl group, and a nitrogen atom-containing heterocyclic group which may have a substituent. 17 ~R 20 are each preferably independently a hydrogen atom, an alkyl group, a cycloalkyl group, or a nitrogen atom-containing heterocyclic group. Specific examples of fluorosulfonates include: Examples of the fluorosulfonate include lithium fluorosulfonate, sodium fluorosulfonate, potassium fluorosulfonate, rubidium fluorosulfonate, and cesium fluorosulfonate, and lithium fluorosulfonate is preferred.

[0122] The fluorosulfonate may be used alone or in any combination and ratio of two or more.The content of the fluorosulfonate relative to the total amount of the non-aqueous electrolyte is not particularly limited, and is any content as long as it does not significantly impair the effect of the present invention, but is usually 0.001 mass% or more, preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and is usually less than 8 mass%, preferably 5 mass% or less, more preferably 3 mass% or less, even more preferably 2 mass% or less, and most preferably 1 mass% or less. When the content of the fluorosulfonate is within this range, the nonaqueous electrolyte secondary battery is likely to exhibit a sufficient effect of improving the cycle characteristics, and it is also likely to avoid situations in which the high-temperature storage characteristics are deteriorated, the amount of gas generated is increased, and the discharge capacity retention rate is reduced.

[0123] <Fluoroboron salt> The counter cation of the fluoroboron salt is not particularly limited, but may be lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, or NR 21 R 22 R 23 R 24 (In the formula, R 21 ~R 24 each independently represents a hydrogen atom or an organic group having 1 to 12 carbon atoms. Examples thereof include ammonium represented by the following formula: Of these, lithium is preferred.

[0124] The above ammonium R 21 ~R 24 The organic group having 1 to 12 carbon atoms represented by the formula (I) is not particularly limited, but examples thereof include an alkyl group which may be substituted with a halogen atom, a cycloalkyl group which may be substituted with a halogen atom or an alkyl group, an aryl group which may be substituted with a halogen atom or an alkyl group, and a nitrogen atom-containing heterocyclic group which may have a substituent. 21 ~R 24 are each preferably independently a hydrogen atom, an alkyl group, a cycloalkyl group, or a nitrogen atom-containing heterocyclic group.

[0125] Specific examples of fluoroboron salts include: LiBF4, LiB(C i F 2i+1 ) j (F) 4-j In addition, i represents an integer of 1 to 10, and j represents an integer of 1 to 4. The fluoroboron salt may be used alone or in any combination and ratio of two or more.The content of the fluoroboron salt relative to the total amount of the non-aqueous electrolyte is not particularly limited, and is any content as long as it does not significantly impair the effects of the present invention, but is usually 0.001 mass% or more, preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and is usually 3 mass% or less, preferably 1 mass% or less, more preferably 0.8 mass% or less, even more preferably 0.5 mass% or less, and most preferably 0.3 mass% or less. If the content of the fluoroboron salt is within this range, the nonaqueous electrolyte secondary battery is likely to exhibit a sufficient effect of improving the cycle characteristics, and it is also likely to avoid situations such as a deterioration in high-temperature storage characteristics, an increase in the amount of gas generated, and a decrease in the discharge capacity retention rate.

[0126] <Fluoroimide salt> The counter cation of the fluoroimide salt is not particularly limited, but examples thereof include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, and NR 31 R 32 R 33 R 34 (In the formula, R 31 ~R 34 Each of the groups independently represents a hydrogen atom or an organic group having 1 to 12 carbon atoms. Examples of the group include ammonium represented by the following formula: Of these, lithium is preferred.

[0127] The above ammonium R 31 ~R 34 The organic group having 1 to 12 carbon atoms represented by the formula (I) is not particularly limited, but examples thereof include an alkyl group which may be substituted with a halogen atom, a cycloalkyl group which may be substituted with a halogen atom or an alkyl group, an aryl group which may be substituted with a halogen atom or an alkyl group, and a nitrogen atom-containing heterocyclic group which may have a substituent. 31 ~R 34 are each preferably independently a hydrogen atom, an alkyl group, a cycloalkyl group, or a nitrogen atom-containing heterocyclic group.

[0128] Specific examples of fluoroimide salts include LiN(FCO)2, LiN(FCO)(FSO2), LiN(FSO2)2, LiN(FSO2)(CF3SO2), LiN(CF3SO2)2, LiN(C2F5SO2)2, lithium cyclic 1,2-perfluoroethane disulfonylimide, lithium cyclic 1,3-perfluoropropane disulfonylimide, and LiN(CF3SO2)(C4F9SO2), with LiN(FSO2)2, LiN(CF3SO2)2, and LiN(C2F5SO2)2 being preferred.

[0129] The fluoroimide salt may be used alone or in any combination and ratio of two or more. The content of the fluoroimide salt relative to the total amount of the non-aqueous electrolyte is not particularly limited and may be any amount as long as it does not significantly impair the effects of the present invention, but is usually 0.001 mass% or more, preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and is usually less than 8 mass%, preferably 5 mass% or less, more preferably 3 mass% or less, even more preferably 2 mass% or less, and most preferably 1 mass% or less. When the content of the fluoroimide salt is within this range, the nonaqueous electrolyte secondary battery is likely to exhibit a sufficient effect of improving the cycle characteristics, and it is also likely to avoid situations such as a deterioration in high-temperature storage characteristics, an increase in the amount of gas generated, and a decrease in the discharge capacity retention rate.

[0130] (Oxalate Salt) The oxalate salt is preferable in that it can react favorably with the decomposition product of the compound represented by general formula (A), (B), (α), (Y), or (Z) to form a composite coating film and reduce the initial battery resistance. The counter cation of the oxalate salt is not particularly limited, but may be lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, or NR 35 R 36 R 37 R 38 (In the formula, R 35 ~R 38 Each of the groups independently represents a hydrogen atom or an organic group having 1 to 12 carbon atoms. Examples of the group include ammonium represented by the following formula: Of these, lithium is preferred.

[0131] The above ammonium R 35 ~R 38 The organic group having 1 to 12 carbon atoms represented by the formula (I) is not particularly limited, but examples thereof include an alkyl group which may be substituted with a halogen atom, a cycloalkyl group which may be substituted with a halogen atom or an alkyl group, an aryl group which may be substituted with a halogen atom or an alkyl group, and a nitrogen atom-containing heterocyclic group which may have a substituent. 35 ~R 38 are each preferably independently a hydrogen atom, an alkyl group, a cycloalkyl group, or a nitrogen atom-containing heterocyclic group.

[0132] Specific examples of oxalate salts include lithium bis(oxalato)borate, lithium tetrafluorooxalatophosphate, lithium difluorobis(oxalato)phosphate, and lithium tris(oxalato)phosphate, of which lithium bis(oxalato)borate and lithium difluorobis(oxalato)phosphate are preferred, and lithium bis(oxalato)borate is particularly preferred.

[0133] The oxalate salt may be used alone or in any combination and ratio of two or more. The content of the oxalate salt with respect to the total amount of the non-aqueous electrolyte is not particularly limited and may be any amount as long as it does not significantly impair the effect of the present invention, but is usually 0.001 mass% or more, preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and is usually less than 8 mass%, preferably 5 mass% or less, more preferably 3 mass% or less, even more preferably 2 mass% or less, and most preferably 1 mass% or less. When the content of the oxalate salt is within this range, the effect of reducing the initial battery resistance is enhanced, and further, the nonaqueous electrolyte secondary battery is likely to exhibit a sufficient effect of improving the cycle characteristics, and it is also likely to avoid situations such as a deterioration in high-temperature storage characteristics, an increase in the amount of gas generated, and a decrease in the discharge capacity retention rate.

