JP2016189327A - Additive of electrolyte for nonaqueous power storage device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an additive compound, suppressing the generation of gas at the inside of a battery during battery usage and thereby causing no battery swelling, while maintaining an effect of a silyl group-containing compound.SOLUTION: An additive of an electrolyte for a nonaqueous power storage device comprises a compound (A) in which at least one of acidic protons included in an acid selected from among a protonic acid, a sulfonic acid and a carboxylic acid having one or more atoms selected from a phosphorous atom and a boron atom is substituted by a group represented by formula (A1). {In formula (A1), R-Reach independently represent a 1-20C substituted/unsubstituted hydrocarbon group; and the total of carbon numbers of R-Ris 5-20.}SELECTED DRAWING: None

Description

  The present invention relates to the use of a specific compound containing a silyl group as an additive for an electrolyte solution for a non-aqueous storage device, an electrolyte solution for a non-aqueous storage device containing the additive, and a lithium ion secondary containing the electrolyte solution It relates to batteries.

In recent years, various electrochemical devices have been developed along with the development of electronic technology and increasing interest in environmental technology. Lithium ion secondary batteries, which are typical examples of power storage devices, have been used mainly as rechargeable batteries for portable devices, but in recent years, they are expected to be used as batteries for hybrid vehicles and electric vehicles. Battery performance is required.
A conventional lithium ion secondary battery operates at a voltage of about 4 V, and a nonaqueous electrolytic solution in which a lithium salt is dissolved in a nonaqueous solvent containing a carbonate-based solvent as a main component is widely used. However, since the carbonate-based solvent is a flammable liquid, a safer electrolyte is required when a lithium ion secondary battery is used for applications such as hybrid vehicles and electric vehicles. For the purpose of improving the safety of the electrolytic solution, a method of adding a phosphoric acid compound having a specific structure to a non-aqueous electrolytic solution is disclosed (for example, see Patent Document 1). Moreover, the method of adding a phosphate ester to electrolyte solution is also disclosed in order to improve the flame retardance or self-extinguishing property of electrolyte solution (for example, refer patent document 2).

In recent years, a lithium ion secondary battery having a higher energy density has been demanded, and as one of the methods, increasing the voltage of the battery has been studied. In order to achieve higher voltage of the battery, a positive electrode active material that operates at 4.2 V (vsLi / Li ⁺ ) or higher has been proposed as a positive electrode that operates at a high potential (see, for example, Patent Document 3). However, in a lithium ion secondary battery including a positive electrode containing a positive electrode active material that operates at a high potential of 4.2 V (vsLi / Li ⁺ ) or higher, a conventional non-aqueous electrolyte mainly composed of a carbonate-based solvent is used. Then, the carbonate-based solvent oxidizes and decomposes on the surface of the positive electrode, resulting in a problem that the cycle life of the battery is reduced and further gas is generated inside the battery. As a method for solving this problem, Patent Document 4 discloses that, by adding a silyl group-containing compound to a nonaqueous electrolytic solution, even if the lithium ion secondary battery is operated at a high voltage, the cycle life of the battery is not reduced. It has been presented.

JP 2001-319685 A Japanese Patent Laid-Open No. 08-88023 JP 2000-515672 A US Patent Application Publication No. 2012/0315536

  However, even if the silyl group-containing compound described in Patent Document 4 is added to the non-aqueous electrolyte, there is room for improvement because gas is generated inside the battery and the battery swells during use. Accordingly, an object of the present invention is to maintain an effect of a silyl group-containing compound as a useful additive of a lithium ion secondary battery, while suppressing gas generation during use of the battery and preventing the battery from swelling. And an electrolyte for a non-aqueous electricity storage device containing the additive, and a lithium ion secondary battery including the electrolyte.

The present inventors have intensively studied to solve the above problems. As a result, in a lithium ion secondary battery using an electrolytic solution containing a compound having a silyl group having a specific structure, it was found that the amount of gas generation can be reduced while maintaining the cycle characteristics of the battery, and the present invention has been completed. It was.
That is, the present invention is as follows.

｛式中、Ｒ^ａ１、Ｒ^ａ２、及びＲ^ａ３は、それぞれ独立に、置換されていてもよい炭素数１〜２０の炭化水素基を示し、且つＲ^ａ１、Ｒ^ａ２、及びＲ^ａ３の炭素数の合計が５〜２０である。｝で表される基で置換された化合物（Ａ）から成ることを特徴とする、非水蓄電デバイス用電解液の添加剤。 [1] At least one of acidic protons having an acid selected from the group consisting of a proton acid having at least one atom selected from a phosphorus atom and a boron atom, a sulfonic acid, and a carboxylic acid is represented by the following general formula (A1 ):

{Wherein R ^a1 , R ^a2 , and R ^a3 each independently represents an ^optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and R ^a1 , R ^a2 , and R ^a3 are carbon numbers. Is a total of 5-20. } The additive of the electrolyte solution for nonaqueous electrical storage devices characterized by comprising the compound (A) substituted by group represented by these.

｛式中、Ｍ^１はリン原子又はホウ素原子であり、
ｍは１〜２０の整数であり、
Ｍ^１がリン原子の場合、ｎは０又は１であり、Ｍ^１がホウ素原子の場合、ｎは０であり、Ａ１は上記一般式（Ａ１）で表される基を示し、そして
Ｒ^ａ４及びＲ^ａ５は、それぞれ独立に、ＯＨ基、ＯＬｉ基、置換されていてもよい炭素数１〜２０の炭化水素基、置換されていてもよい炭素数１〜２０のアルコキシ基、及びＯＡ１基（式中、Ａ１は上記一般式（Ａ１）で表される基を示す。）から成る群より選ばれる基を示す。｝、

｛式中、Ｍ^２はリン原子又はホウ素原子であり、
ｊは２〜２０の整数であり、
Ｍ^２がリン原子の場合、ｋは０又は１であり、Ｍ^２がホウ素原子の場合、ｋは０であり、
そして
Ｒ^ａ６は、ＯＨ基、ＯＬｉ基、置換されていてもよい炭素数１〜２０の炭化水素基、置換されていてもよい炭素数１〜２０のアルコキシ基、ＯＡ１基（式中、Ａ１は上記一般式（Ａ１）で表される基を示す。）、及び一般式ＯＰ（Ｏ）_ｌ（Ｒ^ａ７Ｒ^ａ８）（式中、ｌは、０又は１であり、Ｒ^ａ７及びＲ^ａ８は、それぞれ独立に、ＯＨ基、ＯＬｉ基、置換されていてもよい炭素数１〜２０の炭化水素基、置換されていてもよい炭素数１〜２０のアルコキシ基、又はＯＡ１基（式中、Ａ１は上記一般式（Ａ１）で表される基を示す。）を示す。）で表される基から成る群より選ばれる基を示し、ただし、Ｒ^ａ６のうちの少なくとも１つはＯＡ１基（式中、Ａ１は上記一般式（Ａ１）で表される基を示す。）を有する。｝、

｛式中、Ａ１は上記一般式（Ａ１）表される基を示し、そして
Ｒ^ａ９は置換されていてもよい炭素数１〜２０の炭化水素基を示す。｝のそれぞれで表される化合物、並びに
硫酸の有する酸性プロトンのうちの少なくとも１つが上記一般式（Ａ１）で表される基で置換された化合物、
から成る群より選ばれる１種以上である、[１]に記載の添加剤。 [2] The compound (A) is
The following general formulas (A2) to (A4):

{Wherein M ¹ is a phosphorus atom or a boron atom,
m is an integer of 1 to 20,
When M ¹ is a phosphorus atom, n is 0 or 1, and when M ¹ is a boron atom, n is 0, A1 represents a group represented by the above general formula (A1), and R ^a4 and R ^a5 is each independently an OH group, an OLi group, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 20 carbon atoms, and an OA1 group (formula A1 represents a group selected from the group consisting of the above general formula (A1). },

{Wherein M ² is a phosphorus atom or a boron atom;
j is an integer of 2 to 20,
When M ² is a phosphorus atom, k is 0 or 1, and when M ² is a boron atom, k is 0,
R ^a6 is an OH group, an OLi group, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 20 carbon atoms, an OA1 group (wherein A1 is And a general formula OP (O) _l (R ^a7 R ^a8 ) (wherein l is 0 or 1, and R ^a7 and R ^a8 are Each independently, an OH group, an OLi group, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 20 carbon atoms, or an OA1 group (wherein A1 is A group selected from the group consisting of the groups represented by formula (A1).), Wherein at least one of R ^a6 is an OA1 group (wherein , A1 represents a group represented by the general formula (A1). },

{In formula, A1 shows group represented by the said general formula (A1), and ^Ra9 shows the C1-C20 hydrocarbon group which may be substituted. }, And a compound in which at least one of acidic protons of sulfuric acid is substituted with a group represented by the general formula (A1),
The additive according to [1], which is at least one selected from the group consisting of:

[3] The compound (A) is
In the above general formula (A2), M ¹ is a phosphorus atom, m is an integer of 1 to 4, and all of R ^a4 and R ^a5 are OA1 groups (wherein A1 is represented by the above general formula (A1)). A compound represented by:
In the general formula (A2), M ¹ is a boron atom, m is 1, and R ^a4 is an alkyl group having 1 to 4 carbon atoms or an OA1 group (wherein A1 is represented by the general formula (A1)). A compound represented by:
In the general formula (A3), M ² is a phosphorus atom, j is 3 or 4, and all of R ^a6 is an OA1 group (wherein A1 represents a group represented by the general formula (A1)). A compound that is
A compound in which all of acidic protons of sulfuric acid are substituted with the group represented by the general formula (A1), and acetic acid, oxalic acid, malonic acid, succinic acid, itaconic acid, adipic acid, phthalic acid, isophthalic acid, or The additive according to [2], which is at least one selected from the group consisting of compounds in which all of the acidic protons of terephthalic acid are substituted with a group represented by the general formula (A1).

｛式中、Ｒ^ａ１、Ｒ^ａ２、及びＲ^ａ３は、それぞれ独立に、置換されていてもよい炭素数１〜２０の炭化水素基を示し、且つＲ^ａ１、Ｒ^ａ２、及びＲ^ａ３の炭素数の合計が５〜２０である。｝で表される基で置換された化合物（Ａ）の、非水蓄電デバイス用電解液の添加剤としての使用。 [4] At least one of acidic protons having an acid selected from the group consisting of a proton acid having at least one atom selected from a phosphorus atom and a boron atom, a sulfonic acid, and a carboxylic acid is represented by the following general formula (A1 ):

{Wherein R ^a1 , R ^a2 , and R ^a3 each independently represents an ^optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and R ^a1 , R ^a2 , and R ^a3 are carbon numbers. Is a total of 5-20. } The compound (A) substituted by the group represented by these is used as an additive of the electrolyte solution for non-aqueous electricity storage devices.

｛式中、Ｒ^ｃ１、Ｒ^ｃ２、及びＲ^ｃ３は、それぞれ独立に、置換されていてもよい炭素数１〜２０の炭化水素基、又は置換されていてもよい炭素数１〜２０のアルコキシ基を示し、そして
Ｘ_１は、一般式ＯＲ^１（式中、Ｒ^１は、水素原子、置換されていてもよい炭素数１〜２０の炭化水素基、炭素数１〜２０のシリル基、ＳＯ_２ＣＨ_３、若しくはＳＯ_２ＣＦ_３を示す。）で表される基、又はハロゲン原子を示す。｝で表される１種以上の化合物（Ｃ）
から成る群より選択される少なくとも１種の化合物１質量ｐｐｍ以上１００質量％以下と、
を含有することを特徴とする、非水蓄電デバイス用電解液の添加剤組成物。 [5] (a) 100 parts by mass of the additive according to any one of [1] to [3];
(B) Lewis base and general formula Q ⁺ Y ⁻ {wherein Q ⁺ represents a quaternary ammonium group, a quaternary phosphonium group, or an alkali metal, and Y ⁻ represents an alkoxy group or an aryloxy group. } One or more compounds (B) selected from the group consisting of compounds represented by the formula:

{Wherein R ^c1 , R ^c2 , and R ^c3 each independently represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted alkoxy group having 1 to 20 carbon atoms. And X ₁ represents a general formula OR ¹ (wherein R ¹ represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, SO ₂ Represents a group represented by CH ₃ or SO ₂ CF ₃ ), or a halogen atom. } One or more compounds (C) represented by
1 mass ppm or more and 100 mass% or less of at least one compound selected from the group consisting of:
An additive composition for an electrolyte solution for a non-aqueous electricity storage device, comprising:

[6] a non-aqueous solvent;
Lithium salt,
The additive according to any one of [1] to [4];
An electrolyte for a non-aqueous electricity storage device, comprising:
[7] The content of the additive is 0.01% by mass or more and 10% by mass or less with respect to 100% by mass of the electrolyte solution for a non-aqueous energy storage device. Electrolytic solution.

[8] The lithium salt is LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , Li ₂ SiF ₆ , LiOSO ₂ C _k F _{2k + 1} {wherein, k is an integer of 0 to 8}, LiN (SO ₂ C _k F _{2k + 1} ) ₂ (where k is an integer from 0 to 8), and LiPF _n (C _k F _{2k + 1} ) _6-n {where n is an integer from 1 to 5 and k is The electrolyte solution for non-aqueous electricity storage devices according to [6] or [7], which is one or more selected from the group consisting of} which is an integer of 1 to 8.
[9] The electrolyte solution for a non-aqueous electricity storage device according to any one of [6] to [8], further containing one or more selected from the group consisting of lithium difluorophosphate and lithium monofluorophosphate.
[10] The electrolyte solution for a nonaqueous electricity storage device according to any one of [6] to [9], wherein the nonaqueous solvent contains one or more selected from the group consisting of cyclic carbonates and chain carbonates. .

[11] a positive electrode containing a positive electrode active material;
A negative electrode containing a negative electrode active material;
[6] to [10] The electrolyte solution for nonaqueous electricity storage device according to any one of
A lithium ion secondary battery comprising:
[12] The lithium ion secondary battery according to [11], wherein the positive electrode active material has a discharge capacity of 10 mAh / g or more at a potential of 4.2 V (vsLi / Li ⁺ ) or more.

[13] The positive electrode active material is
Following formula (E1):
_{LiMn 2-x Ma x O 4} (E1)
{In the formula, Ma represents a transition metal, and x is a number in the range of 0.2 ≦ x ≦ 0.7. } Oxides represented by
The following formula (E2):
LiMeO ₂ (E2)
{In the formula, Me represents a transition metal. } Oxides represented by
The following formula (E3):
_{zLi 2 McO 3 - (1-} z) LiMdO 2 (E3)
{Wherein Mc and Md each independently represent a transition metal, and z is a number in the range of 0.1 ≦ z ≦ 0.9. } A composite oxide represented by
The following formula (E4):
LiMb _1-y Fe _y PO ₄ (E4)
{In the formula, Mb represents one or more selected from the group consisting of Mn and Co, and y is a number in the range of 0 ≦ y ≦ 0.9. }; And the following formula (E5):
Li ₂ MfPO ₄ F (E5)
{In the formula, Mf represents one or more selected from the group consisting of transition metals. } The lithium ion secondary battery according to [12], which is at least one selected from the group consisting of compounds represented by:
[14] The lithium ion secondary battery according to any one of [11] to [13], wherein the lithium-based positive electrode potential at full charge is 4.2 V (vsLi / Li ⁺ ) or more.

  According to the present invention, an electrolytic solution containing an additive composed of a compound having a predetermined substituted silyl group according to the present invention is an electrolysis for a non-aqueous storage device that enables a reduction in gas generation while maintaining the cycle characteristics of the battery. And a lithium ion secondary battery using the electrolytic solution.

It is sectional drawing which shows roughly an example of the lithium ion secondary battery in the form for implementing this invention.

  Hereinafter, modes for carrying out the present invention (hereinafter simply referred to as “embodiments”) will be described in detail. However, the present invention is not limited to this, and various modifications can be made without departing from the scope of the invention.

｛式中、Ｒ^ａ１、Ｒ^ａ２、及びＲ^ａ３は、それぞれ独立に、置換されていてもよい炭素数１〜２０の炭化水素基を示し、且つＲ^ａ１、Ｒ^ａ２、及びＲ^ａ３の炭素数の合計が５〜２０である。｝で表される基（以下「シリル基（Ａ１）」という。で置換された化合物である。ここで、「リン原子及びホウ素原子から選択される１種以上の原子を有する」は、「プロトン酸」のみにかかる。スルホン酸及びカルボン酸は、それぞれ、リン原子及びホウ素原子から選択される１種以上の原子を有していてもよいし、有していなくてもよい。また、「酸性プロトン」とは、上記の酸が酸として働く場合にＨ^＋として放出されるべき水素原子を意味する。 [Silyl group-containing compound (A)]
In one embodiment of the present invention, a compound containing a silyl group having a specific structure (compound (A)) is used as an additive for an electrolyte solution for a non-aqueous electricity storage device. In the compound (A), at least one of acidic protons having an acid selected from the group consisting of a protonic acid having at least one atom selected from a phosphorus atom and a boron atom, a sulfonic acid, and a carboxylic acid is represented by the following general formula ( A1):

{Wherein R ^a1 , R ^a2 , and R ^a3 each independently represents an ^optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and R ^a1 , R ^a2 , and R ^a3 are carbon numbers. Is a total of 5-20. } (Hereinafter referred to as “silyl group (A1)”). Here, “having one or more atoms selected from phosphorus atom and boron atom” means “proton” The sulfonic acid and carboxylic acid may or may not have one or more atoms selected from a phosphorus atom and a boron atom, respectively. “Proton” means a hydrogen atom to be released as H ⁺ when the acid acts as an acid.

In the embodiment of the present invention, the “protonic acid having a phosphorus atom” is not particularly limited as long as it is a compound having a phosphorus atom in the molecule and a hydrogen atom that can be dissociated as a proton. The protonic acid having a phosphorus atom includes a halogen atom such as a fluorine atom and a chlorine atom in the molecule; or an organic group such as an alkoxy group and an alkyl group; and a heteroatom such as Si, B, O, and N. Also good. The protonic acid having a phosphorus atom may contain a plurality of phosphorus atoms in the molecule. Examples thereof include condensed phosphoric acid.
Although it does not specifically limit as a proton acid which has a phosphorus atom, For example, orthophosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, or condensed phosphoric acid is preferable. These protonic acids having a phosphorus atom may be substituted. Among these, orthophosphoric acid, phosphorous acid, phosphonic acid, or condensed phosphoric acid is more preferable. The compound (A) in which at least one of the acidic protons of the proton acid having a phosphorus atom is substituted with a silyl group (A1) is excellent in handling and stability as a compound.

  In the embodiment of the present invention, the “protonic acid having a boron atom” is not particularly limited as long as it is a compound having a boron atom in the molecule and a hydrogen atom that can be dissociated as a proton. Protonic acid having a boron atom may contain a halogen atom such as a fluorine atom or a chlorine atom in the molecule; or an organic group such as an alkoxy group or an alkyl group; or a hetero atom such as Si, P, O, or N. Good. The protonic acid having a boron atom may contain a plurality of boron atoms in the molecule. Although it does not specifically limit as a proton acid which has a boron atom, For example, a boric acid, a boronic acid, or a borinic acid is preferable. These protonic acids having boron atoms may be substituted.

