JP5315593B2 - Non-aqueous electrolyte and non-aqueous electrolyte secondary battery using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a non-aqueous electrolyte secondary battery using a negative electrode active material having at least one kind selected from a group of Si atom, Sn atom, and Pb atom which has a high charging capacity and excellent characteristics for a long period, and is superior, in particular, in discharge capacity maintenance rate. <P>SOLUTION: A carbonate having at least one of an unsaturated bonding and a halogen atom and a compound as expressed by a general formula (1) are at least contained in the non-aqueous electrolytic solution. In the formula (1), p and q express respectively and independently integers of 0 or 1, R<SP>1</SP>, R<SP>2</SP>, and R<SP>3</SP>respectively and independently express a hydrocarbon group which may have a halogen atom and have carbon number of 1 or more and 10 or less. Any of two out of R<SP>1</SP>, R<SP>2</SP>, and R<SP>3</SP>may mutually join and form an annular structure. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a non-aqueous electrolyte and a non-aqueous electrolyte secondary battery using the same. Specifically, when used in a non-aqueous electrolyte secondary battery using a negative electrode active material having at least one kind of atom selected from the group consisting of Si atom, Sn atom and Pb atom, excellent charge / discharge cycle characteristics are obtained. The present invention relates to a non-aqueous electrolyte solution and a non-aqueous electrolyte secondary battery using the non-aqueous electrolyte solution.

  With the recent reduction in weight and size of electrical products, development of non-aqueous electrolyte secondary batteries having a high energy density, such as lithium secondary batteries, is being promoted. Further, as the application field of lithium secondary batteries expands, further improvements in battery characteristics are desired.

  Under such circumstances, secondary batteries using metal lithium as a negative electrode have been studied as batteries capable of achieving high capacity. However, metallic lithium has a problem that metallic lithium grows in a dendrite shape due to repeated charge and discharge, which reaches the positive electrode and causes a short circuit inside the battery. This is a lithium secondary battery using metallic lithium as a negative electrode. Has become the biggest obstacle to practical use.

On the other hand, a non-aqueous electrolyte secondary battery using a carbonaceous material capable of occluding and releasing lithium such as coke, artificial graphite or natural graphite instead of metallic lithium as a negative electrode has been proposed. In such a non-aqueous electrolyte secondary battery, since lithium does not grow in a dendrite shape, the battery life and safety can be improved. When these graphites are used as the negative electrode, it is known that the capacity is usually about 300 mAh · g ⁻¹ and 500 mAh · cm ⁻³ .

In recent years, simple metal elements that can be alloyed with lithium, such as silicon (Si), tin (Sn), and lead (Pb), alloys containing at least these metal elements, and metal compounds containing these metal elements are used. Negative electrode active materials (hereinafter sometimes referred to as “negative electrode active materials having Si, Sn, Pb, etc.”) have been proposed. Since these have a capacity per volume of about 2000 mAh · cm ⁻³ or more and about 4 times or more of graphite, a higher capacity can be obtained by using them.

  However, although a secondary battery using a negative electrode active material containing Si, Sn, Pb, etc. is suitable for increasing the capacity, there is a problem that the safety is lowered, and the negative electrode active material is deteriorated due to charge / discharge. There has been a problem that the discharge efficiency is lowered and the cycle characteristics are deteriorated.

  Therefore, as a non-aqueous electrolyte used in such a secondary battery, in order to prevent a decrease in the discharge capacity of the battery while ensuring safety, a cyclic carbonate or carbonate ester multimer in the electrolyte, A non-aqueous electrolyte containing a phosphoric acid triester has been proposed (see Patent Document 1). In addition, for the purpose of improving the charge / discharge cycle characteristics of the battery, a heterocyclic compound containing a sulfur atom and / or an oxygen atom in the ring is added to the non-aqueous electrolyte solution to form a film on the surface of the negative electrode active material. A method for improving the charge / discharge cycle characteristics of the battery has also been proposed (see Patent Document 2).

Japanese Patent Laid-Open No. 11-176470 JP 2004-87284 A

  However, in conventional secondary batteries such as Patent Document 1 and Patent Document 2, a higher capacity can be obtained by using an element such as silicon (Si) as a negative electrode material, but performance in a longer charge / discharge cycle is obtained. In particular, the discharge capacity maintenance rate was still insufficient.

  The present invention has been made in view of the above problems. That is, an object of the present invention is a non-aqueous electrolyte secondary battery using a negative electrode active material having at least one of Si, Sn, and Pb, and has a high charge capacity and excellent characteristics over a long period of time. In particular, it is an object of the present invention to provide a non-aqueous electrolyte secondary battery excellent in discharge capacity maintenance ratio and a non-aqueous electrolyte used for the non-aqueous electrolyte solution.

  As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have found that a non-aqueous electrolyte solution using a negative electrode active material having at least one atom selected from the group consisting of Si atom, Sn atom and Pb atom In the secondary battery, by adding a carbonate having at least one of an unsaturated bond and a halogen atom to the non-aqueous electrolyte and an organic phosphorus compound (specific compound) represented by the formula (1) described below, the above problem is achieved. Has been found to be able to be solved, and the present invention has been completed.

（一般式（１）中、ｐ及びｑはそれぞれ独立に、０又は１の整数を表わし、Ｒ¹、Ｒ²及びＲ³はそれぞれ独立に、ハロゲン原子を有していてもよい、炭素数１以上、６以下の炭化水素基を表わす。また、Ｒ¹、Ｒ²及びＲ³のうち任意の二つが互いに結合して、環構造を形成していてもよい。 That is, the gist of the present invention comprises a lithium ion and a negative electrode and a positive electrode capable of occluding and releasing a non-aqueous electrolyte solution, used in a nonaqueous electrolyte secondary battery including a negative electrode active material negative electrode having a Si atom Non-aqueous electrolyte solution, vinylene carbonate derivatives or ethylene carbonate derivatives substituted with a substituent having a carbon-carbon unsaturated bond, 0.01 wt% or more and 5 wt% or less, and a carbonate having a fluorine atom A non-aqueous electrolyte comprising at least one of 0.01% by weight or more and 50% by weight or less and at least one organic phosphorus compound represented by the following formula (1): Item 1).

(In the general formula (1), p and q each independently represent an integer of 0 or 1, and R ¹ , R ² and R ³ each independently have a halogen atom, 1 carbon atom. The hydrocarbon group is 6 or less, and any two of R ¹ , R ² and R ³ may be bonded to each other to form a ring structure.

  Here, in the said General formula (1), it is preferable that p + q is 1 or 2 (Claim 2).

  In the general formula (1), p + q is preferably 0 (claim 3).

  Moreover, it is preferable that the density | concentration of the compound represented by the said General formula (1) in a non-aqueous electrolyte solution is 0.01 to 10 weight% (Claim 4).

Moreover, it is preferable that the density | concentration of the compound represented by the said General formula (1) in a non-aqueous electrolyte solution is 0.01 to 5 weight% (Claim 5).

The vinylene carbonate derivatives or ethylene carbonate derivatives substituted with a substituent having a carbon-carbon unsaturated bond, or the carbonate having the fluorine atom is vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate, and One or more carbonates selected from the group consisting of difluoroethylene carbonate and derivatives thereof are preferred (Claim 6).

  Moreover, it is preferable to further contain ethylene carbonate and / or propylene carbonate.

  Furthermore, it may further contain at least one carbonate selected from the group consisting of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl-n-propyl carbonate, ethyl-n-propyl carbonate, and di-n-propyl carbonate. Preferred (claim 8).

Another subject of the present invention comprises a lithium ion and a negative electrode and a positive electrode capable of occluding and releasing a non-aqueous electrolyte solution, as well as containing an anode active material negative electrode having a Si atom, nonaqueous electrolyte solution above The present invention resides in a non-aqueous electrolyte secondary battery characterized by being a non-aqueous electrolyte solution .

  The non-aqueous electrolyte secondary battery of the present invention has a high charge capacity, an excellent characteristic over a long period of time, and particularly an excellent discharge capacity maintenance rate.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to the gist of the present invention. It is not specified in the contents of.

[I. Non-aqueous electrolyte]
First, the non-aqueous electrolyte solution of the present invention will be described.
The nonaqueous electrolytic solution of the present invention comprises a negative electrode and a positive electrode capable of occluding and releasing lithium ions, and a nonaqueous electrolytic solution, and the negative electrode is at least one atom selected from the group consisting of Si atoms, Sn atoms, and Pb atoms. It is a non-aqueous electrolyte solution used for the non-aqueous electrolyte secondary battery containing the negative electrode active material which has this.

  The non-aqueous electrolyte solution of the present invention usually has an electrolyte and a non-aqueous solvent that dissolves it as a main component, as in the case of a general non-aqueous electrolyte solution. Furthermore, a compound represented by the following general formula (1) (hereinafter referred to as “specific compound” as appropriate) and a carbonate having at least one of an unsaturated bond and a halogen atom (hereinafter referred to as “specific carbonate” as appropriate). Are contained at least one of each. In addition, other components (additives, etc.) may be contained.

  In the following description, the specific compound and the specific carbonate will be described first, and then the electrolyte and the nonaqueous solvent will be described, and then other components will be touched.

[I-1. Specific compounds]
The specific compound according to the present invention is an organic phosphorus compound represented by the following general formula (1).

(In the general formula (1), p and q each independently represents an integer of 0 or 1.
R ¹ , R ² and R ³ each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may have a halogen atom.
Any two or more of R ¹ , R ² and R ³ may be bonded to each other to form a ring structure. )

In the general formula (1), the type of hydrocarbon groups R ¹ to R ³ are not particularly limited. That is, it may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, or may be a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be a saturated hydrocarbon group and may contain an unsaturated bond (carbon-carbon double bond or carbon-carbon triple bond). Further, the aliphatic hydrocarbon group may be a chain or a ring, and in the case of a chain, it may be a straight chain or a branched chain. Further, a chain and a ring may be combined.

The carbon number of the hydrocarbon group of R ^{1 to} R ³ is usually 1 or more, and usually 20 or less, preferably 10 or less, more preferably 6 or less. When there are too many carbon numbers of the hydrocarbon group of R < ¹ > -R < ³ >, there exists a tendency for the solubility with respect to a non-aqueous electrolyte to fall.

Specific examples of preferred hydrocarbon groups as R ^{1 to} R ³ are given below.

  Specific examples of the chain saturated aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a 2-ethylhexyl group. Etc.

  Specific examples of the cyclic saturated aliphatic hydrocarbon group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and the like.