[0134] (Fluorosilane compounds) The fluorosilane compound is preferable in that it can react favorably with the decomposition product of the compound represented by general formula (A), (B), (α), (Y), or (Z) to form a composite coating film and reduce the initial battery resistance. The non-aqueous electrolyte according to the present embodiment may contain a fluorosilane compound. The fluorosilane compound is not particularly limited as long as it is a compound having at least one silicon-fluorine bond (Si-F bond) in the molecule. Examples of fluorosilane compounds include fluorotrimethylsilane, dimethyl(fluoro)(vinyl)silane, (allyl)dimethyl(fluoro)silane, dimethyl(fluoro)(propargyl)silane, divinylfluoro(methyl)silane, fluorotrivinylsilane, ethynyldimethylfluorosilane, difluorodimethylsilane, difluorodivinylsilane, methyltrifluorosilane, trifluorovinylsilane, fluorotriethylsilane, diethyl(fluoro)(methyl)silane, diethyl(fluoro)(vinyl)silane, ethyldivinylfluorosilane, diethyl(fluoro)(ethynyl)silane, (allyl)diethyl(fluoro)silane, diethyl(fluoro)(propargyl)silane, difluorodiethylsilane, ethyldifluorovinylsilane, trifluoro Examples of compounds include ethylsilane, fluorotripropylsilane, trifluoropropylsilane, fluorotributylsilane, trifluorobutylsilane, fluorotripentylsilane, trifluoropentylsilane, fluorotrihexylsilane, trifluorohexylsilane, fluorotricyclohexylsilane, trifluorocyclohexylsilane, fluorotriphenylsilane, fluorotritriylsilane, fluorotribenzylsilane, difluorodinaphthylsilane, naphthyltrifluorosilane, dibiphenyldifluorosilane, biphenyltrifluorosilane, (cyclohexylphenyl)trifluorosilane, di(cyclohexylphenyl)difluorosilane, fluorotri(biphenyl)silane, and fluorotri(cyclohexylphenyl)silane.

[0135] Of these, preferred are fluorotrimethylsilane, dimethyl(fluoro)(vinyl)silane, dimethyldifluorosilane, and methyl(difluoro)(vinyl)silane.

[0136] The fluorosilane compound may be used alone or in any combination and ratio of two or more. The content of the fluorosilane compound (total amount when two or more) is usually 0.001 mass% or more, preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and usually 3 mass% or less, preferably 1 mass% or less, more preferably 0.5 mass% or less, based on the total amount of the non-aqueous electrolyte. Within this range, the effect of reducing the initial battery resistance is enhanced, and further, the output characteristics, load characteristics, low temperature characteristics, cycle characteristics, high temperature storage characteristics, etc. are easily controlled.

[0137] (Unsaturated cyclic carbonate) In this specification, the term "unsaturated cyclic carbonate" refers to a cyclic carbonate having a carbon-carbon unsaturated bond, and is not particularly limited as long as it is a carbonate having a carbon-carbon unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond, and any unsaturated cyclic carbonate can be used. Examples of unsaturated cyclic carbonates include vinylene carbonates and ethylene carbonates substituted with a substituent having a carbon-carbon unsaturated bond. Specific examples of vinylene carbonates include vinylene carbonate, methylvinylene carbonate, and 4,5-dimethylvinylene carbonate. Specific examples of ethylene carbonates substituted with a substituent having a carbon-carbon unsaturated bond include vinyl ethylene carbonate, 4,5-divinyl ethylene carbonate, ethynyl ethylene carbonate, and propargyl ethylene carbonate. Among these, vinylene carbonate, vinyl ethylene carbonate, and ethynyl ethylene carbonate are preferred, and vinylene carbonate is particularly preferred because it can contribute to the formation of a stable film-like structure. The molecular weight of the unsaturated cyclic carbonate is not particularly limited and may be any value as long as it does not significantly impair the effects of the present invention, but is usually at least 50, preferably at least 80, and usually at most 250, preferably at most 150. Within this range, the solubility of the unsaturated cyclic carbonate in the nonaqueous electrolyte is easily ensured, and the effects of the present invention are easily exhibited. The unsaturated cyclic carbonate may be used alone or in any combination and ratio of two or more. The content of the unsaturated cyclic carbonate is not particularly limited and may be any as long as it does not significantly impair the effects of the present invention, but the content of the unsaturated cyclic carbonate is usually 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.2% by mass or more, based on the total amount of the non-aqueous electrolyte, and is usually 10% by mass or less, preferably 8% by mass or less, and more preferably 5% by mass or less. If the content of the unsaturated cyclic carbonate is within the above range, the effect of reducing the initial resistance of the non-aqueous electrolyte secondary battery is enhanced, and further, sufficient high-temperature storage characteristics and cycle characteristics are easily improved.

[0138] (Fluorinated cyclic carbonates) As used herein, a "fluorinated cyclic carbonate" is a cyclic carbonate having a fluorine atom. The fluorinated cyclic carbonate may be a derivative of a cyclic carbonate having an alkylene group having 2 to 6 carbon atoms, such as an ethylene carbonate derivative. The ethylene carbonate derivative may be, for example, a fluorinated product of ethylene carbonate or ethylene carbonate substituted with an alkyl group (e.g., an alkyl group having 1 to 4 carbon atoms), and among these, those having 1 to 8 fluorine atoms are preferred. Specific examples include monofluoroethylene carbonate, 4,4-difluoroethylene carbonate, 4,5-difluoroethylene carbonate, 4-fluoro-4-methylethylene carbonate, 4,5-difluoro-4-methylethylene carbonate, 4-fluoro-5-methylethylene carbonate, 4,4-difluoro-5-methylethylene carbonate, 4-(fluoromethyl)-ethylene carbonate, 4-(difluoromethyl)-ethylene carbonate, 4-(trifluoromethyl)-ethylene carbonate, 4-(fluoromethyl)-4-fluoroethylene carbonate, 4-(fluoromethyl)-5-fluoroethylene carbonate, 4-fluoro-4,5-dimethylethylene carbonate, 4,5-difluoro-4,5-dimethylethylene carbonate, and 4,4-difluoro-5,5-dimethylethylene carbonate. Among these, at least one selected from the group consisting of monofluoroethylene carbonate, 4,4-difluoroethylene carbonate, 4,5-difluoroethylene carbonate, and 4,5-difluoro-4,5-dimethylethylene carbonate is more preferred in that it provides high ion conductivity and favorably forms an interface protective coating. The fluorinated cyclic carbonates may be used alone or as a mixture of two or more kinds in any combination and in any ratio. The fluorinated cyclic carbonate may be used as an auxiliary agent for the non-aqueous electrolyte or as a non-aqueous solvent. The content of the fluorinated cyclic carbonate when used as a non-aqueous solvent is usually 8% by mass or more, preferably 10% by mass or more, more preferably 12% by mass or more, and usually 85% by mass or less, preferably 80% by mass or less, more preferably 75% by mass or less, based on the total amount of the non-aqueous electrolyte. Within this range, the effect of reducing the initial resistance of the non-aqueous electrolyte secondary battery is enhanced, and furthermore, the effect of improving the cycle characteristics is easily exhibited, and the decrease in the discharge capacity retention rate is easily avoided. In the nonaqueous electrolyte according to one embodiment of the present invention, the unsaturated cyclic carbonate or fluorinated cyclic carbonate is preferably at least one selected from the group consisting of vinylene carbonate, vinyl ethylene carbonate, ethynyl ethylene carbonate, and fluoroethylene carbonate.

[0139] As the fluorinated cyclic carbonate, a cyclic carbonate having an unsaturated bond and a fluorine atom (hereinafter, sometimes abbreviated as "fluorinated unsaturated cyclic carbonate") can be used. The fluorinated unsaturated cyclic carbonate is not particularly limited. Among them, those having one or two fluorine atoms are preferable. The method for producing the fluorinated unsaturated cyclic carbonate is not particularly limited, and it is possible to produce it by arbitrarily selecting a known method. Examples of the fluorinated unsaturated cyclic carbonate include vinylene carbonate derivatives and ethylene carbonate derivatives substituted with a substituent having an aromatic ring or a carbon-carbon unsaturated bond. Examples of the vinylene carbonate derivatives include 4-fluorovinylene carbonate, 4-fluoro-5-methylvinylene carbonate, 4-fluoro-5-phenylvinylene carbonate, and 4,5-difluoroethylene carbonate. Examples of ethylene carbonate derivatives substituted with a substituent having an aromatic ring or a carbon-carbon unsaturated bond include 4-fluoro-4-vinylethylene carbonate, 4-fluoro-5-vinylethylene carbonate, 4,4-difluoro-4-vinylethylene carbonate, 4,5-difluoro-4-vinylethylene carbonate, 4-fluoro-4,5-divinylethylene carbonate, 4,5-difluoro-4,5-divinylethylene carbonate, 4-fluoro-4-phenylethylene carbonate, 4-fluoro-5-phenylethylene carbonate, 4,4-difluoro-5-phenylethylene carbonate, and 4,5-difluoro-4-phenylethylene carbonate. The molecular weight of the fluorinated unsaturated cyclic carbonate is not particularly limited and may be any value as long as it does not significantly impair the effects of the present invention, but is usually at least 50, preferably at least 80, and usually at most 250, preferably at most 150. Within this range, the solubility of the fluorinated cyclic carbonate in the nonaqueous electrolyte solution is easily ensured, and the effects of the present invention are easily exhibited. The fluorinated unsaturated cyclic carbonate may be used alone or in any combination and ratio of two or more. The amount of the fluorinated unsaturated cyclic carbonate is not particularly limited and may be any amount as long as it does not significantly impair the effects of the present invention, but is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and is usually 5% by mass or less, preferably 4% by mass or less, more preferably 3% by mass or less, based on the total amount of the non-aqueous electrolyte. Within this range, the effect of reducing the initial resistance of the non-aqueous electrolyte secondary battery is enhanced, and further, the effect of improving the cycle characteristics is easily exhibited.