In the embodiment of the present invention, the “sulfonic acid” is not particularly limited as long as it is a compound having an SO ₃ H group (sulfonic acid group) in the molecule. It may have a plurality of sulfonic acid groups in the molecule. The concept of sulfonic acid in the present embodiment includes sulfuric acid (HOSO ₃ H). Examples of the sulfonic acid include, but are not limited to, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, 1,2-ethanedisulfonic acid, trifluoromethanesulfonic acid, perfluorobutanesulfonic acid, benzenesulfonic acid, Preferred examples include p-toluenesulfonic acid, sulfuric acid and the like.

In the embodiment of the present invention, the “carboxylic acid” is not particularly limited as long as it is a compound having a CO ₂ H group (carboxylic acid group) in the molecule, and has a plurality of carboxylic acid groups in the molecule. Also good. The carboxylic acid is not particularly limited. Examples include terephthalic acid, salicylic acid, malonic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, and itaconic acid. Among these, dicarboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, malonic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, and itaconic acid are preferred, and adipic acid, itaconic acid, succinic acid, etc. Acid, isophthalic acid, and terephthalic acid are more preferred.

In the general formula (A1), R ^{a1 to} R ^a3 each independently represent an ^optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
With respect to R ^{a1 to} R ^a3 , the “ ^optionally substituted hydrocarbon group” is not particularly limited, and examples thereof include an aliphatic hydrocarbon group; an aromatic hydrocarbon group such as a phenyl group; a hydrogen in the hydrocarbon group And fluorine substituted hydrocarbon groups such as a trifluoromethyl group in which all the atoms are substituted with fluorine atoms. The said hydrocarbon group may have a functional group as needed. Such functional groups are not particularly limited, but include, for example, halogen atoms such as fluorine atom, chlorine atom and bromine atom; nitrile group (—CN), ether group (—O—), carbonate group (—OCO) _2- ), ester group (—CO ₂ —), carbonyl group (—CO—), sulfide group (—S—), sulfoxide group (—SO—), sulfone group (—SO ₂ —), urethane group (— NHCO ₂ —) and the like.

When R ^<a1 > -R <^a3> is a hydrocarbon group, carbon number of each hydrocarbon group is 1-20, 1-10 are preferable and 1-6 are more preferable. When the carbon number of R ^{a1 to} R ^a3 is within the above range, the miscibility with the nonaqueous solvent tends to be superior.
Preferred examples of R ^{a1 to} R ^a3 include, for example, a methyl group, an ethyl group, a vinyl group, an allyl group, a 1-methylvinyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and an iso-butyl group. And aliphatic hydrocarbon groups such as sec-butyl group, tert-butyl group and fluoromethyl group; and aromatic hydrocarbon groups such as benzyl group, phenyl group, nitrile substituted phenyl group and fluorinated phenyl group. Among these, from the viewpoint of availability, handling, and chemical stability, a methyl group, an ethyl group, a vinyl group, an allyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a tert-butyl group, A phenyl group or a fluoromethyl group is more preferable. Two of R ^{a1 to} R ^a3 may be bonded to form a ring. In order to form a ring, for example, two of R ^{a1 to} R ^a3 may be substituted or unsubstituted, saturated or unsaturated, alkylene groups.

In the silyl group (A1), the total carbon number of R ^a1 , R ^a2 and R ^a3 is 5 to 20, more preferably 5 to 15, and particularly preferably 5 to 10. When the compound (A) in which the silyl group (A1) has 5 to 20 carbon atoms is used as an electrolyte solution additive for non-aqueous energy storage devices, gas generation can be suppressed while maintaining the effect of improving battery cycle characteristics. . Although the detailed mechanism for this phenomenon is not clear, the compound (A) acts on the positive electrode or the negative electrode or both of them to improve the input / output characteristics while maintaining the effect of improving the cycle characteristics of the battery. In addition, it is considered that the decomposition of the electrolyte and the generation of gas could be suppressed.

Such a silyl group (A1) is not particularly limited.
_{-Si (CH 3) 2 (CH} 2 CH 2 CH 3),
_{-Si (CH 3) 2 (CH} 2 CH = CH 2),
_{-Si (CH 3) 2 (C} (CH 3) = CH 2),
_{-Si (CH 3) 2 [CH} (CH 3) 2],
_{-Si (CH 3) 2 [(} CH 2) 3 CH 3)],
_{-Si (CH 3) 2 [CH} 2 CH (CH 3) 2],
_{-Si (CH 3) 2 [C} (CH 3) 3],
_{-Si (C 2 H 5) 3} ,
_{-Si (CH = CH 2) 3} ,
_{-Si (CH 3) 2 (C} 6 H 5),
_{-Si (CH 2 CH 2 CH 3} ) 3,
_{-Si [CH (CH 3) 2} ] 3,
_{-Si (CH 2 CH = CH 2} ) 3
_{-Si (CH 3) 2 [(} CH 2) 7 CH 3],
_{-Si [(CH 2) 3 CH} 3] 3,
_{-Si (CH 3) (C 6} H 5) 2,
_{-Si (CH = CH 2) (} C 6 H 5) 2,
_{-Si [(CH 2) 5 CH} 3] 3,
_{-Si (C 6 H 5) 3} ,
_{-Si (CH 3) 2 [(} CH 2) 17 CH 3)],
Etc. can be mentioned as preferred examples,

_{-Si (CH 3) 2 (CH} 2 CH 2 CH 3),
_{-Si (CH 3) 2 (CH} 2 CH = CH 2),
_{-Si (CH 3) 2 (C} (CH 3) = CH 2),
_{-Si (CH 3) 2 [CH} (CH 3) 2],
_{-Si (CH 3) 2 [(} CH 2) 3 CH 3)],
_{-Si (CH 3) 2 [CH} 2 CH (CH 3) 2],
_{-Si (CH 3) 2 [C} (CH 3) 3],
_{-Si (C 2 H 5) 3} ,
_{-Si (CH = CH 2) 3} ,
_{-Si (CH 3) 2 (C} 6 H 5),
_{-Si (CH 2 CH 2 CH 3} ) 3,
_{-Si [CH (CH 3) 2} ] 3,
_{-Si (CH 2 CH = CH 2} ) 3
_{-Si (CH 3) 2 [(} CH 2) 7 CH 3],
_{-Si [(CH 2) 3 CH} 3] 3,
_{-Si (CH 3) (C 6} H 5) 2, and _{-Si (CH = CH 2) (} C 6 H 5) 2,
Is more preferred,

_{-Si (CH 3) 2 (CH} 2 CH 2 CH 3),
_{-Si (CH 3) 2 (CH} 2 CH = CH 2),
_{-Si (CH 3) 2 [CH} (CH 3) 2],
_{-Si (CH 3) 2 [C} (CH 3) 3],
_{-Si (C 2 H 5) 3} ,
_{-Si (CH 3) 2 (C} 6 H 5),
_{-Si (CH 2 CH 2 CH 3} ) 3, and _{-Si [CH (CH 3) 2} ] 3,
Is particularly preferred. When the silyl group (A1) has such a structure, the chemical durability of the compound (A) having the silyl group (A1) in the lithium ion secondary battery tends to be further improved.

In the compound (A), when an acid selected from the group consisting of a protonic acid having at least one atom selected from a phosphorus atom and a boron atom, a sulfonic acid, and a carboxylic acid has a plurality of acidic protons In this case, at least one acidic proton may be substituted with the silyl group (A1). In that case, the compound (A) can also be referred to as a silyl ester compound. The remaining acidic protons that are not substituted may be present as they are, or may be substituted with a functional group other than the silyl group (A1). Such a functional group is not particularly limited, but for example, a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, or a saturated or unsaturated halogenated hydrocarbon group having 1 to 20 carbon atoms is preferable. Such a group is not particularly limited, and examples thereof include an alkyl group, an alkenyl group, an alkynyl group, an allyl group, and a vinyl group.
An acid selected from the group consisting of a proton acid, a sulfonic acid, and a carboxylic acid having one or more atoms selected from a phosphorus atom and a boron atom forms a ring by combining two of the hydrogen atoms of the acid. It may be. In order to form a ring, for example, two of the hydrogen atoms can be joined and substituted with a substituted or unsubstituted, saturated or unsaturated alkylene group.

｛式中、Ｍ^１はリン原子又はホウ素原子であり、
ｍは１〜２０の整数であり、
Ｍ^１がリン原子の場合、ｎは０又は１であり、Ｍ^１がホウ素原子の場合、ｎは０であり、Ａ１は上記一般式（Ａ１）で表される基を示し、そして
Ｒ^ａ４及びＲ^ａ５は、それぞれ独立に、ＯＨ基、ＯＬｉ基、置換されていてもよい炭素数１〜２０の炭化水素基、置換されていてもよい炭素数１〜２０のアルコキシ基、及びＯＡ１基（式中、Ａ１は上記一般式（Ａ１）で表される基を示す。）から成る群より選ばれる基を示す。｝、 Although it does not specifically limit as a compound (A), For example, following general formula (A2)-(A4):

{Wherein M ¹ is a phosphorus atom or a boron atom,
m is an integer of 1 to 20,
When M ¹ is a phosphorus atom, n is 0 or 1, and when M ¹ is a boron atom, n is 0, A1 represents a group represented by the above general formula (A1), and R ^a4 and R ^a5 is each independently an OH group, an OLi group, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 20 carbon atoms, and an OA1 group (formula A1 represents a group selected from the group consisting of the above general formula (A1). },

｛式中、Ｍ^２はリン原子又はホウ素原子であり、
ｊは２〜２０の整数であり、
Ｍ^２がリン原子の場合、ｋは０又は１であり、Ｍ^２がホウ素原子の場合、ｋは０であり、
そして
Ｒ^ａ６は、ＯＨ基、ＯＬｉ基、置換されていてもよい炭素数１〜２０の炭化水素基、置換されていてもよい炭素数１〜２０のアルコキシ基、ＯＡ１基（式中、Ａ１は上記一般式（Ａ１）で表される基を示す。）、及び一般式ＯＰ（Ｏ）_ｌ（Ｒ^ａ７Ｒ^ａ８）（式中、ｌは、０又は１であり、Ｒ^ａ７及びＲ^ａ８は、それぞれ独立に、ＯＨ基、ＯＬｉ基、置換されていてもよい炭素数１〜２０の炭化水素基、置換されていてもよい炭素数１〜２０のアルコキシ基、又はＯＡ１基（式中、Ａ１は上記一般式（Ａ１）で表される基を示す。）を示す。）で表される基から成る群より選ばれる基を示し、ただし、Ｒ^ａ６のうちの少なくとも１つはＯＡ１基（式中、Ａ１は上記一般式（Ａ１）で表される基を示す。）を有する。｝

{Wherein M ² is a phosphorus atom or a boron atom;
j is an integer of 2 to 20,
When M ² is a phosphorus atom, k is 0 or 1, and when M ² is a boron atom, k is 0,
R ^a6 is an OH group, an OLi group, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 20 carbon atoms, an OA1 group (wherein A1 is And a general formula OP (O) _l (R ^a7 R ^a8 ) (wherein l is 0 or 1, and R ^a7 and R ^a8 are Each independently, an OH group, an OLi group, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 20 carbon atoms, or an OA1 group (wherein A1 is A group selected from the group consisting of the groups represented by formula (A1).), Wherein at least one of R ^a6 is an OA1 group (wherein , A1 represents a group represented by the general formula (A1). }

｛式中、Ａ１は上記一般式（Ａ１）表される基を示し、そして
Ｒ^ａ９は置換されていてもよい炭素数１〜２０の炭化水素基を示す。｝のそれぞれで表される化合物、並びに
硫酸の有する酸性プロトンのうちの少なくとも１つが上記一般式（Ａ１）で表される基で置換された化合物、から成る群より選ばれる１種以上である。

{In formula, A1 shows group represented by the said general formula (A1), and ^Ra9 shows the C1-C20 hydrocarbon group which may be substituted. }, And at least one of acidic protons of sulfuric acid is one or more selected from the group consisting of compounds substituted with a group represented by the above general formula (A1).

[Compound represented by formula (A2)]
In the general formula (A2), ^{M 1} is phosphorus atom or a boron atom, m is an integer of from 1 to 20, and n is 0 or 1. When M ¹ is a phosphorus atom, n is 0 or 1. When M ¹ is a boron atom, n is 0. R ^a4 and R ^a5 each independently represent an OH group, an OLi group, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 20 carbon atoms, and OA1. A group selected from the group consisting of groups (wherein A1 represents a group represented by the above general formula (A1)).
When M ¹ is a boron atom and n is 0, the compound represented by the general formula (A2) has a boric acid structure.

｛式中、ｍ、ｎ、Ｒ^ａ４、Ｒ^ａ５、及びＡ１は、それぞれ、上記一般式（Ａ２）において定義されたとおりである。｝で表される化合物である。ｎが０である一般式（Ａ５）で表される化合物は亜リン酸構造となり、ｎが１である一般式（Ａ５）で表される化合物はリン酸構造となる。
上記一般式（Ａ２）及び上記一般式（Ａ５）において、Ｒ^ａ４及びＲ^ａ５は、それぞれ独立に、ＯＨ基、ＯＬｉ基、置換されていてもよい炭素数１〜２０の炭化水素基、置換されていてもよい炭素数１〜２０のアルコキシ基、及びＯＡ１基（式中、Ａ１は上記一般式（Ａ１）で表される基を示す。）から成る群より選ばれる基を示す。 When M ¹ is a phosphorus atom, the compound represented by the general formula (A2) has the following general formula (A5):

{Wherein m, n, R ^a4 , R ^a5 , and A1 are as defined in the general formula (A2). } It is a compound represented. The compound represented by the general formula (A5) in which n is 0 has a phosphorous acid structure, and the compound represented by the general formula (A5) in which n is 1 has a phosphoric acid structure.
In the general formula (A2) and the general formula (A5), R ^a4 and R ^a5 are each independently an OH group, an OLi group, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or a substituted group. And a group selected from the group consisting of an optionally substituted alkoxy group having 1 to 20 carbon atoms and an OA1 group (wherein A1 represents a group represented by the general formula (A1)).

With respect to R ^a4 and R ^a5 , the “ ^optionally substituted hydrocarbon group” is not particularly limited, and examples thereof include an aromatic hydrocarbon such as an aliphatic hydrocarbon group and a phenyl group; a hydrogen atom in the hydrocarbon group And a fluorine-substituted hydrocarbon group such as a trifluoromethyl group, all of which are substituted with fluorine atoms. The hydrocarbon group may have various functional groups as necessary. Such a functional group is not particularly limited. For example, a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; a nitrile group (—CN); an ether group (—O—): a carbonate group (—OCO ₂ —). Ester group (—CO ₂ —); carbonyl group (—CO—); sulfide group (—S—); sulfoxide group (—SO—); sulfone group (—SO ₂ —); urethane group (—NHCO ₂ ); -); Aromatic groups such as phenyl group and benzyl group; and the like.
When R ^a4 and R ^a5 are hydrocarbon groups, the carbon number thereof is 1 to 20, preferably 1 to 10, and more preferably 1 to 6. When the carbon number of the hydrocarbon group is within the above range, the miscibility with the non-aqueous solvent tends to be more excellent.

For R ^a4 and R ^a5 , preferred examples of the hydrocarbon group include a methyl group, an ethyl group, a vinyl group, an allyl group, an isopropyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a fluorohexyl group. An aliphatic hydrocarbon group is mentioned. From the viewpoint of chemical stability, a methyl group, ethyl group, allyl group, propyl group, butyl group, pentyl group, hexyl group, or fluorohexyl group is more preferable.

With respect to R ^a4 and R ^a5 , the “optionally substituted alkoxy group” is not particularly limited. For example, an alkoxy group having an aliphatic group; a trifluoromethoxy group in which a hydrogen atom in the alkoxy group is fluorine-substituted And fluorine-substituted alkoxy groups such as a hexafluoroisopropoxy group. The alkoxy group may be substituted with various functional groups as necessary. Such a functional group is not particularly limited. For example, a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; a nitrile group (—CN); an ether group (—O—); a carbonate group (—OCO ₂ —). Ester group (—CO ₂ —); carbonyl group (—CO—); sulfide group (—S—); sulfoxide group (—SO—); sulfone group (—SO ₂ —); urethane group (—NHCO ₂ ); -); Aromatic groups such as phenyl group and benzyl group; and the like.

About R ^{< a4>} and R ^<a5> , carbon number of an alkoxy group is 1-20, 1-10 are preferable and 1-6 are more preferable. When the number of carbon atoms of the alkoxy group is within the above range, the miscibility with the nonaqueous solvent tends to be superior.
Preferred examples of the alkoxy group include aliphatic alkoxy such as methoxy group, ethoxy group, vinyloxy group, allyloxy group, propoxy group, butoxy group, cyanoethoxy group, fluoroethoxy group, and fluoropropoxy group. Groups. From the viewpoint of chemical stability, a methoxy group, an ethoxy group, a vinyloxy group, an allyloxy group, a propoxy group, a butoxy group, a cyanoethoxy group, a fluoroethoxy group, or a fluoropropoxy group is preferable.

