JPWO2016060038A1 - Nonaqueous electrolyte and nonaqueous electrolyte secondary battery - Google Patents

Abstract

The present invention provides a non-aqueous electrolyte excellent in overcharge prevention ability and capable of maintaining a small internal resistance and high electric capacity even after charging and discharging, and a non-aqueous electrolyte secondary battery using the same, Specifically, in a non-aqueous electrolyte in which a lithium salt is dissolved in an organic solvent, the non-aqueous electrolyte includes at least one compound represented by the following general formula (1) and the non-aqueous electrolysis A non-aqueous electrolyte secondary battery using the solution is provided. Details of the general formula (1) are as described in this specification.

Description

  The present invention relates to a non-aqueous electrolyte secondary battery, and more particularly, to a non-aqueous electrolyte secondary battery having a non-aqueous electrolyte containing a specific compound.

  With the spread of portable electronic devices such as portable personal computers, handy video cameras, and information terminals in recent years, non-aqueous electrolyte secondary batteries having high voltage and high energy density have been widely used as power sources. Also, from the viewpoint of environmental problems, battery cars and hybrid cars using electric power as a part of power have been put into practical use.

  In non-aqueous electrolyte secondary batteries, various additives for non-aqueous electrolyte solutions have been proposed in order to improve the stability and electrical characteristics of non-aqueous electrolyte secondary batteries. Examples of such additives include 1,3-propane sultone (for example, see Patent Document 1), vinyl ethylene carbonate (for example, see Patent Document 2), vinylene carbonate (for example, see Patent Document 3), 1, 3-Propane sultone, butane sultone (for example, refer to Patent Document 4), vinylene carbonate (for example, refer to Patent Document 5), vinyl ethylene carbonate (for example, refer to Patent Document 6), and the like have been proposed. Carbonate is widely used because of its great effect. These additives form a stable coating called SEI (Solid Electrolyte Interface) on the surface of the anode, and this coating covers the surface of the anode, thereby suppressing reductive decomposition of the electrolyte. It is considered.

  A non-aqueous electrolyte secondary battery may be charged beyond a predetermined voltage when an excessive current is supplied due to an erroneous operation or the like, and such a phenomenon is called overcharge. Since the overcharged state may significantly reduce the safety of the nonaqueous electrolyte secondary battery, a mechanism for cutting off the charging current when a predetermined voltage is exceeded is provided. As one of mechanisms for interrupting the charging current, an overcharge inhibitor such as cyclohexylbenzene is used. The overcharge preventing agent is a mechanism that generates a gas when the secondary battery reaches the voltage in the overcharge region and blocks the current by sensing the pressure sensor of the battery.

JP 63-102173 A JP-A-4-87156 Japanese Patent Laid-Open No. 5-74486 Japanese Patent Laid-Open No. 10-50342 US Pat. No. 5,626,981 US Pat. No. 6,919,145

  Accordingly, an object of the present invention is to provide a non-aqueous electrolyte that is excellent in overcharge prevention capability and can maintain a small internal resistance and high electric capacity even after charging and discharging, and a non-aqueous electrolyte secondary battery using the same. There is.

  As a result of intensive studies, the present inventors have found that the above object can be achieved by using a nonaqueous electrolytic solution containing a compound having a specific structure, and completed the present invention.

（式中、Ａｒは、ベンゼン環又はナフタレン環を表し、
Ｚは、Ｒ^１Ｏ−Ｓ（＝Ｏ）_２−、Ｒ^１２−Ｓ（＝Ｏ）_２−、Ｒ^１Ｏ−Ｓ（＝Ｏ）−又はＲ^１２−Ｓ（＝Ｏ）−を表し、
Ｒ^１は、置換基を有する又は無置換の炭素原子数１〜２０の炭化水素基を表し、
Ｒ^２は、ハロゲン原子、ニトリル基、ニトロ基、アミノ基、カルボキシル基、水酸基、チオール基、ホルミル基、−ＳｉＲ^９Ｒ^１０Ｒ^１１、リン酸基、又は置換基を有する若しくは無置換の炭素原子数１〜２０の炭化水素基を表し、
Ｒ^１２は、ハロゲン原子又は置換基を有する若しくは無置換の炭素原子数１〜２０の炭化水素基を表し、
Ｒ^１、Ｒ^２及びＲ^１２が表す炭化水素基を置換する基は、ハロゲン原子、ニトリル基、ニトロ基、アミノ基、カルボキシル基、水酸基、チオール基、ホルミル基、−ＳｉＲ^９Ｒ^１０Ｒ^１１又はリン酸基であり、
Ｒ^１、Ｒ^２及びＲ^１２が表す炭化水素基中のアルキレンは、−Ｏ−、−ＣＯ−、−ＯＣＯ−、−ＣＯＯ−、−Ｏ−ＣＯ−Ｏ−、−ＮＲ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＮＲ−ＣＯ−又は−ＣＯ−ＮＲ−が隣り合わない条件で、１〜３回中断していてもよく、
Ｒは、炭素原子数１〜５の脂肪族炭化水素基を表し、
Ｒ^２が炭化水素基を表す場合、Ｒ^２とＡｒが結合する部位は、−Ｏ−、−ＣＯ−、−ＯＣＯ−、−ＣＯＯ−、−Ｏ−ＣＯ−Ｏ−、−ＮＲ−、−Ｓ−、−ＮＲ−ＣＯ−、−ＣＯ−ＮＲ−又は−Ｎ＝により中断していてもよく、
Ｒ^９、Ｒ^１０及びＲ^１１は、炭素原子数１〜１６の炭化水素基を表し、
ｍ及びｎは、それぞれ１以上の整数を表し、Ａｒがベンゼン環を表す場合、ｍ＋ｎは６以下であり、Ａｒがナフタレン環を表す場合、ｍ＋ｎは１０以下であり、
ｍが２以上の場合、Ｚは同一でも異なっていてもよく、ｎが２以上の場合、Ｒ^２は同一でも異なっていてもよい。
但し、ｎ個のＲ^２のうち、少なくとも１つは、下記一般式（２）又は（３）で表される基である。）

（式中、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶は各々独立に置換基を有するか又は無置換の炭素原子数１〜１８の炭化水素基を表し、
Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶が表す炭化水素基を置換する基は、ハロゲン原子、ニトリル基、ニトロ基、アミノ基、カルボキシル基、水酸基、チオール基、ホルミル基、スルホン基、−ＳｉＲ⁹Ｒ¹⁰Ｒ¹¹又はリン酸基であり、
Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶が表す炭化水素基中のアルキレン基は、−Ｏ−、−ＣＯ−、−ＯＣＯ−、−ＣＯＯ−、−Ｏ−ＣＯ−Ｏ−、−ＮＲ−、−Ｓ−、−ＳＯ−、−ＳＯ₂−、−ＮＲ−ＣＯ−又は−ＣＯ−ＮＲ−が隣り合わない条件で、１〜３回中断していてもよく、
Ｒは、炭素原子数１〜５の脂肪族炭化水素基を表し、
Ｒ⁷及びＲ⁸は、各々独立に水素原子、ハロゲン原子、ニトリル基、ニトロ基、アミノ基、カルボキシル基、水酸基、チオール基、ホルミル基、スルホン基、−ＳｉＲ⁹Ｒ¹⁰Ｒ¹¹又はリン酸基を表し、
Ｒ⁹、Ｒ¹⁰及びＲ¹¹は、各々独立に炭素原子数１〜１６の炭化水素基を表し、
但し、一般式（２）及び（３）は、基全体として炭素原子数が３〜２０の範囲内である。）That is, the present invention provides a non-aqueous electrolyte characterized by containing at least one compound represented by the following general formula (1) in a non-aqueous electrolyte in which a lithium salt is dissolved in an organic solvent. Is.

(In the formula, Ar represents a benzene ring or a naphthalene ring,
Z represents R ¹ O—S (═O) ₂ —, R ¹² —S (═O) ₂ —, R ¹ O—S (═O) — or R ¹² —S (═O) —,
R ¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms,
R ² is a halogen atom, a nitrile group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a thiol group, a formyl group, —SiR ⁹ R ¹⁰ R ¹¹ , a phosphate group, or a substituted or unsubstituted carbon atom. Represents a hydrocarbon group of 1 to 20,
R ¹² represents a halogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms,
The group that replaces the hydrocarbon group represented by R ¹ , R ² and R ¹² is a halogen atom, a nitrile group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a thiol group, a formyl group, —SiR ⁹ R ¹⁰ R ¹¹ or A phosphate group,
The alkylene in the hydrocarbon group represented by R ¹ , R ² and R ¹² is —O—, —CO—, —OCO—, —COO—, —O—CO—O—, —NR—, —S—, _{-SO -, - SO 2 -,} - NR-CO- or -CO-NR- is under conditions which are not adjacent, may also be interrupted 1-3 times,
R represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms,
When R ² represents a hydrocarbon group, the sites where R ² and Ar are bonded are —O—, —CO—, —OCO—, —COO—, —O—CO—O—, —NR—, —S. May be interrupted by-, -NR-CO-, -CO-NR- or -N =,
R ⁹ , R ¹⁰ and R ¹¹ represent a hydrocarbon group having 1 to 16 carbon atoms,
m and n each represent an integer of 1 or more, and when Ar represents a benzene ring, m + n is 6 or less, and when Ar represents a naphthalene ring, m + n is 10 or less,
When m is 2 or more, Z may be the same or different, and when n is 2 or more, R ² may be the same or different.
However, at least one of n R ² is a group represented by the following general formula (2) or (3). )