  Specific examples of the aliphatic hydrocarbon group having an unsaturated bond (hereinafter abbreviated as “unsaturated aliphatic hydrocarbon group” where appropriate) include a vinyl group, a 1-propen-1-yl group, an allyl group, and a crotyl group. Etc.

  Specific examples of the aromatic hydrocarbon group or the hydrocarbon group formed by bonding an aromatic hydrocarbon group and an aliphatic hydrocarbon group include a phenyl group, a toluyl group, a xylyl group, a cinnamyl group, a benzyl group, and the like. Can be mentioned.

Among the hydrocarbon groups exemplified above, R ^{1 to} R ³ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, 2-ethylhexyl group, and cyclopentyl. Group, cyclohexyl group, phenyl group, toluyl group, vinyl group, allyl group, benzyl group and the like are preferable from the viewpoints of solubility in an electrolytic solution, industrial availability, and the like.

Further, any two of R ^{1 to} R ³ may be bonded to form a ring structure. Combinations selected include R ¹ and R ² , R ¹ and R ³ , R ² and R ³ . The number of members of the ring structure formed is usually in the range of 4 or more, especially 5 or more, and usually 10 or less, preferably 7 or less. It is preferable from the viewpoint of easy availability.

When any two of R ^{1 to} R ³ are bonded to form a ring structure, the bonded hydrocarbon group forms a divalent hydrocarbon group, but the divalent hydrocarbon group As a specific example,
A —CH ₂ CH ₂ — group,
A —CH ₂ CH ₂ CH ₂ — group,
A —CH ₂ CH (CH ₃ ) — group,
A —CH ₂ CH (C ₂ H ₅ ) — group,
_{-CH (CH 3) CH (CH} 3) - group,
_{-CH 2 CH 2 CH (CH 3} ) - group,
_{-CH 2 CH 2 CH 2 CH 2} - group,
_{-CH 2 C (CH 3) 2} CH 2 - group,
-CH = CH- group,
A —CH═CHCH ₂ — group,
A —CH═C (CH ₃ ) — group,
A —CH ₂ C (═CH ₂ ) — group,
A —CH═C (C ₂ H ₅ ) — group,
_{-C (CH 3) = C (} CH 3) - group,
A —CH═CHCH (CH ₃ ) — group,
_{-CH 2 CH = C (CH 3} ) - group,
-CH = CHCH ₂ CH ₂ - group,
A —CH ₂ CH═CHCH ₂ — group,
A —CH ₂ C≡CCH ₂ — group, and the like.

Among these, from the viewpoint of chemical stability and industrial availability, the divalent hydrocarbon group is
A —CH ₂ CH ₂ — group,
A —CH ₂ CH ₂ CH ₂ — group,
A —CH ₂ CH (CH ₃ ) — group,
_{-CH (CH 3) CH (CH} 3) - group,
_{-CH 2 CH 2 CH 2 CH 2} - group,
-CH = CH- group,
A —CH═CHCH ₂ — group,
A —CH═C (CH ₃ ) — group,
A —CH═C (C ₂ H ₅ ) — group,
_{-C (CH 3) = C (} CH 3) - group,
A —CH ₂ CH═CHCH ₂ — group and the like are preferable.

The hydrocarbon group of R ^{1 to} R ³ in the general formula (1) may be one in which part or all of the hydrogen atoms bonded to the carbon atom are substituted with a halogen atom.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, but a fluorine atom, a chlorine atom, and a bromine atom are preferable, and further, a fluorine atom and a chlorine atom are chemically stable or electrochemical. More preferable from the viewpoint of stability.

When the hydrocarbon group of R ^{1 to} R ³ is substituted with a halogen atom, the number of halogen atoms is not particularly limited, and only part of the hydrogen atoms of the hydrocarbon group may be replaced with halogen atoms. These hydrogen atoms may be replaced by halogen atoms. In addition, when each of the hydrocarbon groups of R ^{1 to} R ³ has a plurality of halogen atoms, these halogen atoms may be the same or different.

Specific examples of hydrocarbon groups substituted with halogen atoms, which are preferable as R ^{1 to} R ³ , are given below.

Specific examples of the chain saturated aliphatic hydrocarbon group substituted with a fluorine atom include
A fluoromethyl group,
Difluoromethyl group,
A trifluoromethyl group,
1-fluoroethyl group,
2-fluoroethyl group,
2,2,2-trifluoroethyl group,
Perfluoroethyl group,
1-fluoro-n-propyl group,
2-fluoro-n-propyl group,
3-fluoro-n-propyl group,
3,3,3-trifluoro-n-propyl group,
1-fluoro-isopropyl group,
A perfluoro-n-propyl group,
1,1,1,3,3,3-hexafluoroisopropyl group,
4,4,4-trifluoro-n-butyl group,
Perfluoro-n-butyl group,
2-fluoro-tert-butyl group,
A perfluoro-tert-butyl group, and the like.

Specific examples of the cyclic saturated aliphatic hydrocarbon group substituted with a fluorine atom include
2-fluorocyclohexyl group,
3-fluorocyclohexyl group,
4-fluorocyclohexyl group etc. are mentioned.

Specific examples of the unsaturated aliphatic hydrocarbon group substituted with a fluorine atom include
1-fluorovinyl group,
2-fluorovinyl group,
2,2-difluorovinyl group,
Tetrafluorovinyl group,
2-fluoroallyl group,
3-fluoroallyl group, etc. are mentioned.

Specific examples of an aromatic hydrocarbon group substituted with a fluorine atom, or a hydrocarbon group formed by bonding an aromatic hydrocarbon group and an aliphatic hydrocarbon group,
2-fluorophenyl group,
3-fluorophenyl group,
4-fluorophenyl group,
Difluorophenyl group,
A trifluorophenyl group,
Perfluorophenyl group,
2-fluorophenylmethyl group,
3-fluorophenylmethyl group,
4-fluorophenylmethyl group, etc. are mentioned.

As a specific example of a chain saturated aliphatic hydrocarbon group substituted with a chlorine atom,
A chloromethyl group,
Dichloromethyl group,
A trichloromethyl group,
1-chloroethyl group,
2-chloroethyl group,
2,2,2-trichloroethyl group,
Perchloroethyl group,
1-chloro-n-propyl group,
2-chloro-n-propyl group,
3-chloro-n-propyl group,
A perchloro-n-propyl group,
3,3,3-trichloro-n-propyl group,
1-chloro-isopropyl group,
1,1,1,3,3,3-hexachloroisopropyl group,
4,4,4-trichloro-n-butyl group,
Perchloro-n-butyl group,
2-chloro-tert-butyl group,
And a perchloro-tert-butyl group.

Specific examples of the ring-shaped saturated aliphatic hydrocarbon group substituted with a chlorine atom,
2-chlorocyclohexyl group,
3-chlorocyclohexyl group,
4-chlorocyclohexyl group, etc. are mentioned.

Specific examples of the unsaturated aliphatic hydrocarbon group substituted with a chlorine atom include
1-chlorovinyl group,
2-chlorovinyl group,
2,2-dichlorovinyl group,
Tetrachlorovinyl group,
2-chloroallyl group,
3-chloroallyl group, etc. are mentioned.

As a specific example of an aromatic hydrocarbon group substituted with a chlorine atom, or a hydrocarbon group formed by bonding an aromatic hydrocarbon group and an aliphatic hydrocarbon group,
2-chlorophenyl group,
3-chlorophenyl group,
4-chlorophenyl group,
2-chlorophenylmethyl group,
3-chlorophenylmethyl group,
4-chlorophenylmethyl group,
A chlorofluoromethyl group, and the like.

In addition, in the divalent hydrocarbon group formed by bonding any two of R ^{1 to} R ³ , a part or all of the hydrogen atoms bonded to the carbon atom may be substituted with a halogen atom. Good.

Specific examples of the divalent hydrocarbon group having a halogen atom include
A —CH ₂ CHF— group,
A —CHFCHF— group,
A —CH ₂ CF ₂ — group,
-CH ₂ CH ₂ CHF- group,
A —CH ₂ CHFCH ₂ — group,
A —CH ₂ CH (CF ₃ ) — group,
-CHFCH ₂ CH ₂ CH ₂ - group,
-CH ₂ CHFCH ₂ CH ₂ - group,
-CH = CF- group,
-CF = CF- group,
-CH = CFCH ₂ - group,
-CH = CHCHF- group,
-CF = C (CH ₃₎ - group,
A —CH═C (CF ₃ ) — group,
-CHFCH = CHCH ₂ - group,
A —CH ₂ CF═CHCH ₂ — group,
A —CH ₂ CHCl— group,
-CHFCHCl- group,
A —CH ₂ CCl ₂ — group,
A —CH ₂ CH ₂ CHCl— group,
A —CH ₂ CHClCH ₂ — group,
A —CH ₂ CH (CCl ₃ ) — group,
-CHClCH ₂ CH ₂ CH ₂ - group,
A —CH ₂ CHClCH ₂ CH ₂ — group,
-CH = CCl- group,
-CCl = CCl- group,
A —CH═CClCH ₂ — group,
-CH = CHCHCl- group,
A —CCl═C (CH ₃ ) — group,
A —CH═C (CCl ₃ ) — group,
A —CHClCH═CHCH ₂ — group,
A —CH ₂ CCl═CHCH ₂ — group,
-CHFCHCl- group, and the like.

  Subsequently, specific examples of the compound represented by the above formula (1) are classified into the combinations of p and q and described below.

  As described above, in the general formula (1), p and q each independently represents 0 or 1. Therefore, the combinations of p and q include (p, q) = (1, 1), (1, 0), (0, 1), (0, 0).

<Exemplary compounds when p + q = 2>
When p + q = 2, that is, (p, q) = (1, 1), the compound represented by the above formula (1) is a phosphonic acid ester.

Examples of phosphonate esters include
A phosphonic acid diester substituted with an alkyl group,
Phosphonic acid diesters substituted with unsaturated hydrocarbon groups,
And phosphonic acid diesters substituted with an aryl group.