[0140] The auxiliary other than the fluorinated salt, the fluorosilane compound, the unsaturated cyclic carbonate, the fluorinated cyclic carbonate and the oxalate salt (content of the other auxiliary) is not particularly limited and is optional as long as it does not significantly impair the effects of the present invention, but is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and is usually 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, based on the total amount of the non-aqueous electrolyte. Within this range, the effect of the other auxiliary is easily exerted, and the high-temperature storage stability tends to be improved. When two or more kinds of other auxiliary are used in combination, the total amount of the other auxiliary may be set to satisfy the above range.

[0141] <2.Nonaqueous electrolyte battery> The nonaqueous electrolyte battery according to one embodiment of the present invention A is a nonaqueous electrolyte battery including a positive electrode, a negative electrode, and a nonaqueous electrolyte, and includes the nonaqueous electrolyte according to one embodiment of the present invention described above. More specifically, the battery includes a positive electrode having a current collector and a positive electrode active material layer provided on the current collector and capable of absorbing and releasing metal ions, a negative electrode having a current collector and a negative electrode active material layer provided on the current collector and capable of absorbing and releasing metal ions, and a nonaqueous electrolyte containing at least one compound having a Si-O structure represented by the above general formula (A) or general formula (B) together with an alkali metal salt and a nonaqueous solvent, and containing a compound represented by the above general formula (α). The nonaqueous electrolyte battery according to an embodiment of the present invention B is a nonaqueous electrolyte battery including a positive electrode, a negative electrode, and a nonaqueous electrolyte, and includes the nonaqueous electrolyte according to the embodiment of the present invention B. More specifically, the battery includes a positive electrode having a current collector and a positive electrode active material layer provided on the current collector and capable of absorbing and releasing metal ions, a negative electrode having a current collector and a negative electrode active material layer provided on the current collector and capable of absorbing and releasing metal ions, and a nonaqueous electrolyte containing at least one compound having a Si-O structure represented by the above general formula (A2) or general formula (B2) together with an alkali metal salt and a nonaqueous solvent, and at least one compound having a Si-N structure represented by the above general formula (Z) or general formula (Y). The nonaqueous electrolyte battery according to one embodiment of the present invention C is a nonaqueous electrolyte battery comprising a positive electrode, a negative electrode, and a nonaqueous electrolyte, and is provided with the nonaqueous electrolyte according to one embodiment of the present invention C. More specifically, the battery comprises a positive electrode having a current collector and a positive electrode active material layer provided on the current collector and capable of absorbing and releasing metal ions, a negative electrode having a current collector and a negative electrode active material layer provided on the current collector and capable of absorbing and releasing metal ions, and a nonaqueous electrolyte solution containing at least one compound having a Si-O structure represented by the above general formula (A2) or general formula (B2) together with an alkali metal salt and a nonaqueous solvent, and containing at least one compound selected from the group consisting of the compound represented by the above general formula (α), the compound represented by the general formula (Z) or (Z), and the compound represented by the general formula (Y). The following explanation applies to inventions A to C.

[0142] <2-1. Battery configuration> The nonaqueous electrolyte battery of this embodiment is similar to a conventional nonaqueous electrolyte battery in terms of configuration other than the nonaqueous electrolyte. Usually, a positive electrode and a negative electrode are laminated via a porous membrane (separator) impregnated with the nonaqueous electrolyte, and these are housed in a case (exterior body). The shape of the nonaqueous electrolyte battery of this embodiment is not particularly limited, and may be any of cylindrical, rectangular, laminated, coin, large, and the like.

[0143] <2-2. Non-aqueous electrolyte> As the non-aqueous electrolyte solution, the non-aqueous electrolyte solution according to the embodiment of the present invention is used. Note that, within the scope of the present invention, it is also possible to mix other non-aqueous electrolyte solutions with the non-aqueous electrolyte solution.

[0144] <2-3. Positive electrode> In one embodiment of the present invention, the positive electrode has a current collector and a positive electrode active material layer provided on the current collector. Other configurations may be those conventionally known. The positive electrode used in the nonaqueous electrolyte battery of this embodiment will be described in detail below.

[0145] <2-3-1. Positive electrode active material> The positive electrode active material used in the positive electrode will be described below. (1) Composition The positive electrode active material is not particularly limited as long as it is a lithium cobalt oxide or a transition metal oxide containing at least Ni and Co, with 50 mol % or more of the transition metals being Ni and Co, and capable of electrochemically absorbing and releasing metal ions, but for example, a material capable of electrochemically absorbing and releasing lithium ions is preferred, and a transition metal oxide containing lithium, at least Ni and Co, with 60 mol % or more of the transition metals being Ni and Co is preferred. This is because Ni and Co have oxidation-reduction potentials suitable for use as positive electrode materials for secondary batteries and are suitable for high capacity applications.

[0146] Among the transition metal oxides, a transition metal oxide represented by the following composition formula (1) is preferable. Li a1 Ni b1 Co c1 M d1 O2···(1) (In formula (2), the numerical values ​​are 0.9≦a1≦1.1, 0.3≦b1≦0.95, 0.025≦c1≦0.5, and 0.025≦d1≦0.5, and 0.5≦b1+c1 and b1+c1+d1=1 are satisfied. M represents at least one element selected from the group consisting of Mn, Al, Mg, Zr, Fe, Ti, and Er.) When the transition metal oxide used as the positive electrode active material has a specified composition ratio of Ni and Co and a specified composition ratio of other metal species, the transition metal is less likely to dissolve from the positive electrode, and even if it does dissolve, Ni and Co have little adverse effect on the nonaqueous secondary battery. The transition metal oxide represented by the composition formula (1) is, for example, LiNi 0.85 Co 0.10 Al 0.05 O2, LiNi 0.80 Co 0.15 Al 0.05 O2, LiNi 0.33 Co 0.33 Mn 0.33 O2, Li 1.05 Ni 0.33 Mn 0.33 Co 0.33 O2, LiNi 0.5 Co 0.2 Mn 0.3 O2, Li 1.05 Ni 0.50 Mn 0.29 Co 0.21 O2, LiNi 0.6 Co 0.2 Mn 0.2 O2, LiNi 0.8 Co 0.1 Mn 0.1 O2 is one example.

[0147] Among them, the transition metal oxide represented by the following composition formula (2) is more preferable. Li a2 Ni b2 Co c2 M d2 O2···(2) (In formula (2), the numerical values of 0.9 ≦ a2 ≦ 1.1, 0.3 ≦ b2 ≦ 0.9, 0.025 ≦ c2 ≦ 0.5, and 0.025 ≦ d2 ≦ 0.5 are shown, and c2 ≦ b2, 0.6 ≦ b2 + c2, and b2 + c2 + d2 = 1 are satisfied. M represents at least one element selected from the group consisting of Mn, Al, Mg, Zr, Fe, Ti, and Er.) The transition metal oxide represented by the composition formula (2) has Ni and Co as main components, and when the composition ratio of Ni to Co is the same or the composition ratio of Ni to Co is large, it is stable and can extract a high capacity when used as a non-aqueous secondary battery cathode.

[0148] Among them, it is more preferable that the transition metal oxide is represented by the following composition formula (3). Li a3 Ni b3 Co c3 M d3 O2···(3) (In formula (3), the numerical values of 0.9 ≦ a3 ≦ 1.1, 0.5 ≦ b3 ≦ 0.9, 0.025 ≦ c3 ≦ 0.5, and 0.025 ≦ d3 ≦ 0.5 are shown, and c3 < b3, 0.6 ≦ b3 + c3, and b3 + c3 + d3 = 1 are satisfied. M represents at least one element selected from the group consisting of Mn, Al, Mg, Zr, Fe, Ti, and Er.) By setting the composition ratios of Ni and Co and the composition ratios of other metal species of the transition metal oxide used as the cathode active material within the above ranges, the transition metal is less likely to elute from the cathode, and even if it elutes, Ni and Co have the advantage of having a small adverse effect in the non-aqueous secondary battery.

[0149] <2-4. Anode> In one embodiment of the present invention, the anode has a current collector and an anode active material layer provided on the current collector. Other configurations can employ those known in the art. The anode active material used for the anode will be described below.