Specific examples of the compound represented by the general formula (A2) include
As a compound in which M ¹ is B and m is 1, for example,
Tris [dimethyl (n-propyl) silyl] borate,
Tris borate (allyldimethylsilyl),
Tris borate [dimethyl (1-methylvinyl) silyl],
Tris (dimethylisopropylsilyl) borate,
Tris borate [(n-butyl) dimethylsilyl],
Tris borate [(sec-butyl) dimethylsilyl],
Tris borate [(tert-butyl) dimethylsilyl],
Tris borate (dimethylphenylsilyl),
Tris borate (diphenylmethylsilyl),
Tris borate (triphenylsilyl),
Tris borate (triethylsilyl),
Tris borate (trivinylsilyl),
Tris borate [tri (n-propyl) silyl],
Tris borate (triisopropylsilyl),
Tris borate (triallylsilyl) and the like;

As a compound in which M ¹ is P (that is, a compound represented by the general formula (A5)), for example,
Tris phosphate (dimethyl (n-propyl) silyl) when m is 1,
Tris phosphate (allyldimethylsilyl),
Tris phosphate (dimethyl (1-methylvinyl) silyl),
Tris phosphate (dimethylisopropylsilyl),
Tris phosphate (n-butyldimethylsilyl),
Tris phosphate (sec-butyldimethylsilyl),
Tris phosphate (tert-butyldimethylsilyl),
Tris phosphate (dimethylphenylsilyl),
Tris phosphate (diphenylmethylsilyl),
Tris phosphate (triphenylsilyl),
Tris phosphate (triethylsilyl),
Tris phosphate (trivinylsilyl),
Tris phosphate (tri (n-propyl) silyl),
Tris phosphate (triisopropylsilyl),
Tris phosphate (triallylsilyl),
Monomethylbisphosphate (triethylsilyl) phosphate,
Monoethylbisphosphate (triethylsilyl) phosphate,
Mono (trifluoroethyl) bis (triethylsilyl) phosphate,
Mono (hexafluoroisopropyl) bis (triethylsilyl) phosphate and the like; and

Tris phosphite (dimethyl (n-propyl) silyl),
Tris phosphite (allyldimethylsilyl),
Tris phosphite (dimethyl (1-methylvinyl) silyl),
Tris phosphite (dimethylisopropylsilyl),
Tris phosphite (n-butyldimethylsilyl),
Tris phosphite (sec-butyldimethylsilyl),
Tris phosphite (tert-butyldimethylsilyl),
Tris phosphite (dimethylphenylsilyl),
Tris phosphite (diphenylmethylsilyl),
Tris phosphite (triphenylsilyl),
Tris phosphite (triethylsilyl),
Tris phosphite (trivinylsilyl),
Tris phosphite (tri (n-propyl) silyl),
Tris phosphite (triisopropylsilyl),
Tris phosphite (triallylsilyl),

Bis [dimethyl (n-propyl) silyl] methylphosphonate,
Bis (allyldimethylsilyl) methylphosphonate,
Bis [dimethyl (1-methylvinyl) silyl] methylphosphonate,
Bis (dimethylisopropylsilyl) methylphosphonate,
Bis [(n-butyl) dimethylsilyl] methylphosphonate,
Bis [(sec-butyl) dimethylsilyl] methylphosphonate,
Bis [(tert-butyl) dimethylsilyl] methylphosphonate,
Bis (dimethylphenylsilyl) methylphosphonate,
Bis (diphenylmethylsilyl) methylphosphonate,
Bis (triphenylsilyl) methylphosphonate,
Bis (triethylsilyl) methylphosphonate,
Bis (trivinylsilyl) methylphosphonate,
Bis [(n-propyl) silyl] methylphosphonate,
Bis (triisopropylsilyl) methylphosphonate,
Bis (triallylsilyl) methylphosphonate,

Bis [dimethyl (n-propyl) silyl] ethylphosphonate,
Bis (allyldimethylsilyl) ethylphosphonate,
Bis [dimethyl (1-methylvinyl) silyl] ethylphosphonate,
Bis (dimethylisopropylsilyl) ethylphosphonate,
Bis [(n-butyl) dimethylsilyl] ethylphosphonate,
Bis [(sec-butyl) dimethylsilyl] ethylphosphonate,
Bis [(tert-butyl) dimethylsilyl] ethylphosphonate,
Bis (dimethylphenylsilyl) ethylphosphonate,
Bis (diphenylmethylsilyl) ethylphosphonate,
Bis (triphenylsilyl) ethylphosphonate,
Bis (triethylsilyl) ethylphosphonate,
Bis (trivinylsilyl) ethylphosphonate,
Bis [tri (n-propyl) silyl] ethylphosphonate,
Bis (triisopropylsilyl) ethylphosphonate,
Bis (triallylsilyl) ethylphosphonate,

Bis [propyl (dimethyl-silyl) propylphosphonate],
Bis (propyldimethylsilyl) propylphosphonate,
Bis [propyl (1-methylvinyl) silyl] propyl phosphonate,
Bis (dimethylisopropylsilyl) propyl phosphonate,
Bis [(n-butyl) dimethylsilyl] propyl phosphonate,
Bis [(sec-butyl) dimethylsilyl] propylphosphonate,
Bis [(tert-butyl) dimethylsilyl] propylphosphonate,
Bis (dimethylphenylsilyl) propyl phosphonate,
Bis (diphenylmethylsilyl) propyl phosphonate,
Bis (triphenylsilyl) propyl phosphonate,
Bis (triethylsilyl) propyl phosphonate,
Bis (trivinylsilyl) propylphosphonate,
Bis [tri (n-propyl) silyl] propyl phosphonate,
Bis (triisopropylsilyl) propylphosphonate,
Bis (propylallylsilyl) propyl phosphonate,

Bis [dimethyl (n-propyl) silyl] butylphosphonate,
Bis (butyldimethylsilyl) butylphosphonate,
Bis [dimethyl (1-methylvinyl) silyl] butylphosphonate,
Bis (butyl isopropylsilyl) butylphosphonate,
Bis [(n-butyl) dimethylsilyl] butylphosphonate,
Butyl phosphonate bis [(sec-butyl) dimethylsilyl],
Bis [(tert-butyl) dimethylsilyl] butylphosphonate,
Bis (butylphenylsilyl) butylphosphonate,
Butyl phosphonate bis (diphenylmethylsilyl),
Bis (triphenylsilyl) butylphosphonate,
Bis (triethylsilyl) butylphosphonate,
Butyl phosphonate (trivinylsilyl),
Bis [tri (n-propyl) silyl] butylphosphonate,
Bis (triisopropylsilyl) butylphosphonate,
Butyl phosphonate bis (triallylsilyl) and the like;

tetrakis pyrophosphate (dimethyl (n-propyl) silyl) when m is 2;
Tetrakis pyrophosphate (allyldimethylsilyl),
Tetrakis pyrophosphate (dimethyl (1-methylvinyl) silyl),
Tetrakis pyrophosphate (dimethylisopropylsilyl),
Tetrakis pyrophosphate (n-butyldimethylsilyl),
Tetrakis pyrophosphate (sec-butyldimethylsilyl),
Tetrakis pyrophosphate (tert-butyldimethylsilyl),
Tetrakis pyrophosphate (dimethylphenylsilyl),
Tetrakis pyrophosphate (diphenylmethylsilyl),
Tetrakis pyrophosphate (triphenylsilyl),
Tetrakis pyrophosphate (triethylsilyl),
Tetrakis pyrophosphate (trivinylsilyl),
Tetrakis pyrophosphate (tri (n-propyl) silyl),
Tetrakis pyrophosphate (triisopropylsilyl),
Tetrakis pyrophosphate (triallylsilyl) and the like;

pentakis (dimethyl (n-propyl) silyl) tripolyphosphate when m is 3,
Pentakis (allyldimethylsilyl) tripolyphosphate,
Pentakis tripolyphosphate (dimethyl (1-methylvinyl) silyl),
Pentakis (dimethylisopropylsilyl) tripolyphosphate,
Pentakis (n-butyldimethylsilyl) tripolyphosphate,
Pentakis tripolyphosphate (sec-butyldimethylsilyl),
Pentakis (tert-butyldimethylsilyl) tripolyphosphate,
Pentakis tripolyphosphate (dimethylphenylsilyl),
Pentakis (diphenylmethylsilyl) tripolyphosphate,
Pentakis triphosphate (triphenylsilyl),
Pentakis tripolyphosphate (triethylsilyl),
Pentakis tripolyphosphate (trivinylsilyl),
Pentakis tripolyphosphate (tri (n-propyl) silyl),
Pentakis (triisopropylsilyl) tripolyphosphate,
Pentakis tripolyphosphate (triallylsilyl) and the like;

tetrakisphosphate hexakis (dimethyl (n-propyl) silyl) when m is 4;
Hexakis tetrapolyphosphate (allyldimethylsilyl),
Hexakis tetrapolyphosphate (dimethyl (1-methylvinyl) silyl),
Hexakis (dimethylisopropylsilyl) tetrapolyphosphate,
Hexakis tetrapolyphosphate (n-butyldimethylsilyl),
Hexakis tetrapolyphosphate (sec-butyldimethylsilyl),
Hexakis (tert-butyldimethylsilyl) tetrapolyphosphate,
Tetrakisphosphate hexakis (dimethylphenylsilyl),
Hexakis tetrapolyphosphate (diphenylmethylsilyl),
Hexakis (triphenylsilyl) tetrapolyphosphate,
Hexakis (triethylsilyl) tetrapolyphosphate,
Tetrapolyphosphate hexakis (trivinylsilyl),
Hexakis tetrapolyphosphate (tri (n-propyl) silyl),
Hexakis (triisopropylsilyl) tetrapolyphosphate,
Hexakis tetrapolyphosphate (triallylsilyl),
Tetrapolyphosphate hexakis [tris (trifluoromethyl) silyl] and the like;
Can be mentioned respectively.

Among these, from the viewpoint of cycle life and gas generation suppression,
Tris [dimethyl (n-propyl) silyl] borate,
Tris borate (allyldimethylsilyl),
Tris borate [(tert-butyl) dimethylsilyl],
Tris borate (dimethylphenylsilyl),
Tris borate (triethylsilyl),
Tris borate (triisopropylsilyl),
Tris phosphate (triethylsilyl),
Tris phosphate (triisopropylsilyl),
Tris phosphate (allyldimethylsilyl),
Tris phosphate (n-propyldimethylsilyl),
Tris phosphate (tert-butyldimethylsilyl),
Tris phosphate (phenyldimethylsilyl),

Tris phosphite (triethylsilyl),
Tris phosphite (triisopropylsilyl),
Tris phosphite (allyldimethylsilyl),
Tris phosphite (n-propyldimethylsilyl),
Tris phosphite (tert-butyldimethylsilyl),
Tris phosphite (phenyldimethylsilyl),

Bis [dimethyl (n-propyl) silyl] methylphosphonate,
Bis (allyldimethylsilyl) methylphosphonate,
Bis [(tert-butyl) dimethylsilyl] methylphosphonate,
Bis (dimethylphenylsilyl) methylphosphonate,
Bis (triethylsilyl) methylphosphonate,
Bis (triisopropylsilyl) methylphosphonate,

Bis [dimethyl (n-propyl) silyl] ethylphosphonate,
Bis (allyldimethylsilyl) ethylphosphonate,
Bis [(n-butyl) dimethylsilyl] ethylphosphonate,
Bis [(tert-butyl) dimethylsilyl] ethylphosphonate,
Bis (triethylsilyl) ethylphosphonate,
Bis (triisopropylsilyl) ethylphosphonate,

Bis [propyl (dimethyl-silyl) propylphosphonate],
Bis (propyldimethylsilyl) propylphosphonate,
Bis [(tert-butyl) dimethylsilyl] propylphosphonate,
Bis (dimethylphenylsilyl) propyl phosphonate,
Bis (triethylsilyl) propyl phosphonate,
Bis (triisopropylsilyl) propylphosphonate,

Bis [dimethyl (n-propyl) silyl] butylphosphonate,
Bis (butyldimethylsilyl) butylphosphonate,
Bis [(tert-butyl) dimethylsilyl] butylphosphonate,
Bis (butylphenylsilyl) butylphosphonate,
Bis (triethylsilyl) butylphosphonate,
Bis (triisopropylsilyl) butylphosphonate,

Tetrakis pyrophosphate (triethylsilyl),
Tetrakis pyrophosphate (triisopropylsilyl),
Tetrakis pyrophosphate (allyldimethylsilyl),
Tetrakis pyrophosphate (n-propyldimethylsilyl),
Tetrakis pyrophosphate (tert-butyldimethylsilyl),
Tetrakis pyrophosphate (phenyldimethylsilyl),

Pentakis tripolyphosphate (triethylsilyl),
Pentakis (triisopropylsilyl) tripolyphosphate,
Pentakis (allyldimethylsilyl) tripolyphosphate,
Pentakis (n-propyldimethylsilyl) tripolyphosphate,
Pentakis (tert-butyldimethylsilyl) tripolyphosphate,
Pentakis triphenyl phosphate (phenyldimethylsilyl),
Hexakis (triethylsilyl) tetrapolyphosphate,
Hexakis (triisopropylsilyl) tetrapolyphosphate,
Hexakis tetrapolyphosphate (allyldimethylsilyl),
Hexakis (n-propyldimethylsilyl) tetrapolyphosphate,
Tetrapolyphosphate hexakis (tert-butyldimethylsilyl) and tetrapolyphosphate hexakis (phenyldimethylsilyl)
Is preferred.

[Compound represented by formula (A3)]
In the general formula (A3), M ² is a phosphorus atom or a boron atom, j is an integer of 2 to 20, and k is 0 or 1. When M ² is a phosphorus atom, k is 0 or 1. If M ² is a boron atom, k is 0. R ^a6 is an OH group, an OLi group, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 20 carbon atoms, an OA1 group (wherein A1 represents the above And a general formula OP (O) _l (R ^a7 R ^a8 ) (wherein l is 0 or 1, and R ^a7 and R ^a8 are independent of each other). In addition, an OH group, an OLi group, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 20 carbon atoms, or an OA1 group (wherein A1 represents the above general formula) A group selected from the group consisting of groups represented by formula (A1).), Provided that at least one of R ^a6 is an OA1 group (wherein A1 Represents a group represented by the above general formula (A1). Here, “at least one of R ^a6 has an OA1 group” means
At least one of R ^a6 is an OA1 group, or
At least one of R ^a6 is a group represented by the general formula ^{_{OP (O) l (R a7}} R a8), and refers to the case where at least one OA1 group of ^{R a7} and ^{R a8.}

R ^a6 , and “optionally substituted hydrocarbon group” and “optionally substituted alkoxy group” of R ^a7 and R ^a8 in general formula OP (O) ₁ (R ^a7 R ^a8 ) These are the same as R ^a4 and R ^a5 in the general formula (A2), respectively.

As a specific example of the compound represented by the general formula (A3), a compound in which M ² is P is preferable,
tris (methyl (n-propyl) silyl) trimetaphosphate when j is 3;
Trimetaphosphate tris (allyldimethylsilyl),
Trimetaphosphate tris (dimethyl (1-methylvinyl) silyl),
Tris-triphosphate (dimethylisopropylsilyl),
Tris trimetaphosphate (n-butyldimethylsilyl),
Tris trimetaphosphate (sec-butyldimethylsilyl),
Tris-triphosphate (tert-butyldimethylsilyl),
Trimetaphosphate tris (dimethylphenylsilyl),
Tris (diphenylmethylsilyl) trimetaphosphate,
Tris (triphenylsilyl) trimetaphosphate,
Tris (triethylsilyl) trimetaphosphate,
Trimetaphosphate tris (trivinylsilyl),
Tris (tri (n-propyl) silyl) trimetaphosphate,
Tris (triisopropylsilyl) trimetaphosphate,
Trimetaphosphate tris (triallylsilyl) etc .;

tetrakistetrametaphosphate (dimethyl (n-propyl) silyl) when j is 4;
Tetrakistetrakisphosphate (allyldimethylsilyl),
Tetrakisphosphate tetrakis (dimethyl (1-methylvinyl) silyl),
Tetrakisphosphate tetrakis (dimethylisopropylsilyl),
Tetrakistetrametaphosphate (n-butyldimethylsilyl),
Tetrakistetrametaphosphate (sec-butyldimethylsilyl),
Tetrakistetrametaphosphate (tert-butyldimethylsilyl),
Tetrakisphosphate tetrakis (dimethylphenylsilyl),
Tetrakistetrakisphosphate (diphenylmethylsilyl),
Tetrakisphosphate tetrakis (triphenylsilyl),
Tetrakisphosphate tetrakis (triethylsilyl),
Tetrametaphosphate tetrakis (trivinylsilyl),
Tetrakisphosphate tetrakis (tri (n-propyl) silyl),
Tetrakisphosphate tetrakis (triisopropylsilyl),
Other examples include tetrametaphosphate tetrakis (triallylsilyl) and the like;

Dimethyl (n-propyl) silyl polyphosphate,
Allyldimethylsilyl polyphosphate,
Dimethyl (1-methylvinyl) silyl polyphosphate,
Dimethyl isopropylsilyl polyphosphate,
(N-butyl) dimethylsilyl polyphosphate,
Polyphosphate (sec-butyl) dimethylsilyl,
Poly (tert-butyl) dimethylsilyl polyphosphate,
Dimethylphenylsilyl polyphosphate,
Diphenylmethylsilyl polyphosphate,
Triphenylsilyl polyphosphate,
Triethylsilyl polyphosphate,
Trivinylsilyl polyphosphate,
Tri (n-propyl) silyl polyphosphate,
Triisopropylsilyl polyphosphate,
Mention may be made of mixtures of condensed silyl phosphate compounds having a cyclic structure or a chain structure, such as polyallylsilyl polyphosphate.

Among these, from the viewpoint of cycle life and gas generation suppression,
Tris (triethylsilyl) trimetaphosphate,
Tris (triisopropylsilyl) trimetaphosphate,
Trimetaphosphate tris (allyldimethylsilyl),
Tris (n-propyldimethylsilyl) trimetaphosphate,
Tris-triphosphate (tert-butyldimethylsilyl),
Trimetaphosphate tris (phenyldimethylsilyl)

Tetrakisphosphate tetrakis (triethylsilyl),
Tetrakisphosphate tetrakis (triisopropylsilyl),
Tetrakistetrakisphosphate (allyldimethylsilyl),
Tetrakistetrametaphosphate (n-propyldimethylsilyl),
Tetrakistetrametaphosphate (tert-butyldimethylsilyl),
Tetrametaphosphate tetrakis (phenyldimethylsilyl)

Triethylsilyl polyphosphate,
Triisopropylsilyl polyphosphate,
Allyldimethylsilyl polyphosphate,
Polyphosphoric acid (n-propyldimethylsilyl),
Polyphosphoric acid (tert-butyldimethylsilyl) and phenyldimethylsilyl polyphosphate are more preferred.

｛式中、Ｒ^ａ１０は、置換されていてもよい２価の炭化水素基を示し、Ｒ^ａ１１は置換されていてもよい炭化水素基、又はシリル基（Ａ１）を示す。ただし、Ｒ^ａ１０の炭素数とＲ^ａ１１の炭素数との合計は１〜１９である。｝で表される基を、好ましい例としてあげることができる。この場合、上記一般式（Ａ４）で表される化合物の基本骨格は、ジカルボン酸誘導体構造となる。Ｒ^ａ９が一般式（Ａ６）で表される基ではない場合の一般式（Ａ４）で表される化合物の基本骨格は、カルボン酸誘導体構造である。 [Compound (A) Represented by General Formula (A4)]
In the general formula (A4), R ^a9 represents an ^optionally substituted hydrocarbon group having 1 to 20 carbon atoms.
The “ ^optionally substituted hydrocarbon group” for R ^a9 can be the same as R ^a4 and R ^a5 in General Formula (A2) above;
The following general formula (A6):

{In the formula, R ^a10 represents a divalent hydrocarbon group which may be substituted, and R ^a11 represents a hydrocarbon group which may be substituted, or a silyl group (A1). ^However, the sum of the carbon number of carbon atoms and ^{R a11} of ^{R a10} is 1 to 19. } Can be mentioned as a preferable example. In this case, the basic skeleton of the compound represented by the general formula (A4) has a dicarboxylic acid derivative structure. The basic skeleton of the compound represented by the general formula (A4) when R ^a9 is not a group represented by the general formula (A6) is a carboxylic acid derivative structure.

In the general formula (A6), R ^a10 is preferably a methylene group, an ethylene group, a propylene group, a butylene group, a phenyl group, a fluoromethylene group, a fluoroethylene, from the viewpoint of the chemical stability of the compound (A). Group, fluoropropylene group, or fluorobutylene group.
In the general formula (A6), R ^a11 is preferably a methyl group, an ethyl group, a vinyl group, an allyl group, a trimethylsilyl group, a triethylsilyl group, or the like from the viewpoint of the chemical stability of the compound (A). A trialkylsilyl group is mentioned, More preferably, trialkylsilyl groups, such as a trimethylsilyl group and a triethylsilyl group, are mentioned.