Specific examples of alkylphosphonic acid diesters substituted with an alkyl group include:
Dimethyl methylphosphonate,
Diethyl ethylphosphonate,
n-propyl phosphonate di-n-propyl,
Diisopropyl isopropylphosphonate,
di-n-butyl n-butylphosphonate,
Diisobutyl isobutylphosphonate,
di-tert-butyl tert-butylphosphonate,
Dicyclopentyl cyclopentylphosphonate,
Cyclohexyl phosphonate dicyclohexyl,
Diethyl methylphosphonate,
Di-n-propyl methylphosphonate,
Di-n-butyl methylphosphonate,
Dicyclopentyl methylphosphonate,
Dicyclohexyl methylphosphonate,
Methylphosphonate di (2-cyclohexenyl),
Methylphosphonate di (3-cyclohexenyl),
Divinyl methylphosphonate,
Diallyl methylphosphonate,
Dipropargyl methylphosphonate,
Diphenyl methylphosphonate,
Methylphosphonate di (2-tolyl),
Methylphosphonate di (3-tolyl),
Methylphosphonate di (4-tolyl),
Dimethyl ethylphosphonate,
Di-n-propyl ethylphosphonate,
Di-n-butyl ethylphosphonate,
Dicyclopentyl ethylphosphonate,
Dicyclohexyl ethylphosphonate,
Di (2-cyclohexenyl) ethylphosphonate,
Di (3-cyclohexenyl) ethylphosphonate,
Divinyl ethylphosphonate,
Diallyl ethylphosphonate,
Dipropargyl ethylphosphonate,
Diphenyl ethylphosphonate,
Di (2-tolyl) ethylphosphonate,
Di (3-tolyl) ethylphosphonate,
Di (4-tolyl) ethylphosphonate,
dimethyl n-butylphosphonate,
diethyl n-butylphosphonate,
Dimethyl cyclohexylphosphonate,
Diethyl cyclohexylphosphonate,
Ethyl methyl phosphonate,
Methyl n-propyl methylphosphonate,
N-butylmethyl methylphosphonate,
Cyclopentylmethyl methylphosphonate,
Cyclohexylmethyl methylphosphonate,
Methyl (2-cyclohexenyl) methylphosphonate,
Methyl phosphonate (3-cyclohexenyl) methyl,
Methyl vinyl phosphonate,
Allylmethyl methylphosphonate,
Methyl propargyl methylphosphonate,
Methyl phenyl methylphosphonate,
Methyl methylphosphonate (2-tolyl),
Methyl methylphosphonate (3-tolyl),
Methyl methylphosphonate (4-tolyl),
Ethyl n-propyl methylphosphonate,
Cyclohexylethyl methylphosphonate,
Ethyl phenyl methylphosphonate,
Cyclohexylphenyl methylphosphonate,
Vinyl phenyl methylphosphonate,
Allylphenyl methylphosphonate,
Methyl phenylphosphonate (2-tolyl),
Methyl phenylphosphonate (4-tolyl),
Ethyl methyl ethylphosphonate,
Methyl n-propyl ethylphosphonate,
N-butylmethyl ethylphosphonate,
Cyclopentylmethyl ethylphosphonate,
Cyclohexylmethyl ethylphosphonate,
(2-cyclohexenyl) methyl ethylphosphonate,
(3-cyclohexenyl) methyl ethylphosphonate,
Methyl vinyl ethylphosphonate,
Allyl methyl ethylphosphonate,
Methyl propargyl ethylphosphonate,
Methyl phenyl ethylphosphonate,
Methyl ethylphosphonate (2-tolyl),
Methyl ethylphosphonate (3-tolyl),
Methyl ethylphosphonate (4-tolyl),
Ethyl n-propyl ethylphosphonate,
Cyclohexylethyl ethylphosphonate,
Ethyl phenyl ethylphosphonate,
Cyclohexyl phenyl ethylphosphonate,
Vinyl phenyl ethylphosphonate,
Allylphenyl ethylphosphonate,
Ethyl ethylphosphonate (2-tolyl),
Ethyl ethylphosphonate (4-tolyl),
ethyl methyl n-butylphosphonate,
n-propyl methyl n-butylphosphonate,
n-butylmethyl n-butylphosphonate,
cyclopentylmethyl n-butylphosphonate,
cyclohexylmethyl n-butylphosphonate,
n-butylphosphonic acid (2-cyclohexenyl) methyl,
n-butylphosphonic acid (3-cyclohexenyl) methyl,
methyl vinyl n-butylphosphonate,
allylmethyl n-butylphosphonate,
methyl propargyl n-butylphosphonate,
methyl phenyl n-butylphosphonate,
methyl n-butylphosphonate (2-tolyl),
methyl n-butylphosphonate (3-tolyl),
methyl n-butylphosphonate (4-tolyl),
n-butyl ethyl n-butylphosphonate,
cyclohexylethyl n-butylphosphonate,
ethyl phenyl n-butylphosphonate,
cyclohexyl phenyl n-butylphosphonate,
vinyl phenyl n-butylphosphonate,
allylphenyl n-butylphosphonate,
n-butylphosphonate phenyl (2-tolyl),
n-butylphosphonate phenyl (4-tolyl),
Ethyl methyl cyclohexylphosphonate,
Methyl n-propyl cyclohexylphosphonate,
N-butylmethyl cyclohexylphosphonate,
Cyclopentylmethyl cyclohexylphosphonate,
Cyclohexylmethyl cyclohexylphosphonate,
(2-cyclohexenyl) methyl cyclohexylphosphonate,
Cyclohexyl (3-cyclohexenyl) methyl cyclohexylphosphonate,
Methyl vinyl cyclohexylphosphonate,
Allylmethyl cyclohexylphosphonate,
Methyl propargyl cyclohexylphosphonate,
Methylphenyl cyclohexylphosphonate,
Methyl cyclohexylphosphonate (2-tolyl),
Methyl cyclohexylphosphonate (3-tolyl),
Methyl cyclohexylphosphonate (4-tolyl),
Ethyl n-propyl cyclohexylphosphonate,
Cyclohexylethyl cyclohexylphosphonate,
Cyclohexyl ethyl phosphonate,
Cyclohexyl phenyl cyclohexylphosphonate,
Cyclohexyl vinyl phosphonate vinyl phenyl,
Allylphenyl cyclohexylphosphonate,
Cyclohexyl phenylphosphonate (2-tolyl),
Examples include phenyl (4-tolyl) cyclohexyl phosphonate.