(Wherein R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a substituent or an unsubstituted hydrocarbon group having 1 to 18 carbon atoms,
The groups that replace the hydrocarbon groups represented by R ³ , R ⁴ , R ⁵ and R ⁶ are halogen atoms, nitrile groups, nitro groups, amino groups, carboxyl groups, hydroxyl groups, thiol groups, formyl groups, sulfone groups, —SiR. ⁹ R ¹⁰ R ¹¹ or a phosphate group,
The alkylene group in the hydrocarbon group represented by R ³ , R ⁴ , R ⁵ and R ⁶ is —O—, —CO—, —OCO—, —COO—, —O—CO—O—, —NR—, -S -, - SO -, - SO 2 -, - NR-CO- or -CO-NR- is under conditions which are not adjacent, may also be interrupted 1-3 times,
R represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms,
R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, a nitrile group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a thiol group, a formyl group, a sulfone group, —SiR ⁹ R ¹⁰ R ¹¹ or a phosphate group. Represents
R ⁹ , R ¹⁰ and R ¹¹ each independently represents a hydrocarbon group having 1 to 16 carbon atoms,
However, general formula (2) and (3) are in the range of 3-20 carbon atoms as the whole group. )

  The present invention also provides a non-aqueous electrolyte secondary battery comprising a non-aqueous electrolyte secondary battery having an anode from which lithium can be inserted and removed, a cathode containing a transition metal and lithium, and a non-aqueous electrolyte in which a lithium salt is dissolved in an organic solvent. The present invention provides a non-aqueous electrolyte secondary battery, wherein the solution is the non-aqueous electrolyte described above.

（式中、Ａｒ’は、ベンゼン環又はナフタレン環を表し、
Ｚ’は、Ｒ^１’Ｏ−Ｓ（＝Ｏ）_２−、Ｒ^１２’−Ｓ（＝Ｏ）_２−、Ｒ^１’Ｏ−Ｓ（＝Ｏ）−又はＲ^１２’−Ｓ（＝Ｏ）−を表し、
Ｒ^１’は、置換基を有する炭素原子数１〜２０の炭化水素基を表し、
Ｒ^２’は、ハロゲン原子、ニトリル基、ニトロ基、アミノ基、カルボキシル基、水酸基、チオール基、ホルミル基、−ＳｉＲ^９’Ｒ^１０’Ｒ^１１’、リン酸基、又は置換基を有する若しくは無置換の炭素原子数１〜２０の炭化水素基を表し、
Ｒ^１２’は、ハロゲン原子又は置換基を有する炭素原子数１〜２０の炭化水素基を表し、
Ｒ^１’、Ｒ^２’及びＲ^１２’が表す炭化水素基を置換する基は、ハロゲン原子、ニトリル基、ニトロ基、アミノ基、カルボキシル基、水酸基、チオール基、ホルミル基、−ＳｉＲ^９’Ｒ^１０’Ｒ^１１’又はリン酸基であり、
Ｒ^１’、Ｒ^２’及びＲ^１２’が表す炭化水素基中のアルキレンは、−Ｏ−、−ＣＯ−、−ＯＣＯ−、−ＣＯＯ−、−Ｏ−ＣＯ−Ｏ−、−ＮＲ’−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＮＲ’−ＣＯ−又は−ＣＯ−ＮＲ’−が隣り合わない条件で、１〜３回中断していてもよく、
Ｒ’は、炭素原子数１〜５の脂肪族炭化水素基を表し、
Ｒ^２’が炭化水素基を表す場合、Ｒ^２’とＡｒ’が結合する部位は、−Ｏ−、−ＣＯ−、−ＯＣＯ−、−ＣＯＯ−、−Ｏ−ＣＯ−Ｏ−、−ＮＲ’−、−Ｓ−、−ＮＲ’−ＣＯ−、−ＣＯ−ＮＲ’−又は−Ｎ＝により中断していてもよく、
Ｒ^９’、Ｒ^１０’及びＲ^１１’は、炭素原子数１〜１６の炭化水素基を表し、
ｍ’及びｎ’は、それぞれ１以上の整数を表し、Ａｒ’がベンゼン環を表す場合、ｍ’＋ｎ’は６以下であり、Ａｒ’がナフタレン環を表す場合、ｍ’＋ｎ’は１０以下であり、
ｍ’が２以上の場合、Ｚ’は同一でも異なっていてもよく、ｎ’が２以上の場合、Ｒ^２’は同一でも異なっていてもよい。
が２以上の場合、Ｒ^２’は同一でも異なっていてもよい。
但し、ｎ’個のＲ^２’のうち、少なくとも１つは、下記一般式（２’）又は（３’）で表される基である。）

（式中、Ｒ³’、Ｒ⁴’、Ｒ⁵’及びＲ⁶’は各々独立に置換基を有するか又は無置換の炭素原子数１〜１８の炭化水素基を表し、
Ｒ³’、Ｒ⁴’、Ｒ⁵’及びＲ⁶’が表す炭化水素基を置換する基は、ハロゲン原子、ニトリル基、ニトロ基、アミノ基、カルボキシル基、水酸基、チオール基、ホルミル基、スルホン基、−ＳｉＲ⁹’Ｒ¹⁰’Ｒ¹¹’又はリン酸基であり、
Ｒ³’、Ｒ⁴’、Ｒ⁵’及びＲ⁶’が表す炭化水素基中のアルキレン基は、−Ｏ−、−ＣＯ−、−ＯＣＯ−、−ＣＯＯ−、−Ｏ−ＣＯ−Ｏ−、−ＮＲ’−、−Ｓ−、−ＳＯ−、−ＳＯ₂−、−ＮＲ’−ＣＯ−又は−ＣＯ−ＮＲ’−が隣り合わない条件で、１〜３回中断していてもよく、
Ｒ’は、炭素原子数１〜５の脂肪族炭化水素基を表し、
Ｒ⁷’及びＲ⁸’は、各々独立に水素原子、ハロゲン原子、ニトリル基、ニトロ基、アミノ基、カルボキシル基、水酸基、チオール基、ホルミル基、スルホン基、−ＳｉＲ⁹’Ｒ¹⁰’Ｒ¹¹’又はリン酸基を表し、
Ｒ⁹’、Ｒ¹⁰’及びＲ¹¹’は、各々独立に炭素原子数１〜１６の炭化水素基を表し、
但し、一般式（２’）及び（３’）は、基全体として炭素原子数が３〜２０の範囲内である。）The present invention also provides a compound represented by the following general formula (1 ′).

(In the formula, Ar ′ represents a benzene ring or a naphthalene ring,
Z ′ represents R ¹ ′ O—S (═O) ₂ —, R ¹² ′ —S (═O) ₂ —, R ¹ ′ O—S (═O) — or R ¹² ′ —S (═O). -
R ¹ ′ represents a hydrocarbon group having 1 to 20 carbon atoms having a substituent,
R ² ′ has a halogen atom, a nitrile group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a thiol group, a formyl group, —SiR ⁹ ′ R ¹⁰ ′ R ¹¹ ′, a phosphoric acid group, or a substituent. Represents a substituted hydrocarbon group having 1 to 20 carbon atoms,
R ¹² ′ represents a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms having a substituent,
R ¹ ', ^{R 2'} and ^{R 12} 'group substituting the hydrocarbon group represented by a halogen atom, a nitrile group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a thiol group, a formyl group, -SiR ^9' R ¹⁰ is a ^{'R 11'} or phosphoric acid group,
The alkylene in the hydrocarbon group represented by R ¹ ′, R ² ′ and R ¹² ′ is —O—, —CO—, —OCO—, —COO—, —O—CO—O—, —NR′—, _{-S -, - SO -, -} SO 2 -, - NR'-CO- or -CO-NR'- is under conditions which are not adjacent, may also be interrupted 1-3 times,
R ′ represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms,
When R ² ′ represents a hydrocarbon group, the sites where R ² ′ and Ar ′ are bonded to each other are —O—, —CO—, —OCO—, —COO—, —O—CO—O—, —NR ′. May be interrupted by-, -S-, -NR'-CO-, -CO-NR'- or -N =,
R ⁹ ′, R ¹⁰ ′ and R ¹¹ ′ represent a hydrocarbon group having 1 to 16 carbon atoms,
m ′ and n ′ each represents an integer of 1 or more, and when Ar ′ represents a benzene ring, m ′ + n ′ is 6 or less, and when Ar ′ represents a naphthalene ring, m ′ + n ′ is 10 or less. And
When m ′ is 2 or more, Z ′ may be the same or different. When n ′ is 2 or more, R ² ′ may be the same or different.
Are 2 or more, R ² ′ may be the same or different.
However, at least one of n ′ R ² ′ is a group represented by the following general formula (2 ′) or (3 ′). )

(Wherein R ³ ′, R ⁴ ′, R ⁵ ′ and R ⁶ ′ each independently represents a substituent or an unsubstituted hydrocarbon group having 1 to 18 carbon atoms,
The hydrocarbon group represented by R ³ ′, R ⁴ ′, R ⁵ ′ and R ⁶ ′ is a halogen atom, nitrile group, nitro group, amino group, carboxyl group, hydroxyl group, thiol group, formyl group, sulfone. A group, -SiR ⁹ 'R ¹⁰ ' R ¹¹ 'or a phosphate group,
The alkylene group in the hydrocarbon group represented by R ³ ′, R ⁴ ′, R ⁵ ′ and R ⁶ ′ is —O—, —CO—, —OCO—, —COO—, —O—CO—O—, -NR '-, - S -, - SO -, - SO 2 -, - NR'-CO- or -CO-NR'- is under conditions which are not adjacent, may also be interrupted 1-3 times,
R ′ represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms,
R ⁷ ′ and R ⁸ ′ are each independently a hydrogen atom, halogen atom, nitrile group, nitro group, amino group, carboxyl group, hydroxyl group, thiol group, formyl group, sulfone group, —SiR ⁹ ′ R ¹⁰ ′ R ¹¹ 'Or represents a phosphate group,
R ⁹ ′, R ¹⁰ ′ and R ¹¹ ′ each independently represents a hydrocarbon group having 1 to 16 carbon atoms,
However, general formula (2 ') and (3') are in the range whose carbon atom number is 3-20 as the whole group. )

  According to the present invention, a non-aqueous electrolyte solution that is excellent in overcharge prevention capability by using a non-aqueous electrolyte solution containing a compound having a specific structure and that can maintain a small internal resistance and high electric capacity even after charging and discharging. A secondary battery can be provided.