Specific examples of the compound represented by the general formula (A4) include
As an example having a carboxylic acid derivative structure, for example,
Acetic acid [dimethyl (n-propyl) silyl],
Acetic acid (allyldimethylsilyl),
Acetic acid [dimethyl (1-methylvinyl) silyl],
Acetic acid (dimethylisopropylsilyl),
Acetic acid [(n-butyl) dimethylsilyl],
Acetic acid [(sec-butyl) dimethylsilyl],
Acetic acid [(tert-butyl) dimethylsilyl],
Acetic acid (dimethylphenylsilyl),
Acetic acid (diphenylmethylsilyl),
Acetic acid (triphenylsilyl),
Acetic acid (triethylsilyl),
Acetic acid (trivinylsilyl),
Acetic acid [tri (n-propyl) silyl],
Acetic acid (triisopropylsilyl),
Acetic acid (triallylsilyl) and the like;

As an example having a dicarboxylic acid derivative structure, for example,
Bis [dimethyl (n-propyl) silyl] oxalate,
Bis (allyldimethylsilyl) oxalate,
Bis [dimethyl (1-methylvinyl) silyl] oxalate,
Bis (dimethylisopropylsilyl) oxalate,
Bis [oxalic acid bis [(n-butyl) dimethylsilyl],
Bis [oxalic acid bis [(sec-butyl) dimethylsilyl],
Bis [bis (tert-butyl) dimethylsilyl] oxalate,
Bis (dimethylphenylsilyl) oxalate,
Bis (diphenylmethylsilyl) oxalate,
Bis (triphenylsilyl) oxalate,
Bis (triethylsilyl) oxalate,
Bis oxalate (trivinylsilyl),
Bis [tri (n-propyl) silyl] oxalate,
Bis (triisopropylsilyl) oxalate,
Bis (triallylsilyl) oxalate,

Bis [dimethyl (n-propyl) silyl] malonate,
Bis (allyldimethylsilyl) malonate,
Bis [dimethyl (1-methylvinyl) silyl] malonate,
Bis (dimethylisopropylsilyl) malonate,
Bis [(n-butyl) dimethylsilyl] malonate,
Bis [(sec-butyl) dimethylsilyl] malonate,
Bis [(tert-butyl) dimethylsilyl] malonate,
Bis (dimethylphenylsilyl) malonate,
Bis (diphenylmethylsilyl) malonate,
Bis (triphenylsilyl) malonate,
Bis (triethylsilyl) malonate,
Bis (trivinylsilyl) malonate,
Bis [tri (n-propyl) silyl] malonate,
Bis (triisopropylsilyl) malonate,
Bis (triallylsilyl) malonate,

Bis [dimethyl (n-propyl) silyl] succinate,
Bis (allyldimethylsilyl) succinate,
Bis [dimethyl (1-methylvinyl) silyl] succinate,
Bis (dimethylisopropylsilyl) succinate,
Bis [(n-butyl) dimethylsilyl] succinate,
Bis [(sec-butyl) dimethylsilyl] succinate,
Bis [(tert-butyl) dimethylsilyl] succinate,
Bis (dimethylphenylsilyl) succinate,
Bis (diphenylmethylsilyl) succinate,
Bis (triphenylsilyl) succinate,
Bis (triethylsilyl) succinate,
Bis (trivinylsilyl) succinate,
Bis [tri (n-propyl) silyl] succinate,
Bis (triisopropylsilyl) succinate,
Bis (triallylsilyl) succinate,

Bis [dimethyl (n-propyl) silyl] itaconate,
Bis itaconate (allyldimethylsilyl),
Bis itaconate [dimethyl (1-methylvinyl) silyl],
Bis itaconate (dimethylisopropylsilyl),
Bis [itan butyl itaconate] (silyl),
Bis itaconate [(sec-butyl) dimethylsilyl],
Bis [itachibutyl] dimethylsilyl itaconate,
Bis itaconate (dimethylphenylsilyl),
Bis (diphenylmethylsilyl) itaconate,
Bis (triphenylsilyl) itaconate,
Bis itaconate (triethylsilyl),
Itaconic acid bis (trivinylsilyl),
Bis [tri (n-propyl) silyl] itaconate,
Bis (triisopropylsilyl) itaconate,
Bis itaconate (triallylsilyl),

Bis [dimethyl (n-propyl) silyl] adipate,
Bis (allyldimethylsilyl) adipate,
Bis [dimethyl (1-methylvinyl) silyl] adipate,
Bis (dimethylisopropylsilyl) adipate,
Bis [(n-butyl) dimethylsilyl] adipate,
Bis [(sec-butyl) dimethylsilyl] adipate,
Bis [(tert-butyl) dimethylsilyl] adipate,
Bis (dimethylphenylsilyl) adipate,
Bis (diphenylmethylsilyl) adipate,
Bis (triphenylsilyl) adipate,
Bis (triethylsilyl) adipate,
Bis adipate (trivinylsilyl),
Bis [tri (n-propyl) silyl] adipate,
Bis (triisopropylsilyl) adipate,
Bis (atriallylsilyl) adipate,

Bis [dimethyl (n-propyl) silyl] phthalate,
Bis (allyldimethylsilyl) phthalate,
Bis [dimethyl (1-methylvinyl) silyl] phthalate,
Bis (dimethylisopropylsilyl) phthalate,
Bis [(n-butyl) dimethylsilyl] phthalate,
Bis [(sec-butyl) dimethylsilyl] phthalate,
Bis [(tert-butyl) dimethylsilyl] phthalate,
Bis (dimethylphenylsilyl) phthalate,
Bis (diphenylmethylsilyl) phthalate,
Bis (triphenylsilyl) phthalate,
Bis (triethylsilyl) phthalate,
Bis (trivinylsilyl) phthalate,
Bis [tri (n-propyl) silyl] phthalate,
Bis (triisopropylsilyl) phthalate,
Bis (triallylsilyl) phthalate,

Bis [dimethyl (n-propyl) silyl] isophthalate,
Bis (allyldimethylsilyl) isophthalate,
Bis [dimethyl (1-methylvinyl) silyl] isophthalate,
Bis (dimethylisopropylsilyl) isophthalate,
Bis [(n-butyl) dimethylsilyl] isophthalate,
Bis [(sec-butyl) dimethylsilyl] isophthalate,
Bis [(tert-butyl) dimethylsilyl] isophthalate,
Bis (dimethylphenylsilyl) isophthalate,
Bis (diphenylmethylsilyl) isophthalate,
Bis (triphenylsilyl) isophthalate,
Bis (triethylsilyl) isophthalate,
Bis (trivinylsilyl) isophthalate,
Bis [tri (n-propyl) silyl] isophthalate,
Bis (triisopropylsilyl) isophthalate,
Bis (triallylsilyl) isophthalate,

Bis [dimethyl (n-propyl) silyl] terephthalate,
Bis (allyldimethylsilyl) terephthalate,
Bis [dimethyl (1-methylvinyl) silyl] terephthalate,
Bis (dimethylisopropylsilyl) terephthalate,
Bis [(n-butyl) dimethylsilyl] terephthalate,
Bis [(sec-butyl) dimethylsilyl] terephthalate,
Bis [(tert-butyl) dimethylsilyl] terephthalate,
Bis (dimethylphenylsilyl) terephthalate,
Bis (diphenylmethylsilyl) terephthalate,
Bis (triphenylsilyl) terephthalate,
Bis (triethylsilyl) terephthalate,
Bis (trivinylsilyl) terephthalate,
Bis [tri (n-propyl) silyl] terephthalate,
Bis (triisopropylsilyl) terephthalate,
Bis (triallylsilyl) terephthalate, etc .;
Can be mentioned respectively.

Among these, from the viewpoint of cycle life and gas generation suppression,
A compound in which at least one of acidic protons of acetic acid or a dicarboxylic acid having 2 to 8 carbon atoms is substituted with a silyl group (A1) is preferable,
A compound in which all of the acidic protons of acetic acid, oxalic acid, malonic acid, succinic acid, itaconic acid, adipic acid, phthalic acid, isophthalic acid, or terephthalic acid are substituted with a silyl group (A1) is more preferred. In particular,

Acetic acid [dimethyl (n-propyl) silyl],
Acetic acid (allyldimethylsilyl),
Acetic acid [(tert-butyl) dimethylsilyl],
Acetic acid (dimethylphenylsilyl),
Acetic acid (triethylsilyl),
Acetic acid (triisopropylsilyl),

Bis [dimethyl (n-propyl) silyl] oxalate,
Bis (allyldimethylsilyl) oxalate,
Bis [bis (tert-butyl) dimethylsilyl] oxalate,
Bis (dimethylphenylsilyl) oxalate,
Bis (triethylsilyl) oxalate,
Bis (triisopropylsilyl) oxalate,

Bis [dimethyl (n-propyl) silyl] malonate,
Bis (allyldimethylsilyl) malonate,
Bis [(tert-butyl) dimethylsilyl] malonate,
Bis (dimethylphenylsilyl) malonate,
Bis (triethylsilyl) malonate,
Bis (triisopropylsilyl) malonate,

Bis [dimethyl (n-propyl) silyl] succinate,
Bis (allyldimethylsilyl) succinate,
Bis [(tert-butyl) dimethylsilyl] succinate,
Bis (dimethylphenylsilyl) succinate,
Bis (triethylsilyl) succinate,
Bis (triisopropylsilyl) succinate,

Bis [dimethyl (n-propyl) silyl] itaconate,
Bis itaconate (allyldimethylsilyl),
Bis [itachibutyl] dimethylsilyl itaconate,
Bis itaconate (dimethylphenylsilyl),
Bis itaconate (triethylsilyl),
Bis (triisopropylsilyl) itaconate,

Bis [dimethyl (n-propyl) silyl] adipate,
Bis (allyldimethylsilyl) adipate,
Bis [(tert-butyl) dimethylsilyl] adipate,
Bis (dimethylphenylsilyl) adipate,
Bis (triethylsilyl) adipate,
Bis (triisopropylsilyl) adipate,

Bis [dimethyl (n-propyl) silyl] phthalate,
Bis (allyldimethylsilyl) phthalate,
Bis [(tert-butyl) dimethylsilyl] phthalate,
Bis (dimethylphenylsilyl) phthalate,
Bis (triethylsilyl) phthalate,
Bis (triisopropylsilyl) phthalate,

Bis [dimethyl (n-propyl) silyl] isophthalate,
Bis (allyldimethylsilyl) isophthalate,
Bis [(tert-butyl) dimethylsilyl] isophthalate,
Bis (dimethylphenylsilyl) isophthalate,
Bis (triethylsilyl) isophthalate,
Bis (triisopropylsilyl) isophthalate,

Bis [dimethyl (n-propyl) silyl] terephthalate,
Bis (allyldimethylsilyl) terephthalate,
Bis [(tert-butyl) dimethylsilyl] terephthalate,
Bis (dimethylphenylsilyl) terephthalate,
Bis (triethylsilyl) terephthalate and bis (triisopropylsilyl) terephthalate;
Can be illustrated as a more preferable example.

[Compound in which at least one of acidic protons of sulfonic acid is substituted with silyl group (A1)]
As this type of compound (A),
A compound in which at least one of acidic protons of sulfuric acid is substituted with a silyl group (A1) is preferable,
A compound in which all of the acidic protons of sulfuric acid are substituted with silyl groups (A1) is more preferred. Specific examples of such compounds include, for example,

Bis [dimethyl (n-propyl) silyl] sulfate,
Bis (allyldimethylsilyl) sulfate,
Bis [dimethyl (1-methylvinyl) silyl] sulfate,
Bis (dimethylisopropylsilyl) sulfate,
Bis [(n-butyl) dimethylsilyl] sulfate,
Bis [(sec-butyl) dimethylsilyl] sulfate,
Bis [(tert-butyl) dimethylsilyl] sulfate,
Bis (dimethylphenylsilyl) sulfate,
Bis (diphenylmethylsilyl) sulfate,
Bis (triphenylsilyl) sulfate,
Bis (triethylsilyl) sulfate,
Bis (trivinylsilyl) sulfate,
Bis [tri (n-propyl) silyl] sulfate,
Bis (triisopropylsilyl) sulfate,
Examples thereof include bis (triallylsilyl) sulfate.

Among these, from the viewpoint of cycle life and gas generation suppression,
Bis [dimethyl (n-propyl) silyl] sulfate,
Bis (allyldimethylsilyl) sulfate,
Bis [(tert-butyl) dimethylsilyl] sulfate,
Bis (dimethylphenylsilyl) sulfate,
Bis (triethylsilyl) sulfate,
Bis (triisopropylsilyl) sulfate,
Is more preferable.
The compound (A) enumerated above is suitable as an additive for the electrolyte solution for non-aqueous electricity storage devices. As the compound (A) as an additive, the compounds listed above can be used alone or in combination of two or more.

[Additive composition]
In another embodiment of the invention,
(A) Compound (A) as described above (component (a)),
(B) at least one selected from the group consisting of a basic compound (B) and a silicon compound (C) (component (b));
An additive composition is provided. This additive composition is suitable as an agent for adding to the electrolyte solution for non-aqueous electricity storage devices. The basic compound (B) and the silicon compound (C) will be described below.

[Basic compound (B)]
The basic compound (B) is a Lewis base, and a general formula Q ⁺ Y ⁻ {wherein Q ⁺ represents a quaternary ammonium group, a quaternary phosphonium group, or an alkali metal, and Y ⁻ represents an alkoxy group or aryl. An oxy group is represented. } It is 1 or more types chosen from the group which consists of a compound represented.

(Lewis base)
In an embodiment of the present invention, a Lewis base is defined as “a substance comprising an atom having a pair of electrons for chemical bonding”. Accordingly, the Lewis base is not particularly limited as long as it is a substance containing an atom having a lone electron pair for chemical bonding, and includes, for example, an oxygen atom, a nitrogen atom, and the like. However, from the viewpoint of availability and handling properties, at least one nitrogen-containing organic Lewis selected from the group consisting of amine compounds, amide compounds, imide compounds, compounds having Si-N bonds, and compounds having PN bonds A base is preferred.
Examples of the amine compound include alkylamines in which at least one hydrogen atom of ammonia (NH ₃ ) is substituted with an alkyl group having 20 or less carbon atoms, or cyclic amines.

When the alkylamine has a plurality of alkyl groups, the plurality of alkyl groups may be the same or different. Examples of the alkylamine include ethylamine, n-propylamine, iso-propylamine, n-butylamine, iso-butylamine, sec-butylamine, tert-butylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, and the like. Monoalkylamines whose side chains may be substituted;
Dialkyls whose side chain may be substituted, such as dimethylamine, ethylmethylamine, diethylamine, dipropylamine, diisopropylamine, butylethylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dicyclohexylamine Amines;
Side chains such as trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecanylamine, tridodecylamine, dimethylethylamine, diisopropylethylamine An optionally substituted trialkylamine;
Etc. Of these, trialkylamine is preferable from the viewpoint of the cycle life of the battery described later.

  Examples of the cyclic amine include a heterocyclic compound containing a nitrogen atom as a hetero atom and an aromatic amine. The heterocyclic compound may be either a monocyclic compound (aliphatic monocyclic amine) or a polycyclic compound (aliphatic polycyclic amine). Specific examples of the aliphatic monocyclic amine include piperidine, piperazine, 1,4,7-trimethyl-1,4,7-triazacyclononane and the like. Specific examples of these are as follows.

  Examples of the aliphatic polycyclic amine include 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, hexamethylenetetramine, 1 , 4-diazabicyclo [2.2.2] octane. Examples of the aromatic amine include aniline, pyridine, 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole, or derivatives thereof; diphenylamine, triphenylamine, tribenzylamine, 2,2′-bipyridyl, 1, 10-phenanthroline etc. are mentioned.

  The amine compound used in the embodiment of the present invention may contain a plurality of nitrogen atoms in one molecule. Examples of the amine compound containing a plurality of nitrogen atoms in one molecule include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetraethylethylenediamine, triethylenediamine, para Examples include phenylenediamine. From the viewpoint of cycle life, ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, or N, N, N ′, N′-tetraethylethylenediamine is preferred.

As the amide compound, the following formula (B1):
R ^B1 —CO—NR ^B2 R ^B3 (B1)
The compound represented by these is mentioned. In formula (B1), R ^{B1 to} R ^B3 each independently represent a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or a group having an optionally substituted cyclic skeleton. . R ^{B1 to} R ^B3 may be the same or different, and may be bonded to each other to form a ring.
In the above formula (B1), R ^B1 is the following formula (B1 ′):
R ^{B1 ′} —O— (B1 ′)
{Wherein, R ^{B1 ′} represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms or an optionally substituted cyclic skeleton. }, The amide compound represented by the formula (B1) is generally called a carbamic acid ester, but is included in the amide compound in this specification.

  Examples of amide compounds include acetamides such as N, N-dimethylacetamide and N, N-dimethyltrifluoroacetamide, N, N-dimethylformamide, α-lactam, β-lactam, γ-lactam, δ-lactam, and carbamine. Examples thereof include methyl acid, ethyl carbamate, methyl N, N-dimethylcarbamate, and ethyl N, N-dimethylcarbamate.

As the imide compound, the following formula (B2):
R ^B4 —CO—NR ^B5 —CO—R ^B6 (B2)
The compound represented by these is mentioned. In formula (B2), R ^{B4 to} R ^B6 each independently represent a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or a group having an optionally substituted cyclic skeleton. . R ^{B4 to} R ^B6 may be the same or different, and may be bonded to each other to form a ring.
Examples of the imide compound include maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, phthalimide, N-methylphthalimide, N-ethylphthalimide, N-phenylphthalimide, and the like.

で表される化合物が挙げられる。
上記一般式（Ｂ３）において、ｋは１〜３の整数である。化学的安定性の観点から、上記一般式（Ｂ３）においてｋが１であるモノシラザン構造の化合物、及び上記一般式（Ｂ３）においてｋが２であるジシラザン構造の化合物が好ましい。
上記一般式（Ｂ３）において、Ｒ^Ｂ７は、水素原子、又は置換されていてもよい炭素数１〜２０の炭化水素基を示す。３つのＲ^Ｂ７は、同じでも異なっていてもよい。
Ｒ^Ｂ７の炭素数は、１〜２０であり、一般式（Ｂ３）で表される化合物のハンドリング及び入手性の観点から、１〜１０が好ましく、１〜６がより好ましい。 As the compound having a Si—N bond, a compound having a high ability of at least one of dehydration and acid neutralization may be used. Examples of the compound having a Si—N bond and having at least one ability of dehydration and acid neutralization include compounds represented by general formulas (B3) to (B5) described later, for example. Can be mentioned.
As an example of a compound in which 1 to 3 Si elements are bonded to an N element among compounds having an Si—N bond, the following general formula (B3):

The compound represented by these is mentioned.
In the said general formula (B3), k is an integer of 1-3. From the viewpoint of chemical stability, a compound having a monosilazane structure in which k is 1 in the general formula (B3) and a compound having a disilazane structure in which k is 2 in the general formula (B3) are preferable.
In the general formula (B3), R ^B7 represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms. Three R ^B7 may be the same or different.
R ^B7 has 1 to 20 carbon atoms, and is preferably 1 to 10 and more preferably 1 to 6 from the viewpoint of handling and availability of the compound represented by General Formula (B3).

In the general formula (B3), the (R ^B7 ) ₃ Si group is not particularly limited.
(CH ₃ ) ₃ Si, (C ₂ H ₅ ) (CH ₃ ) ₂ Si, (CH ₂ ═CH) (CH ₃ ) ₂ Si, (CH ₃ CH ₂ CH ₂ ) (CH ₃ ) ₂ Si, (CH _{2 = CHCH 2) (CH 3} ) 2 Si, [(CH 3) 2 CH] (CH 3) 2 Si, [(CH 3) 2 CHCH 2] (CH 3) 2 Si, [(CH 3) 3 C _{] (CH 3) 2 Si,} (C 6 H 5) (CH 3) 2 Si, (C 2 H 5) 3 Si, (CH 3 CH 2 CH 2) 3 Si, [(CH 3) 2 CH] 3 Si or (C ₆ H ₅ ) ₃ Si is preferred,
_{(CH 3) 3 Si, (} CH 2 = CH) (CH 3) 2 Si, (CH 3 CH 2 CH 2) (CH 3) 2 Si, (CH 2 = CHCH 2) (CH 3) 2 Si, [ (CH ₃ ) ₂ CH] (CH ₃ ) ₂ Si, [(CH ₃ ) ₃ C] (CH ₃ ) ₂ Si, (C ₂ H ₅ ) ₃ Si, or [(CH ₃ ) ₂ CH] ₃ Si More preferred,
(CH ₃ CH ₂ CH ₂ ) (CH ₃ ) ₂ Si, (C ₂ H ₅ ) ₃ Si, or (CH ₃ ) ₃ Si is particularly preferred.