[0150] <2-4-1. Negative electrode active material> The negative electrode active material is not particularly limited as long as it can electrochemically absorb and release metal ions. Specific examples include carbonaceous materials; metal compound materials such as particles containing a metal capable of being alloyed with Li, lithium-containing metal composite oxide materials, and mixtures thereof. These may be used alone or in any combination of two or more. In terms of good cycle characteristics and safety, as well as excellent continuous charging characteristics, it is preferable to use carbonaceous materials, metal particles capable of being alloyed with Li, or a mixture of metal particles capable of being alloyed with Li and graphite particles. As the negative electrode active material, as described above, there may be mentioned carbonaceous materials; metal compound-based materials such as particles containing a metal capable of being alloyed with Li; and the like.

[0151] Examples of the carbonaceous material include natural graphite, artificial graphite, amorphous carbon, carbon-coated graphite, graphite-coated graphite, resin-coated graphite, etc. Of these, natural graphite is preferred.

[0152] Examples of natural graphite include scaly graphite, scaly graphite, soil graphite, and / or graphite particles obtained by subjecting these graphites to treatments such as spheroidization and densification. Among these, from the viewpoints of particle packing and charge / discharge rate characteristics, spherical or ellipsoidal graphite that has been subjected to a spheroidization treatment is particularly preferred.

[0153] The metal compound-based material used as the negative electrode active material is not particularly limited as long as it can occlude and release lithium ions, and can be any of lithium metal, simple metals and alloys that form lithium alloys, or compounds such as their oxides, carbides, nitrides, silicides, sulfides or phosphides. The simple metals and alloys that form lithium alloys are preferably materials containing group 13 and group 14 metal and metalloid elements (i.e., excluding carbon), more preferably simple metals of aluminum, silicon and tin, and alloys or compounds containing these atoms, and still more preferably those having silicon or tin as a constituent element, such as simple metals of silicon and tin, and alloys or compounds containing these atoms. Most preferably, it is silicon, and amorphous Si or nano-sized Si crystals are preferable in that the entry and exit of alkali ions such as lithium ions are easy and a high capacity can be obtained. These may be used alone or in any combination and ratio of two or more.

[0154] <Particles containing a metal alloyable with Li> When using a simple metal and alloy that form an alloy with lithium, or a compound such as their oxides, carbides, nitrides, silicides, sulfides or phosphides as the negative electrode active material, the metal alloyable with Li is in particle form.

[0155] As the particles containing a metal alloyable with Li, any conventionally known ones can be used, but from the viewpoints of the capacity and cycle life of the non-aqueous electrolyte battery, for example, particles of a metal or its compound selected from the group consisting of Fe, Co, Sb, Bi, Pb, Ni, Ag, Si, Sn, Al, Zr, Cr, P, S, V, Mn, As, Nb, Mo, Cu, Zn, Ge, In, Ti and W are preferable. Also, when the particles containing a metal alloyable with Li contain two or more metals, the particles may be alloy particles composed of an alloy of these metals. Among these, particles of a metal or its metal compound selected from the group consisting of Si, Sn, As, Sb, Al, Zn and W are preferable.

[0156] In addition, examples of compounds of metals that can be alloyed with Li include metal oxides, metal nitrides, metal carbides, etc. The compound may contain two or more metals that can be alloyed with Li.

[0157] Among them, metallic Si (hereinafter sometimes referred to as Si) or Si metal compounds are preferable in terms of increasing the capacity of the battery. In this specification, Si or Si metal compounds are collectively referred to as Si compounds. Specific examples of Si compounds include SiO x , SiN x , SiC x , SiZ x O y (Z = C, N), etc. As Si compounds, Si metal oxides (SiO x ) are preferable in that they have a larger theoretical capacity compared to graphite, or amorphous Si or nano-sized Si crystals are preferable in that alkali ions such as lithium ions can easily enter and exit, and a high capacity can be obtained. This general formula SiO x is obtained using silicon dioxide (SiO2) and Si as raw materials, and the value of x is usually 0 < x < 2.

[0158] <Negative electrode active material containing particles containing a metal alloyable with Li and graphite particles> The negative electrode active material may contain particles containing a metal alloyable with Li and graphite particles. The negative electrode active material may be a mixture in which particles containing a metal alloyable with Li and graphite particles are mixed in a state of independent particles, or a composite in which particles containing a metal alloyable with Li are present on the surface and / or inside of the graphite particles.

[0159] <Content ratio of particles containing a metal alloyable with Li> The content ratio of the particles containing a metal capable of being alloyed with Li to the total of the particles containing a metal capable of being alloyed with Li and the graphite particles is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and even more preferably 2.0% by mass or more. Also, it is usually 99% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 25% by mass or less, even more preferably 20% by mass or less, particularly preferably 15% by mass or less, and most preferably 10% by mass or less. This range is preferable in that it is possible to control side reactions on the Si surface and to obtain sufficient capacity in a nonaqueous electrolyte battery.

[0160] <2-5. 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 one embodiment of the present invention is usually impregnated into the separator. The separator may be a conventional one. EXAMPLES

[0161] The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to these examples as long as the gist of the present invention is not exceeded.

[0162] [Example A1] The compounds used in the present examples and comparative examples are shown below.

[0163] [ka] Compound A11

[0164] [ka] Compound A12

[0165] [ka] Compound A13

[0166]

change

[0167]

change

[0168]

change

[0169]

change

[0170]

change

[0171]

change

[0172]

change

[0173]

change

[0174]

change

[0175] [ka] Compound A113

[0176] [ka] Compound A114

[0177] [ka] Compound A115

[0178] <Examples A1-1 to A1-18 and Comparative Examples A1-1 to A1-19> [Preparation of positive electrode] The positive electrode active material was lithium nickel cobalt manganese composite oxide (Li 1.0 Ni 0.5 Co 0.2 Mn 0.3 90 parts by mass of O2), 7 parts by mass of acetylene black as a conductive material, and 3 parts by mass of polyvinylidene fluoride (PVdF) as a binder were mixed in N-methylpyrrolidone solvent with a disperser to form a slurry. This slurry was evenly applied to both sides of a 15 μm thick aluminum foil, dried, and pressed to form a positive electrode.

[0179] [Preparation of negative electrode] 98 parts by mass of natural graphite was mixed with 1 part by mass of an aqueous dispersion of sodium carboxymethylcellulose (concentration of sodium carboxymethylcellulose: 1% by mass) and 1 part by mass of an aqueous dispersion of styrene-butadiene rubber (concentration of styrene-butadiene rubber: 50% by mass) as a thickener and binder, and the mixture was mixed in a disperser to form a slurry. The obtained slurry was applied to one side of a copper foil having a thickness of 10 μm, dried, and pressed to form a negative electrode.

[0180] [Preparation of non-aqueous electrolyte] In a dry argon atmosphere, 1.2 mol / L (14.8 mass%, as the concentration in the non-aqueous electrolyte) of LiPF6, which had been thoroughly dried as an electrolyte, was dissolved in a mixture of ethylene carbonate (EC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC) (volume ratio EC:DEC:EMC=3:3:4), and further, 2.0 mass% (as the concentration in the non-aqueous electrolyte) of vinylene carbonate (VC) and fluoroethylene carbonate (FEC) were added (hereinafter, this is referred to as reference electrolyte A1-1). Compounds A11 to A115 were added to the reference electrolyte A1-1 in the amounts shown in Table 1 below to prepare non-aqueous electrolytes. In addition, the "content (mass%)" in the table is the content when the total amount of each non-aqueous electrolyte is 100 mass%.

[0181] [Manufacturing non-aqueous electrolyte batteries] The above positive electrode, negative electrode, and polyethylene separator were laminated in the order of negative electrode, separator, and positive electrode to prepare a battery element. This battery element was inserted into a bag made of a laminate film of aluminum (thickness 40 μm) coated on both sides with a resin layer while the positive and negative terminals were protruding, and the above prepared nonaqueous electrolyte was then injected into the bag and vacuum sealed to prepare a laminate type nonaqueous electrolyte battery.

[0182] <Evaluation of non-aqueous electrolyte batteries> [OCV measurement after injection] The OCV of the non-aqueous electrolyte battery prepared by the above method was measured in a thermostatic chamber at 25°C. [Initial conditioning] After constant current charging at 0.05C for 6 hours in a thermostatic chamber at 25°C, the battery was discharged at 0.2C to 3.0V. CC-CV charging was performed at 0.2C to 4.1V. Then, aging was performed at 45°C for 72 hours. After that, the battery was discharged at 0.2C to 3.0V to stabilize the laminated battery. Furthermore, CC-CV charging was performed at 0.2C to 4.4V, and then discharged at 0.2C to 3.0V to perform initial conditioning. [Initial conditioning gas generation volume measurement] After the initial conditioning, the battery was immersed in an ethanol bath and the volume was measured. The amount of generated gas was calculated from the change in volume before and after the initial conditioning, and this was defined as the "initial gas amount." Table 1 below shows ΔOCV, which is the difference from the OCV of Comparative Example A1-1, and the initial gas amount when the initial gas amount of Comparative Example A1-1 is set to 100. In the table, "initial gas amount" is shown as "initial gas."