FIG. 1 is a longitudinal sectional view schematically showing an example of the structure of a coin-type battery of the nonaqueous electrolyte secondary battery of the present invention. FIG. 2 is a schematic diagram showing a basic configuration of a cylindrical battery of the nonaqueous electrolyte secondary battery of the present invention. FIG. 3 is a perspective view showing the internal structure of the cylindrical battery of the nonaqueous electrolyte secondary battery of the present invention as a cross section.

Hereinafter, the non-aqueous electrolyte and the non-aqueous electrolyte secondary battery of the present invention will be described in detail based on preferred embodiments.
<Non-aqueous electrolyte>
A nonaqueous electrolytic solution in which a lithium salt used in the present invention is dissolved in an organic solvent (hereinafter also referred to as a nonaqueous electrolytic solution of the present invention) will be described. The nonaqueous electrolytic solution of the present invention contains a compound represented by the above general formula (1). Hereinafter, this compound will be described.
Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ , R ² and R ¹² in the general formula (1) include saturated and unsaturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms and the number of carbon atoms. A 6-20 aromatic hydrocarbon group is mentioned. Examples of saturated and unsaturated hydrocarbon groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, 2-propynyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, s-pentyl, Saturated hydrocarbon groups such as hexyl, 2-ethylhexyl, decyl, dodecyl, octadecyl, and unsaturated hydrocarbons such as vinyl, ethynyl, allyl, propargyl, 3-butenyl, isobutenyl, 3-butynyl, 4-pentenyl, 5-hexenyl Groups. Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl, naphthyl, cyclohexylphenyl, biphenyl, fluoryl, 2′-phenyl-propylphenyl, benzyl, naphthylmethyl and the like.
The alkylene in the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ , R ² and R ¹² (in the case of R ² , including a site bonded to Ar) is -O-, -CO-, -OCO. -, - COO -, - O -COO -, - NR -, - S -, - SO -, - SO 2 -, - NR-CO -, - CO, -NR- or -N = are adjacent to each other May be interrupted 1 to 3 times, and R is an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
However, when the interrupting group includes a carbon atom, the number of carbon atoms including the number of carbon atoms of the interrupting group is 1 to 20.
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms representing R include saturated and unsaturated aliphatic hydrocarbon groups having 1 to 5 carbon atoms among those described for R ¹ .
R ¹ , R ² and R ¹² represent a group which substitutes a hydrocarbon group having 1 to 20 carbon atoms, which is a halogen atom, a nitrile group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a thiol group, a formyl group, It is SiR ⁹ R ¹⁰ R ¹¹ or a phosphate group, and R ⁹ , R ¹⁰ and R ¹¹ are hydrocarbon groups having 1 to 16 carbon atoms. In addition, when the group to be substituted is a group containing a carbon atom, the number of carbon atoms including the number of carbon atoms of the group to be substituted is 1 to 20.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In addition, all the halogen atoms in this specification are the same as this.
Examples of the aliphatic hydrocarbon group having 1 to 16 carbon atoms represented by R ⁹ , R ¹⁰ and R ¹¹ include the same groups as those having 1 to 16 carbon atoms among those described in R ¹ .

At least one of the n R ^{2 in} the general formula (1) is a group represented by the general formula (2) or (3).
Hydrocarbon group R ^3, R ^4, R ⁵ and 18 carbon atoms and R ⁶ represents in the general formula (2) or (3), among those described in R ^1, the number of carbon atoms 1 to 18 And the same groups as those mentioned above.
The alkylene group in the hydrocarbon group having 1 to 18 carbon atoms represented by R ³ , R ⁴ , R ⁵ and R ⁶ is —O—, —CO—, —OCO—, —COO—, —O—CO—. O—, —NR—, —S—, —SO—, —SO ₂ —, —NR—CO—, —CO or —NR— may be interrupted 1 to 3 times under the condition that they are not adjacent to each other, R is an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
However, when the interrupting group includes a carbon atom, the number of carbon atoms including the number of carbon atoms of the interrupting group is 1 to 18.
R ³ , R ⁴ , R ^5, and R ⁶ can be substituted with a hydrocarbon group having 1 to 18 carbon atoms such as a halogen atom, nitrile group, nitro group, amino group, carboxyl group, hydroxyl group, thiol group, formyl A group, a sulfone group, —SiR ⁹ R ¹⁰ R ¹¹ or a phosphoric acid group, and R ⁹ , R ¹⁰ and R ¹¹ are each a hydrocarbon group having 1 to 16 carbon atoms. In addition, when the group to be substituted is a group containing a carbon atom, the number of carbon atoms including the number of carbon atoms of the group to be substituted is 1 to 16.

In the general formula (1), examples of the number and position of substitution of Z and R ² with respect to Ar are as follows: # 1 to # 7.
Further, in ♯1～♯7, of ^{R 2,} a group represented by the general formula (2) or ^{(3), R 2A,} the other ^group, as ^{R 2B,} Z for ^{Ar, R 2A} and Reflecting the number of R ^2B substitutions and the substitution position, the following # 8 to # 17 are given as an example.

Among the compounds represented by the general formula (1), a compound in which at least one of n R ² is a group represented by the general formula (2), particularly isopropyl, s-butyl, s A compound that is pentyl is preferable because it is excellent as an overcharge inhibitor.
In addition, among R ² , preferred groups in the group (R ^2B ) other than the general formula (2) or (3) include a halogen atom, an ester group, an amide group and the like.
In addition, as Z, when Z is R ¹ O—S (═O) ₂ — or R ¹ O—S (═O) —, R ¹ is the number of carbon atoms substituted or unsubstituted by a halogen atom 1-6 saturated or unsaturated aliphatic hydrocarbon groups (methyl, ethyl, propyl, isopropyl, 2-propynyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, s-pentyl, hexyl, vinyl Ethynyl, allyl, propargyl, 3-butenyl, isobutenyl, 3-butynyl, 4-pentenyl, 5-hexenyl, or a group in which a part of these groups is substituted with a halogen atom, etc.)
When Z is R ¹² —S (═O) ₂ — or R ¹² —S (═O) —, R ¹² is a halogen atom, a halogen atom-substituted or unsubstituted carbon atom having 1 to 6 carbon atoms. Saturated or unsaturated aliphatic hydrocarbon group (methyl, ethyl, propyl, isopropyl, 2-propynyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, s-pentyl, hexyl, vinyl, ethynyl, allyl , Propargyl, 3-butenyl, isobutenyl, 3-butynyl, 4-pentenyl, 5-hexenyl, or a group in which a part of these groups is substituted with a halogen atom is preferred.

  Specific examples of the compound represented by the general formula (1) include Compound No. Although 1-23 are mentioned, this invention is not limited at all by these compounds.

  The compound represented by the general formula (1) can be produced by sulfonating and esterifying an aromatic compound having a substituent.

In the nonaqueous electrolytic solution of the present invention, the compound represented by the general formula (1) may be used alone or in combination of two or more.
Further, in the nonaqueous electrolytic solution of the present invention, when the content of the compound represented by the general formula (1) is too small, a sufficient effect cannot be exhibited, and when the content is too large, the compounding amount is met. The content of the compound represented by the general formula (1) is 0.001 in the non-aqueous electrolyte because not only the increase effect is obtained but also the characteristics of the non-aqueous electrolyte may be adversely affected. Is preferably 10 to 10% by mass, more preferably 0.01 to 8% by mass, and most preferably 0.1 to 5% by mass.

  As an organic solvent used for the non-aqueous electrolyte of the present invention, those usually used for non-aqueous electrolytes can be used alone or in combination of two or more. Specific examples include saturated cyclic carbonate compounds, saturated cyclic ester compounds, sulfoxide compounds, sulfone compounds, amide compounds, saturated chain carbonate compounds, chain ether compounds, cyclic ether compounds, and saturated chain ester compounds.