In the general formula (B3), R ^B8 represents a hydrogen atom or an ^optionally substituted hydrocarbon group having 1 to 20 carbon atoms. R ^B8 may form a double bond with the nitrogen atom. When R ^B8 is plural, R ^B8 may be the same or different, ring bound may form a ring, and is formed by binding a plurality of R ^B8 each other, N And a heterocyclic ring containing O, etc.

で表される環が挙げられる。 From the viewpoint of further improving battery performance, R ^B8 in the general formula (B3) is more preferably a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 10 carbon atoms.
Specific examples of R ^B8 include, for example, hydrogen atom, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl, sec-butyl group, tert-butyl group, trifluoro Examples include a methyl group, a cyclohexyl group, an acetylimino group, a trifluoroacetylimino group, and the like; as a ring formed by combining two R ^B8 , for example, the following formula (B3a):

The ring represented by these is mentioned.

で表される化合物が挙げられる。 As an example of a compound in which one or more N elements are bonded to an Si element among compounds having an Si—N bond, the following general formula (B4):

The compound represented by these is mentioned.

｛式中、ｎは１〜５の整数を示す。｝
のいずれかで示される基を、好ましい例としてあげることができる。 In general formula (B4), m is an integer of 1-4. R ^B9 represents a hydrogen atom or an ^optionally substituted hydrocarbon group having 1 to 20 carbon atoms. Two R ^{B9 s} may be the same or different, may be bonded to each other to form a ring, and the ring formed by the bonding of the two R ^B9 is a heterocyclic ring containing N, O, etc. There may be. Examples of R ^B9 include a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl, sec-butyl group, tert-butyl group and the like; Examples of the ring formed by bonding ^B9 to each other include, for example, the following formulas (B4a) to (B4d):

{Wherein n represents an integer of 1 to 5. }
The group shown by either of these can be mentioned as a preferable example.

In the general formula (B4), R ^B10 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms. When R ^B10 is two or more, two or more ^{R B10} may all be the same or different. When R ^B9 , R ^B10 , and m are as described above, the affinity between the additive composition and the electrolytic solution according to the present embodiment tends to be improved.

In the general formula (B4), R ^B10 is a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, an ethyl group, an n-propyl group, in order to improve the chemical stability of the compound having a Si—N bond. An iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, or a tert-butyl group is preferable.

で表される化合物が挙げられる。 As an example of a compound having a cyclic structure formed through Si atom and N atom among compounds having Si—N bond, for example, the following general formula (B5):

The compound represented by these is mentioned.

In the general formula (B5), R ^B11 , R ^B12, and R ^B13 each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 20 carbon atoms. A methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, or a tert-butyl group is preferable, and a methyl group is more preferable. The plurality of R ^B11 , the plurality of R ^B12 , or the plurality of R ^B13 in the compound represented by the general formula (B5) may be all the same or different from each other. R ^B11 , R ^B12, and R ^B13 may be the same or different.
When R ^B11 , R ^B12 , and R ^B13 are as described above, the chemical stability of the resulting compound (B) tends to be improved. In the general formula (B5), w is an integer of 0 to 4, and 1 or 2 is preferable from the viewpoint of chemical stability.

  Preferable specific examples of the compound having a Si—N bond include, for example, 1,1,1,3,3,3-hexamethyldisilazane (HMDS), 1,1,3,3, from the viewpoint of cycle life. 5,5-hexamethylcyclotrisilazane, N, O-bis (trimethylsilyl) acetamide (BSA), N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA), N-trimethylsilylimidazole (TMSI), 1,3- Diphenyl-1,1,3,3-tetramethyldisilazane, 1,3-bis (chloromethyl) tetramethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, heptamethyl Disilazane, octamethylcyclotetrasilazane, N, N′-bis (trimethylsilyl) -1,4-butanediamine, N— Tyl-N- (trimethylsilyl) acetamide (MTMSA), N-methyl-N- (trimethylsilyl) trifluoroacetamide (MSTFA), N- (trimethylsilyl) dimethylamine (TMSDMA), N- (trimethylsilyl) diethylamine (TMSDEA), N -Methyl-N- (tert-butyldimethylsilyl) trifluoroacetamide (MTBSTFA), N, N'-bis (trimethylsilyl) urea (BTSU), tris (dimethylamino) silane, tetrakis (dimethylamido) silane, tris (dimethyl) Amino) chlorosilane, methyltris (dimethylamino) silane, N, N-diethylaminosilane, N, N-diisopropylaminosilane and the like.

  More preferred specific examples of the compound having a Si—N bond include 1,1,1,3,3,3-hexamethyldisilazane (HMDS), 1,1,3, from the viewpoint of cycle life and gas generation suppression. 3,5,5-hexamethylcyclotrisilazane, heptamethyldisilazane, N- (trimethylsilyl) dimethylamine (TMSDMA), octamethylcyclotetrasilazane, or methyltris (dimethylamino) silane, particularly preferred examples thereof 1,1,1,3,3,3-hexamethyldisilazane (HMDS), N- (trimethylsilyl) dimethylamine (TMSDMA), or heptamethyldisilazane.

で表されるフォスファゼン化合物が挙げられる。
一般式（Ｂ６）において、Ｒ^Ｂ１４は炭素数１〜２０の炭化水素基であり、かつＲ^Ｂ１５〜Ｒ^Ｂ１７は、それぞれ独立に、下記一般式（Ｂ７）：

｛式中、Ｒ^Ｂ１８、Ｒ^Ｂ１９、及びＲ^Ｂ２０は、それぞれ独立に、炭素数１〜１０の炭化水素基であり、ｓは０〜１０の整数を示し、Ｒ^Ｂ１８〜Ｒ^Ｂ２０は同じであっても異なっていてもよく、そして２つのＲ^Ｂ１８、２つのＲ^Ｂ１９、及び２つのＲ^Ｂ２０は、それぞれ独立に、連結して環を形成してもよい。｝で表される基である。 In the embodiment of the present invention, examples of the compound having a PN bond include the following general formula (B6):

The phosphazene compound represented by these is mentioned.
In General Formula (B6), R ^B14 is a hydrocarbon group having 1 to 20 carbon atoms, and R ^{B15 to} R ^B17 are each independently the following General Formula (B7):

{In the formula, R ^B18 , R ^B19 and R ^B20 are each independently a hydrocarbon group having 1 to 10 carbon atoms, s represents an integer of 0 to 10, and R ^{B18 to} R ^B20 are the same. Or may be different, and two R ^B18 , two R ^B19 , and two R ^B20 may be independently connected to form a ring. } Is a group represented by:

から選択される少なくとも１つが好ましい。 Although it does not specifically limit as a phosphazene compound represented by the said general formula (B6), From a viewpoint of availability and handling, the following compound groups, for example:

At least one selected from is preferred.

(Compound represented by the general formula Q ⁺ Y ⁻ )
In an embodiment of the present invention, as the basic compound (B), the general formula Q ⁺ Y ⁻ {wherein Q ⁺ represents a quaternary ammonium group, a quaternary phosphonium group, or an alkali metal, and Y ⁻ represents Represents an alkoxy group or an aryloxy group. }
You may use the compound represented by these.
Q ⁺ includes the following:
Quaternary ammonium groups such as tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetraoctylammonium;
Quaternary phosphonium groups such as tetramethylphosphonium, tetraethylphosphonium, tetrapropylphosphonium, tetrabutylphosphonium, tetraoctylphosphonium;
Alkali metals such as Li, Na, K;
Etc. are exemplified.

｛式中、Ｒは、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルコキシ基、アミノ基、ニトロ基、又はハロゲン原子を表す。｝で表されるアリールオキシ基；
等が例示される。 Y ^- as the following:
Alkoxy groups such as methoxy group, ethoxy group, propoxy group, allyloxy group, butoxy group, benzyloxy group;
The following general formula:

{In the formula, R represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an amino group, a nitro group, or a halogen atom. } An aryloxy group represented by:
Etc. are exemplified.

The general formula Q ⁺ Y ^- as the basic compound represented by, but are not limited to, availability and from the viewpoint of handling, the following compounds:

から成る群より選択される少なくとも１つが好ましい。 CH ₃ OLi C ₂ H ₅ OLi (CH ₃ ) ₃ COLi
_{CH 3 ONa C 2 H 5 ONa} (CH 3) 3 CONa
CH ₃ OK C ₂ H ₅ OK (CH ₃ ) ₃ COK

At least one selected from the group consisting of

｛式中、Ｒ^ｃ１、Ｒ^ｃ２、及びＲ^ｃ３は、それぞれ独立に、置換されていてもよい炭素数１〜２０の炭化水素基、又は置換されていてもよい炭素数１〜２０のアルコキシ基を示し、そして、Ｘ_１は、一般式ＯＲ^１（式中、Ｒ^１は、水素原子、置換されていてもよい炭素数１〜２０の炭化水素基、炭素数１〜２０のシリル基、ＳＯ_２ＣＨ_３、又はＳＯ_２ＣＦ_３を示す。）で表される基、又はハロゲン原子を示す。｝で表される化合物である。 [Silicon compound (C)]
The silicon compound (C) has the following general formula (C):

{Wherein R ^c1 , R ^c2 , and R ^c3 each independently represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted alkoxy group having 1 to 20 carbon atoms. X ₁ represents a general formula OR ¹ (wherein R ¹ represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, SO ₂ CH ₃ or SO ₂ CF _3. ) Or a halogen atom. } It is a compound represented.

“Optionally substituted hydrocarbon group” in R ^{c1 to} R ^c3 and R ¹ in the general formula OR ¹ and “ ^optionally substituted hydrocarbon group” and “substituted” in R ^{c1 to} R ^c3 The “optional alkoxy group” is the same as R ^a4 and R ^a5 in the general formula (A2).

X ¹ is a halogen atom selected from fluorine, chlorine, bromine and iodine. From the viewpoint of availability of the compound and stability in the electrolytic solution, fluorine or chlorine is more preferable.
Corresponding to R ¹ in the general formula OR ¹ "silyl group" is a group having a structure that will have carbon atoms bonded to the O atom via a silicon atom. Such a silyl group is not particularly limited, and examples thereof include a silyl group having an aliphatic group; a fluorine-substituted silyl group such as a trifluoromethylsilyl group in which a hydrogen atom in the silyl group is fluorine-substituted; . The silyl group may be substituted with various functional groups as necessary. Such a functional group is not particularly limited. For example, a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; a nitrile group (—CN); an ether group (—O—); a carbonate group (—OCO ₂ —). Ester group (—CO ₂ —); carbonyl group (—CO—); sulfide group (—S—); sulfoxide group (—SO—); sulfone group (—SO ₂ —); urethane group (—NHCO ₂ ); -): Aromatic groups such as phenyl group and benzyl group;

For ^{R 1} in the general formula OR ^1, the number of carbon atoms in the silyl group is a 1-20, 1-10 preferably, 1-6 is more preferable. When the number of carbon atoms in the silyl group is within the above range, the miscibility with the nonaqueous solvent tends to be superior.
As the R ^c1 R ^c2 R ^c3 Si group in the general formula (C), (CH ₃ ) ₃ Si, (C ₂ H ₅ ) ₃ Si, (C ₃ H ₇ ) ₃ Si, (tert-C ₄ H ₉ ) (CH ₃ ) ₂ Si, (CH ₂ ═CH) ₃ Si, (CH ₂ ═CHCH ₂ ) ₃ Si, or (CF ₃ ) ₃ Si are preferred, (C ₂ H ₅ ) ₃ Si or (CH ₃ ) ₃ Si is more preferred. When the R ^c1 R ^c2 R ^c3 Si group has the above structure, chemical durability in the lithium ion secondary battery tends to be further improved.

As a more preferable specific example of the silicon compound (C), from the viewpoint of availability and handling, when X ₁ is OR ¹ :
(CH ₃ ) ₃ SiOH
(CH ₃ ) ₃ SiOSi (CH ₃ ) ₃
(C ₂ H ₅ ) ₃ SiOSi (C ₂ H ₅ ) ₃
(C ₂ H ₅ ) (CH ₃ ) ₂ SiOSi (CH ₃ ) ₂ (C ₂ H ₅ )
_{(CH 2 = CH) (CH} 3) 2 SiOSi (CH 3) 2 (CH = CH 2)
(C ₃ H ₇ ) ₃ SiOSi (C ₃ H ₇ ) ₃
(C ₃ H ₇ ) (CH ₃ ) ₂ SiOSi (CH ₃ ) ₂ (C ₃ H ₇ )
(C ₄ H ₉ ) (CH ₃ ) ₂ SiOSi (CH ₃ ) ₂ (C ₄ H ₉ )
(C ₄ H ₉ ) ₃ SiOSi (C ₄ H ₉ ) ₃
(CH ₃ ) ₃ SiOSO ₂ CF ₃
(CH ₃ ) ₃ SiOSO ₂ CH ₃
Etc., and

When X ₁ is a halogen atom:
(CH ₃ ) ₃ SiF
(CH ₃ ) ₃ SiCl
(C ₂ H ₅ ) ₃ SiF
(C ₂ H ₅ ) ₃ SiCl
_{(Iso-C 3 H 7)} 3 SiF
_{(Iso-C 3 H 7)} 3 SiCl
_{(Tert-C 4 H 9)} (CH 3) 2 SiF
_{(Tert-C 4 H 9)} (CH 3) 2 SiCl
(ClCH ₂ ) (CH ₃ ) ₂ SiF
(ClCH ₂ ) (CH ₃ ) ₂ SiCl
(C ₆ H ₅ ) ₃ SiF
(C ₆ H ₅ ) ₃ SiCl
Etc.

[Combination of component (a) and component (b)]
The electrolytic solution to which the additive composition containing the component (a) and the component (b) is added maintains the advantageous effects of the compound (A) as the component (a) and suppresses the decomposition thereof. Storage stability is greatly improved. Therefore, the lithium ion secondary battery using the electrolytic solution can improve the input / output characteristics and suppress gas generation while maintaining the effect of improving the cycle characteristics of the battery. Although the detailed mechanism is not clear for this reason, the decomposition of component (a) is suppressed by the cooperation of compound (A) (component (a)) having a silyl group and component (b). Thus, the storage stability of the electrolytic solution containing this will be improved, and further, both the component (a) and the component (b) will act on the positive electrode, the negative electrode, or both. And it is thought that by this, while improving the cycling characteristics of a battery, while improving input-output characteristics, decomposition | disassembly of electrolyte solution and gas generation can be suppressed.

Here, in the composition containing both the component (a) and the component (b), the composition ratio of both is important. By controlling the amount of component (b) used relative to component (a) within a specific range, the input / output characteristics can be sufficiently improved while maintaining the cycle characteristics of the battery.
Specifically, the content of the component (b) in the additive composition for the electrolytic solution is set to 100% by mass of the component (a) from the viewpoint of the viscosity of the electrolytic solution, the input / output characteristics of the battery, and the cycle life. On the other hand, it is 1 mass ppm or more and 100 mass% or less. The content of the component (b) is preferably 10 ppm to 50% by mass, more preferably 50 ppm to 20% by mass, with respect to 100% by mass of the component (a). It is particularly preferable that the content is 1% by mass or more and 10% by mass or less. The content of this component (b) or the composition ratio of the additive composition is ¹⁹ F-NMR, ³¹ P-NMR, ²⁹ Si-NMR and other NMR measurements; ICP-MS, ICP-AES and other elemental analysis; It can be confirmed by gas chromatograph measurement and GC-MS measurement. In various measurement methods, the content of component (b) or the composition ratio of the additive composition can be determined by preparing a calibration curve using a standard substance and comparing the measured values.

[Production method and form of additive composition]
Examples of the method for producing an additive composition for an electrolyte solution according to this embodiment include the following methods 1) and 2).
1) A method of obtaining an additive composition by adding a predetermined amount of the component (b) to the component (a);
2) The component (b) is used as a raw material when the component (a) is synthesized, and a predetermined amount of (b) is added to the component (a) by controlling the purification (distillation) conditions after the synthesis reaction. Method for obtaining an additive composition by leaving components

  The additive composition of the present embodiment may be composed of only the component (a) and the component (b), or may contain other components other than these as necessary. Examples of such other components include, but are not limited to, lithium salts, unsaturated bond-containing carbonates, halogen atom-containing carbonates, carboxylic acid anhydrides, sulfur atom-containing compounds (for example, sulfides, disulfides, sulfonate esters, Sulfite, sulfate, sulfonic acid anhydride, etc.), nitrile group-containing compounds and the like.

Specific examples of other components include, for example,
Lithium salts such as lithium monofluorophosphate, lithium difluorophosphate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium tetrafluoro (oxalato) phosphate, lithium difluorobis (oxalato) phosphate, etc .;
Unsaturated bond-containing carbonates such as vinylene carbonate, vinyl ethylene carbonate and the like;
Halogen atom-containing carbonates such as fluoroethylene carbonate, 4,5-difluoroethylene carbonate, trifluoromethylethylene carbonate and the like;
Carboxylic anhydrides such as acetic anhydride, benzoic anhydride, succinic anhydride, maleic anhydride and the like;
Sulfur atom-containing compounds such as ethylene sulfite, 1,3-propane sultone, 1,3-propene sultone, 1,4-butane sultone, ethylene sulfate, vinylene sulfate, and the like; and nitrile group-containing compounds such as acetonitrile, Propionitrile, adiponitrile, succinonitrile, glutaronitrile, etc .;
Is mentioned.

By including such other components in the additive composition, the cycle characteristics of the lithium ion secondary battery using the additive composition tend to be further improved.
The form of the additive composition in the embodiment of the present invention may be liquid, solid, or a mixture of liquid and solid (slurry state).
By adding the additive composition of the present embodiment to an electrolyte prepared from a nonaqueous solvent and a lithium salt, which will be described later, an electrolyte for a nonaqueous electricity storage device can be produced. Alternatively, the additive composition of the present embodiment may be added to the solid electrolyte.

<Electrolyte for non-aqueous storage device>
In one embodiment of the present invention, an electrolyte solution for a non-aqueous electricity storage device (hereinafter also simply referred to as “electrolyte solution”) includes a non-aqueous solvent, a lithium salt, and the additive (compound) of the embodiment described above. (A)). In this embodiment, an electrolyte for a nonaqueous electricity storage device containing a nonaqueous solvent and a lithium salt may be prepared in advance, and the additive of the present embodiment may be added to the electrolyte for a nonaqueous electricity storage device. Generally in the art, additives are added in relatively small amounts relative to the electrolyte. In this embodiment, specifically, it is preferable to set it as 50 mass% or less with respect to the whole quantity of electrolyte solution, 40 mass% or less is more preferable, 30 mass% or less is further more preferable, and 20 mass% or less is especially preferable. Preferably, 10% by weight or less is particularly preferred, and in particular, 5% by weight or less, 1% by weight or less, or 0.5% by weight can be added. By adding the additive (compound (A)) in an amount of preferably 0.01% by mass or more based on the total amount of the electrolytic solution, the effect of using the additive is effectively expressed. The addition amount of the additive is more preferably 0.02% by mass or more, still more preferably 0.1% by mass or more, and particularly preferably 0.5% by mass or more with respect to the total amount of the electrolytic solution. .