Specific examples of a phosphonic acid diester substituted with an alkyl group and having a moiety substituted with a fluorine atom include:
Diperfluoromethyl methylphosphonate,
Di (2,2,2-trifluoroethyl) methylphosphonate,
Diperfluoroethyl methylphosphonate,
Methylphosphonate di (2-fluorocyclohexyl),
Methylphosphonate di (3-fluorocyclohexyl),
Methylphosphonate di (4-fluorocyclohexyl),
Methylphosphonate di (2-fluorovinyl),
Methylphosphonate di (2,2-difluorovinyl),
Methylphosphonate di (2-fluorophenyl),
Methylphosphonate di (3-fluorophenyl),
Methylphosphonate di (4-fluorophenyl),
Diperfluoromethyl ethylphosphonate,
Di (2,2,2-trifluoroethyl) ethylphosphonate,
Diperfluoroethyl ethylphosphonate,
Di (2-fluorocyclohexyl) ethylphosphonate,
Di (3-fluorocyclohexyl) ethylphosphonate,
Di (4-fluorocyclohexyl) ethylphosphonate,
Ethylphosphonic acid di (2-fluorovinyl),
Di (2,2-difluorovinyl) ethylphosphonate,
Ethylphosphonic acid di (2-fluorophenyl),
Ethylphosphonic acid di (3-fluorophenyl),
Di (4-fluorophenyl) ethylphosphonate,
n-butylphosphonate di (2,2,2-trifluoroethyl),
diperfluoroethyl n-butylphosphonate,
n-butylphosphonic acid di (2-fluorophenyl),
Cyclohexylphosphonic acid di (2,2,2-trifluoroethyl),
Diperfluoroethyl cyclohexylphosphonate,
Cyclohexylphosphonic acid di (2-fluorophenyl),
Methyl perfluoromethyl methylphosphonate,
Methyl methylphosphonate (2,2,2-trifluoroethyl),
Methyl perfluoroethyl methylphosphonate,
Methyl (2-fluorocyclohexyl) methylphosphonate,
Methyl (3-fluorocyclohexyl) methylphosphonate,
Methyl (4-fluorocyclohexyl) methylphosphonate,
Methyl (2-fluorovinyl) methylphosphonate,
Methyl phosphonate (2,2-difluorovinyl) methyl,
Methyl (2-fluorophenyl) methylphosphonate,
Methyl (3-fluorophenyl) methylphosphonate,
Methyl (4-fluorophenyl) methylphosphonate,
Ethyl methylphosphonate (2,2,2-trifluoroethyl),
Ethyl perfluoroethyl methylphosphonate,
(2-fluorophenyl) ethyl methylphosphonate,
Cyclohexyl methylphosphonate (2,2,2-trifluoroethyl),
Cyclohexyl perfluoroethyl methylphosphonate,
Cyclohexyl methylphosphonate (2-fluorophenyl),
Vinyl methylphosphonate (2,2,2-trifluoroethyl),
Vinyl methylphosphonate (2-fluorophenyl),
Allyl methylphosphonate (2,2,2-trifluoroethyl),
Allyl methylphosphonate (2-fluorophenyl),
Methyl phenylphosphonate (2,2,2-trifluoroethyl),
Phenylperfluoroethyl methylphosphonate,
Methyl phenylphosphonate (2-fluorophenyl),
Perfluoroethyl methylphosphonate (2,2,2-trifluoroethyl),
Perfluoroethyl methylphosphonate (2-fluorophenyl),
Methylphosphonic acid (2-fluorocyclohexyl) (2,2,2-trifluoroethyl),
Methylphosphonic acid (2-fluorocyclohexyl) (2-fluorophenyl),
Methylphosphonic acid (2-fluorophenyl) (4-fluorophenyl),
Ethyl ethylphosphonate (2,2,2-trifluoroethyl),
Ethyl perfluoroethyl ethylphosphonate,
Ethyl (2-fluorophenyl) ethylphosphonate,
Cyclohexyl ethylphosphonate (2,2,2-trifluoroethyl),
Cyclohexyl perfluoroethyl ethylphosphonate,
Cyclohexyl ethylphosphonate (2-fluorophenyl),
Vinyl ethylphosphonate (2,2,2-trifluoroethyl),
Vinyl ethylphosphonate (2-fluorophenyl),
Allyl ethylphosphonate (2,2,2-trifluoroethyl),
Allyl ethylphosphonate (2-fluorophenyl),
Phenyl ethylphosphonate (2,2,2-trifluoroethyl),
Phenylperfluoroethyl ethylphosphonate,
Ethyl ethylphosphonate (2-fluorophenyl),
Perfluoroethyl ethylphosphonate (2,2,2-trifluoroethyl),
Perfluoroethyl (2-fluorophenyl) ethylphosphonate,
Ethylphosphonic acid (2-fluorocyclohexyl) (2,2,2-trifluoroethyl),
Ethylphosphonic acid (2-fluorocyclohexyl) (2-fluorophenyl),
Ethylphosphonic acid (2-fluorophenyl) (4-fluorophenyl),
ethyl n-butylphosphonate (2,2,2-trifluoroethyl),
n-butyl ethyl phosphonate perfluoroethyl;
n-butylphosphonic acid (2-fluorophenyl) ethyl;
cyclohexyl n-butylphosphonate (2,2,2-trifluoroethyl),
cyclohexyl perfluoroethyl n-butylphosphonate,
cyclohexyl n-butylphosphonate (2-fluorophenyl),
vinyl n-butylphosphonate (2,2,2-trifluoroethyl),
vinyl n-butylphosphonate (2-fluorophenyl),
allyl n-butylphosphonate (2,2,2-trifluoroethyl),
allyl n-butylphosphonate (2-fluorophenyl),
n-butylphosphonate phenyl (2,2,2-trifluoroethyl),
phenylperfluoroethyl n-butylphosphonate,
n-butylphosphonic acid phenyl (2-fluorophenyl),
perfluoroethyl n-butylphosphonate (2,2,2-trifluoroethyl),
perfluoroethyl n-butylphosphonate (2-fluorophenyl),
n-butylphosphonic acid (2-fluorocyclohexyl) (2,2,2-trifluoroethyl),
n-butylphosphonic acid (2-fluorocyclohexyl) (2-fluorophenyl),
n-butylphosphonic acid (2-fluorophenyl) (4-fluorophenyl),
Ethyl cyclohexylphosphonate (2,2,2-trifluoroethyl),
Cyclohexyl ethyl phosphonate perfluoroethyl,
(2-fluorophenyl) ethyl cyclohexylphosphonate,
Cyclohexyl cyclohexylphosphonate (2,2,2-trifluoroethyl),
Cyclohexyl perfluoroethyl cyclohexylphosphonate,
Cyclohexyl phosphonate cyclohexyl (2-fluorophenyl),
Vinyl cyclohexylphosphonate (2,2,2-trifluoroethyl),
Cyclohexyl vinyl phosphonate (2-fluorophenyl),
Allyl cyclohexylphosphonate (2,2,2-trifluoroethyl),
Allyl cyclohexylphosphonate (2-fluorophenyl),
Phenyl cyclohexylphosphonate (2,2,2-trifluoroethyl),
Phenylperfluoroethyl cyclohexylphosphonate,
Cyclohexyl phenylphosphonate (2-fluorophenyl),
Perfluoroethyl cyclohexylphosphonate (2,2,2-trifluoroethyl),
Perfluoroethyl cyclohexylphosphonate (2-fluorophenyl),
Cyclohexylphosphonic acid (2-fluorocyclohexyl) (2,2,2-trifluoroethyl),
Cyclohexylphosphonic acid (2-fluorocyclohexyl) (2-fluorophenyl),
Cyclohexylphosphonic acid (2-fluorophenyl) (4-fluorophenyl),
Perfluoromethylphosphonate diperfluoromethyl,
(2,2,2-trifluoroethyl) phosphonic acid di (2,2,2-trifluoroethyl),
Perfluoroethyl phosphonate diperfluoroethyl,
(2-fluorocyclohexyl) phosphonic acid di (2-fluorocyclohexyl),
(3-fluorocyclohexyl) phosphonic acid di (3-fluorocyclohexyl),
(4-fluorocyclohexyl) phosphonic acid di (4-fluorocyclohexyl),
Dimethyl (2,2,2-trifluoroethyl) phosphonate,
(2,2,2-trifluoroethyl) diethyl phosphonate,
Di-n-butyl (2,2,2-trifluoroethyl) phosphonate,
(2,2,2-trifluoroethyl) phosphonic acid dicyclohexyl,
(2,2,2-trifluoroethyl) phosphonic acid di (2-cyclohexenyl),
(2,2,2-trifluoroethyl) phosphonic acid divinyl,
Diallyl (2,2,2-trifluoroethyl) phosphonate,
Dipropargyl (2,2,2-trifluoroethyl) phosphonate,
(2,2,2-trifluoroethyl) phosphonic acid diphenyl,
(2,2,2-trifluoroethyl) phosphonic acid di (2-tolyl),
(2,2,2-trifluoroethyl) phosphonic acid di (4-tolyl),
(2,2,2-trifluoroethyl) phosphoric acid diperfluoroethyl,
(2,2,2-trifluoroethyl) phosphonic acid di (2-fluorocyclohexyl),
(2,2,2-trifluoroethyl) phosphonic acid di (2-fluorovinyl),
(2,2,2-trifluoroethyl) phosphonic acid di (2-fluorophenyl),
(2,2,2-trifluoroethyl) phosphonic acid di (4-fluorophenyl),
(2,2,2-trifluoroethyl) ethyl methylphosphonate,
N-butylmethyl (2,2,2-trifluoroethyl) phosphonate,
(2,2,2-trifluoroethyl) cyclohexylmethyl phosphonate,
Methyl vinyl (2,2,2-trifluoroethyl) phosphonate,
Allylmethyl (2,2,2-trifluoroethyl) phosphonate,
(2,2,2-trifluoroethyl) methyl phenylphosphonate,
Methyl (2,2,2-trifluoroethyl) phosphonate (2,2,2-trifluoroethyl),
(2,2,2-trifluoroethyl) methyl perfluoroethyl phosphonate,
(2,2,2-trifluoroethyl) phosphonic acid (2-fluorocyclohexyl) methyl,
(2,2,2-trifluoroethyl) phosphoric acid (2-fluorovinyl) methyl,
(2,2,2-trifluoroethyl) phosphonic acid (2-fluorophenyl) methyl,
(2,2,2-trifluoroethyl) cyclohexylethyl phosphonate,
(2,2,2-trifluoroethyl) ethyl phenylphosphonate,
(2,2,2-trifluoroethyl) ethyl phosphonate (2,2,2-trifluoroethyl),
(2,2,2-trifluoroethyl) phosphonic acid (2-fluorophenyl) ethyl;
(2,2,2-trifluoroethyl) cyclohexyl phenylphosphonate,
(2,2,2-trifluoroethyl) phosphonic acid cyclohexyl (2,2,2-trifluoroethyl),
Cyclohexyl (2,2,2-trifluoroethyl) phosphonate (2-fluorophenyl),
(2,2,2-trifluoroethyl) vinyl phosphonate (2,2,2-trifluoroethyl),
(2,2,2-trifluoroethyl) vinylphosphonate (2-fluorophenyl),
(2,2,2-trifluoroethyl) allylphosphonate (2,2,2-trifluoroethyl),
(2,2,2-trifluoroethyl) allylphosphonate (2-fluorophenyl),
(2,2,2-trifluoroethyl) phosphonic acid phenyl (2,2,2-trifluoroethyl),
(2,2,2-trifluoroethyl) phenyl phosphonate (2-fluorophenyl),
(2,2,2-trifluoroethyl) phosphonic acid (2,2,2-trifluoroethyl) (2-fluorophenyl),
(2,2,2-trifluoroethyl) phosphonic acid phenyl (2,2,2-trifluoroethyl),
(2,2,2-trifluoroethyl) phenyl phosphonate (2-fluorophenyl),
(2-fluorocyclohexyl) dimethyl phosphonate,
(2-fluorocyclohexyl) diethyl phosphonate,
(2-fluorocyclohexyl) phosphoric acid dicyclohexyl,
(2-fluorocyclohexyl) phosphonic acid diphenyl,
(2-fluorocyclohexyl) phosphonic acid bis (2,2,2-trifluoroethyl),
(2-fluorocyclohexyl) phosphonic acid di (2-fluorophenyl),
(2-fluorocyclohexyl) ethyl methylphosphonate,
(2-fluorocyclohexyl) cyclohexylmethyl phosphonate,
(2-fluorocyclohexyl) methyl phenylphosphonate,
(2-fluorocyclohexyl) methyl phosphonate (2,2,2-trifluoroethyl),
(2-fluorocyclohexyl) phosphonic acid (2-fluorophenyl) methyl, and the like.

Specific examples of phosphonic acid diesters substituted with an unsaturated hydrocarbon group include:
Divinyl vinylphosphonate,
Diallyl allylphosphonate,
Propargyl phosphonate dipropargyl,
Dimethyl vinylphosphonate,
Diethyl vinylphosphonate,
Di-n-butyl vinylphosphonate,
Dicyclohexyl vinylphosphonate,
Diphenyl vinylphosphonate,
Ethyl methyl vinylphosphonate,
Methyl n-propyl vinylphosphonate,
N-butylmethyl vinylphosphonate,
Cyclopentylmethyl vinylphosphonate,
Cyclohexylmethyl vinylphosphonate,
(2-cyclohexenyl) methyl vinylphosphonate,
(3-cyclohexenyl) methyl vinylphosphonate,
Methyl vinyl vinyl phosphonate,
Allyl methyl vinylphosphonate,
Methyl propargyl vinylphosphonate,
Methyl phenyl vinylphosphonate,
Methyl vinylphosphonate (2-tolyl),
Methyl vinylphosphonate (3-tolyl),
Methyl vinylphosphonate (4-tolyl),
Ethyl n-propyl vinylphosphonate,
Cyclohexylethyl vinylphosphonate,
Ethyl phenyl vinylphosphonate,
Cyclohexyl phenyl vinylphosphonate,
Vinyl phenyl vinylphosphonate,
Allylphenyl vinylphosphonate,
Phenyl vinylphosphonate (2-tolyl),
Phenyl vinylphosphonate (4-tolyl),
Dimethyl allylphosphonate,
Diethyl allylphosphonate,
Di-n-butyl allylphosphonate,
Dicyclohexyl allylphosphonate,
Diphenyl allylphosphonate,
Allylphosphonic acid di (2,2,2-trifluoroethyl),
Allylphosphonic acid di (2-fluorocyclohexyl),
Allylphosphonic acid di (2-fluorophenyl),
Ethyl methyl allylphosphonate,
Methyl n-propyl allylphosphonate,
N-butylmethyl allylphosphonate,
Cyclopentylmethyl allylphosphonate,
Cyclohexylmethyl allylphosphonate,
Allylphosphonic acid (2-cyclohexenyl) methyl,
Allylphosphonic acid (3-cyclohexenyl) methyl,
Methyl vinyl allylphosphonate,
Allylmethyl allylphosphonate,
Methyl propargyl allylphosphonate,
Methylphenyl allylphosphonate,
Methyl allylphosphonate (2-tolyl),
Methyl allylphosphonate (3-tolyl),
Methyl allylphosphonate (4-tolyl),
Ethyl allylphosphonate n-propyl,
Cyclohexylethyl allylphosphonate,
Ethyl phenyl allylphosphonate,
Cyclohexyl phenyl allylphosphonate,
Vinyl phenyl allylphosphonate,
Allylphenyl allylphosphonate,
Phenyl allylphosphonate (2-tolyl),
And phenyl allylphosphonate (4-tolyl).