[0183] [Table 1]

[0184] As is clear from Table 1, the batteries produced in Examples A1-1 to A1-18 have larger ΔOCV and, as a result, smaller initial gas amounts than the batteries produced in Comparative Examples A1-1 to A1-18. From the comparison of Comparative Example A1-1 with Comparative Examples A1-2, A1-14, A1-15, A1-17 to A1-19, when a non-aqueous electrolyte solution containing only a compound having an Si-O structure represented by formula (A) or (B) without containing a compound having an Si-O structure represented by formula (α) is used, ΔOCV is almost the same as Comparative Example A1-1, and the initial gas amount tends to be larger than that of Comparative Example A1-1. Also, from the comparison of Comparative Example A1-1 with Comparative Examples A1-3 to A1-9 and A1-16, when a non-aqueous electrolyte solution containing only a compound having an Si-O structure represented by formula (α) without containing a compound having an Si-O structure represented by formula (A) or (B) is used, ΔOCV is almost the same as Comparative Example A1-1, and the initial gas amount tends to be larger than that of Comparative Example A1-1. From the results of Comparative Examples A1-1, A1-2, and A1-4, it is predicted that the initial gas amount would increase when the nonaqueous electrolyte of Example A1-1 was used. In contrast, the results of Example A1-1 showed that ΔOCV was large and the initial gas amount was significantly reduced to 62% compared to Comparative Example A1-1. From the results of Comparative Examples A1-1, A1-2, and A1-5, it is predicted that the initial gas amount would increase when the nonaqueous electrolyte of Example A1-2 was used. In contrast, the results of Example A1-2 showed that ΔOCV was large and the initial gas amount was significantly reduced to 64% compared to Comparative Example A1-1. From the results of Comparative Examples A1-1, A1-2, and A1-6, it is predicted that the initial gas amount would increase when the nonaqueous electrolyte of Example A1-3 was used. In contrast, the results of Example A1-3 showed that ΔOCV was large and the initial gas amount was significantly reduced to 63% compared to Comparative Example A1-1. From the results of Comparative Examples A1-1, A1-2, and A1-7, it is predicted that the initial gas amount would increase when the nonaqueous electrolyte of Example A1-4 was used. In contrast, the results of Example A1-4 showed that ΔOCV was large and the initial gas amount was significantly reduced to 57% compared to Comparative Example A1-1. From the results of Comparative Examples A1-1, A1-2, and A1-3, it is predicted that the initial gas amount would increase significantly when the nonaqueous electrolyte of Example A1-5 was used. In contrast, the results of Example A1-5 showed that ΔOCV was large and the initial gas amount was significantly reduced to 42% compared to Comparative Example A1-1. From the results of Comparative Examples A1-1, A1-2, and A1-14, it is predicted that the initial gas amount would increase when the nonaqueous electrolyte of Example A1-8 was used. In contrast, the results of Example A1-8 showed that ΔOCV was large and the initial gas amount was significantly reduced to 44% compared to Comparative Example A1-1. From the results of Comparative Examples A1-1, A1-2, and A1-15, it is predicted that the initial gas amount would increase when the nonaqueous electrolyte of Example A1-9 was used. In contrast, the results of Example A1-9 showed that ΔOCV was large and the initial gas amount was significantly reduced to 56% compared to Comparative Example A1-1. From the results of Comparative Examples A1-1, A1-6, and A1-17, it is predicted that the initial gas amount would increase when the nonaqueous electrolyte of Example A1-10 was used. In contrast, the results of Example A1-10 showed that ΔOCV was large and the initial gas amount was suppressed to 80% of that of Comparative Example A1-1. From the results of Comparative Examples A1-1, A1-3, and A1-17, it is predicted that the initial gas amount would increase when the nonaqueous electrolyte of Example A1-11 was used. In contrast, the results of Example A1-11 showed that ΔOCV was large and the initial gas amount was significantly reduced to 45% compared to Comparative Example A1-1. From the results of Comparative Examples A1-1, A1-6, and A1-18, it is predicted that the initial gas amount would increase when the nonaqueous electrolyte of Example A1-12 was used. In contrast, the results of Example A1-12 showed that ΔOCV was large and the initial gas amount was significantly reduced to 45% compared to Comparative Example A1-1. From the results of Comparative Examples A1-1, A1-3, and A1-18, it is predicted that the initial gas amount would increase when the nonaqueous electrolyte of Example A1-13 was used. In contrast, the results of Example A1-13 showed a large ΔOCV and a suppression of the initial gas amount to 82% of that of Comparative Example A1-1. From the results of Comparative Examples A1-1, A1-2, A1-4, A1-6, and A1-8, it is predicted that the initial gas amount would increase when the nonaqueous electrolyte of Example A1-14 was used. In contrast, the results of Example A1-14 showed a large ΔOCV and a suppression of the initial gas amount to 71% of that of Comparative Example A1-1. From the results of Comparative Examples A1-1, A1-2, and A1-8, it is predicted that the initial gas amount would increase when the nonaqueous electrolyte of Example A1-15 was used. In contrast, the results of Example A1-15 showed a large ΔOCV and a suppression of the initial gas amount to 86% of that of Comparative Example A1-1. From the results of Comparative Examples A1-1, A1-2, and A1-16, it is predicted that the initial gas amount would increase when the nonaqueous electrolyte of Example A1-16 was used. In contrast, the results of Example A1-16 showed a large ΔOCV and a suppression of the initial gas amount to 76% of that of Comparative Example A1-1. From the results of Examples A1-1, A1-14, and A1-15, when the compound having a Si-O structure represented by formula (A) and the compound represented by formula (α) were used in combination, the initial gas amount was suppressed as the content of the compound represented by formula (α) was reduced. In addition, from the results of Examples A1-5, A1-16, and A1-17, when the compound having a Si-O structure represented by formula (A) and the compound represented by formula (α) were used in combination, the initial gas amount was suppressed as the content of the compound represented by formula (α) was reduced. From the results of Comparative Examples A1-1, A1-2, and A1-16, it is predicted that the initial gas amount would increase when the nonaqueous electrolyte of Example A1-18 was used. In contrast, the results of Example A1-18 showed that ΔOCV was large and the initial gas amount was significantly reduced to 59% compared to Comparative Example A1-1. Moreover, in Example A1-6, the initial gas amount was significantly reduced to 25% compared to Comparative Example A1-1. In addition, in Comparative Examples A1-10 to A1-12, which used a compound represented by formula (α) in combination with a compound having a Si-O structure but not corresponding to the compound represented by formula (A) or (B), the ΔOCV was almost the same as that of Comparative Example A1-1, and the initial gas amount was increased by 127% to 176% compared to Comparative Example A1-1. In addition, in Comparative Example A1-13, which used a compound having a Si-O structure represented by formula (A) in combination with a compound having a Si-N structure but not corresponding to the compound represented by formula (α), the ΔOCV was almost the same as that of Comparative Example A1-1, and the initial gas amount was increased to 169% compared to Comparative Example A1-1. It is presumed that the battery of the embodiment has a large amount of adsorption of the compound represented by general formula (α) and the compound having a Si-O structure represented by general formula (A) or (B) to the positive electrode active material and / or the negative electrode active material after injection, so that the compound localized on the electrode during the initial charge is electrochemically decomposed to form a composite insulating coating on the surface of the positive electrode active material and / or the negative electrode active material. ΔTherefore, by combining the compound represented by general formula (α) with the compound having a Si-O structure represented by general formula (A) or (B), the adsorption of the compound to the electrode can be controlled and the amount of initial gas generation can be suitably suppressed.

[0185] [Example A2] The compounds used in the present examples and comparative examples are shown below.

[0186] [ka] Compound A21

[0187]

change

[0188]

change

[0189]

change

[0190]

change

[0191]

change

[0192]

change

[0193]

change

[0194]

change

[0195]

change

[0196] [ka] Compound A211

[0197] [ka] Compound A212

[0198] [ka] Compound A213

[0199] <Examples A2-1 to A2-20, Comparative Examples A2-1 to A2-16> [Preparation of positive electrode] The positive electrode active material was lithium nickel cobalt manganese composite oxide (Li 1.0 Ni 0.5 Co 0.2 Mn 0.3 90 parts by mass of O2), 7 parts by mass of acetylene black as a conductive material, and 3 parts by mass of polyvinylidene fluoride (PVdF) as a binder were mixed in N-methylpyrrolidone solvent with a disperser to form a slurry. This was evenly applied to both sides of a 15 μm thick aluminum foil, dried, and pressed to form a positive electrode.