Among the above organic solvents, saturated cyclic carbonate compounds, saturated cyclic ester compounds, sulfoxide compounds, sulfone compounds and amide compounds have a high relative dielectric constant, and thus serve to increase the dielectric constant of non-aqueous electrolytes. Compounds are preferred. Examples of such saturated cyclic carbonate compounds include ethylene carbonate, 1-fluoroethylene carbonate, 1,2-propylene carbonate, 1,3-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 1, Examples include 1, -dimethylethylene carbonate. Examples of the saturated cyclic ester compound include γ-butyrolactone, γ-valerolactone, γ-caprolactone, δ-hexanolactone, and δ-octanolactone. Examples of the sulfoxide compound include dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, diphenyl sulfoxide, thiophene, and the like. Examples of the sulfone compounds include dimethyl sulfone, diethyl sulfone, dipropyl sulfone, diphenyl sulfone, sulfolane (also referred to as tetramethylene sulfone), 3-methyl sulfolane, 3,4-dimethyl sulfolane, 3,4-diphenimethyl sulfolane, sulfolene. , 3-methylsulfolene, 3-ethylsulfolene, 3-bromomethylsulfolene and the like, and sulfolane and tetramethylsulfolane are preferable. Examples of the amide compound include N-methylpyrrolidone, dimethylformamide, dimethylacetamide and the like.
Among the above organic solvents, saturated chain carbonate compounds, chain ether compounds, cyclic ether compounds and saturated chain ester compounds can lower the viscosity of the non-aqueous electrolyte and increase the mobility of electrolyte ions. Battery characteristics such as output density can be made excellent. Moreover, since it is low-viscosity, the performance of the non-aqueous electrolyte at a low temperature can be enhanced, and among them, a saturated chain carbonate compound is preferable. Examples of such saturated chain carbonate compounds include dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), ethyl butyl carbonate, methyl-t-butyl carbonate, diisopropyl carbonate, and t-butyl propyl carbonate. Etc. Examples of the chain ether compound or the cyclic ether compound include dimethoxyethane (DME), ethoxymethoxyethane, diethoxyethane, tetrahydrofuran, dioxolane, dioxane, 1,2-bis (methoxycarbonyloxy) ethane, 1,2 -Bis (ethoxycarbonyloxy) ethane, 1,2-bis (ethoxycarbonyloxy) propane, ethylene glycol bis (trifluoroethyl) ether, propylene glycol bis (trifluoroethyl) ether, ethylene glycol bis (trifluoromethyl) ether And diethylene glycol bis (trifluoroethyl) ether. Among these, dioxolane is preferred.
As the saturated chain ester compound, monoester compounds and diester compounds having a total number of carbon atoms in the molecule of 2 to 8 are preferable. Specific compounds include methyl formate, ethyl formate, methyl acetate, ethyl acetate, Propyl acetate, isobutyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl trimethyl acetate, ethyl trimethyl acetate, methyl malonate, ethyl malonate, methyl succinate, ethyl succinate, 3- Methyl methoxypropionate, ethyl 3-methoxypropionate, ethylene glycol diacetyl, propylene glycol diacetyl, etc., including methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, methyl propionate, and Professional Ethyl propionic acid are preferred.

  In addition, acetonitrile, propionitrile, nitromethane, and derivatives thereof can also be used as the organic solvent.

As the lithium salt used in the non-aqueous electrolyte of the present invention, a conventionally known lithium salt is used. For example, LiPF ₆ , LiBF ₄ , LiAsF ₆ , LiCF ₃ SO ₃ , LiCF ₃ CO ₂ , LiN (CF ₃ SO _{2) 2, LiC (CF 3} SO 2) 3, LiB (CF 3 SO 3) 4, LiB (C 2 O 4) 2, LiBF 2 (C 2 O 4), LiSbF 6, LiSiF 5, LiAlF 4, LiSCN , LiClO ₄ , LiCl, LiF, LiBr, LiI, LiAlF ₄ , LiAlCl ₄ , and derivatives thereof, among these, LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , LiCF ₃ SO ₃ , and LiC derivatives of (CF ₃ SO _{2) 3} and LiCF ₃ SO _3, and LiC the (CF ₃ SO ₂₎ 1 or more selected from the group consisting of ₃ derivatives Are the are preferred because of excellent electrical characteristics.

  The lithium salt can be dissolved in the organic solvent so that the concentration in the non-aqueous electrolyte of the present invention is 0.1 to 3.0 mol / L, particularly 0.5 to 2.0 mol / L. preferable. If the concentration of the lithium salt is less than 0.1 mol / L, a sufficient current density may not be obtained, and if it is more than 3.0 mol / L, the stability of the nonaqueous electrolyte may be impaired. The lithium salt may be used in combination of two or more lithium salts.

As an effect of adding the compound represented by the general formula (1), an overcharge preventing effect can be mentioned, but another overcharge preventing agent can be further added to the nonaqueous electrolytic solution of the present invention. As an overcharge inhibitor, aromatic compounds such as biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether, dibenzofuran; 2-fluorobiphenyl, Partially fluorinated products of the above aromatic compounds such as o-cyclohexylfluorobenzene and p-cyclohexylfluorobenzene; 2,4-difluoroanisole, 2,5-difluoroanisole, 2,6-difluoroanisole, 3,5-difluoroanisole and the like And a fluorine-containing anisole compound. Of these, aromatic compounds such as biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether, and dibenzofuran are preferable.
Moreover, the compound represented by following General formula (4) can also be used preferably.

（式中、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４及びＲ^２５は、それぞれ独立して、置換基を有しているか若しくは無置換の炭素原子数１〜２０の脂肪族炭化水素基、ハロゲン原子、ニトリル基、ニトロ基、アミノ基、カルボキシル基、水酸基、チオール基、ホルミル基、スルホン基、−ＳｉＲ^２９Ｒ^３０Ｒ^３１又はリン酸基を表し、
炭素原子数１〜２０の脂肪族炭化水素基は、基中のアルキレン（ベンゼン環と結合する部位も含む）が、−Ｏ−、−ＣＯ−、−ＯＣＯ−、−ＣＯＯ−、−Ｏ−ＣＯ−Ｏ−、−ＮＲ^a−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＮＲ^a−ＣＯ−又は−ＣＯ−ＮＲ^a−が隣り合わない条件で、１〜３回中断していてもよく、
Ｒ^aは、炭素原子数１〜５の脂肪族炭化水素基を表し、
Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４及びＲ^２５の少なくとも一つはハロゲン原子により少なくとも一つ置換された炭素原子数１〜２０の脂肪族炭化水素基を表し、
Ｒ^２８は、ｐ価の基を表し、
Ｒ^２６、Ｒ^２７、Ｒ^２９、Ｒ^３０及びＲ^３１は、それぞれ独立して、置換基を有している若しくは無置換の炭素原子数１〜２０の脂肪族炭化水素基又は置換基を有している若しくは無置換の炭素原子数６〜２０の芳香族炭化水素基を表し、
ｐは、１〜３の整数を表す。）

(Wherein R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are each independently a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, halogen, Represents an atom, a nitrile group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a thiol group, a formyl group, a sulfone group, -SiR ²⁹ R ³⁰ R ³¹ or a phosphate group;
In the aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkylene (including a site bonded to a benzene ring) in the group is -O-, -CO-, -OCO-, -COO-, -O-CO. ^{-O -, - NR a -,} - S -, - SO -, - SO 2 -, - NR a -CO- or -CO-NR ^a - On the condition that not adjacent, optionally interrupted 1-3 times Well,
R ^a represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms,
At least one of R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms substituted with at least one halogen atom;
R ²⁸ represents a p-valent group,
R ²⁶ , R ²⁷ , R ²⁹ , R ³⁰ and R ³¹ each independently have a substituent or an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms or a substituent. Represents an unsubstituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms,
p represents an integer of 1 to 3. )

In the general formula (4), R ^{21 to} R ²⁷ and R ^{29 to} R ³¹ represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ^a. Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms include the same groups as those described in the general formula (1).
In addition, R ^{21 to} R ²⁶ and R ^{29 to} R ³¹ represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms and R ²⁶ , R ²⁷ , R ²⁹ , R ^30, and R ³¹ represent 6 to 20 carbon atoms. Examples of the group for substituting the aromatic hydrocarbon group include the same groups as those described in the general formula (1).
Specific examples of the compound represented by the general formula (4) include, but are not limited to, the following 4-1 to 4-4.

  When other overcharge inhibitors are added, the addition amount is not particularly limited, but is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the compound represented by the general formula (1).

  In addition, halogen-based, phosphorus-based, and other flame retardants can be appropriately added to the nonaqueous electrolytic solution of the present invention in order to impart flame retardancy. If the amount of flame retardant added is too small, sufficient flame retarding effect cannot be exerted.If it is too large, not only an increase effect corresponding to the blending amount can be obtained, but on the other hand, the characteristics of the non-aqueous electrolyte Since it may have a bad influence, it is preferable that it is 1-50 mass% with respect to the organic solvent which comprises the non-aqueous electrolyte of this invention, and it is still more preferable that it is 3-10 mass%.

  The non-aqueous electrolyte of the present invention can be used as a non-aqueous electrolyte of either a primary battery or a secondary battery. However, a non-aqueous electrolyte secondary battery such as the present invention, particularly a lithium ion secondary battery, is used. By using it as a non-aqueous electrolyte to constitute, the above effects are exhibited.

<Nonaqueous electrolyte secondary battery>
A non-aqueous electrolyte secondary battery according to the present invention includes an anode from which lithium can be inserted and removed, a cathode containing a transition metal and lithium, and a non-aqueous electrolyte in which a lithium salt is dissolved in an organic solvent. In the secondary battery, the nonaqueous electrolytic solution of the present invention is used as the nonaqueous electrolytic solution.