In another embodiment of the present invention, the electrolytic solution includes a non-aqueous solvent, a lithium salt, and the additive composition of the present embodiment described above. In this embodiment, an electrolyte solution for a non-aqueous electricity storage device containing a non-aqueous solvent and a lithium salt is prepared in advance, and the additive composition of this embodiment is added to the electrolyte solution for the non-aqueous electricity storage device. Good. In this case, the additive amount of the additive composition is adjusted so that the amount of the component (a) (compound (A)) in the additive composition is within the above range with respect to the total amount of the electrolytic solution. Is preferred.
Then, the nonaqueous solvent and lithium salt in the electrolyte solution of this embodiment are demonstrated below.

[Nonaqueous solvent]
Examples of the non-aqueous solvent used in the electrolyte solution of the present embodiment include an aprotic polar solvent.
Examples of the aprotic polar solvent include ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, and trifluoromethylethylene. Cyclic carbonates such as carbonate, fluoroethylene carbonate and 4,5-difluoroethylene carbonate; lactones such as γ-butyrolactone and γ-valerolactone; cyclic sulfones such as sulfolane; cyclic ethers such as tetrahydrofuran and dioxane; ethyl methyl carbonate, dimethyl carbonate and diethyl Carbonate, methyl propyl carbonate, methyl isopropyl carbonate, dipropyl carbonate, methyl butyl carbonate, dibutyl carbonate, Chain carbonates such as ethyl propyl carbonate and methyl trifluoroethyl carbonate; Nitriles such as acetonitrile and propionitrile; Chain ethers such as dimethyl ether; Chain carboxylic esters such as methyl propionate and ethyl propionate; and dimethoxyethane Of the chain diethers.
Among these, carbonates such as cyclic carbonate and chain carbonate are preferable. Therefore, carbonate will be described below.

[Carbonate]
Although it does not specifically limit as carbonate, For example, it is more preferable to use carbonate type solvents, such as cyclic carbonate and chain carbonate. It is more preferable to use a combination of a cyclic carbonate and a chain carbonate as the carbonate solvent. The electrolytic solution tends to be more excellent in ionic conductivity by including such a carbonate.

(Cyclic carbonate)
Although it does not specifically limit as cyclic carbonate, For example, ethylene carbonate, propylene carbonate, fluoroethylene carbonate, etc. are mentioned. Among these, at least one selected from the group consisting of ethylene carbonate and propylene carbonate is preferable. The electrolytic solution tends to be more excellent in ionic conductivity by including such a cyclic carbonate.

(Chain carbonate)
Although it does not specifically limit as a chain carbonate, For example, 1 or more types chosen from the group which consists of dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate is preferable. The electrolytic solution tends to be more excellent in ionic conductivity by including such a chain carbonate.

(Carbonate solvent)
When a combination of cyclic carbonate and chain carbonate is used as the carbonate solvent, the mixing ratio of cyclic carbonate and chain carbonate is 1:10 in volume ratio (volume of cyclic carbonate: volume of chain carbonate). 5: 1 is preferable, 1: 5 to 3: 1 is more preferable, and 1: 5 to 1: 1 is still more preferable. By using a carbonate-based solvent having a mixing ratio within the above range, the ion conductivity of the lithium ion secondary battery tends to be more excellent.
When a carbonate-based solvent is used, other non-aqueous solvents such as acetonitrile and sulfolane can be further added to the electrolytic solution as necessary. By using another non-aqueous solvent, the battery physical properties of the lithium ion secondary battery tend to be further improved.
The non-aqueous solvent demonstrated above can be used individually by 1 type or in combination of 2 or more types.

[Lithium salt]
A lithium salt will not be specifically limited if it has a function as an electrolyte which bears the ionic conductivity of electrolyte solution. The lithium salt may have a function of suppressing oxidative decomposition of the electrolytic solution by acting on the positive electrode or the negative electrode, or both the positive electrode and the negative electrode.
Suitable lithium salts include, for example, LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , Li ₂ SiF ₆ , LiOSO ₂ C _k F _{2k + 1} {wherein k is an integer from 0 to 8}, LiN (SO ₂ C _k F _{2k + 1} ) ₂ {where k is an integer from 0 to 8}, LiPF _n (C _k F _{2k + 1} ) _6-n {where n is an integer from 1 to 5 and k is 1 to 8}, LiB (C ₂ O ₄ ) ₂ , LiBF ₂ (C ₂ O ₄ ), LiPF ₂ (C ₂ O ₄ ) _{2 and the} like. LiPF ₆ , LiBF ₄ , LiN (SO ₂ C _k F _{2k + 1} ) ₂ {wherein k is an integer of 0 to 8 from the viewpoint of availability as a lithium salt, ease of handling, and ease of dissolution LiPF _n (C _k F _{2k + 1} ) _6-n {n is an integer from 1 to 5 and k is an integer from 1 to 8}, LiB (C ₂ O ₄ ) ₂ , LiBF ₂ ( C ₂ O ₄ ) is preferable, LiPF ₆ , LiBF ₄ , LiN (SO ₂ C _k F _{2k + 1} ) ₂ {wherein k is an integer of 0 to 8}, LiB (C ₂ O ₄ ) ₂ is more preferable. LiPF ₆ is particularly preferred. Among the plurality of lithium salts having the structures listed above, one or a combination of two or more may be used.

The content of the lithium salt is preferably 1% by mass or more and 40% by mass or less, more preferably 5% by mass or more and 35% by mass or less, and more preferably 7% by mass or more with respect to 100% by mass of the nonaqueous solvent. It is particularly preferably 30% by mass or less. When the content of the lithium salt is 1% by mass or more, the ion conductivity of the lithium ion secondary battery tends to be superior. When the content is 40% by mass or less, the solubility of the lithium salt at a low temperature tends to be further improved. The content of the lithium salt relative to the non-aqueous solvent can be confirmed by NMR measurement such as ¹⁹ F-NMR, ¹¹ B-NMR, ³¹ P-NMR. Further, the content of the lithium salt in the electrolyte solution in the lithium ion secondary battery is also measured by NMR measurement such as ¹⁹ F-NMR, ¹¹ B-NMR, ³¹ P-NMR, etc .; and ICP-MS, ICP. -It can be confirmed by elemental analysis such as AES.

[Other additives to the electrolyte]
The electrolyte solution according to the present embodiment may contain other additives other than the above-described additives (compounds (A) to (a)) and the above-mentioned component (b) as necessary. Such additives are not particularly limited, and include the compounds exemplified for the non-aqueous solvent and the lithium salt. For example, lithium salt, unsaturated bond-containing carbonate, halogen atom-containing carbonate, carboxylic acid anhydride, sulfur atom-containing compound (for example, sulfide, disulfide, sulfonate ester, sulfite, sulfate, sulfonic acid anhydride, etc.), nitrile group-containing Compounds and the like.
Specific examples of other additives are as follows:
Lithium salts: for example, lithium monofluorophosphate, lithium difluorophosphate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium tetrafluoro (oxalato) phosphate, lithium difluorobis (oxalato) phosphate, etc .;
Unsaturated bond-containing carbonate: for example, vinylene carbonate, vinyl ethylene carbonate, etc .;
Halogen atom-containing carbonate: for example, fluoroethylene carbonate, 4,5-difluoroethylene carbonate, trifluoromethylethylene carbonate, etc .;
Carboxylic anhydride: for example, acetic anhydride, benzoic anhydride, succinic anhydride, maleic anhydride, etc .;
Sulfur atom-containing compounds: for example, ethylene sulfite, 1,3-propane sultone, 1,3-propene sultone, 1,4-butane sultone, ethylene sulfate, vinylene sulfate, etc.
Nitrile group-containing compounds: for example, acetonitrile, propionitrile, adiponitrile, succinonitrile, glutaronitrile and the like.

By using such other additives, the cycle characteristics of the battery tend to be further improved.
Especially, it is preferable that at least 1 sort (s) selected from the group which consists of lithium difluorophosphate and lithium monofluorophosphate is included from a viewpoint of improving the cycling characteristics of a battery further. The content of at least one additive selected from the group consisting of lithium difluorophosphate and lithium monofluorophosphate is preferably 0.001% by mass or more, and 0.005% by mass with respect to 100% by mass of the electrolytic solution. % Or more is more preferable, and 0.02 mass% or more is more preferable. When the content is 0.001% by mass or more, the cycle life of the lithium ion secondary battery tends to be further improved. Further, the content is preferably 3% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less. When the content is 3% by mass or less, the ion conductivity of the lithium ion secondary battery tends to be further improved.
The content of other additives in the electrolytic solution can be confirmed by NMR measurement such as ³¹ P-NMR and ¹⁹ F-NMR.

<Non-aqueous storage device>
The electrolyte solution according to the present embodiment is suitably used as an electrolyte solution for non-aqueous electricity storage devices. Here, the non-aqueous electricity storage device refers to an electricity storage device that uses a solvent other than water as the solvent in the electrolytic solution in the electricity storage device, and is preferably an electricity storage device that does not use water. Examples of non-aqueous storage devices include lithium ion secondary batteries, lithium-sulfur batteries, lithium-air batteries, sodium ion secondary batteries, calcium ion secondary batteries, and lithium ion capacitors. Among these, from the viewpoints of practicality and durability, a lithium ion secondary battery and a lithium ion capacitor are preferable, and a lithium ion secondary battery is more preferable.

<Lithium ion secondary battery>
In one embodiment of the present invention, a lithium ion secondary battery (hereinafter, also simply referred to as “battery”) includes the above electrolytic solution, a positive electrode containing a positive electrode active material, and a negative electrode containing a negative electrode active material. . This battery may have the same configuration as a conventional lithium ion secondary battery except that it includes the above-described electrolyte solution.

[Positive electrode]
A positive electrode will not be specifically limited if it acts as a positive electrode of a lithium ion secondary battery. Therefore, a known positive electrode may be used. The positive electrode preferably includes one or more materials selected from the group consisting of materials capable of inserting and extracting lithium ions as a positive electrode active material. Examples of such a material include the following general formulas (6a) and (6b):
Li _x MO ₂ (6a)
Li _y M ₂ O ₄ (6b)
{In the formula, M represents one or more metals selected from transition metals, x is a number from 0 to 1, and y is a number from 0 to 2. }, A lithium-containing compound represented by each of the above and other lithium-containing compounds.
Examples of the lithium-containing compound represented by each of the general formulas (6a) and (6b) include lithium cobalt oxides typified by LiCoO ₂ ; LiMnO ₂ , LiMn ₂ O ₄ , and Li ₂ Mn ₂ O ₄ . Lithium manganese oxide typified; Lithium nickel oxide typified by LiNiO ₂ ; Li _z MO ₂ {wherein M represents two or more elements selected from the group consisting of Ni, Mn, Co, Al and Mg. Z is a number greater than 0.9 and less than 1.2. } Lithium-containing composite metal oxide represented by :; and iron phosphate olivine represented by LiFePO ₄ may be used.

Examples of the lithium-containing compound other than the lithium-containing compound represented by each of the general formulas (6a) and (6b) include a composite oxide containing lithium and a transition metal element, a metal chalcogenide containing lithium, and lithium and transition. A metal phosphate compound containing a metal element, and a metal silicate compound containing lithium and a transition metal element (for example, Li _t M _u SiO ₄ , M is synonymous with the general formula (6a), and t is 0 to 1 Number, u represents a number from 0 to 2.). From the viewpoint of obtaining a higher voltage, as the lithium-containing compound, in particular,
With lithium,
Selected from the group consisting of cobalt (Co), nickel (Ni), manganese (Mn), iron (Fe), copper (Cu), zinc (Zn), chromium (Cr), vanadium (V), and titanium (Ti) At least one transition metal element,
The composite oxide containing and a metal phosphate compound are preferable.
More specifically, the lithium-containing compound is more preferably a composite oxide containing lithium and a transition metal element or a metal chalcogenide containing lithium and a transition metal element, and a metal phosphate compound containing lithium. General formulas (7a) and (7b):
^{_{Li v M I D 2 (7a}} )
Li _w M ^II PO ₄ (7b)
{Wherein D represents oxygen or a chalcogen element, M ^I and M ^II each represent one or more transition metal elements, and the values of v and w depend on the charge / discharge state of the battery, and v is 0.05 -1.10, w shows the number of 0.05-1.10. }, Compounds represented by each of the above.

The lithium-containing compound represented by the above general formula (7a) has a layered structure, and the compound represented by the above general formula (7b) has an olivine structure. These lithium-containing compounds are obtained by substituting a part of the transition metal element with Al, Mg, or other transition metal elements for the purpose of stabilizing the structure, and include these metal elements in the grain boundaries. It is also possible that the oxygen atom is partially substituted with a fluorine atom or the like, or at least a part of the surface of the positive electrode active material is coated with another positive electrode active material.
Examples of the positive electrode active material other than the lithium-containing compound include S, MnO ₂ , FeO ₂ , FeS ₂ , V ₂ O ₅ , V ₆ O ₁₃ , TiO ₂ , TiS ₂ , MoS ₂ , and NbSe _2. , Oxides of metals other than lithium. Examples thereof include sulfides and selenides.
Examples of the conductive polymer include conductive polymers represented by polyaniline, polythiophene, polyacetylene, and polypyrrole.
It is preferable to use a lithium-containing compound as the positive electrode active material because a high voltage and a high energy density tend to be obtained.
The positive electrode active material demonstrated above is used individually by 1 type or in combination of 2 or more types.

  The number average particle diameter (primary particle diameter) of the positive electrode active material is preferably 0.05 μm to 100 μm, more preferably 1 μm to 10 μm. The number average particle size of the positive electrode active material can be measured by a wet particle size measuring device (for example, a laser diffraction / scattering particle size distribution meter and a dynamic light scattering particle size distribution meter). Alternatively, 100 particles observed with a transmission electron microscope are randomly extracted and analyzed with image analysis software (for example, image analysis software manufactured by Asahi Kasei Engineering Co., Ltd., trade name “A Image-kun”). By calculating the arithmetic average, the number average particle diameter of the positive electrode active material can also be obtained. In this case, when the number average particle diameter differs between measurement methods for the same sample, a calibration curve created for the standard sample may be used.

In the present embodiment, from the viewpoint of realizing a higher voltage, the positive electrode preferably includes a positive electrode active material having a discharge capacity of 10 mAh / g or higher at a potential of 4.2 V (vsLi / Li ⁺ ) or higher. The battery according to this embodiment is useful in that the cycle life can be improved even if such a positive electrode is provided. Here, 4.2 V and a positive electrode active material having a 10 mAh / g or more discharge capacity (vsLi / Li ⁺⁾ or more potential, 4.2V (vsLi / Li ⁺⁾ of the lithium ion secondary battery or a potential A positive electrode active material that can cause a charge and discharge reaction as a positive electrode and has a discharge capacity of 10 mAh or more with respect to 1 g of mass of the active material at a constant current discharge of 0.1 C. Therefore, as long as the positive electrode active material has a discharge capacity of 10 mAh / g or more at a potential of 4.2 V (vsLi / Li ⁺ ) or more, it has a discharge capacity at a potential of 4.2 V (vsLi / Li ⁺ ) or less. May be.
The discharge capacity of the positive electrode active material used in the present embodiment is preferably 10 mAh / g or more, more preferably 15 mAh / g or more, and further preferably 20 mAh / g or more at a potential of 4.2 V (vsLi / Li ⁺ ) or more. When the discharge capacity of the positive electrode active material is 10 mAh / g or more at a potential of 4.2 V (vsLi / Li ⁺ ) or more, the battery can be driven at a high voltage to achieve a high energy density. The discharge capacity of the positive electrode active material can be measured by the method described in Examples.

As the positive electrode active material, the following formula (E1):
_{LiMn 2-x Ma x O 4} (E1)
{In the formula, Ma represents one or more selected from transition metals, and x is a number in the range of 0.2 ≦ x ≦ 0.7. }
An oxide represented by:
The following formula (E2):
LiMeO ₂ (E2)
{In the formula, Me represents one or more selected from transition metals. } Oxides represented by
The following formula (E3):
_{zLi 2 McO 3 - (1-} z) LiMdO 2 (E3)
{In the formula, Mc and Md each independently represent one or more selected from transition metals, and z is a number in the range of 0.1 ≦ z ≦ 0.9. } A composite oxide represented by
The following formula (E4):
LiMb _1-y Fe _y PO ₄ (E4)
{In the formula, Mb represents one or more selected from the group consisting of Mn and Co, and y is a number in the range of 0 ≦ y ≦ 0.9. }; And the following formula (E5):
Li ₂ MfPO ₄ F (E5)
{In the formula, Mf represents one or more selected from transition metals. } A compound represented by
It is preferably at least one selected from the group consisting of By using such a positive electrode active material, the structural stability of the positive electrode active material tends to be more excellent.

The oxide represented by the formula (E1) may be a spinel positive electrode active material. Although it does not specifically limit as a spinel type positive electrode active material, following formula (E1a):
LiMn _2-x Ni _x O ₄ (E1a)
{Wherein x is a number within a range of 0.2 ≦ x ≦ 0.7. } Is preferable, and the following formula (E1b):
LiMn _2-x Ni _x O ₄ (E1b)
{Wherein x is a number within a range of 0.3 ≦ x ≦ 0.6. } Is more preferable.
The oxide represented by the formula (E1a) or (E1b), is not particularly _limited, and examples thereof include LiMn _{1.5 Ni} 0.5 _{O 4.} By using the spinel oxide represented by the formula (E1), the stability of the positive electrode active material tends to be more excellent.
The spinel oxide represented by the formula (E1) has a structure other than the above structure in a range of 10 mol% or less with respect to the number of moles of Mn atoms from the viewpoints of stability of the positive electrode active material and electronic conductivity. Further, a transition metal or a transition metal oxide may be contained. The compound represented by Formula (E1) is used individually by 1 type or in combination of 2 or more types.

The oxide represented by the formula (E2) may be a layered oxide positive electrode active material. Although it does not specifically limit as a layered oxide positive electrode active material, For example, following formula (E2a):
_{LiMn 1-v-w Co v} Ni w O 2 (E2a)
{Wherein v is a number within a range of 0.1 ≦ v ≦ 0.4, and w is a number within a range of 0.1 ≦ w ≦ 0.8. }
LiCoO ₂ (E2b)
_{LiNi 1-u-t Co u} Al t O 2 (E2c)
{Wherein 0.1 ≦ u ≦ 0.2 and 0.01 ≦ u ≦ 0.1. } Is preferable.

The layered oxide represented by the formula (E2a) is not particularly limited. For example, LiNi _1/3 Co _1/3 Mn _1/3 O ₂ , LiNi _0.5 Co _0.2 Mn _0.3 O ₂ , LiNi _0.6 Co _0.2 Mn _0.2 O ₂ , LiNi _0.7 Co _0.2 Mn _0.1 O ₂ , LiNi _0.8 Co _0.1 Mn _0.1 O ₂ , etc. . Examples of the layered oxide represented by the above formula (E2c) include LiNi _0.8 Co _0.15 Al _0.05 O ₂ . By using such a compound represented by the formula (E2), the stability of the positive electrode active material tends to be more excellent. The compound represented by Formula (E2) is used individually by 1 type or in combination of 2 or more types.
The composite oxide represented by the formula (E3) may be a composite layered oxide. Although it does not specifically limit as a composite layered oxide, For example, following formula (E3a):
_{zLi 2 MnO 3 - (1-} z) LiNi a Mn b Co c O 2 (E3a)
{Wherein z is a number within the range of 0.3 ≦ z ≦ 0.7, a is a number within the range of 0.2 ≦ a ≦ 0.6, and b is 0.2 ≦ 0.2 The number is in the range of b ≦ 0.6, c is the number in the range of 0.05 ≦ c ≦ 0.4, and satisfies the relationship of a + b + c = 1. } Is preferable.