[0200] [Preparation of negative electrode] 98 parts by mass of natural graphite was mixed with 1 part by mass of an aqueous dispersion of sodium carboxymethylcellulose (concentration of sodium carboxymethylcellulose: 1% by mass) as a thickener and 1 part by mass of an aqueous dispersion of styrene-butadiene rubber (concentration of styrene-butadiene rubber: 50% by mass) as a binder, and 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 pressed to form a negative electrode.

[0201] [Preparation of non-aqueous electrolyte] In a dry argon atmosphere, 1.2 mol / L (14.8 mass%, as the concentration in the non-aqueous electrolyte) of LiPF6, which had been thoroughly dried as an electrolyte, was dissolved in a mixture of ethylene carbonate (EC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC) (volume ratio EC:DEC:EMC=3:3:4), and further, 2.0 mass% (as the concentration in the non-aqueous electrolyte) of vinylene carbonate (VC) and fluoroethylene carbonate (FEC) were added (hereinafter, this is referred to as reference electrolyte A2-1). Compounds A21 to A213 were added to the reference electrolyte 1 so as to have the contents shown in Table 1 below, to prepare the non-aqueous electrolytes of Examples A2-1 to A2-20 and Comparative Examples A2-2 to A2-16. In addition, the "content (mass%)" in the table is the content when the total amount of each non-aqueous electrolyte is 100 mass%. In addition, in Comparative Example A2-1, the reference electrolyte A2-1 was used.

[0202] [Manufacturing non-aqueous electrolyte batteries] The above positive electrode, negative electrode, and polyethylene separator were laminated in the order of negative electrode, separator, and positive electrode to prepare a battery element. This battery element was inserted into a bag made of a laminate film of aluminum (thickness 40 μm) coated on both sides with a resin layer so that the positive and negative terminals were protruding, and the above prepared nonaqueous electrolyte was then injected into the bag and vacuum sealed to prepare a laminate type nonaqueous electrolyte battery.

[0203] <Evaluation of non-aqueous electrolyte batteries> [OCV measurement after injection] The OCV of the non-aqueous electrolyte battery prepared by the above method was measured in a thermostatic chamber at 25°C. [Initial conditioning] After constant current charging at 0.05C for 6 hours in a thermostatic chamber at 25°C, the battery was discharged at 0.2C to 3.0V. CC-CV charging was performed at 0.2C to 4.1V. Then, aging was performed at 45°C for 72 hours. After that, the battery was discharged at 0.2C to 3.0V to stabilize the laminated battery. Furthermore, CC-CV charging was performed at 0.2C to 4.4V, and then discharged at 0.2C to 3.0V to perform initial conditioning. [Initial conditioning gas generation volume measurement] After the initial conditioning, the battery was immersed in an ethanol bath and the volume was measured. The amount of generated gas was calculated from the change in volume before and after the initial conditioning, and this was defined as the "initial gas amount." Table 2 below shows ΔOCV, which is the difference from the OCV of Comparative Example A2-1, and the initial gas amount when the initial gas amount of Comparative Example A2-1 is set to 100. In the table, "initial gas amount" is shown as "initial gas."

[0204] [Table 2]

[0205] From the comparison of Comparative Example A2-1 with Comparative Examples A2-2, 12, 15 and 16, it can be seen that when a non-aqueous electrolyte solution containing only a compound having an Si-O structure represented by formula (A) or (B) without containing a compound represented by formula (α) is used, ΔOCV is almost the same as that of Comparative Example A2-1, and the initial gas amount tends to be larger than that of Comparative Example A2-1. Also, from the comparison of Comparative Example A2-1 with Comparative Examples A2-3 to 8, 11, 13 and 14, it can be seen that when a non-aqueous electrolyte solution containing only a compound represented by formula (α) without containing a compound having an Si-O structure represented by formula (A) or (B) is used, ΔOCV is almost the same as that of Comparative Example A2-1, and the initial gas amount tends to be larger than that of Comparative Example A2-1. From these, when using a nonaqueous electrolyte solution containing both a compound having a Si-O structure represented by formula (A) or (B) and a compound represented by formula (α), the initial gas amount of the nonaqueous electrolyte battery is expected to increase compared to when these compounds are not included or when either one is included. However, as is clear from Table 2, the nonaqueous electrolyte batteries manufactured in Examples A2-1 to A2-20 have a larger ΔOCV than the batteries manufactured in Comparative Examples A2-1 to A2-10, and as a result, the initial gas amount is smaller. It can be seen that the use of a nonaqueous electrolyte solution containing both a compound having a Si-O structure represented by formula (A) or (B) and a compound represented by formula (α) suppresses gas generation during initial conditioning of the nonaqueous electrolyte battery. In particular, the results of Comparative Examples A2-1, A2-3, and A2-16 predict that the amount of initial gas would increase when the nonaqueous electrolyte of Example A2-17 was used. In contrast, the results of Example A2-17 showed that ΔOCV was large and the amount of initial gas was significantly reduced to 59% compared to Comparative Example A2-1. Furthermore, a comparison of Examples A2-3 and A2-4 with Comparative Example A2-10 reveals that even in a nonaqueous electrolyte solution that contains a compound having a Si-O structure represented by formula (A) or (B) and an amide compound having a structure similar to that of the compound represented by formula (α), if the amide compound is a compound that does not have a Si-NH structure, the ΔOCV does not increase and the initial gas amount is large. In addition, in Comparative Example A2-9, which used a nonaqueous electrolyte solution containing only a compound having an NH structure represented by formula (α2) and not a compound having an Si-O structure represented by formula (A) or (B), the ΔOCV was the same as in Comparative Example A2-1, but the initial gas amount increased significantly. In addition, in Comparative Example A2-12, which used a nonaqueous electrolyte solution containing only a compound having a Si-O structure represented by formula (A) or (B) without containing a compound represented by formula (α), the ΔOCV was almost the same as that of Comparative Example A2-1, and the initial gas amount was significantly increased.

[0206] [Example A3] The compounds used in the present examples and comparative examples are shown below.

[0207] [ka] Compound A31

[0208] [ka] Compound A32

[0209] [ka] Compound A33

[0210] [ka] Compound A34

[0211] [ka] Compound A35

[0212] [ka] Compound A36

[0213] [ka] Compound A37

[0214] [ka] Compound A38

[0215] [ka] Compound A39

[0216] [ka] Compound A310

[0217] [ka] Compound A311

[0218] <Examples A3-1 to A3-12 and Comparative Examples A3-1 to A3-5> [Preparation of positive electrode] The positive electrode active material was lithium nickel cobalt manganese composite oxide (Li 1.0 Ni 0.5 Co 0.2 Mn 0.3 90 parts by mass of O2), 7 parts by mass of acetylene black as a conductive material, and 3 parts by mass of polyvinylidene fluoride (PVdF) as a binder were mixed in N-methylpyrrolidone solvent with a disperser to form a slurry. This was evenly applied to both sides of a 15 μm thick aluminum foil, dried, and pressed to form a positive electrode.

[0219] [Preparation of negative electrode] 98 parts by mass of natural graphite was mixed with 1 part by mass of an aqueous dispersion of sodium carboxymethylcellulose (concentration of sodium carboxymethylcellulose: 1% by mass) as a thickener and 1 part by mass of an aqueous dispersion of styrene-butadiene rubber (concentration of styrene-butadiene rubber: 50% by mass) as a binder, and 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 pressed to form a negative electrode.

[0220] [Preparation of non-aqueous electrolyte] In a dry argon atmosphere, 1.2 mol / L (14.8 mass%, as the concentration in the non-aqueous electrolyte) of LiPF6, which had been thoroughly dried as an electrolyte, was dissolved in a mixture of ethylene carbonate (EC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC) (volume ratio EC:DEC:EMC=3:3:4), and further, 2.0 mass% (as the concentration in the non-aqueous electrolyte) of vinylene carbonate (VC) and fluoroethylene carbonate (FEC) were added (hereinafter, this is referred to as reference electrolyte A3-1). Compounds A31 to A311 were added to the reference electrolyte 1 so as to have the contents shown in Table 3 below, to prepare the non-aqueous electrolytes of Examples A3-1 to A3-12 and Comparative Examples A3-1 to A3-5. In addition, the "content (mass%)" in the table is the content when the total amount of each non-aqueous electrolyte is 100 mass%. In addition, in Comparative Example A3-1, the reference electrolyte A3-1 was used.