<Anode>
The anode from which lithium can be inserted / removed is not particularly limited as long as lithium can be inserted / removed, but is preferably as follows. That is, as the anode of the non-aqueous electrolyte secondary battery of the present invention, a slurry obtained by slurrying an anode active material and a binder with an organic solvent or water was applied to a current collector and dried to form a sheet. A thing is used and a electrically conductive material is mix | blended as needed.

As the anode active material, natural graphite, artificial graphite, non-graphitizable carbon, graphitizable carbon, lithium, lithium alloy, tin alloy, silicon alloy, silicon oxide, titanium oxide, and the like are used, but not limited thereto. .
Examples of the binder for the anode include, but are not limited to, polyvinylidene fluoride, polytetrafluoroethylene, EPDM, SBR, NBR, fluororubber, and polyacrylic acid. The amount of the binder used for the anode is preferably 0.001 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and most preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the anode active material. .
Examples of the solvent for slurrying the anode include N-methylpyrrolidone, dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine, N, N-dimethylaminopropylamine, polyethylene oxide, tetrahydrofuran and the like. However, it is not limited to this. The amount of the solvent used is preferably 30 to 300 parts by mass, and more preferably 50 to 200 parts by mass with respect to 100 parts by mass of the anode active material.
Usually, copper, nickel, stainless steel, nickel-plated steel or the like is used for the current collector of the anode.
Further, as the conductive material blended as necessary, graphene, fine particles of graphite, carbon black such as acetylene black and ketjen black, fine particles of amorphous carbon such as needle coke, carbon nanofiber, etc. are used. However, it is not limited to these.

<Cathode>
The cathode containing a transition metal and lithium used in the present invention is a current collector obtained by slurrying a cathode active material, a binder, a conductive material, etc. with an organic solvent or water, as in a normal secondary battery. It is used after being applied to and dried to form a sheet. The cathode active material contains a transition metal and lithium, and a material containing one kind of transition metal and lithium is preferable. Examples thereof include a lithium transition metal composite oxide and a lithium-containing transition metal phosphate compound. These may be used in combination. As the transition metal of the lithium transition metal composite oxide, vanadium, titanium, chromium, manganese, iron, cobalt, nickel, copper and the like are preferable. Specific examples of the lithium transition metal composite oxide include lithium cobalt composite oxide such as LiCoO ₂ , lithium nickel composite oxide such as LiNiO ₂ , and lithium manganese composite oxide such as LiMnO ₂ , LiMn ₂ O ₄ , and Li ₂ MnO _3. Some of the transition metal atoms that are the main components of these lithium transition metal composite oxides are aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, lithium, nickel, copper, zinc, magnesium, gallium, zirconium, etc. The thing substituted with the other metal etc. are mentioned. Specific examples of the substituted ones include, for example, LiNi _0.5 Mn _0.5 O ₂ , LiNi _0.80 Co _0.17 Al _0.03 O ₂ , LiNi _1/3 Co _1/3 Mn _1/3 O ₂ , LiMn _1.8 Al _0.2 O ₄ , LiMn _1.5 Ni _0.5 O ₄ or the like. As the transition metal of the lithium-containing transition metal phosphate compound, vanadium, titanium, manganese, iron, cobalt, nickel and the like are preferable. Specific examples thereof include iron phosphates such as LiFePO ₄ and phosphorus such as LiCoPO _4. Cobalt acids, some of the transition metal atoms that are the main components of these lithium transition metal phosphate compounds are aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, lithium, nickel, copper, zinc, magnesium, gallium, zirconium And those substituted with other metals such as niobium.

The cathode binder and slurry solvent are the same as those used in the anode. The amount of the binder used for the cathode is preferably 0.001 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, and most preferably 0.02 to 8 parts by mass with respect to 100 parts by mass of the cathode active material. . The amount of the solvent used for the cathode is preferably from 30 to 300 parts by weight, more preferably from 50 to 200 parts by weight, based on 100 parts by weight of the cathode active material.
Examples of the conductive material for the cathode include graphene, graphite fine particles, carbon black such as acetylene black and ketjen black, amorphous carbon fine particles such as needle coke, and carbon nanofibers, but are not limited thereto. The amount of the conductive material used for the cathode is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the cathode active material.
As the cathode current collector, aluminum, stainless steel, nickel-plated steel or the like is usually used.

  In the non-aqueous electrolyte secondary battery of the present invention, it is preferable to use a separator between the cathode and the anode. As the separator, a commonly used polymer microporous film can be used without any particular limitation. Examples of the film include polyethylene, polypropylene, polyvinylidene fluoride, polyvinylidene chloride, polyacrylonitrile, polyacrylamide, polytetrafluoroethylene, polysulfone, polyethersulfone, polycarbonate, polyamide, polyimide, polyethylene oxide and polypropylene oxide. Films composed of ethers, various celluloses such as carboxymethylcellulose and hydroxypropylcellulose, polymer compounds mainly composed of poly (meth) acrylic acid and various esters thereof, derivatives thereof, copolymers and mixtures thereof. Etc. These films may be used alone, or may be used as a multilayer film by superimposing these films. Furthermore, various additives may be used for these films, and the kind and content thereof are not particularly limited. Among these films, a film made of polyethylene, polypropylene, polyvinylidene fluoride, or polysulfone is preferably used for the nonaqueous electrolyte secondary battery of the present invention.

  These films are microporous so that the electrolyte can penetrate and ions can easily pass therethrough. The microporosity method includes a phase separation method in which a polymer compound and a solvent solution are formed into a film while microphase separation is performed, and the solvent is extracted and removed to make it porous. The film is extruded and then heat treated, the crystals are arranged in one direction, and a “stretching method” or the like is performed by forming a gap between the crystals by stretching, and is appropriately selected depending on the film used.

  In the non-aqueous electrolyte secondary battery of the present invention, the cathode material, the non-aqueous electrolyte, and the separator include a phenol-based antioxidant, a phosphorus-based antioxidant, and a thioether-based antioxidant for the purpose of improving safety. A hindered amine compound or the like may be added.

  The shape of the non-aqueous electrolyte secondary battery of the present invention having the above configuration is not particularly limited, and can be various shapes such as a coin shape, a cylindrical shape, and a square shape. FIG. 1 shows an example of a coin-type battery of the nonaqueous electrolyte secondary battery of the present invention, and FIGS. 2 and 3 show examples of a cylindrical battery, respectively.

  In the coin-type non-aqueous electrolyte secondary battery 10 shown in FIG. 1, 1 is a cathode capable of releasing lithium ions, 1a is a cathode current collector, and 2 is a carbonaceous material capable of occluding and releasing lithium ions released from the cathode. An anode current collector, 2a is an anode current collector, 3 is a non-aqueous electrolyte of the present invention, 4 is a stainless steel cathode case, 5 is a stainless steel anode case, 6 is a polypropylene gasket, and 7 is a polyethylene separator. It is.

  Further, in the cylindrical nonaqueous electrolyte secondary battery 10 ′ shown in FIGS. 2 and 3, 11 is an anode, 12 is an anode current collector, 13 is a cathode, 14 is a cathode current collector, and 15 is the present invention. Nonaqueous electrolyte, 16 is a separator, 17 is a cathode terminal, 18 is an anode terminal, 19 is an anode plate, 20 is an anode lead, 21 is a cathode plate, 22 is a cathode lead, 23 is a case, 24 is an insulating plate, 25 is A gasket, 26 is a safety valve, and 27 is a PTC element.

<New compound>
The novel compound of the present invention is represented by the general formula (1 ′), and among the compounds represented by the general formula (1) described in the above item <Non-aqueous electrolyte>, Z (Z ′) is R ¹ O—S (═O) ₂ —, R ¹² —S (═O) ₂ —, R ¹ O—S (═O) — or R ¹² —S (═O) —, and R ¹ (R ¹ ′) is a hydrocarbon group having 1 to 20 carbon atoms having a substituent, or R ¹² (R ¹² ′) is a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms having a substituent. To do.
Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ ′ and R ¹² ′ include the groups exemplified as the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ and R ¹² .
Note that group substituting the hydrocarbon group represented by ^{R 1} 'and ^{R 12'} is a halogen atom, a nitrile group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a thiol group, a formyl group, -SiR ^{9 'R 10'} R ¹¹ ′ or a phosphate group.
The 'Ar in the general formula (1)' is the same as Ar in formula (1), identical to the ^{'R 1} in the general formula (1)', ^{R 1} in the formula (1) ' R ′ in the general formula (1 ′) is the same as R in the general formula (1), and R ⁹ ′, R ¹⁰ ′ and R ¹¹ ′ in the general formula (1 ′) are respectively R ⁹ , R ¹⁰ and R ¹¹ in general formula (1) are the same, and m ′ and n ′ in general formula (1 ′) are the same as m and n in general formula (1), respectively. .

It can be produced by the same method as the compound represented by the general formula (1) described above.
Moreover, the novel compound of this invention can be used for uses, such as surfactant and its precursor other than the use as an additive of the non-aqueous electrolyte mentioned above.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples. In the examples, “parts” and “%” are based on mass unless otherwise specified.

  The following synthesis examples 1 to 3 are synthesis examples of the compound represented by the general formula (1) used in the nonaqueous electrolytic solution of the present invention.