Specific examples of the phosphonic acid diester substituted with an unsaturated hydrocarbon group and having a moiety substituted with a fluorine atom include:
Vinylphosphonate di (2,2,2-trifluoroethyl),
Di (2-fluorocyclohexyl) vinylphosphonate,
Di (2-fluorophenyl) vinylphosphonate,
Methyl vinylphosphonate (2,2,2-trifluoroethyl),
Methyl vinylphosphonate (2-fluorocyclohexyl),
Methyl vinylphosphonate (2-fluorophenyl),
Allylphosphonic acid di (2,2,2-trifluoroethyl),
Allylphosphonic acid di (2-fluorocyclohexyl),
Allylphosphonic acid di (2-fluorophenyl),
Methyl allylphosphonate (2,2,2-trifluoroethyl),
Methyl allylphosphonate (2-fluorocyclohexyl),
Methyl allylphosphonate (2-fluorophenyl),
(2-fluorovinyl) dimethyl phosphonate,
(2-fluorovinyl) diethyl phosphonate,
Di-n-butyl (2-fluorovinyl) phosphonate,
(2-fluorovinyl) phosphonic acid dicyclohexyl,
(2-fluorovinyl) phosphonic acid di (2-fluorovinyl),
(2,2-difluorovinyl) phosphonic acid di (2,2-difluorovinyl),
(2-fluorovinyl) phosphonic acid diphenyl,
(2-fluorovinyl) phosphonic acid di (2,2,2-trifluoroethyl),
(2-fluorovinyl) phosphonic acid di (2-fluorocyclohexyl),
(2-fluorovinyl) phosphonic acid di (2-fluorophenyl),
(2-fluorovinyl) ethyl methylphosphonate,
(2-fluorovinyl) cyclohexylmethyl phosphonate,
(2-fluorovinyl) methyl phenylphosphonate,
Methyl (2-fluorovinyl) phosphonate (2,2,2-trifluoroethyl),
(2-fluorovinyl) phosphonic acid (2-fluorophenyl) methyl, and the like.

Specific examples of phosphonic acid diesters substituted with an aryl group include:
Diphenyl phenylphosphonate,
(2-tolyl) phosphonic acid di (2-tolyl),
(3-tolyl) phosphonic acid di (3-tolyl),
(4-Tolyl) phosphonic acid di (4-tolyl),
(2-fluorophenyl) phosphonic acid di (2-fluorophenyl),
(3-fluorophenyl) phosphonic acid di (3-fluorophenyl),
(4-fluorophenyl) phosphonic acid di (4-fluorophenyl),
Dimethyl phenylphosphonate,
Diethyl phenylphosphonate,
Di-n-butyl phenylphosphonate,
Dicyclohexyl phenylphosphonate,
Diphenyl phenylphosphonate,
Ethyl methyl phenylphosphonate,
Methyl n-propyl phenylphosphonate,
N-butylmethyl phenylphosphonate,
Cyclopentylmethyl phenylphosphonate,
Cyclohexylmethyl phenylphosphonate,
(2-cyclohexenyl) methyl phenylphosphonate,
(3-cyclohexenyl) methyl phenylphosphonate,
Methyl vinyl phenylphosphonate,
Allylmethyl phenylphosphonate,
Methyl propargyl phenylphosphonate,
Methyl phenyl phenylphosphonate,
Methyl phenylphosphonate (2-tolyl),
Methyl phenylphosphonate (3-tolyl),
Methyl phenylphosphonate (4-tolyl),
N-propyl phenylphosphonate,
Cyclohexylethyl phenylphosphonate,
Ethyl phenyl phosphonate,
Cyclohexyl phenyl phenylphosphonate,
Vinyl phenyl phenylphosphonate,
Allylphenyl phenylphosphonate,
Phenylphenylphosphonate (2-tolyl),
Phenylphenylphosphonate (4-tolyl),
Dimethyl 2-tolylphosphonate,
Diethyl 2-tolylphosphonate,
Di-n-butyl 2-tolylphosphonate,
Dicyclohexyl 2-tolylphosphonate,
Diphenyl 2-tolylphosphonate,
2-tolylphosphonic acid di (2,2,2-trifluoroethyl),
2-tolylphosphonic acid di (2-fluorocyclohexyl),
2-tolylphosphonic acid di (2-fluorophenyl),
Ethyl methyl 2-tolylphosphonate,
Methyl n-propyl 2-tolylphosphonate,
N-butylmethyl 2-tolylphosphonate,
Cyclopentylmethyl 2-tolylphosphonate,
Cyclohexylmethyl 2-tolylphosphonate,
2-tolylphosphonic acid (2-cyclohexenyl) methyl,
2-tolylphosphonic acid (3-cyclohexenyl) methyl,
Methyl vinyl 2-tolylphosphonate,
Allylmethyl 2-tolylphosphonate,
Methyl propargyl 2-tolylphosphonate,
Methyl phenyl 2-tolylphosphonate,
Methyl 2-tolylphosphonate (2-tolyl),
Methyl 2-tolylphosphonate (3-tolyl),
Methyl 2-tolylphosphonate (4-tolyl),
Ethyl n-propyl 2-tolylphosphonate,
Cyclohexylethyl 2-tolylphosphonate,
Ethyl phenyl 2-tolylphosphonate,
Cyclohexyl phenyl 2-tolylphosphonate,
Vinyl phenyl 2-tolylphosphonate,
Allylphenyl 2-tolylphosphonate,
Phenyl 2-tolylphosphonate (2-tolyl),
Phenyl 2-tolylphosphonate (4-tolyl),
Dimethyl 4-tolylphosphonate,
4-tolylphosphonate diethyl,
Di-n-butyl 4-tolylphosphonate,
4-tolylphosphonic acid dicyclohexyl,
Diphenyl 4-tolylphosphonate,
4-tolylphosphonic acid di (2,2,2-trifluoroethyl),
4-tolylphosphonic acid di (2-fluorocyclohexyl),
4-tolylphosphonic acid di (2-fluorophenyl),
Ethyl methyl 4-tolylphosphonate,
Methyl n-propyl 4-tolylphosphonate,
N-butylmethyl 4-tolylphosphonate,
Cyclopentylmethyl 4-tolylphosphonate,
Cyclohexylmethyl 4-tolylphosphonate,
4-tolylphosphonic acid (2-cyclohexenyl) methyl,
4-tolylphosphonic acid (3-cyclohexenyl) methyl,
Methyl vinyl 4-tolylphosphonate,
Allylmethyl 4-tolylphosphonate,
Methyl propargyl 4-tolylphosphonate,
Methylphenyl 4-tolylphosphonate,
Methyl 4-tolylphosphonate (2-tolyl),
Methyl 4-tolylphosphonate (3-tolyl),
Methyl 4-tolylphosphonate (4-tolyl),
Ethyl n-propyl 4-tolylphosphonate,
Cyclohexylethyl 4-tolylphosphonate,
Ethyl phenyl 4-tolylphosphonate,
Cyclohexyl phenyl 4-tolylphosphonate,
4-tolylphosphonate vinyl phenyl,
Allylphenyl 4-tolylphosphonate,
4-tolylphosphonic acid phenyl (2-tolyl),
4-Tolylphosphonic acid phenyl (4-tolyl), etc. are mentioned.

Specific examples of a phosphonic acid diester substituted with an aryl group and having a moiety substituted with a fluorine atom include:
Di (2,2,2-trifluoroethyl) phenylphosphonate,
Phenylphosphonic acid di (2-fluorocyclohexyl),
Phenylphosphonic acid di (2-fluorophenyl),
Methyl phenylphosphonate (2,2,2-trifluoroethyl),
Methyl phenylphosphonate (2-fluorocyclohexyl),
Methyl phenylphosphonate (2-fluorophenyl),
Dimethyl (2-fluorophenyl) phosphonate,
Diethyl (2-fluorophenyl) phosphonate,
(2-fluorophenyl) phosphonic acid dicyclohexyl,
(2-fluorophenyl) phosphonic acid diphenyl,
(2-fluorophenyl) phosphonic acid bis (2,2,2-trifluoroethyl),
(2-fluorophenyl) phosphonic acid di (2-fluorophenyl),
Ethyl methyl (2-fluorophenyl) phosphonate,
Cyclohexylmethyl (2-fluorophenyl) phosphonate,
(2-fluorophenyl) methyl phenylphosphonate,
Methyl (2-fluorophenyl) phosphonate (2,2,2-trifluoroethyl),
(2-Fluorophenyl) phosphonic acid (2-fluorophenyl) methyl and the like.

As specific examples of the phosphonic acid ester forming a ring structure by bonding any two of R ^{1 to} R ³ ,
2-methyl-1,3,2-dioxaphosphorane-2-oxide,
2-methyl-1,3,2-dioxaphosphinane-2-oxide,
2-ethyl-1,3,2-dioxaphosphorane-2-oxide,
2-butyl-1,3,2-dioxaphosphorane-2-oxide,
2-cyclohexyl-1,3,2-dioxaphosphorane-2-oxide,
2-vinyl-1,3,2-dioxaphosphorane-2-oxide,
2-phenyl-1,3,2-dioxaphosphorane-2-oxide,
2- (2,2,2-trifluoroethyl) -1,3,2-dioxaphosphorane-2-oxide,
2-perfluoroethyl-1,3,2-dioxaphosphorane-2-oxide,
2- (2-fluorophenyl) -1,3,2-dioxaphosphorane-2-oxide,
4-fluoro-2-methyl-1,3,2-dioxaphosphorane-2-oxide,
2-methoxy-1,2-oxaphosphorane-2-oxide,
2-ethoxy-1,2-oxaphosphorane-2-oxide,
2-phenoxy-1,2-oxaphosphorane-2-oxide,
2-methoxy-1,2-oxaphosphinane-2-oxide, and the like.