[0221] [Manufacturing non-aqueous electrolyte batteries] The above positive electrode, negative electrode, and polyethylene separator were laminated in the order of negative electrode, separator, and positive electrode to prepare a battery element. This battery element was inserted into a bag made of a laminate film of aluminum (thickness 40 μm) coated on both sides with a resin layer so that the positive and negative terminals were protruding, and the above prepared nonaqueous electrolyte was then injected into the bag and vacuum sealed to prepare a laminate type nonaqueous electrolyte battery.

[0222] <Evaluation of non-aqueous electrolyte batteries> [OCV measurement after injection] The OCV of the non-aqueous electrolyte battery prepared by the above method was measured in a thermostatic chamber at 25°C. [Initial conditioning] After constant current charging at 0.05C for 6 hours in a thermostatic chamber at 25°C, the battery was discharged at 0.2C to 3.0V. CC-CV charging was performed at 0.2C to 4.1V. Then, aging was performed at 45°C for 72 hours. After that, the battery was discharged at 0.2C to 3.0V to stabilize the laminated battery. Furthermore, CC-CV charging was performed at 0.2C to 4.4V, and then discharged at 0.2C to 3.0V to perform initial conditioning. [Initial conditioning] In a thermostatic bath at 25°C, the nonaqueous electrolyte battery prepared by the above method was charged at a constant current of 0.1C (1C refers to the current value required for charging or discharging for 1 hour. The same applies below.) to 3.2V, and then constant current-constant voltage charging (hereinafter referred to as CC-CV charging) was performed at 0.2C to 4.2V. The battery was then held at 45°C for 120 hours for aging. The battery was then discharged at 0.2C to 2.5V to stabilize the nonaqueous electrolyte battery. The battery was then CC-CV charged to 4.2V at 0.2C, and then discharged at 0.2C to 2.5V for initial conditioning. [Initial conditioning gas generation volume measurement] After the initial conditioning, the battery was immersed in an ethanol bath and the volume was measured. The amount of generated gas was calculated from the change in volume before and after the initial conditioning, and this was defined as the "initial gas amount." [Initial resistance measurement] After the initial conditioning, the batteries were CC-CV charged at 0.2 C to half the initial discharge capacity. They were discharged at 1.0 C, 2.0 C, and 3.0 C at 25°C, and the voltage was measured 5 seconds into each discharge process. The average slope of the current-voltage line at 1.0 C, 2.0 C, and 3.0 C was taken as the "initial resistance." Table 3 below shows ΔOCV, which is the difference from the OCV of Comparative Example A3-1, the initial gas amount when the initial gas amount of Comparative Example A3-1 is set to 100, and the initial resistance value when the initial resistance of Comparative Example A3-1 is set to 100. In the table, "initial gas amount" is shown as "initial gas."

[0223] [Table 3]

[0224] As is clear from Table 3, the batteries produced in Examples A3-1 to A3-12 had less initial gas and initial resistance than the batteries produced in Comparative Examples A3-1 to A3-5. In addition, it is understood that the initial resistance is also reduced by using the compound represented by the compound (α1) and the compound represented by the compound (α2) in combination as the compound represented by the compound (α). In particular, it is understood that Example A3-3 can suppress not only the initial resistance but also the initial gas compared to Example A3-1. It is also apparent that the initial resistance is further reduced by using the auxiliary compounds A37 to A312 in combination.

[0225] [Example B] The compounds used in the present examples and comparative examples are shown below.

[0226] [ka] Compound B1

[0227] [ka] Compound B2

[0228] [ka] Compound B3

[0229] [ka] Compound B4

[0230] [ka] Compound B5

[0231] [ka] Compound B6

[0232] [ka] Compound B7

[0233] [ka] Compound B8

[0234] [ka] Compound B9

[0235] [ka] Compound B10

[0236] [ka] Compound B11

[0237] <Examples B1 to B6 and Comparative Examples B1 to B11> [Preparation of positive electrode] The positive electrode active material was lithium nickel cobalt manganese composite oxide (Li 1.0 Ni 0.5 Co 0.2 Mn 0.3 90 parts by mass of O2), 7 parts by mass of acetylene black as a conductive material, and 3 parts by mass of polyvinylidene fluoride (PVdF) as a binder were mixed in N-methylpyrrolidone solvent with a disperser to form a slurry. This was evenly applied to both sides of a 15 μm thick aluminum foil, dried, and pressed to form a positive electrode.

[0238] [Preparation of negative electrode] 98 parts by mass of natural graphite was mixed with 1 part by mass of an aqueous dispersion of sodium carboxymethylcellulose (concentration of sodium carboxymethylcellulose: 1% by mass) as a thickener and 1 part by mass of an aqueous dispersion of styrene-butadiene rubber (concentration of styrene-butadiene rubber: 50% by mass) as a binder, and the mixture was mixed in a disperser to form a slurry. The obtained slurry was applied to one side of a copper foil having a thickness of 10 μm, dried, and pressed to form a negative electrode.

[0239] [Preparation of non-aqueous electrolyte] In a dry argon atmosphere, 1.2 mol / L (14.8 mass%, as the concentration in the non-aqueous electrolyte) of LiPF6, which had been thoroughly dried as an electrolyte, was dissolved in a mixture of ethylene carbonate (EC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC) (volume ratio EC:DEC:EMC=3:3:4), and further, 2.0 mass% (as the concentration in the non-aqueous electrolyte) of vinylene carbonate (VC) and fluoroethylene carbonate (FEC) were added (hereinafter, this is referred to as reference electrolyte B1). Compounds B1 to B11 were added to the reference electrolyte B1 in the amounts shown in Table 4 below to prepare non-aqueous electrolytes. In addition, the "content (mass%)" in the table is the content when the total amount of each non-aqueous electrolyte is 100 mass%.

[0240] [Manufacturing non-aqueous electrolyte batteries] The above positive electrode, negative electrode, and polyethylene separator were laminated in the order of negative electrode, separator, and positive electrode to prepare a battery element. This battery element was inserted into a bag made of a laminate film of aluminum (thickness 40 μm) coated on both sides with a resin layer while the positive and negative terminals were protruding, and the above prepared nonaqueous electrolyte was then injected into the bag and vacuum sealed to prepare a laminate type nonaqueous electrolyte battery.

[0241] <Evaluation of non-aqueous electrolyte batteries> [OCV measurement after injection] The OCV of the non-aqueous electrolyte battery prepared by the above method was measured in a thermostatic chamber at 25°C. [Initial conditioning] After constant current charging at 0.05C for 6 hours in a thermostatic chamber at 25°C, the battery was discharged at 0.2C to 3.0V. CC-CV charging was performed at 0.2C to 4.1V. Then, aging was performed at 45°C for 72 hours. After that, the battery was discharged at 0.2C to 3.0V to stabilize the laminated battery. Furthermore, CC-CV charging was performed at 0.2C to 4.4V, and then discharged at 0.2C to 3.0V to perform initial conditioning. [Measurement of gas volume generated during initial conditioning] After the initial conditioning, the battery was immersed in an ethanol bath and the volume was measured. The amount of generated gas was calculated from the change in volume before and after the initial conditioning, and this was defined as the "initial gas amount." Table 4 below shows ΔOCV, which is the difference from the OCV of Comparative Example B1, and the initial gas amount when the initial gas amount of Comparative Example B1 is set to 100. In the table, "initial gas amount" is shown as "initial gas."