[Synthesis Example 1] Compound No. 1 Synthesis of 9 Sodium hydride (3.20 g, 80.0 mmol) was added to the flask, dried under reduced pressure, and purged with argon. Tetrahydrofuran (20.0 mL) was added, and 2-propanol (6.12 mL, 80.0 mmol) and tetrahydrofuran (5.00 mL) were slowly added dropwise under ice cooling. Thereafter, 2,4,6-triisopropylbenzenesulfonyl chloride (9.692 g, 32.0 mmol) and 20.0 mL of tetrahydrofuran were added dropwise under ice cooling, followed by stirring at room temperature for 3 hours. Next, 40.0 mL of distilled water and 40.0 mL of ethyl acetate were added to separate the oil and water, and further washed twice with 40.0 mL of distilled water. Anhydrous sodium sulfate was added to the obtained organic layer, filtered and evaporated. The crude product was isolated by a medium pressure column (developing solvent, ethyl acetate: hexane = 19: 1) to obtain 6.77 g (yield 67.7%) of the desired product as a white solid. It was confirmed by ¹ H-NMR and IR that the obtained solid was the target product. The data is shown in [Table 1].

[Synthesis Example 2] Compound No. 2 Synthesis of 22 2,4,6-triisopropylbenzenesulfonyl chloride (4.12 g, 13.6 mmol) was added to the flask, dried under reduced pressure, and purged with argon. Tetrahydrofuran (10.0 mL) and triethylamine (4.74 mL, 34.0 mmol) were added, and 2,2,2-trifluoroethanol (2.43 mL, 34.0 mmol) was slowly added dropwise under ice cooling. After stirring at 40 ° C. for 1 hour and 30 minutes, 20.0 mL of distilled water and 20.0 mL of ethyl acetate were added to separate the oil and water, and further washed twice with 20.0 mL of distilled water. Anhydrous sodium sulfate was added to the obtained organic layer, filtered and evaporated. The crude product was recrystallized (poor solvent, hexane) to obtain 1.47 g (yield 29.3%) of the desired product as a white solid. It was confirmed by ¹ H-NMR and IR that the obtained solid was the target product. The data is shown in [Table 1].

[Synthesis Example 3] Compound No. Synthesis of 23 In a flask, 2,4,6-triisopropylbenzenesulfonyl chloride (5.30 g, 17.5 mmol), potassium fluoride (1.32 g, 22.8 mmol), 1,4,7,10,13,16 -Hexaoxacyclooctadecane (0.25 g, 0.95 mmol) was added, dried under reduced pressure, and then purged with argon. 40.0 mL of acetonitrile was added and stirred overnight at room temperature. Next, 40 mL of distilled water was added to crystallize the solid. The obtained solid was separated by filtration to obtain 4.05 g (yield: 81.0%) of the desired product as a white solid. It was confirmed by ¹ H-NMR and IR that the obtained solid was the target product. The data is shown in [Table 1].

  The following Example 1 and Comparative Examples 1 and 2 are examples of the non-aqueous electrolyte secondary battery of the present invention and comparative examples thereof.

[Examples 1 to 5 and Comparative Examples 1 and 2] Production and Evaluation of Nonaqueous Electrolyte Secondary Batteries In Examples and Comparative Examples, nonaqueous electrolyte secondary batteries (lithium secondary batteries) are prepared as follows. Was made according to

<Production procedure>
[Production of cathode]
After mixing 90 parts by mass of LiMn ₂ O ₄ as an active material, 5 parts by mass of acetylene black as a conductive material, and 5 parts by mass of polyvinylidene fluoride (PVDF) as a binder, 140 parts by mass of N-methyl-2-pyrrolidone (NMP) To form a slurry. This slurry was applied to an aluminum current collector, dried and press-molded. Thereafter, the cathode was cut into a predetermined size to produce a disc-shaped cathode.

[Production of anode]
97.0 parts by weight of artificial graphite as an active material, 1.5 parts by weight of styrene butadiene rubber as a binder, and 1.5 parts by weight of carboxymethyl cellulose as a thickener are mixed in 120 parts by weight of water to form a slurry. . This slurry was applied to a copper negative electrode current collector, dried and press-molded. Thereafter, this anode was cut into a predetermined size to produce a disc-shaped anode.

(Preparation of electrolyte solution)
LiPF ₆ was dissolved at a concentration of 1 mol / L in a mixed solvent consisting of 30% by volume of ethylene carbonate, 40% by volume of ethyl methyl carbonate, and 30% by volume of dimethyl carbonate to prepare an electrolyte solution.

(Preparation of non-aqueous electrolyte)
As the electrolytic solution additive, the compounds shown in [Table 1] were dissolved in the electrolytic solution at the stated ratios to prepare the nonaqueous electrolytic solution of the present invention and the comparative nonaqueous electrolytic solution. Comparative compound 1 is cyclohexylbenzene, manufactured by Tokyo Chemical Industry Co., Ltd.
Compound No. 4 was synthesized with reference to J. Chem. Soc., Perkin trans. 1, 1980, (5), 1076-1079. In addition, the number in () in [Table 1] represents the concentration (% by mass) in the non-aqueous electrolyte.

[Assembling the battery]
The obtained disc-shaped positive electrode and disc-shaped negative electrode were held in a case with a microporous film made of polyethylene having a thickness of 25 μm interposed therebetween. Thereafter, each non-aqueous electrolyte was poured into the case, the case was sealed and sealed, and the lithium secondary batteries of Examples 1 to 5 and Comparative Examples 1 and 2 (a coin having a diameter of 20 mm and a thickness of 3.2 mm). Mold).

  Using the lithium secondary batteries of Examples 1 to 5 and Comparative Examples 1 and 2, an initial discharge capacity ratio and an overcharge resistance test were performed by the following test methods. The test results are shown in [Table 2] below. In addition, it is a nonaqueous electrolyte secondary battery which is excellent in initial characteristics, so that discharge capacity ratio is high, and it represents that it is excellent in overcharge tolerance, so that the value of overcharge tolerance is high.

<Discharge capacity ratio test method>
The lithium secondary battery was placed in a constant temperature bath at 20 ° C., charged at a constant current and a constant voltage up to 4.2 V with a charging current of 0.3 mA / cm ² (current value corresponding to 0.2 C), and a discharge current of 0.3 mA / The operation of discharging a constant current to 3.0 V at cm ² (current value corresponding to 0.2 C) was performed 5 times. Thereafter, the battery was charged at a constant current and a constant voltage up to 4.2 V at a charging current of 0.3 mA / cm ² and discharged at a constant current of 3.0 mA at a discharge current of 0.3 mA / cm ² . The discharge capacity measured at the sixth time is defined as the initial discharge capacity of the battery. As shown in the following formula, the discharge capacity ratio (%) is defined as 100 as the initial discharge capacity of Comparative Example 1 (no addition of electrolyte additive). Calculated.
Discharge capacity ratio (%) = [(initial discharge capacity) / (initial discharge capacity in Comparative Example 1)] × 100

<Overcharge resistance test>
When a lithium secondary battery is placed in a constant temperature bath at 20 ° C. and charged at a constant current and constant voltage to an overcharged state (5.5 V) at a charging current of 0.3 mA / cm ² (current value equivalent to 0.2 C). The capacity (mAh / g) was measured. The capacity of Comparative Example 1 (no addition of electrolytic solution additive) was calculated as 100.

  From the above results, it is clear that the compound represented by the general formula (1) used in the non-aqueous electrolyte of the present invention can suppress an increase in voltage during overcharging without deteriorating battery characteristics (discharge capacity). is there.

DESCRIPTION OF SYMBOLS 1 Cathode 1a Cathode current collector 2 Anode 2a Anode current collector 3 Electrolyte 4 Cathode case 5 Anode case 6 Gasket 7 Separator 10 Coin type non-aqueous electrolyte secondary battery 10 ′ Cylindrical non-aqueous electrolyte secondary battery 11 Anode 12 Anode current collector 13 Cathode 14 Cathode current collector 15 Electrolyte 16 Separator 17 Cathode terminal 18 Anode terminal 19 Anode plate 20 Anode lead 21 Cathode 22 Cathode lead 23 Case 24 Insulating plate 25 Gasket 26 Safety valve 27 PTC element