  In formula (E3a), 0.4 ≦ z ≦ 0.6, a + b + c = 1, 0.3 ≦ a ≦ 0.4, 0.3 ≦ b ≦ 0.4, and 0.2 ≦ c ≦ 0.3 The composite oxide is more preferable. By using the composite oxide represented by the formula (E3), the stability of the positive electrode active material tends to be more excellent. The composite oxide represented by the formula (E3) is 10 mol% or less with respect to the total number of moles of Mn, Ni, and Co atoms from the viewpoints of stability of the positive electrode active material, electronic conductivity, and the like. In addition to the above structure, a transition metal may be further contained. The composite oxide represented by the formula (E3) is used singly or in combination of two or more.

The compound represented by the formula (E4) may be an olivine type positive electrode active material. Although it does not specifically limit as an olivine type positive electrode active material, For example, following formula (E4a):
LiMn _1-y Fe _y PO ₄ (E4a)
{Wherein y is a number within a range of 0.05 ≦ y ≦ 0.8. }, Or the following formula (E4b):
LiCo _1-y Fe _y PO ₄ (E4b)
{Wherein y is a number within a range of 0.05 ≦ y ≦ 0.8. } Is preferable.
By using the compound represented by the formula (E4), the stability and electronic conductivity of the positive electrode active material tend to be more excellent. The compound represented by Formula (E4) is used individually by 1 type or in combination of 2 or more types.

The compound represented by the formula (E5) may be a fluorinated olivine type positive electrode active material. The fluoride olivine-type positive electrode active material is not particularly limited, for _{example, Li 2 FePO 4 F, Li} 2 MnPO 4 F, and _Li 2 CoPO ₄ F are preferred. By using the compound represented by the formula (E5), the stability of the positive electrode active material tends to be more excellent. The compound represented by the formula (E5) is within a range of 10 mol% or less with respect to the total number of moles of Mn, Fe, and Co atoms from the viewpoint of stability of the positive electrode active material, electronic conductivity, and the like In addition to the above structure, a transition metal may be further contained. The compound represented by Formula (E5) is used individually by 1 type or in combination of 2 or more types.
The positive electrode active material having a discharge capacity of 10 mAh / g or more at a potential of 4.2 V (vsLi / Li ⁺ ) or more can be used alone or in combination of two or more. As the positive electrode active material, 4.2 V and the positive electrode active material having a 10 mAh / g or more discharge capacity (vsLi / Li ⁺⁾ or more potential, 4.2 V in (vsLi / Li ⁺⁾ or more potential 10 mAh / g or more A positive electrode active material having no discharge capacity can also be used in combination. Examples of the positive electrode active material that does not have a discharge capacity of 10 mAh / g or more at a potential of 4.2 V (vsLi / Li ⁺ ) or more include LiFePO ₄ and LiV ₃ O ₈ .

[Lithium standard positive electrode potential at full charge]
The positive electrode potential of the lithium reference when fully charged lithium ion secondary battery according to the present embodiment is preferably 4.2V (vsLi / Li ⁺⁾ or more, more preferably 4.25V (vsLi / Li ⁺⁾ or higher, 4 More preferably, 3 V (vsLi / Li ⁺ ) or more. When the positive electrode potential at full charge is 4.2 V (vsLi / Li ⁺ ) or more, the charge / discharge capacity of the positive electrode active material of the lithium ion secondary battery tends to be efficiently utilized. When the positive electrode potential at full charge is 4.2 V (vsLi / Li ⁺ ) or more, the energy density of the lithium ion secondary battery tends to be further improved. The positive electrode potential based on lithium when fully charged can be controlled by controlling the voltage of the battery when fully charged.
Lithium-based positive electrode potential at full charge is to disassemble a fully charged lithium ion secondary battery in an Ar glove box, take out the positive electrode, reassemble the battery using metallic lithium as the counter electrode, and measure the voltage Therefore, it can be easily measured. When a carbon negative electrode active material is used for the negative electrode, since the potential of the carbon negative electrode active material at full charge is 0.05 V (vsLi / Li ⁺ ), the voltage of the lithium ion secondary battery at full charge (Va ) Can be easily calculated by adding 0.05 V to the positive electrode at full charge. For example, in a lithium ion secondary battery using a carbon negative electrode active material for the negative electrode, when the voltage (Va) of the lithium ion secondary battery at full charge is 4.2 V, the potential of the positive electrode at full charge is It can be calculated as 4.2V + 0.05V = 4.25V. “(VsLi / Li ⁺ )” indicates a lithium-based potential.

[Method for producing positive electrode active material]
The positive electrode active material can be produced by the same method as that for producing a general inorganic oxide. Although it does not specifically limit as a manufacturing method of a positive electrode active material, For example, the mixture which mixed metal salt (For example, 1 or more types selected from sulfate and nitrate) by a predetermined ratio is baked in the atmospheric environment containing oxygen. A method of obtaining a positive electrode active material containing a desired inorganic oxide can be given. Alternatively, one or more selected from carbonates and hydroxide salts are allowed to act on a solution in which the metal salt is dissolved to precipitate a hardly soluble metal salt, and the resulting solution is extracted and separated. A method of obtaining a positive electrode active material containing an inorganic oxide by mixing at least one selected from lithium carbonate and lithium hydroxide as a source and firing in an atmosphere containing oxygen is given.

[Method for producing positive electrode]
An example of a method for producing the positive electrode is shown below. First, if necessary, a positive electrode mixture prepared by adding a conductive additive, a binder, and the like to the positive electrode active material is dispersed in a solvent to prepare a paste containing the positive electrode mixture. Next, this paste is applied to a positive electrode current collector, dried to form a positive electrode mixture layer, and the positive electrode mixture layer is pressurized as necessary to adjust the thickness, thereby producing a positive electrode. it can.
Although it does not specifically limit as a positive electrode electrical power collector, For example, what is comprised with metal foil, such as aluminum foil or stainless steel foil, is mentioned.

[Negative electrode]
A negative electrode will not be specifically limited if it acts as a negative electrode of a lithium ion secondary battery, Therefore You may use a known negative electrode. It is preferable that a negative electrode contains 1 or more types chosen from the group which consists of a material which can occlude and discharge | release lithium ion as a negative electrode active material. Such a negative electrode active material is not particularly limited. For example, a negative electrode active material made of metallic lithium; a carbon negative electrode active material; an alloy formation with lithium represented by a silicon alloy negative electrode active material and a tin alloy negative electrode active material 1 type or more selected from the group consisting of a lithium-containing compound typified by a negative electrode active material containing a possible element; a silicon oxide negative electrode active material; a tin oxide negative electrode active material; and a lithium titanate negative electrode active material . These negative electrode active materials are used singly or in combination of two or more.

The carbon negative electrode active material is not particularly limited. For example, hard carbon, soft carbon, artificial graphite, natural graphite, graphite, pyrolytic carbon, coke, glassy carbon, organic polymer compound fired body, mesocarbon Examples include microbeads, carbon fibers, activated carbon, carbon colloids, and carbon black. Although it does not specifically limit as said coke, For example, pitch coke, needle coke, and petroleum coke are mentioned. Although it does not specifically limit as a sintered body of the said organic polymer compound, For example, what baked and carbonized polymeric materials, such as a phenol resin and a furan resin, is mentioned.
The negative electrode active material containing an element capable of forming an alloy with lithium is not particularly limited. For example, it is a metal or metalloid simple substance; a metal or metalloid alloy, or a metal or metalloid compound. Alternatively, a material having one or more of these phases in at least a part thereof may be used. The first “alloy” in the present life includes an alloy having one or more metal elements and one or more metalloid elements, in addition to an alloy composed of two or more metal elements. Further, the alloy may contain a nonmetallic element as long as it has metal properties as a whole.

Although it does not specifically limit as a metal element and a metalloid element, For example, lithium (Li), titanium (Ti), tin (Sn), lead (Pb), aluminum (Al), indium (In), silicon (Si) , Zinc (Zn), antimony (Sb), bismuth (Bi), gallium (Ga), germanium (Ge), arsenic (As), silver (Ag), hafnium (Hf), zirconium (Zr), and yttrium (Y ). Among these, lithium and the metal element and metalloid element of the 4th group or the 14th group in the long-period type periodic table are preferable, and lithium, titanium, silicon, and tin are particularly preferable.
As an alloy of silicon, for example, as a second constituent element other than silicon, a group consisting of tin, magnesium, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony and chromium Those having one or more elements selected from the above are listed.
Examples of the titanium compound, the tin compound, and the silicon compound include those having oxygen (O) or carbon (C). In addition to titanium, tin, or silicon, the compound selected from those described above It may have two constituent elements.
As the lithium-containing compound, the same compounds as those exemplified as the positive electrode material can be used.
A negative electrode active material is used individually by 1 type or in combination of 2 or more types.
The number average particle diameter (primary particle diameter) of the negative electrode active material is preferably 0.1 μm to 100 μm, more preferably 1 μm to 10 μm. The number average particle size of the negative electrode active material is measured in the same manner as the number average particle size of the positive electrode active material.

[Method for producing negative electrode]
A negative electrode is obtained as follows, for example.
First, if necessary, a negative electrode mixture prepared by adding a conductive additive, a binder, and the like to the negative electrode active material is dispersed in a solvent to prepare a paste containing the negative electrode mixture. Next, this paste is applied to a negative electrode current collector and dried to form a negative electrode mixture layer, which is pressurized as necessary, and the thickness can be adjusted to produce a negative electrode.
Although a negative electrode collector is not specifically limited, For example, what is comprised with metal foil, such as copper foil, nickel foil, or stainless steel foil, is mentioned.

(Conductive aids and binders used to make positive and negative electrodes)
In the production of the positive electrode and the negative electrode, the conductive aid used as necessary is not particularly limited, and examples thereof include carbon blacks such as graphite, acetylene black, and ketjen black; and carbon fibers.
In the production of the positive electrode and the negative electrode, the binder used as necessary is not particularly limited. For example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyacrylic acid, styrene butadiene rubber, and fluorine rubber. Is mentioned.

[Separator]
The lithium ion secondary battery according to the present embodiment preferably includes a separator between the positive electrode and the negative electrode from the viewpoint of providing the battery with safety such as prevention of short circuit between the positive and negative electrodes and shutdown. As the separator, for example, a separator provided in a known lithium ion secondary battery can be used. As the separator, an insulating thin film having high ion permeability and excellent mechanical strength is preferable.
Although it does not specifically limit as a separator, For example, a woven fabric, a nonwoven fabric, and a synthetic resin microporous film are mentioned. Although it does not specifically limit as a nonwoven fabric, For example, the porous film made from heat resistant resin, such as the product made from a ceramic, the product made from polyolefin, the product made from polyester, the product made from polyamide, the product made from liquid crystal polyester, an aramid, is mentioned. The microporous membrane made of synthetic resin is not particularly limited, and examples thereof include a polyolefin microporous membrane such as a microporous membrane containing polyethylene or polypropylene as a main component, or a microporous membrane containing both polyethylene and polypropylene. It is done. Among these, a synthetic resin microporous membrane is preferable.
The separator may be a single microporous membrane or a laminate of a plurality of microporous membranes, or may be a laminate of two or more microporous membranes.

[Configuration of lithium ion secondary battery]
Although the lithium ion secondary battery according to the present embodiment is not particularly limited, for example, a separator, a laminate formed by a positive electrode and a negative electrode sandwiching the separator from both sides, and a positive electrode current collector (positive electrode sandwiching the laminate) And a negative electrode current collector (arranged outside the negative electrode), and a battery exterior housing them. The laminated body which laminated | stacked the positive electrode, the separator, and the negative electrode is impregnated with the electrolyte solution concerning this embodiment.
FIG. 1 is a schematic cross-sectional view showing an example of a lithium ion secondary battery according to the present embodiment. A lithium ion secondary battery 100 shown in FIG. 1 includes a separator 110, a laminate composed of a positive electrode 120 and a negative electrode 130 sandwiching the separator 110 from both sides, and a positive electrode current collector 140 sandwiching the laminate (outside of the positive electrode). ), A negative electrode current collector 150 (arranged outside the negative electrode), and a battery exterior 160 that accommodates all of them. A laminate in which the positive electrode 120, the separator 110, and the negative electrode 130 are laminated is impregnated with the electrolytic solution of the present embodiment.

[Production method of lithium ion secondary battery]
The lithium ion secondary battery according to the present embodiment can be produced by a known method using the above-described electrolyte solution, positive electrode, negative electrode, and, if necessary, a separator. For example, a positive electrode and a negative electrode are wound in a laminated state with a separator interposed therebetween and formed into a laminated body of a wound structure, or a plurality of layers laminated alternately by bending, laminating a plurality of layers, etc. Molded into a laminate in which a separator is interposed between the positive electrode and the negative electrode,
Next, the laminated body is accommodated in a battery case (exterior), the electrolytic solution according to the present embodiment is injected into the case, and the laminated body is immersed in the electrolytic solution and sealed to thereby form lithium ions. A secondary battery can be manufactured.
When the laminate composed of the positive electrode, the negative electrode, and optionally the separator is immersed in the electrolyte,
(I) You may use the electrolyte solution containing a nonaqueous solvent, lithium salt, and the additive or additive composition concerning this embodiment;
(Ii) The additive or additive composition according to this embodiment is compared with the electrolyte solution that includes a non-aqueous solvent and a lithium salt but does not include the additive or additive composition according to this embodiment. Or (iii) a non-aqueous solvent and a lithium salt, but with respect to an electrolyte solution that does not contain the additive or additive composition according to this embodiment, the component (a) and the component You may add (b) component separately so that each may become predetermined | prescribed content.

  The shape of the lithium ion secondary battery according to the present embodiment is not particularly limited. For example, a cylindrical shape, an elliptical shape, a rectangular tube shape, a button shape, a coin shape, a flat shape, a laminate shape, and the like are preferably employed.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
The analysis methods and evaluation methods employed in the examples and comparative examples are as follows.

(1) Nuclear magnetic resonance analysis (NMR): Molecular structure analysis by ¹ H-NMR, ¹³ C-NMR, and ³¹ P-NMR Measurement was performed according to a conventional method using the following apparatus and conditions.
Measuring apparatus: JNM-GSX400G type nuclear magnetic resonance apparatus (manufactured by JEOL Ltd.)
Solvent: deuterated chloroform Reference material: ¹ H-NMR chloroform (7.26 ppm)
¹³ C-NMR chloroform (77.16 ppm)
³¹ P-NMR 85% phosphoric acid (0 ppm)

(2) Battery performance evaluation by lithium ion secondary battery using LiNi _1/3 Mn _1/3 Co _1/3 O ₂ positive electrode (Examples 1 to 7, and Comparative Examples 1 and 2)
<Preparation of positive electrode sheet>
Lithium / nickel / manganese / cobalt composite oxide (LiNi _1/3 Mn _1/3 Co _1/3 O ₂ ) having a number average particle diameter of 11 μm as a positive electrode active material and a number average particle diameter of 6.5 μm as a conductive additive Graphite carbon powder and acetylene black powder having a number average particle diameter of 48 nm and PVDF as a binder, composite oxide: graphite carbon powder: acetylene black powder: PVDF = 100: 4.2: 1.8: 4.6 Mixed by mass ratio. To the resulting mixture, N-methyl-2-pyrrolidone was added so as to have a solid content of 68% by mass and further mixed to prepare a slurry. This slurry was applied to one surface of an aluminum foil having a thickness of 20 μm, and after removing the solvent by drying, the positive electrode sheet was obtained by rolling with a roll press.

<Preparation of negative electrode sheet>
Graphite carbon powder (I) having a number average particle diameter of 12.7 μm and graphite carbon powder (II) having a number average particle diameter of 6.5 μm as a negative electrode active material, and an aqueous carboxymethyl cellulose solution (solid content concentration: 1.83% by mass) as a binder ) And diene rubber (glass transition temperature: −5 ° C., dry number average particle size: 120 nm, dispersion medium: water, solid content concentration: 40 mass%), graphite carbon powder (I): graphite carbon Powder (II): Carboxymethylcellulose solution: Diene rubber = 90: 10: 1.44: 1.76 The solid content is mixed at a mass ratio, and water is added so that the total solid content concentration is 45 mass%. And mix further
A slurry was prepared. This slurry was applied to one side of a 10 μm thick copper foil, the solvent was dried and removed, and then rolled with a roll press to obtain a negative electrode sheet.

<Production of battery>
The positive electrode sheet and the negative electrode sheet produced as described above were each punched into squares to obtain a positive electrode and a negative electrode. The obtained positive electrode and negative electrode were superposed on both sides of a separator (film thickness 25 μm, porosity 50%, pore diameter 0.1 μm to 1 μm) made of a polyethylene microporous film to obtain a laminate. Next, the laminate was inserted into a bag made of a laminate film in which both surfaces of an aluminum foil (thickness: 40 μm) were covered with a resin layer while projecting positive and negative terminals. Thereafter, 1 mL of the electrolyte solution described in each of the following Examples or Comparative Examples was injected into the bag and vacuum sealed to prepare a sheet-like lithium ion secondary battery.

<Battery performance evaluation and gas generation evaluation>
The obtained sheet-like lithium ion secondary battery is housed in a thermostatic chamber set at 25 ° C. (trade name “PLM-73S” manufactured by Futaba Kagaku Co., Ltd.), and a charge / discharge device (manufactured by Asuka Electronics Co., Ltd. Name “ACD-01”) and allowed to stand for 20 hours. Charge the battery after standing at a constant current of 0.2C, reach 4.35V, charge at a constant voltage of 4.35V for 8 hours, and further to 3.0V at a constant current of 0.2C The charge / discharge cycle of discharging was repeated three times to perform initial charge / discharge of the battery. In addition, 1C shows the electric current value in the case of discharging the full capacity of a battery in 1 hour.
The battery after the initial charge / discharge was immersed in a water bath and its volume (V ₀ ) was measured.
Thereafter, in the thermostat set at 50 ° C., the battery was charged to 4.35 V at a constant current of 1 C, charged for 1 hour at a constant voltage of 4.35 V, and then to 3.0 V at a constant current of 1 C. Discharged. This series of charging / discharging was made into 1 cycle, and the cycle charging / discharging of a total of 180 cycles was performed. And the discharge capacity per positive electrode active material mass of the 1st cycle and the 180th cycle was confirmed.
Here, the discharge capacity retention ratio was calculated by dividing the discharge capacity at the 180th cycle by the discharge capacity at the first cycle.
In addition, after the battery after cycle charge / discharge was cooled to room temperature, it was immersed in a water bath and the volume (V ₁₈₀ ) was measured. From the volume change (V ₁₈₀ −V ₀ ) of the battery before and after charging, the gas after battery operation was The amount generated (mL) was determined.