Among the phosphonates exemplified above, as the specific compound according to the present invention,
Dimethyl methylphosphonate,
Diethyl ethylphosphonate,
di-n-butyl n-butylphosphonate,
Diisobutyl isobutylphosphonate,
Diethyl methylphosphonate,
Di-n-butyl methylphosphonate,
Diphenyl methylphosphonate,
Dimethyl ethylphosphonate,
Di-n-butyl ethylphosphonate,
Diphenyl ethylphosphonate,
Di (2,2,2-trifluoroethyl) methylphosphonate,
Di (2,2,2-trifluoroethyl) ethylphosphonate,
Diphenyl phenylphosphonate,
Dimethyl phenylphosphonate,
Particularly preferred is diethyl phenylphosphonate.

<Exemplary compounds when p + q = 1>
When p + q = 1, that is, (p, q) = (1, 0) or (0, 1), the compound represented by the above formula (1) is a phosphinic acid ester.

Examples of phosphinic acid esters include
Phosphinic acid ester in which the ester moiety is an alkyl group,
Phosphinic acid ester in which the ester moiety is an unsaturated hydrocarbon group,
And phosphinic acid esters in which the ester moiety is an aryl group.

As a specific example of the phosphinic acid ester in which the ester moiety is an alkyl group,
Methyl dimethylphosphinate,
Ethyl diethylphosphinate,
N-propyl di-n-propylphosphinate,
Isopropyl diisopropylphosphinate,
N-butyl di-n-butylphosphinate,
Isobutyl diisobutylphosphinate,
Tert-butyl ditert-butylphosphinate,
Cyclopentyl dicyclopentylphosphinate,
Cyclohexyl dicyclohexylphosphinate,
Methyl diethylphosphinate,
Methyl n-propylphosphinate,
Methyl diisopropylphosphinate,
Methyl n-butylphosphinate,
Methyl diisobutylphosphinate,
Methyl tert-butylphosphinate,
Methyl dicyclopentylphosphinate,
Methyl dicyclohexylphosphinate,
Methyl di (2-cyclohexenyl) phosphinate,
Methyl di (3-cyclohexenyl) phosphinate,
Methyl divinylphosphinate,
Methyl diallylphosphinate,
Methyl dipropargylphosphinate,
Methyl diphenylphosphinate,
Methyl di (2-tolyl) phosphinate,
Methyl di (3-tolyl) phosphinate,
Methyl di (4-tolyl) phosphinate,
Ethyl dimethylphosphinate,
Ethyl di-n-propylphosphinate,
Ethyl diisopropylphosphinate,
Ethyl di-n-butylphosphinate,
Ethyl diisobutylphosphinate,
Ethyl ditert-butylphosphinate,
Ethyl dicyclopentylphosphinate,
Ethyl dicyclohexylphosphinate,
Ethyl di (2-cyclohexenyl) phosphinate,
Ethyl di (3-cyclohexenyl) phosphinate,
Ethyl divinylphosphinate,
Ethyl diallylphosphinate,
Ethyl dipropargylphosphinate,
Ethyl diphenylphosphinate,
Ethyl di (2-tolyl) phosphinate,
Ethyl di (3-tolyl) phosphinate,
Ethyl di (4-tolyl) phosphinate,
N-butyl dimethylphosphinate,
N-butyl diethylphosphinate,
N-butyl dicyclohexylphosphinate,
N-butyl diphenylphosphinate,
Cyclohexyl dimethylphosphinate,
Cyclohexyl diethylphosphinate,
Cyclohexyl di-n-butylphosphinate,
Cyclohexyl divinylphosphinate,
Cyclohexyl diphenylphosphinate,
Ethyl methylmethylphosphinate,
Methyl n-butylphosphinate methyl,
Methyl cyclohexylmethylphosphinate,
Methyl methyl vinylphosphinate,
Methyl phenylphosphinate,
methyl n-butylethylphosphinate,
Methyl cyclohexylethylphosphinate,
Methyl ethyl vinylphosphinate,
Methyl ethyl phenylphosphinate,
methyl n-butylcyclohexylphosphinate,
methyl n-butylvinylphosphinate,
methyl n-butylphenylphosphinate,
Methyl cyclohexylvinylphosphinate,
Methyl cyclohexylphenylphosphinate,
Ethyl ethyl phosphinate,
Methyl n-butylphosphinate,
Ethyl cyclohexylmethylphosphinate,
Ethyl methyl vinylphosphinate,
Ethyl methylphenylphosphinate,
n-butylethyl ethylphosphinate,
Cyclohexyl ethyl phosphinate,
Ethyl ethyl phosphinate,
Ethyl ethyl phenylphosphinate,
n-butylcyclohexyl ethyl phosphinate,
ethyl n-butylvinylphosphinate,
ethyl n-butylphenylphosphinate,
Ethyl cyclohexylvinylphosphinate,
Ethyl cyclohexylphenylphosphinate,
Ethyl phenylvinylphosphinate,
N-butyl ethylmethylphosphinate,
N-butyl methyl n-butylphosphinate,
N-butyl cyclohexylmethylphosphinate,
N-butyl methylvinylphosphinate,
N-butyl methylphenylphosphinate,
n-butyl n-butylethylphosphinate,
N-butyl cyclohexylethylphosphinate,
N-butyl ethylvinylphosphinate,
N-butyl ethylphenylphosphinate,
n-butylcyclohexylphosphinate n-butyl,
n-butyl vinylphosphinate n-butyl,
n-butyl n-butylphenylphosphinate,
N-butyl cyclohexylvinylphosphinate,
N-butyl cyclohexylphenylphosphinate,
N-butyl phenylvinylphosphinate,
Cyclohexyl ethyl methylphosphinate,
Cyclohexyl methyl n-butylphosphinate,
Cyclohexylmethylphosphinic acid cyclohexyl,
Cyclohexyl methyl vinylphosphinate,
Cyclohexyl methylphenylphosphinate,
cyclohexyl n-butylethylphosphinate,
Cyclohexyl ethyl phosphinate cyclohexyl,
Cyclohexyl ethyl vinylphosphinate,
Cyclohexyl ethyl phenylphosphinate,
n-butylcyclohexyl phosphinic acid cyclohexyl,
cyclohexyl n-butylvinylphosphinate,
n-butylphenylphosphinic acid cyclohexyl,
Cyclohexyl vinylphosphinic acid cyclohexyl,
Cyclohexyl phenylphosphinic acid cyclohexyl,
Examples include cyclohexyl phenyl vinylphosphinate.