（式中、Ａｒ’は、ベンゼン環又はナフタレン環を表し、
Ｚ’は、Ｒ¹’Ｏ−Ｓ（＝Ｏ）₂−、Ｒ¹²’−Ｓ（＝Ｏ）₂−、Ｒ¹’Ｏ−Ｓ（＝Ｏ）−又はＲ¹²’−Ｓ（＝Ｏ）−を表し、
Ｒ¹’は、置換基を有する炭素原子数１〜２０の炭化水素基を表し、
Ｒ²’は、ハロゲン原子、ニトリル基、ニトロ基、アミノ基、カルボキシル基、水酸基、チオール基、ホルミル基、−ＳｉＲ⁹’Ｒ¹⁰’Ｒ¹¹’、リン酸基、又は置換基を有する若しくは無置換の炭素原子数１〜２０の炭化水素基を表し、
Ｒ¹²’は、ハロゲン原子又は置換基を有する炭素原子数１〜２０の炭化水素基を表し、
Ｒ¹’、Ｒ²’及びＲ¹²’が表す炭化水素基を置換する基は、ハロゲン原子、ニトリル基、ニトロ基、アミノ基、カルボキシル基、水酸基、チオール基、ホルミル基、−ＳｉＲ⁹’Ｒ¹⁰’Ｒ¹¹’又はリン酸基であり、
Ｒ¹’、Ｒ²’及びＲ¹²’が表す炭化水素基中のアルキレンは、−Ｏ−、−ＣＯ−、−ＯＣＯ−、−ＣＯＯ−、−Ｏ−ＣＯ−Ｏ−、−ＮＲ’−、−Ｓ−、−ＳＯ−、−ＳＯ₂−、−ＮＲ’−ＣＯ−又は−ＣＯ−ＮＲ’−が隣り合わない条件で、１〜３回中断していてもよく、
Ｒ’は、炭素原子数１〜５の脂肪族炭化水素基を表し、
Ｒ²’が炭化水素基を表す場合、Ｒ²’とＡｒ’が結合する部位は、−Ｏ−、−ＣＯ−、−ＯＣＯ−、−ＣＯＯ−、−Ｏ−ＣＯ−Ｏ−、−ＮＲ’−、−Ｓ−、−ＮＲ’−ＣＯ−、−ＣＯ−ＮＲ’−又は−Ｎ＝により中断していてもよく、
Ｒ⁹’、Ｒ¹⁰’及びＲ¹¹’は、炭素原子数１〜１６の炭化水素基を表し、
ｍ’及びｎ’は、それぞれ１以上の整数を表し、Ａｒ’がベンゼン環を表す場合、ｍ’＋ｎ’は６以下であり、Ａｒ’がナフタレン環を表す場合、ｍ’＋ｎ’は１０以下であり、
ｍ’が２以上の場合、Ｚ’は同一でも異なっていてもよく、ｎ’が２以上の場合、Ｒ²’は同一でも異なっていてもよい。
但し、ｎ’個のＲ²’のうち、少なくとも１つは、下記一般式（２’）又は（３’）で表される基である。）

（式中、Ｒ³’、Ｒ⁴’、Ｒ⁵’及びＲ⁶’は各々独立に置換基を有するか又は無置換の炭素原子数１〜１８の炭化水素基を表し、
Ｒ³’、Ｒ⁴’、Ｒ⁵’及びＲ⁶’が表す炭化水素基を置換する基は、ハロゲン原子、ニトリル基、ニトロ基、アミノ基、カルボキシル基、水酸基、チオール基、ホルミル基、スルホン基、−ＳｉＲ⁹’Ｒ¹⁰’Ｒ¹¹’又はリン酸基であり、
Ｒ³’、Ｒ⁴’、Ｒ⁵’及びＲ⁶’が表す炭化水素基中のアルキレン基は、−Ｏ−、−ＣＯ−、−ＯＣＯ−、−ＣＯＯ−、−Ｏ−ＣＯ−Ｏ−、−ＮＲ’−、−Ｓ−、−ＳＯ−、−ＳＯ₂−、−ＮＲ’−ＣＯ−又は−ＣＯ−ＮＲ’−が隣り合わない条件で、１〜３回中断していてもよく、
Ｒ’は、炭素原子数１〜５の脂肪族炭化水素基を表し、
Ｒ⁷’及びＲ⁸’は、各々独立に水素原子、ハロゲン原子、ニトリル基、ニトロ基、アミノ基、カルボキシル基、水酸基、チオール基、ホルミル基、スルホン基、−ＳｉＲ⁹’Ｒ¹⁰’Ｒ¹¹’又はリン酸基を表し、
Ｒ⁹’、Ｒ¹⁰’及びＲ¹¹’は、各々独立に炭素原子数１〜１６の炭化水素基を表し、
但し、一般式（２’）及び（３’）は、基全体として炭素原子数が３〜２０の範囲内である。） The present invention also provides a compound represented by the following general formula (1 ′).

(In the formula, Ar ′ represents a benzene ring or a naphthalene ring,
Z ′ represents R ¹ ′ O—S (═O) ₂ —, R ¹² ′ —S (═O) ₂ —, R ¹ ′ O—S (═O) — or R ¹² ′ —S (═O). -
R ¹ ′ represents a hydrocarbon group having 1 to 20 carbon atoms having a substituent,
R ² 'is a halogen atom, a nitrile group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a thiol group, a formyl ^{group, -SiR 9' R 10 'R} 11', a phosphate group, or having a substituent or unsubstituted Represents a substituted hydrocarbon group having 1 to 20 carbon atoms,
R ¹² ′ represents a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms having a substituent,
The groups substituting the hydrocarbon groups represented by R ¹ ′, R ² ′ and R ¹² ′ are halogen atoms, nitrile groups, nitro groups, amino groups, carboxyl groups, hydroxyl groups, thiol groups, formyl groups, —SiR ⁹ ′ R ¹⁰ 'R ¹¹ ' or a phosphate group,
The alkylene in the hydrocarbon group represented by R ¹ ′, R ² ′ and R ¹² ′ is —O—, —CO—, —OCO—, —COO—, —O—CO—O—, —NR′—, -S -, - SO -, - SO 2 -, - NR'-CO- or -CO-NR'- is under conditions which are not adjacent, may also be interrupted 1-3 times,
R ′ represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms,
When R ² ′ represents a hydrocarbon group, the sites where R ² ′ and Ar ′ are bonded are —O—, —CO—, —OCO—, —COO—, —O—CO—O—, —NR ′. May be interrupted by-, -S-, -NR'-CO-, -CO-NR'- or -N =,
R ⁹ ′, R ¹⁰ ′ and R ¹¹ ′ represent a hydrocarbon group having 1 to 16 carbon atoms,
m ′ and n ′ each represents an integer of 1 or more, and when Ar ′ represents a benzene ring, m ′ + n ′ is 6 or less, and when Ar ′ represents a naphthalene ring, m ′ + n ′ is 10 or less. And
When m ′ is 2 or more, Z ′ may be the same or different. When n ′ is 2 or more, R ² ′ may be the same or different .
However and, n 'number of R ^2' of at least one is a group represented by the following general formula (2 ') or (3'). )

(Wherein R ³ ′, R ⁴ ′, R ⁵ ′ and R ⁶ ′ each independently represents a substituent or an unsubstituted hydrocarbon group having 1 to 18 carbon atoms,
The hydrocarbon group represented by R ³ ′, R ⁴ ′, R ⁵ ′ and R ⁶ ′ is a halogen atom, nitrile group, nitro group, amino group, carboxyl group, hydroxyl group, thiol group, formyl group, sulfone. A group, -SiR ⁹ 'R ¹⁰ ' R ¹¹ 'or a phosphate group,
The alkylene group in the hydrocarbon group represented by R ³ ′, R ⁴ ′, R ⁵ ′ and R ⁶ ′ is —O—, —CO—, —OCO—, —COO—, —O—CO—O—, -NR '-, - S -, - SO -, - SO 2 -, - NR'-CO- or -CO-NR'- is under conditions which are not adjacent, may also be interrupted 1-3 times,
R ′ represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms,
R ⁷ ′ and R ⁸ ′ are each independently a hydrogen atom, halogen atom, nitrile group, nitro group, amino group, carboxyl group, hydroxyl group, thiol group, formyl group, sulfone group, —SiR ⁹ ′ R ¹⁰ ′ R ¹¹ 'Or represents a phosphate group,
R ⁹ ′, R ¹⁰ ′ and R ¹¹ ′ each independently represents a hydrocarbon group having 1 to 16 carbon atoms,
However, general formula (2 ') and (3') are in the range whose carbon atom number is 3-20 as the whole group. )

Hereinafter, the non-aqueous electrolyte and the non-aqueous electrolyte secondary battery of the present invention will be described in detail based on preferred embodiments.
<Non-aqueous electrolyte>
A nonaqueous electrolytic solution in which a lithium salt used in the present invention is dissolved in an organic solvent (hereinafter also referred to as a nonaqueous electrolytic solution of the present invention) will be described. The nonaqueous electrolytic solution of the present invention contains a compound represented by the above general formula (1). Hereinafter, this compound will be described.
Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ , R ² and R ¹² in the general formula (1) include saturated and unsaturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms, and the number of carbon atoms. A 6-20 aromatic hydrocarbon group is mentioned. Examples of saturated and unsaturated hydrocarbon groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, 2-propynyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, s-pentyl, Saturated hydrocarbon groups such as hexyl, 2-ethylhexyl, decyl, dodecyl, octadecyl, and unsaturated hydrocarbons such as vinyl, ethynyl, allyl, propargyl, 3-butenyl, isobutenyl, 3-butynyl, 4-pentenyl, 5-hexenyl Groups. The aromatic hydrocarbon group having 6 to 20 carbon atoms, phenyl, naphthyl, phenyl, biphenyl, fluorenyl two Le, 2'-phenyl - propyl phenyl, benzyl, naphthylmethyl, and the like.
The alkylene in the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ , R ² and R ¹² (in the case of R ² , including a site bonded to Ar) is —O—, —CO—, —OCO. -, - COO -, - O -COO -, - NR -, - S -, - SO -, - SO 2 -, - NR-CO -, - C O- NR- or -N = are adjacent to each other May be interrupted 1 to 3 times, and R is an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
However, when the interrupting group includes a carbon atom, the number of carbon atoms including the number of carbon atoms of the interrupting group is 1 to 20.
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms that represents R include saturated and unsaturated aliphatic hydrocarbon groups having 1 to 5 carbon atoms among those described for R ¹ .
R ¹ , R ² and R ¹² represent a group which substitutes a hydrocarbon group having 1 to 20 carbon atoms, which is a halogen atom, a nitrile group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a thiol group, a formyl group, It is SiR ⁹ R ¹⁰ R ¹¹ or a phosphate group, and R ⁹ , R ¹⁰ and R ¹¹ are hydrocarbon groups having 1 to 16 carbon atoms. In addition, when the group to be substituted is a group containing a carbon atom, the number of carbon atoms including the number of carbon atoms of the group to be substituted is 1 to 20.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In addition, all the halogen atoms in this specification are the same as this.
Examples of the aliphatic hydrocarbon group having 1 to 16 carbon atoms represented by R ⁹ , R ¹⁰ and R ¹¹ include the same groups as those having 1 to 16 carbon atoms among those described for R ¹ .