[0242] [Table 4]

[0243] As is clear from Table 4, the batteries produced in Examples B1 to B6 have a larger ΔOCV and, as a result, a smaller initial gas amount than the batteries produced in Comparative Examples B1 to B11. From the comparison between Comparative Example B1 and Comparative Example B2, when a non-aqueous electrolyte solution containing only a compound having a Si-O structure represented by general formula (A2) or (B2) without a compound having a Si-N structure represented by general formula (Y) or (Z) was used, ΔOCV was slightly higher than Comparative Example B1, but the initial gas amount was increased by 3% from Comparative Example B1. Also, from the comparison between Comparative Example B1 and Comparative Examples B4, B5, and B6, when a non-aqueous electrolyte solution containing only a Si-N structure represented by general formula (Y) or (Z) without a compound having a Si-O structure represented by general formula (A2) or (B2) was used, ΔOCV was almost the same as Comparative Example B1, and the initial gas amount tended to be larger than Comparative Example B1. From the results of Comparative Examples B1, B2, and B4, it is predicted that the initial gas amount would increase when the nonaqueous electrolyte of Example B1 was used. In contrast, the results of Example B1 showed that ΔOCV was large and the initial gas amount was significantly reduced to 47% compared to Comparative Example 1. From the results of Comparative Examples B1, B2, and B5, it is predicted that the initial gas amount would increase when the nonaqueous electrolyte of Example B2 was used. In contrast, the results of Example B1 showed that ΔOCV was large and the initial gas amount was significantly reduced to 75% compared to Comparative Example B1. In addition, when a compound having a Si-N structure represented by general formula (Y) or (Z) was used in combination with a compound having a Si-O structure but not a compound having a Si-O structure represented by general formula (A2) or (B2), the ΔOCV was almost the same as that of Comparative Example B1, and in Comparative Examples B8 and B9, it increased to 146% compared to Comparative Example B1, and in Comparative Example B7, it increased to 169% compared to Comparative Example B1. In the battery of the embodiment, the amount of the compound having the Si-N structure represented by the general formula (Y) or (Z) and the compound having the Si-O structure represented by the general formula (A2) or (B2) adsorbed to the positive electrode active material and / or the negative electrode active material after the injection is large, so that the compound localized on the electrode during the initial charge is electrochemically decomposed and a composite insulating film is formed on the surface of the positive electrode and / or the negative electrode active material. In addition, from Comparative Examples B4 to B6, it is considered that when the content of the compound having the Si-N structure is large, the ΔOCV after the injection is small, so that the amount of the compound adsorbed to the electrode is small. Therefore, it is presumed that the insulating film is not suitably formed during charging, and therefore the effect of suppressing the initial gas amount was not obtained. From this, it was shown that by combining the compound having the Si-N structure represented by the general formula (Y) or (Z) and the compound having the Si-O structure represented by the general formula (A2) or (B2), the adsorption of these compounds to the electrode can be controlled and the initial gas can be suitably suppressed.

[0244] This application is based on Japanese patent applications filed on August 8, 2019 (Patent Application No. 2019-146414), August 8, 2019 (Patent Application No. 2019-146415), and November 28, 2019 (Patent Application No. 2019-215635), the contents of which are incorporated herein by reference. < / b1> < / b1> < / b1> < / b1> < / b1> < / b1> < / a1> < / a1> < / a1> < / a1>

Claims

1. The nonaqueous electrolyte solution is for use in a nonaqueous electrolyte battery having a positive electrode and a negative electrode capable of absorbing and releasing metal ions, the nonaqueous electrolyte solution comprising an alkali metal salt, a nonaqueous solvent, at least one compound having a Si-O structure represented by general formula (A) or general formula (B), and a compound represented by general formula (α). 【Chemistry 1】 (In formula (A), R １ ~R ５ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; X represents a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR ｏ R ｐ R ｑ R represents a silyl group represented by the formula: ｏ ~R ｑ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; n represents an integer of 0 to 5. When n is 2 or more, multiple R ４ may be the same or different, and multiple R ５ may be the same or different.) 【Chemistry 2】 (In formula (B), R ６ ~R ７ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; and k represents an integer of 3 to 6. ６ may be the same or different, and multiple R ７ may be the same or different.) 【Chemistry 3】 (In formula (α), R ８９ is a hydrogen atom or -SiR ８ R ９ R １０ R represents a silyl group represented by the formula: ８ ~R １０ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; R １１ represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR ｄ R ｅ R ｆ R represents a silyl group represented by the formula: ｄ ~R ｆ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; Y represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, an alkoxy group having 1 to 12 carbon atoms which may have a substituent, -NR ｇ -SiR ｈ R ｉ R ｊ or a group represented by -NR ｇ R represents a group represented by —H; ｇ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent; R ｈ ~R ｊ R each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. １１ and R ｇ may be bonded to each other to form a ring.)

2. The nonaqueous electrolyte solution according to claim 1, wherein the content of the compound having a Si-O structure represented by the general formula (A) or (B) is 0.001% by mass to 10% by mass with respect to the total amount of the nonaqueous electrolyte solution.

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

4. The nonaqueous electrolyte solution according to any one of claims 1 to 3, wherein the ratio of the content of the compound having the Si-O structure represented by the general formula (A) or the general formula (B) to the content of the compound represented by the general formula (α) in the nonaqueous electrolyte solution is 1.0 or more and 10000 or less.

5. The R １ ~R ３ 5. The nonaqueous electrolyte solution according to claim 1, wherein at least one of the groups is a hydrocarbon group having 2 to 12 carbon atoms and a carbon-carbon unsaturated bond.

6. The non-aqueous electrolyte solution according to any one of claims 1 to 5, further comprising at least one selected from the group consisting of fluorinated salts, fluorosilane compounds, unsaturated cyclic carbonates, cyclic carbonates having fluorine atoms, and oxalate salts.

7. A non-aqueous electrolyte for a non-aqueous electrolyte battery having a positive electrode and a negative electrode capable of absorbing and releasing metal ions, comprising: a non-aqueous electrolyte containing an alkali metal salt and a non-aqueous solvent; and at least one compound having a Si-O structure represented by general formula (A2) or general formula (B2) in a ratio of 0.01 to 0.01 based on the total amount of the non-aqueous electrolyte. % by mass or more, and at least one compound having a Si-N structure represented by general formula (Z) or general formula (Y). 【Chemistry 5】 (In formula (A2), R １２ ~R １６ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; X' represents a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent (excluding the case where X' is an acyl group), or -SiR ｏ２ R ｐ２ R ｑ２ R represents a silyl group represented by the formula: ｏ２ ~R ｑ２ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; n′ represents an integer of 0 to 5; R １２ ~R １４ At least one of R is a hydrocarbon group having 2 to 12 carbon atoms and a carbon-carbon unsaturated bond. １５ may be the same or different, and multiple R １６ may be the same or different.) 【Chemistry 6】 (In formula (B2), R １７ ~R １８ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent, and k′ represents an integer of 3 to 6. １７ Or R １８ At least one of R is a hydrocarbon group having 2 to 12 carbon atoms and a carbon-carbon unsaturated bond. １７ may be the same or different, and multiple R １８ may be the same or different.) 【Chemistry 7】 (In formula (Z), R １９ ~R ２１ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; R ２２ ~R ２３ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR ｘ R ｙ R ｚ R represents a silyl group represented by the formula: ｘ ~R ｚ R each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent. ２２ and R ２３ may be bonded to each other to form a ring.) 【Chemistry 8】 (In formula (Y), R ２４ represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or -SiR ａ R ｂ R ｃ R represents a silyl group represented by the formula: ａ ~R ｃ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; R ２５ ~R ２６ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy group having 1 to 12 carbon atoms which may have a substituent; and l represents an integer of 3 to 6. ２５ may be the same or different, and multiple R ２６ may be the same or different.)

8. The nonaqueous electrolyte solution according to claim 7, wherein the content of the compound having a Si-O structure represented by general formula (A2) or (B2) is 0.1 mass% or more and 10 mass% or less with respect to the total amount of the nonaqueous electrolyte solution.

9. The content of the compound having a Si-N structure represented by the general formula (Z) or the general formula (Y) is 0.01 mass ppm or more and less than 0.5 mass% with respect to the total amount of the nonaqueous electrolyte solution. The nonaqueous electrolyte solution according to claim 7 or 8.

10. The non-aqueous electrolyte solution according to any one of claims 7 to 9, wherein the ratio of the content of the compound represented by the general formula (A2) or the general formula (B2) to the content of the compound having a Si-N structure represented by the general formula (Z) or the general formula (Y) in the non-aqueous electrolyte solution is 1.0 or more and 10000 or less.

11. The nonaqueous electrolyte solution according to any one of claims 7 to 10, wherein the nonaqueous electrolyte solution contains a compound represented by the general formula (A2), and in the formula (A2), at least one of R 12 to R 14 is a vinyl group or an allyl group.

12. The nonaqueous electrolyte solution contains a compound represented by the general formula (B2), and in the formula (B2), R ２５ Or R ２６ At least one of the above is a vinyl group or an allyl group.

13. In the formula (Z), R ２２ ~R ２３ At least one of the groups is -SiR ｘ R ｙ R ｚ The nonaqueous electrolyte solution according to any one of claims 7 to 12, wherein the silyl group is represented by the following formula:

14. The non-aqueous electrolyte solution according to any one of claims 7 to 13, further comprising at least one selected from the group consisting of fluorinated salts, fluorosilane compounds, unsaturated cyclic carbonates, cyclic carbonates having fluorine atoms, and oxalate salts.

15. A non-aqueous electrolyte battery comprising a positive electrode and a negative electrode capable of absorbing and releasing metal ions, and a non-aqueous electrolyte solution, the non-aqueous electrolyte solution being the non-aqueous electrolyte solution according to any one of claims 1 to 14.

Images