As a specific example of the phosphinic acid ester in which the ester moiety is an alkyl group and having a moiety substituted by a fluorine atom,
Perfluoromethyl bisperfluoromethylphosphinate,
Bis (2,2,2-trifluoroethyl) phosphinic acid (2,2,2-trifluoroethyl),
Perfluoroethyl bisperfluoroethylphosphinate,
Di (2-fluorocyclohexyl) phosphinic acid (2-fluorocyclohexyl),
Di (3-fluorocyclohexyl) phosphinic acid (3-fluorocyclohexyl),
Di (4-fluorocyclohexyl) phosphinic acid (4-fluorocyclohexyl),
Methyl bisperfluoromethylphosphinate,
Methyl bis (2,2,2-trifluoroethyl) phosphinate,
Methyl bisperfluoroethylphosphinate,
Methyl di (2-fluorocyclohexyl) phosphinate,
Methyl di (3-fluorocyclohexyl) phosphinate,
Methyl di (4-fluorocyclohexyl) phosphinate,
Methyl di (2-fluorovinyl) phosphinate,
Methyl di (2,2-difluorovinyl) phosphinate,
Methyl di (2-fluorophenyl) phosphinate,
Methyl di (3-fluorophenyl) phosphinate,
Methyl di (4-fluorophenyl) phosphinate,
Ethyl bisperfluoromethylphosphinate,
Ethyl bis (2,2,2-trifluoroethyl) phosphinate,
Ethyl bisperfluoroethylphosphinate,
Ethyl di (2-fluorocyclohexyl) phosphinate,
Ethyl di (3-fluorocyclohexyl) phosphinate,
Ethyl di (4-fluorocyclohexyl) phosphinate,
Ethyl di (2-fluorovinyl) phosphinate,
Ethyl di (2,2-difluorovinyl) phosphinate,
Ethyl di (2-fluorophenyl) phosphinate,
Ethyl di (3-fluorophenyl) phosphinate,
Ethyl di (4-fluorophenyl) phosphinate,
N-butyl bis (2,2,2-trifluoroethyl) phosphinate,
N-butyl di (2-fluorophenyl) phosphinate,
Bis (2,2,2-trifluoroethyl) phosphinic acid cyclohexyl,
Cyclohexyl di (2-fluorophenyl) phosphinate,
Dimethylphosphinic acid (2,2,2-trifluoroethyl),
Diethylphosphinic acid (2,2,2-trifluoroethyl),
Di-n-butylphosphinic acid (2,2,2-trifluoroethyl),
Dicyclohexylphosphinic acid (2,2,2-trifluoroethyl),
Divinylphosphinic acid (2,2,2-trifluoroethyl),
Diphenylphosphinic acid (2,2,2-trifluoroethyl),
Di (2-fluorophenyl) phosphinic acid (2,2,2-trifluoroethyl),
Methyl methyl (2,2,2-trifluoroethyl) phosphinate,
Methyl methyl (2-fluorophenyl) phosphinate,
Ethyl (2,2,2-trifluoroethyl) phosphinate,
Ethyl (2-fluorophenyl) phosphinate,
methyl n-butyl (2,2,2-trifluoroethyl) phosphinate,
methyl n-butyl (2-fluorophenyl) phosphinate,
Cyclohexyl (2,2,2-trifluoroethyl) phosphinate methyl,
Cyclohexyl (2-fluorophenyl) methyl phosphinate,
Methyl phenylvinylphosphinate,
(2,2,2-trifluoroethyl) methyl vinylphosphinate,
Methyl (2-fluorophenyl) vinylphosphinate,
Methyl (2,2,2-trifluoroethyl) phenylphosphinate,
(2-fluorophenyl) methyl phenylphosphinate,
(2,2,2-trifluoroethyl) (2-fluorophenyl) phosphinic acid methyl ester,
Methyl (2,2,2-trifluoroethyl) ethyl phosphinate,
Ethyl methyl (2-fluorophenyl) phosphinate,
Ethyl (2,2,2-trifluoroethyl) phosphinate,
Ethyl (2-fluorophenyl) phosphinate,
n-butyl (2,2,2-trifluoroethyl) ethyl phosphinate,
ethyl n-butyl (2-fluorophenyl) phosphinate,
Cyclohexyl (2,2,2-trifluoroethyl) ethyl phosphinate,
Cyclohexyl (2-fluorophenyl) ethyl phosphinate,
(2,2,2-trifluoroethyl) ethyl vinylphosphinate,
Ethyl (2-fluorophenyl) vinylphosphinate,
(2,2,2-trifluoroethyl) ethyl phenylphosphinate,
(2-fluorophenyl) ethyl phenylphosphinate,
(2,2,2-trifluoroethyl) (2-fluorophenyl) ethyl phosphinate,
N-butyl methyl (2,2,2-trifluoroethyl) phosphinate,
N-butyl methyl (2-fluorophenyl) phosphinate,
N-butyl ethyl (2,2,2-trifluoroethyl) phosphinate,
N-butyl ethyl (2-fluorophenyl) phosphinate,
n-butyl n-butyl (2,2,2-trifluoroethyl) phosphinate,
n-butyl n-butyl (2-fluorophenyl) phosphinate,
N-butyl cyclohexyl (2,2,2-trifluoroethyl) phosphinate,
N-butyl cyclohexyl (2-fluorophenyl) phosphinate,
N-butyl (2,2,2-trifluoroethyl) vinylphosphinate,
N-butyl (2-fluorophenyl) vinylphosphinate,
N-butyl (2,2,2-trifluoroethyl) phenylphosphinate,
N-butyl (2-fluorophenyl) phenylphosphinate,
N-butyl (2,2,2-trifluoroethyl) (2-fluorophenyl) phosphinate,
Cyclohexyl methyl (2,2,2-trifluoroethyl) phosphinate,
Cyclohexyl methyl (2-fluorophenyl) phosphinate,
Cyclohexyl ethyl (2,2,2-trifluoroethyl) phosphinate,
Cyclohexyl ethyl (2-fluorophenyl) phosphinate,
n-butyl (2,2,2-trifluoroethyl) phosphinic acid cyclohexyl,
n-butyl (2-fluorophenyl) phosphinic acid cyclohexyl,
Cyclohexyl (2,2,2-trifluoroethyl) phosphinic acid cyclohexyl,
Cyclohexyl (2-fluorophenyl) phosphinic acid cyclohexyl,
(2,2,2-trifluoroethyl) vinylphosphinic acid cyclohexyl,
(2-fluorophenyl) vinylphosphinic acid cyclohexyl,
(2,2,2-trifluoroethyl) phenylphosphinic acid cyclohexyl,
(2-fluorophenyl) phenylphosphinic acid cyclohexyl,
(2,2,2-trifluoroethyl) (2-fluorophenyl) phosphinic acid cyclohexyl,
Ethylmethylphosphinic acid (2,2,2-trifluoroethyl),
Methyl n-butylphosphinic acid (2,2,2-trifluoroethyl),
Cyclohexylmethylphosphinic acid (2,2,2-trifluoroethyl),
Methyl vinylphosphinic acid (2,2,2-trifluoroethyl),
Methylphenylphosphinic acid (2,2,2-trifluoroethyl),
Methyl (2,2,2-trifluoroethyl) phosphinic acid (2,2,2-trifluoroethyl),
Methyl (2-fluorophenyl) phosphinic acid (2,2,2-trifluoroethyl),
n-butylethylphosphinic acid (2,2,2-trifluoroethyl),
Cyclohexylethylphosphinic acid (2,2,2-trifluoroethyl),
Ethyl vinylphosphinic acid (2,2,2-trifluoroethyl),
Ethylphenylphosphinic acid (2,2,2-trifluoroethyl),
Ethyl (2,2,2-trifluoroethyl) phosphinic acid (2,2,2-trifluoroethyl),
Ethyl (2-fluorophenyl) phosphinic acid (2,2,2-trifluoroethyl),
n-butylcyclohexylphosphinic acid (2,2,2-trifluoroethyl),
n-butylvinylphosphinic acid (2,2,2-trifluoroethyl),
n-butylphenylphosphinic acid (2,2,2-trifluoroethyl),
n-butyl (2,2,2-trifluoroethyl) phosphinic acid (2,2,2-trifluoroethyl),
n-butyl (2-fluorophenyl) phosphinic acid (2,2,2-trifluoroethyl),
Cyclohexyl vinyl phosphinic acid (2,2,2-trifluoroethyl),
Cyclohexylphenylphosphinic acid (2,2,2-trifluoroethyl),
Cyclohexyl (2,2,2-trifluoroethyl) phosphinic acid (2,2,2-trifluoroethyl),
Cyclohexyl (2-fluorophenyl) phosphinic acid (2,2,2-trifluoroethyl),
Phenylvinylphosphinic acid (2,2,2-trifluoroethyl),
(2,2,2-trifluoroethyl) vinylphosphinic acid (2,2,2-trifluoroethyl),
(2-fluorophenyl) vinylphosphinic acid (2,2,2-trifluoroethyl),
(2,2,2-trifluoroethyl) phenylphosphinic acid (2,2,2-trifluoroethyl),
(2-fluorophenyl) phenylphosphinic acid (2,2,2-trifluoroethyl),
(2,2,2-trifluoroethyl) (2-fluorophenyl) phosphinic acid (2,2,2-trifluoroethyl), and the like.

As a specific example of a phosphinic acid ester in which the ester moiety is an unsaturated hydrocarbon group,
Di (2-cyclohexenyl) phosphinic acid (2-cyclohexenyl),
Di (3-cyclohexenyl) phosphinic acid (3-cyclohexenyl),
Vinyl divinylphosphinate,
Allyl diallylphosphinate,
Dipropargyl phosphinate propargyl,
Vinyl dimethylphosphinate,
Vinyl diethylphosphinate,
Vinyl di-n-butylphosphinate,
Vinyl dicyclohexylphosphinate,
Vinyl diphenylphosphinate,
Vinyl bis (2,2,2-trifluoroethyl) phosphinate,
And vinyl di (2-fluorophenyl) phosphinate.

Specific examples of the phosphinic acid ester in which the ester moiety is an unsaturated hydrocarbon group and having a moiety substituted with a fluorine atom include:
Di (2-fluorovinyl) phosphinic acid (2-fluorovinyl),
Di (2,2-difluorovinyl) phosphinic acid (2,2-difluorovinyl),
Vinyl bis (2,2,2-trifluoroethyl) phosphinate,
And vinyl di (2-fluorophenyl) phosphinate.

Specific examples of phosphinic acid esters in which the ester moiety is an aryl group include
Phenyl diphenylphosphinate,
Di (2-tolyl) phosphinic acid (2-tolyl),
Di (3-tolyl) phosphinic acid (3-tolyl),
Di (4-tolyl) phosphinic acid (4-tolyl),
Phenyl dimethylphosphinate,
Phenyl diethylphosphinate,
Phenyl di-n-butylphosphinate,
Phenyl dicyclohexylphosphinate,
And phenyl divinylphosphinate.

Specific examples of the phosphinic acid ester in which the ester moiety is an aryl group and having a moiety substituted with a fluorine atom include:
Di (2-fluorophenyl) phosphinic acid (2-fluorophenyl),
Di (3-fluorophenyl) phosphinic acid (3-fluorophenyl),
Di (4-fluorophenyl) phosphinic acid (4-fluorophenyl),
Bis (2,2,2-trifluoroethyl) phosphinic acid phenyl,
Di (2-fluorophenyl) phenylphosphinate,
Dimethylphosphinic acid (2-fluorophenyl),
Diethylphosphinic acid (2-fluorophenyl),
Di-n-butylphosphinic acid (2-fluorophenyl),
Dicyclohexylphosphinic acid (2-fluorophenyl),
Divinylphosphinic acid (2-fluorophenyl),
Diphenylphosphinic acid (2-fluorophenyl),
And di (2,2,2-trifluoroethyl) phosphinic acid (2-fluorophenyl).

As specific examples of the phosphinic acid ester forming a ring structure by bonding any two of R ^{1 to} R ³ ,
2-methyl-1,2-oxaphosphorane-2-oxide,
2-methyl-1,2-oxaphosphinane-2-oxide,
2-ethyl-1,2-oxaphosphorane-2-oxide,
2-butyl-1,2-oxaphosphorane-2-oxide,
2-cyclohexyl-1,2-oxaphosphorane-2-oxide,
2-vinyl-1,2-oxaphosphorane-2-oxide,
2-phenyl-1,2-oxaphosphorane-2-oxide,
2- (2,2,2-trifluoroethyl) -1,2-oxaphosphorane-2-oxide,
2-perfluoroethyl-1,2-oxaphosphorane-2-oxide,
2- (2-fluorophenyl) -1,2-oxaphosphorane-2-oxide,
4-fluoro-2-methyl-1,2-oxaphosphorane-2-oxide,
1-methoxyphosphorane-1-oxide,
1-ethoxyphosphorane-1-oxide,
1-phenoxyphosphorane-1-oxide,
1-methoxy-phosphinan-1-oxide and the like.

Among the phosphinic acid esters exemplified above, as the specific compound according to the present invention,
Ethyl diethylphosphinate,
N-butyl di-n-butylphosphinate,
Cyclohexyl dicyclohexylphosphinate,
Phenyl diphenylphosphinate,
Bis (2,2,2-trifluoroethyl) phosphinic acid (2,2,2-trifluoroethyl),
Methyl n-butylphosphinate methyl,
Methyl phenylphosphinate,
Methyl methyl (2,2,2-trifluoroethyl) phosphinate,
Ethyl ethyl phenylphosphinate,
Ethyl (2,2,2-trifluoroethyl) phosphinate,
Particularly preferred is n-butyl n-butylphenylphosphinate.

  When the compound represented by the above formula (1) is an organic phosphorus compound in which p + q is 1 or 2, the combination with the specific carbonate described below maintains a high capacity and excellent characteristics over a long period of time. In particular, it is possible to provide a non-aqueous electrolyte secondary battery having a particularly high discharge capacity retention rate.

Among the organic phosphorus compounds exemplified above, p + q in the above formula (1) is represented by 1 or 2,
Dimethyl methylphosphonate,
Diethyl ethylphosphonate,
di-n-butyl n-butylphosphonate,
Dimethyl phenylphosphonate,
Diethyl phenylphosphonate,
Ethyl diethylphosphinate,
N-butyl di-n-butylphosphinate,
Methyl n-butylphosphinate methyl,
Methyl phenylphosphinate,
Particularly preferred is ethyl ethyl phenylphosphinate.