<New compound>
The novel compound of the present invention is represented by the general formula (1 ′), and among the compounds represented by the general formula (1) described in the above item <Non-aqueous electrolyte>, Z (Z ′) is R ¹ O—S (═O) ₂ —, R ¹² —S (═O) ₂ —, R ¹ O—S (═O) — or R ¹² —S (═O) —, and R ¹ (R ¹ ′) is a hydrocarbon group having 1 to 20 carbon atoms having a substituent, or R ¹² (R ¹² ′) is a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms having a substituent. To do.
Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ ′ and R ¹² ′ include the groups exemplified as the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ and R ¹² .
Note that group substituting the hydrocarbon group represented by R ¹ 'and R ^12' is a halogen atom, a nitrile group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a thiol group, a formyl group, -SiR ⁹ 'R ^10' R ¹¹ ′ or a phosphate group.
The 'Ar in the general formula (1)' is the same as Ar in formula (1), 'R ¹ in the general formula (1)' is the general formula (1) the same as R ¹ in Yes, R ′ in the general formula (1 ′) is the same as R in the general formula (1), and R ⁹ ′, R ¹⁰ ′ and R ¹¹ ′ in the general formula (1 ′) are R ⁹ , R ¹⁰ and R ¹¹ in the formula (1) are the same, and m ′ and n ′ in the general formula (1 ′) are the same as m and n in the general formula (1), respectively.

Claims (3)

In a non-aqueous electrolyte solution in which a lithium salt is dissolved in an organic solvent,
A nonaqueous electrolytic solution comprising at least one compound represented by the following general formula (1).

(In the formula, Ar represents a benzene ring or a naphthalene ring,
Z represents R ¹ O—S (═O) ₂ —, R ¹² —S (═O) ₂ —, R ¹ O—S (═O) — or R ¹² —S (═O) —,
R ¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms,
R ² is a halogen atom, a nitrile group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a thiol group, a formyl group, —SiR ⁹ R ¹⁰ R ¹¹ , a phosphate group, or a substituted or unsubstituted carbon atom. Represents a hydrocarbon group of 1 to 20,
R ¹² represents a halogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms,
The group that replaces the hydrocarbon group represented by R ¹ , R ² and R ¹² is a halogen atom, a nitrile group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a thiol group, a formyl group, —SiR ⁹ R ¹⁰ R ¹¹ or A phosphate group,
The alkylene in the hydrocarbon group represented by R ¹ , R ² and R ¹² is —O—, —CO—, —OCO—, —COO—, —O—CO—O—, —NR—, —S—, _{-SO -, - SO 2 -,} - NR-CO- or -CO-NR- is under conditions which are not adjacent, may also be interrupted 1-3 times,
R represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms,
When R ² represents a hydrocarbon group, the sites where R ² and Ar are bonded are —O—, —CO—, —OCO—, —COO—, —O—CO—O—, —NR—, —S. May be interrupted by-, -NR-CO-, -CO-NR- or -N =,
R ⁹ , R ¹⁰ and R ¹¹ represent a hydrocarbon group having 1 to 16 carbon atoms,
m and n each represent an integer of 1 or more, and when Ar represents a benzene ring, m + n is 6 or less, and when Ar represents a naphthalene ring, m + n is 10 or less,
When m is 2 or more, Z may be the same or different, and when n is 2 or more, R ² may be the same or different.
However, at least one of n R ² is a group represented by the following general formula (2) or (3). )

(Wherein R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a substituent or an unsubstituted hydrocarbon group having 1 to 18 carbon atoms,
The groups that replace the hydrocarbon groups represented by R ³ , R ⁴ , R ⁵ and R ⁶ are halogen atoms, nitrile groups, nitro groups, amino groups, carboxyl groups, hydroxyl groups, thiol groups, formyl groups, sulfone groups, —SiR. ⁹ R ¹⁰ R ¹¹ or a phosphate group,
The alkylene group in the hydrocarbon group represented by R ³ , R ⁴ , R ⁵ and R ⁶ is —O—, —CO—, —OCO—, —COO—, —O—CO—O—, —NR—, -S -, - SO -, - SO 2 -, - NR-CO- or -CO-NR- is under conditions which are not adjacent, may also be interrupted 1-3 times,
R represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms,
R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, a nitrile group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a thiol group, a formyl group, a sulfone group, —SiR ⁹ R ¹⁰ R ¹¹ or a phosphate group. Represents
R ⁹ , R ¹⁰ and R ¹¹ each independently represents a hydrocarbon group having 1 to 16 carbon atoms,
However, general formula (2) and (3) are in the range of 3-20 carbon atoms as the whole group. )   A nonaqueous electrolyte secondary battery comprising an anode from which lithium can be inserted and removed, a cathode containing a transition metal and lithium, and a nonaqueous electrolyte in which a lithium salt is dissolved in an organic solvent. A nonaqueous electrolyte secondary battery, which is the nonaqueous electrolyte solution according to 1. A compound represented by the following general formula (1 ′).

(In the formula, Ar ′ represents a benzene ring or a naphthalene ring,
Z ′ represents R ¹ ′ O—S (═O) ₂ —, R ¹² ′ —S (═O) ₂ —, R ¹ ′ O—S (═O) — or R ¹² ′ —S (═O). -
R ¹ ′ represents a hydrocarbon group having 1 to 20 carbon atoms having a substituent,
R ² ′ has a halogen atom, a nitrile group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a thiol group, a formyl group, —SiR ⁹ ′ R ¹⁰ ′ R ¹¹ ′, a phosphoric acid group, or a substituent. Represents a substituted hydrocarbon group having 1 to 20 carbon atoms,
R ¹² ′ represents a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms having a substituent,
R ¹ ', ^{R 2'} and ^{R 12} 'group substituting the hydrocarbon group represented by a halogen atom, a nitrile group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a thiol group, a formyl group, -SiR ^9' R ¹⁰ is a ^{'R 11'} or phosphoric acid group,
The alkylene in the hydrocarbon group represented by R ¹ ′, R ² ′ and R ¹² ′ is —O—, —CO—, —OCO—, —COO—, —O—CO—O—, —NR′—, _{-S -, - SO -, -} SO 2 -, - NR'-CO- or -CO-NR'- is under conditions which are not adjacent, may also be interrupted 1-3 times,
R ′ represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms,
When R ² ′ represents a hydrocarbon group, the sites where R ² ′ and Ar ′ are bonded to each other are —O—, —CO—, —OCO—, —COO—, —O—CO—O—, —NR ′. May be interrupted by-, -S-, -NR'-CO-, -CO-NR'- or -N =,
R ⁹ ′, R ¹⁰ ′ and R ¹¹ ′ represent a hydrocarbon group having 1 to 16 carbon atoms,
m ′ and n ′ each represents an integer of 1 or more, and when Ar ′ represents a benzene ring, m ′ + n ′ is 6 or less, and when Ar ′ represents a naphthalene ring, m ′ + n ′ is 10 or less. And
When m ′ is 2 or more, Z ′ may be the same or different. When n ′ is 2 or more, R ² ′ may be the same or different.
Are 2 or more, R ² ′ may be the same or different.
However, at least one of n ′ R ² ′ is a group represented by the following general formula (2 ′) or (3 ′). )

(Wherein R ³ ′, R ⁴ ′, R ⁵ ′ and R ⁶ ′ each independently represents a substituent or an unsubstituted hydrocarbon group having 1 to 18 carbon atoms,
The hydrocarbon group represented by R ³ ′, R ⁴ ′, R ⁵ ′ and R ⁶ ′ is a halogen atom, nitrile group, nitro group, amino group, carboxyl group, hydroxyl group, thiol group, formyl group, sulfone. A group, -SiR ⁹ 'R ¹⁰ ' R ¹¹ 'or a phosphate group,
The alkylene group in the hydrocarbon group represented by R ³ ′, R ⁴ ′, R ⁵ ′ and R ⁶ ′ is —O—, —CO—, —OCO—, —COO—, —O—CO—O—, -NR '-, - S -, - SO -, - SO 2 -, - NR'-CO- or -CO-NR'- is under conditions which are not adjacent, may also be interrupted 1-3 times,
R ′ represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms,
R ⁷ ′ and R ⁸ ′ are each independently a hydrogen atom, halogen atom, nitrile group, nitro group, amino group, carboxyl group, hydroxyl group, thiol group, formyl group, sulfone group, —SiR ⁹ ′ R ¹⁰ ′ R ¹¹ 'Or represents a phosphate group,
R ⁹ ′, R ¹⁰ ′ and R ¹¹ ′ each independently represents a hydrocarbon group having 1 to 16 carbon atoms,
However, general formula (2 ') and (3') are in the range whose carbon atom number is 3-20 as the whole group. )

Images