(3) Battery performance evaluation by lithium ion secondary battery using LiNi _0.5 Co _0.2 Mn _0.3 O ₂ positive electrode (Example 8, and Comparative Examples 3 and 4)
<Preparation of positive electrode sheet>
Lithium / nickel / manganese / cobalt composite oxide (LiNi _0.5 Co _0.2 Mn _0.3 O ₂ ) having a particle diameter of 7.9 μm (D50) as a positive electrode active material, and carbon black powder ( Timcal, SuperP Li) and PVDF as a binder were mixed at a mass ratio of composite oxide: conductive aid: binder = 100: 3.5: 3. To the resulting mixture, N-methyl-2-pyrrolidone was added so as to have a solid content of 58% by mass, and further mixed to prepare a slurry. This slurry was applied to both surfaces of a 15 μm thick aluminum foil, the solvent was removed by drying, and then pressed with a roll press to obtain a positive electrode sheet (double-side coated positive electrode sheet).

<Preparation of negative electrode sheet>
Graphite powder with a particle size of 22 μm (D50) (manufactured by Hitachi Chemical Co., Ltd., MAG) as a negative electrode active material, binder (manufactured by Nippon Zeon Co., Ltd., BM400B), and carboxymethyl cellulose (manufactured by Daicel Corp., # 2200) as a thickener. , Graphite powder: binder: thickener = 100: 1.5: 1.1 is mixed at a solid content mass ratio, and water is added so that the total solid content concentration is 45% by mass, and further mixed. A slurry was prepared. This slurry is applied to one or both sides of a 10 μm thick copper foil, and after removing the solvent by drying, a negative electrode sheet (single-side coated negative electrode sheet and double-sided coated negative electrode sheet) is obtained by pressing with a roll press. It was.

<Production of battery>
The positive electrode sheet and the negative electrode sheet produced as described above were each punched into squares to obtain a positive electrode and a negative electrode. The obtained positive electrode and negative electrode are sandwiched between polyethylene separators on the respective opposing surfaces, with a single-side coated negative electrode / double-sided coated positive electrode / double-sided coated negative electrode / double-sided coated positive electrode / single-sided coated negative electrode. In this order, a four-opposed laminate was obtained. The obtained 4-opposing laminate was inserted into a bag made of a laminate film in which both surfaces of an aluminum foil (thickness: 40 μm) were coated with a resin layer while projecting positive and negative terminals. Thereafter, 0.8 mL of the electrolytic solution described in the following Examples or Comparative Examples was injected into the bag and vacuum sealed to produce a sheet-like lithium ion secondary battery.

<Battery performance evaluation and gas generation evaluation>
The obtained sheet-like lithium ion secondary battery is housed in a thermostatic chamber set at 25 ° C. (trade name “PLM-73S” manufactured by Futaba Kagaku Co., Ltd.), and a charge / discharge device (manufactured by Asuka Electronics Co., Ltd. Name “ACD-01”) and allowed to stand for 16 hours. The battery after standing for 16 hours is charged with a constant current of 0.05 C, reaches 4.35 V, then charged with a constant voltage of 4.35 V for 2 hours, and further 3 with a constant current of 0.2 C. A charge / discharge cycle of discharging to 0.0 V was repeated three times to perform initial charge / discharge of the battery.
After the initial charge / discharge, to confirm the battery capacity, the battery is charged to 4.35V with a constant current of 0.33C in a thermostat set at 25 ° C., and further charged for 1 hour with a constant voltage of 4.35V. The battery was discharged to 3 V with a constant current of 0.33C. The discharge capacity at this time was defined as the discharge capacity before the test. Next, the battery was charged to 4.35 V with a constant current of 0.33 C and charged with a constant voltage of 4.35 V for 1 hour to obtain a fully charged battery.

The obtained fully charged battery was measured for open circuit voltage (hereinafter referred to as “OCV”) and volume, and was then placed in a thermostat set at 60 ° C., and a 60 ° C. storage test was performed.
In the 60 ° C. storage test, the fully charged battery was left in a 60 ° C. thermostat, and after 24 hours and 168 hours, the battery was removed from the thermostat and the OCV and volume were measured at room temperature. The amount of gas generation was calculated from the volume difference before and after the storage test, and ΔOCV was calculated from the difference in OCV before and after the storage test. The volume of the battery was measured by a method of immersing in a water bath at room temperature.
Further, after standing at 60 ° C., the remaining capacity after the storage test was measured by a method in which the battery after 168 hours had elapsed was discharged to 3 V at a constant current of 0.33 C in a thermostat set at 25 ° C. Furthermore, after charging to 4.35V with a constant current of 0.33C in a thermostat set at 25 ° C., charging is performed for 1 hour with a constant voltage of 4.35V, and further to 3V with a constant current of 0.33C. The recovery capacity after the storage test was measured by the method of discharging.

(4) Storage performance evaluation of the prepared electrolyte (Examples 9 to 11)
In a dry atmosphere where the dew point was controlled to −50 ° C. or lower, the prepared electrolyte was poured into a SUS316 container, and the container was sealed. The SUS316 container containing the electrolytic solution was housed in a thermostatic chamber (trade name “PLM-73S” manufactured by Futaba Kagaku Co., Ltd.) set at 25 ° C. A part of the electrolyte in a container placed in a thermostat was taken out every two weeks, and ³¹ P-NMR measurement was performed by nuclear magnetic resonance analysis (NMR) described in (1). The concentration of the additive contained in the electrolytic solution was calculated from the area of the ³¹ P peak observed in the vicinity of −24.3 ppm. Then, the additive concentration before storage was set to 100%, and the residual rate of the additive contained in the electrolyte after storage was evaluated.
It can be said that the higher the residual ratio, the higher the storage performance.

<Production of Compound (A)>
[Production Example 1]
Triethylchlorosilane (9.93 g) was added dropwise to a mixture of sodium phosphate (3.00 g) and formamide (6 mL) at room temperature under a nitrogen atmosphere, and the mixture was stirred for 5 hours for reaction. Petroleum ether (20 mL) was added to the resulting reaction mixture, stirred, and allowed to stand to separate into two layers. The upper layer which was separated and collected was concentrated under reduced pressure, and further distilled under reduced pressure (67 Pa) to obtain a colorless liquid (4.90 g). ^From the results of ¹ H-NMR, ³¹ P-NMR, and ¹³ C-NMR, it was found that the obtained liquid was tris (triethylsilyl) phosphate which is the compound (A) in the present embodiment.

[Production Examples 2 to 5]
In the above Production Example 1, various compounds (A) were produced in the same manner as in Production Example 1 except that instead of triethylchlorosilane, raw material compounds of the types and amounts described in Table 1 were used. The properties and yield of the obtained compound (A) and the names of the compounds examined by various NMR are shown in Table 1, respectively.

The assignment of chemical shift in ¹ H-NMR, ¹³ C-NMR, and ³¹ P-NMR for each product in Production Examples 1 to 5 is shown below.
Production Example 1 Tris phosphate (triethylsilyl)
¹ H-NMR: 1.24 ppm (q, 18 H), 0.95 ppm (t, 27 H)
¹³ C-NMR: 5.73 ppm, 5.15 ppm
³¹ P-NMR: -24.30 ppm

Production Example 2 Tris [dimethyl (n-propyl) silyl] phosphate
¹ H-NMR: 1.73 ppm (m, 6H), 1.28 ppm (t, 9H), 1.00 ppm (t, 6H), 0.52 ppm (s, 18H)
¹³ C-NMR: 19.28 ppm, 17.62 ppm, 16.08 ppm, −1.33 ppm
³¹ P-NMR: -24.32 ppm

Production Example 3 Tris phosphate (triisopropylsilyl)
¹ H-NMR: 1.20-1.11 ppm (m, 9H), 1.11 ppm (d, 54H)
¹³ C-NMR: 17.14 ppm, 12.43 ppm,
³¹ P-NMR: -27.38 ppm

Production Example 4 Tris [(tert-butyl) dimethylsilyl] phosphate:
¹ H-NMR: 0.86 ppm (s, 27 H), 0.24 ppm (s, 18 H),
¹³ C-NMR: 24.99 ppm, 17.45 ppm, −4.44 ppm
³¹ P-NMR: -24.10 ppm

Production Example 5 Tris (dimethylphenylsilyl) phosphate:
¹ H-NMR: 7.54 ppm (d, 6H), 7.48-7.30 ppm (m, 9H), 0.46 ppm (s, 18H)
¹³ C-NMR: 135.35 ppm, 132.78 ppm, 129.54 ppm, 127.31 ppm, −1.20 ppm
³¹ P-NMR: -25.60 ppm

Example 1
<Preparation of electrolyte>
In a mixed solvent obtained by mixing ethylene carbonate and ethyl methyl carbonate at a volume ratio of 1: 2 and containing 1 mol / L of LiPF ₆ as a lithium salt (9.80 g), the above production example 1 The electrolytic solution (D-1) was prepared by containing tris (triethylsilyl) phosphate (0.20 g) obtained in the above. The content of tris (triethylsilyl) phosphate in the electrolytic solution (D-1) was 2.0% by mass, and the content of LiPF ₆ was 13% by mass.

<Production and evaluation of lithium ion secondary battery>
Using the electrolytic solution (D-1), a sheet-like lithium ion secondary battery using a LiNi _1/3 Mn _1/3 Co _1/3 O ₂ positive electrode was prepared according to the procedure described in (2) above. The battery performance was evaluated. As a result, the discharge capacity retention rate was 84%, and the amount of gas generated after battery operation was 0.20 mL.

Examples 2-7 and Comparative Examples 1 and 2
In the above-mentioned <Preparation of electrolyte solution> in Example 1, the compound (A) of the type shown in Table 2 was used instead of tris (triethylsilyl) phosphate so that the concentrations shown in Table 2 were used. In the same manner as in Example 1, electrolytic solutions (D-2) to (D-7) were prepared. In Examples 6 and 7, additives of the type specified in Table 2 were further used together with the compound (A) so as to achieve the concentrations shown in Table 2. In Comparative Example 1, compound (A) was not used.
Using each of these electrolytic solutions, a sheet-like lithium ion secondary battery using a LiNi _1/3 Mn _1/3 Co _1/3 O ₂ positive electrode was produced according to the procedure described in (2) above, and battery performance Evaluation was performed. The evaluation results are shown in Table 2.

  From the results of the above examples, it was verified that the lithium ion secondary battery using the electrolytic solution containing the predetermined compound (A) of the present invention has a high discharge capacity retention rate and a small amount of gas generation.

[Example 8]
Using the electrolytic solution (D-1) obtained by the method described in Example 1, the sheet-like lithium ion 2 using the LiNi _0.5 Co _0.2 Mn _0.3 O ₂ positive electrode described in (3). A secondary battery was prepared and a 60 ° C. storage test was performed. As a result, the gas generation amounts after storage at 60 ° C. for 24 hours and after storage for 168 hours were as small as 0.16 mL and 0.32 mL, respectively. Further, ΔOCV after storage at 60 ° C. for 24 hours and after storage for 168 hours showed low values of 70 mV and 144 mV, respectively.

[Comparative Examples 3 and 4]
In the said Example 8, instead of electrolyte solution (D-1),
In Comparative Example 3, the electrolytic solution (C-1) obtained by the method described in Comparative Example 1 was used.
In Comparative Example 4, the electrolytic solution (C-2) obtained by the method described in Comparative Example 2 was used.
Using each of them, a 60 ° C. storage test was carried out in the same manner as in Example 8. The evaluation results are shown in Table 3.

  From the results of the above examples, it was verified that the lithium ion secondary battery using the electrolytic solution containing the predetermined compound (A) of the present invention can achieve both the suppression of gas generation and the suppression of the decrease in OCV. It was.

[Examples 9 and 10]
Electrolytic solutions D-1 and D-6 were prepared in the same manner as in <Preparation of electrolytic solution> in Examples 1 and 6 above, and the storage performance of the electrolytic solution was evaluated according to the procedure described in (4) above.
The evaluation results are shown in Table 4.

[Example 11]
Except that the concentration of heptamethyldisilazane was changed to 300 ppm by mass, an electrolytic solution D-8 was prepared in the same manner as in <Preparation of electrolytic solution> in Example 6, and the electrolytic solution was prepared according to the procedure described in (4) above. Storage performance evaluation was performed.
The evaluation results are shown in Table 4.

DESCRIPTION OF SYMBOLS 100 Lithium ion secondary battery 110 Separator 120 Positive electrode 130 Negative electrode 140 Positive electrode collector 150 Negative electrode collector 160 Battery exterior

Claims (14)

At least one of acidic protons having an acid selected from the group consisting of a protonic acid having at least one atom selected from a phosphorus atom and a boron atom, a sulfonic acid, and a carboxylic acid is represented by the following general formula (A1):

{Wherein R ^a1 , R ^a2 , and R ^a3 each independently represents an ^optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and R ^a1 , R ^a2 , and R ^a3 are carbon numbers. Is a total of 5-20. } The additive of the electrolyte solution for nonaqueous electrical storage devices characterized by comprising the compound (A) substituted by group represented by these. The compound (A) is
The following general formulas (A2) to (A4):

{Wherein M ¹ is a phosphorus atom or a boron atom,
m is an integer of 1 to 20,
When M ¹ is a phosphorus atom, n is 0 or 1, when M ¹ is a boron atom, n is 0, A1 represents a group represented by the general formula (A1), and R ^a4 and R ^a5 each independently represents an OH group, an OLi group, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 20 carbon atoms, or an OA1 group (wherein , A1 represents a group selected from the group consisting of the above formula (A1). },

{Wherein M ² is a phosphorus atom or a boron atom;
j is an integer of 2 to 20,
When M ² is a phosphorus atom, k is 0 or 1, and when M ² is a boron atom, k is 0,
R ^a6 is an OH group, an OLi group, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 20 carbon atoms, an OA1 group (wherein A1 is And a general formula OP (O) _l (R ^a7 R ^a8 ) (wherein l is 0 or 1, and R ^a7 and R ^a8 are Each independently, an OH group, an OLi group, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 20 carbon atoms, or an OA1 group (wherein A1 is A group selected from the group consisting of the groups represented by formula (A1).), Wherein at least one of R ^a6 is an OA1 group (wherein , A1 represents a group represented by the general formula (A1). },

{In formula, A1 shows group represented by the said general formula (A1), and ^Ra9 shows the C1-C20 hydrocarbon group which may be substituted. }, And a compound in which at least one of acidic protons of sulfuric acid is substituted with a group represented by the general formula (A1),
The additive according to claim 1, which is at least one selected from the group consisting of: The compound (A) is
In the above general formula (A2), M ¹ is a phosphorus atom, m is an integer of 1 to 4, and all of R ^a4 and R ^a5 are OA1 groups (wherein A1 is represented by the above general formula (A1)). A compound represented by:
In the general formula (A2), M ¹ is a boron atom, m is 1, and R ^a4 is an alkyl group having 1 to 4 carbon atoms or an OA1 group (wherein A1 is represented by the general formula (A1)). A compound represented by:
In the general formula (A3), M ² is a phosphorus atom, j is 3 or 4, and all of R ^a6 is an OA1 group (wherein A1 represents a group represented by the general formula (A1)). A compound that is
A compound in which all of acidic protons of sulfuric acid are substituted with the group represented by the general formula (A1), and acetic acid, oxalic acid, malonic acid, succinic acid, itaconic acid, adipic acid, phthalic acid, isophthalic acid, or The additive according to claim 2, wherein all of the acidic protons of terephthalic acid are at least one selected from the group consisting of compounds substituted with a group represented by the general formula (A1). At least one of acidic protons having an acid selected from the group consisting of a protonic acid having at least one atom selected from a phosphorus atom and a boron atom, a sulfonic acid, and a carboxylic acid is represented by the following general formula (A1):

{Wherein R ^a1 , R ^a2 , and R ^a3 each independently represents an ^optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and R ^a1 , R ^a2 , and R ^a3 are carbon numbers. Is a total of 5-20. } The compound (A) substituted by the group represented by these is used as an additive of the electrolyte solution for non-aqueous electricity storage devices. (A) 100 parts by mass of the additive according to any one of claims 1 to 3;
(B) Lewis base and general formula Q ⁺ Y ⁻ {wherein Q ⁺ represents a quaternary ammonium group, a quaternary phosphonium group, or an alkali metal, and Y ⁻ represents an alkoxy group or an aryloxy group. } One or more compounds (B) selected from the group consisting of compounds represented by the formula:

{Wherein R ^c1 , R ^c2 , and R ^c3 each independently represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted alkoxy group having 1 to 20 carbon atoms. And X ₁ represents a general formula OR ¹ (wherein R ¹ represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, a silyl group having 1 to 20 carbon atoms, SO ₂ Represents a group represented by CH ₃ or SO ₂ CF ₃ ), or a halogen atom. } One or more compounds (C) represented by
1 mass ppm or more and 100 mass% or less of at least one compound selected from the group consisting of:
An additive composition for an electrolyte solution for a non-aqueous electricity storage device, comprising: A non-aqueous solvent;
Lithium salt,
The additive according to any one of claims 1 to 4,
An electrolyte for a non-aqueous electricity storage device, comprising:   The electrolyte solution for nonaqueous electricity storage devices according to claim 6, wherein the content of the additive is 0.01% by mass or more and 10% by mass or less with respect to 100% by mass of the electrolyte solution for nonaqueous electricity storage devices. The lithium salt is LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , Li ₂ SiF ₆ , LiOSO ₂ C _k F _{2k + 1} {wherein, k is an integer of 0 to 8}, LiN (SO ₂ C _k F _{2k + 1} ) ₂ (where k is an integer from 0 to 8), and LiPF _n (C _k F _{2k + 1} ) _6-n {where n is an integer from 1 to 5 and k is from 1 to 8 The electrolyte solution for a non-aqueous electricity storage device according to claim 6 or 7, which is at least one selected from the group consisting of:   The electrolyte solution for non-aqueous electricity storage devices according to any one of claims 6 to 8, further comprising one or more selected from the group consisting of lithium difluorophosphate and lithium monofluorophosphate.   10. The electrolyte solution for a non-aqueous electricity storage device according to claim 6, wherein the non-aqueous solvent contains at least one selected from the group consisting of cyclic carbonates and chain carbonates. A positive electrode containing a positive electrode active material;
A negative electrode containing a negative electrode active material;
Electrolyte for non-aqueous electricity storage device according to any one of claims 6 to 10,
A lithium ion secondary battery comprising: The lithium ion secondary battery according to claim 11, wherein the positive electrode active material has a discharge capacity of 10 mAh / g or more at a potential of 4.2 V (vsLi / Li ⁺ ) or more. The positive electrode active material is
Following formula (E1):
_{LiMn 2-x Ma x O 4} (E1)
{In the formula, Ma represents a transition metal, and x is a number in the range of 0.2 ≦ x ≦ 0.7. } Oxides represented by
The following formula (E2):
LiMeO ₂ (E2)
{In the formula, Me represents a transition metal. } Oxides represented by
The following formula (E3):
_{zLi 2 McO 3 - (1-} z) LiMdO 2 (E3)
{Wherein Mc and Md each independently represent a transition metal, and z is a number in the range of 0.1 ≦ z ≦ 0.9. } A composite oxide represented by
The following formula (E4):
LiMb _1-y Fe _y PO ₄ (E4)
{In the formula, Mb represents one or more selected from the group consisting of Mn and Co, and y is a number in the range of 0 ≦ y ≦ 0.9. }; And the following formula (E5):
Li ₂ MfPO ₄ F (E5)
{In the formula, Mf represents one or more selected from the group consisting of transition metals. The lithium ion secondary battery according to claim 12, which is at least one selected from the group consisting of compounds represented by: The lithium ion secondary battery according to any one of claims 11 to 13, wherein a positive electrode potential based on lithium at a full charge is 4.2 V (vsLi / Li ⁺ ) or more.

Images