<Exemplary compounds when p + q = 0>
When p + q = 0, that is, (p, q) = (0, 0), the compound represented by the above formula (1) is phosphine oxide.

Examples of phosphine oxide include
Phosphine oxide consisting only of alkyl groups,
A phosphine oxide having an unsaturated hydrocarbon group,
And phosphine oxide having an aryl group.

As a specific example of a phosphine oxide consisting only of an alkyl group,
Trimethylphosphine oxide,
Triethylphosphine oxide,
Tri-n-propylphosphine oxide,
Triisopropylphosphine oxide,
Tri-n-butylphosphine oxide,
Triisobutylphosphine oxide,
Tri-tert-butylphosphine oxide,
Tricyclopentylphosphine oxide,
Tricyclohexylphosphine oxide,
Ethyldimethylphosphine oxide,
Dimethyl n-propylphosphine oxide,
Isopropyldimethylphosphine oxide,
n-butyldimethylphosphine oxide,
Isobutyldimethylphosphine oxide,
tert-butyldimethylphosphine oxide,
Cyclopentyldimethylphosphine oxide,
Cyclohexyldimethylphosphine oxide,
Diethylmethylphosphine oxide,
Diethyl n-butylphosphine oxide,
Cyclohexyl diethyl phosphine oxide,
Di-n-butylmethylphosphine oxide,
Di-n-butylethylphosphine oxide,
Di-n-butylcyclohexylphosphine oxide,
Dicyclohexylmethylphosphine oxide,
Dicyclohexylethylphosphine oxide,
n-butyldicyclohexylphosphine oxide,
Ethylmethyl n-propylphosphine oxide,
Ethylmethylisopropylphosphine oxide,
Ethylmethyl n-butylphosphine oxide,
Ethyl methyl isobutyl phosphine oxide,
Ethylmethyl tert-butylphosphine oxide,
Ethylmethylcyclopentylphosphine oxide,
Ethylmethylcyclohexylphosphine oxide,
n-butylmethyl n-propylphosphine oxide,
n-butylmethylcyclohexylphosphine oxide,
Examples include cyclohexylmethyl (2,2,2-trifluoroethyl) phosphine oxide.

Specific examples of the trialkylphosphine oxide substituted with a fluorine atom include
Triperfluoromethylphosphine oxide,
Tri (2,2,2-trifluoroethyl) phosphine oxide,
Triperfluoroethylphosphine oxide,
Tri (2-fluorocyclohexyl) phosphine oxide,
Tri (3-fluorocyclohexyl) phosphine oxide,
Tri (4-fluorocyclohexyl) phosphine oxide,
Perfluoromethyldimethylphosphine oxide,
(2,2,2-trifluoroethyl) dimethylphosphine oxide,
Perfluoroethyldimethylphosphine oxide,
(2-fluorocyclohexyl) dimethylphosphine oxide,
(3-fluorocyclohexyl) dimethylphosphine oxide,
(4-fluorocyclohexyl) dimethylphosphine oxide,
Diethyl (2,2,2-trifluoroethyl) phosphine oxide,
Di-n-butyl (2,2,2-trifluoroethyl) phosphine oxide,
Dicyclohexyl (2,2,2-trifluoroethyl) phosphine oxide,
Di (2,2,2-trifluoroethyl) methylphosphine oxide,
Ethyl (2,2,2-trifluoroethyl) phosphine oxide,
n-butyldi (2,2,2-trifluoroethyl) phosphine oxide,
Cyclohexyldi (2,2,2-trifluoroethyl) phosphine oxide,
Ethylmethylperfluoromethylphosphine oxide,
Ethylmethyl (2,2,2-trifluoroethyl) phosphine oxide,
Ethylmethylperfluoroethylphosphine oxide,
Ethylmethyl (2-fluorocyclohexyl) phosphine oxide,
Ethylmethyl (3-fluorocyclohexyl) phosphine oxide,
Ethylmethyl (4-fluorocyclohexyl) phosphine oxide,
n-butylmethyl (2,2,2-trifluoroethyl) phosphine oxide,
n-butylethyl n-propylphosphine oxide,
n-butylethylcyclohexylphosphine oxide,
n-butylethyl (2,2,2-trifluoroethyl) phosphine oxide,
Cyclohexylethyl (2,2,2-trifluoroethyl) phosphine oxide,
and n-butylcyclohexyl (2,2,2-trifluoroethyl) phosphine oxide.

Specific examples of the phosphine oxide having an unsaturated hydrocarbon group include
Tri (2-cyclohexenyl) phosphine oxide,
Tri (3-cyclohexenyl) phosphine oxide,
Trivinylphosphine oxide,
Triallylphosphine oxide,
Tripropargylphosphine oxide,
(2-cyclohexenyl) dimethylphosphine oxide,
(3-cyclohexenyl) dimethylphosphine oxide,
Dimethylvinylphosphine oxide,
Allyldimethylphosphine oxide,
Dimethylpropargylphosphine oxide,
Ethylmethyl (2-cyclohexenyl) phosphine oxide,
Ethylmethyl (3-cyclohexenyl) phosphine oxide,
Ethyl methyl vinyl phosphine oxide,
Ethylmethylallylphosphine oxide,
And ethyl methyl propargyl phosphine oxide.

Specific examples of the phosphine oxide having an unsaturated hydrocarbon group substituted with a fluorine atom include:
Tri (2-fluorovinyl) phosphine oxide,
Tri (2,2-difluorovinyl) phosphine oxide,
(2-fluorovinyl) dimethylphosphine oxide,
(2,2-difluorovinyl) dimethylphosphine oxide,
Ethylmethyl (2-fluorovinyl) phosphine oxide,
And ethylmethyl (2,2-difluorovinyl) phosphine oxide.

Specific examples of the phosphine oxide having an aryl group include
Triphenylphosphine oxide, tri (2-tolyl) phosphine oxide,
Tri (3-tolyl) phosphine oxide, tri (4-tolyl) phosphine oxide,
Dimethylphenylphosphine oxide, dimethyl (2-tolyl) phosphine oxide,
Dimethyl (3-tolyl) phosphine oxide,
Dimethyl (4-tolyl) phosphine oxide,
Diethylphenylphosphine oxide,
Di-n-butylphenylphosphine oxide,
Dicyclohexylphenylphosphine oxide,
Diphenylmethylphosphine oxide,
Ethyldiphenylphosphine oxide,
n-butyldiphenylphosphine oxide,
Cyclohexyl diphenylphosphine oxide,
Ethylmethylphenylphosphine oxide,
Ethylmethyl (2-tolyl) phosphine oxide,
Ethylmethyl (3-tolyl) phosphine oxide,
Ethylmethyl (4-tolyl) phosphine oxide,
n-butylmethylphenylphosphine oxide,
Cyclohexylmethylphenylphosphine oxide,
n-butylethylphenylphosphine oxide,
Cyclohexyl ethyl phenyl phosphine oxide,
and n-butylcyclohexylphenylphosphine oxide.

Specific examples of phosphine oxides having an aryl group substituted with a fluorine atom include
Tri (2-fluorophenyl) phosphine oxide,
Tri (3-fluorophenyl) phosphine oxide,
Tri (4-fluorophenyl) phosphine oxide,
(2-fluorophenyl) dimethylphosphine oxide ,
( 3-fluorophenyl) dimethylphosphine oxide ,
( 4-fluorophenyl) dimethylphosphine oxide,
(2-fluorophenyl) diethylphosphine oxide,
(2-fluorophenyl) di n-butylphosphine oxide,
(2-fluorophenyl) dicyclohexylphosphine oxide,
Diphenyl (2,2,2-trifluoroethyl) phosphine oxide,
(2-fluorophenyl) diphenylphosphine oxide,
Phenyldi (2,2,2-trifluoroethyl) phosphine oxide,
(2-fluorophenyl) di (2,2,2-trifluoroethyl) phosphine oxide, di (2-fluorophenyl) methylphosphine oxide,
Ethyl (2-fluorophenyl) phosphine oxide,
n-butyldi (2-fluorophenyl) phosphine oxide,
Cyclohexyl di (2-fluorophenyl) phosphine oxide,
Phenyldi (2-fluorophenyl) phosphine oxide,
Di (2-fluorophenyl) (2,2,2-trifluoroethyl) phosphine oxide, ethylmethyl (2-fluorophenyl) phosphine oxide,
Ethylmethyl (3-fluorophenyl) phosphine oxide,
Ethylmethyl (4-fluorophenyl) phosphine oxide,
n-butylmethyl (2-fluorophenyl) phosphine oxide,
Cyclohexylmethyl (2-fluorophenyl) phosphine oxide,
Phenylmethyl (2,2,2-trifluoroethyl) phosphine oxide,
Phenylmethyl (2-fluorophenyl) phosphine oxide,
(2,2,2-trifluoroethyl) methyl (2-fluorophenyl) phosphine oxide,
n-butylethyl (2-fluorophenyl) phosphine oxide,
Cyclohexylethyl (2-fluorophenyl) phosphine oxide,
Ethylphenyl (2,2,2-trifluoroethyl) phosphine oxide,
Ethylphenyl (2-fluorophenyl) phosphine oxide,
Ethyl (2,2,2-trifluoroethyl) (2-fluorophenyl) phosphine oxide,
n-butylcyclohexyl (2-fluorophenyl) phosphine oxide,
n-butylphenyl (2,2,2-trifluoroethyl) phosphine oxide,
n-butylphenyl (2-fluorophenyl) phosphine oxide,
n-butyl (2,2,2-trifluoroethyl) (2-fluorophenyl) phosphine oxide,
Cyclohexylphenyl (2,2,2-trifluoroethyl) phosphine oxide,
Cyclohexylphenyl (2-fluorophenyl) phosphine oxide,
Cyclohexylphenyl (2,2,2-trifluoroethyl) (2-fluorophenyl) phosphine oxide,
Phenyl (2,2,2-trifluoroethyl) (2-fluorophenyl) phosphine oxide,
Examples include perfluoroethyl (2,2,2-trifluoroethyl) (2-fluorophenyl) phosphine oxide.

As specific examples of the phosphine oxide that forms a ring structure by bonding any two of R ^{1 to} R ³ ,
1-methylphosphorane-1-oxide,
1-ethylphosphorane-1-oxide,
1-n-butylphosphorane-1-oxide,
1-phenylphosphorane-1-oxide,
1- (2,2,2-trifluoroethyl) -1-oxide,
1- (2-furphenyl) -1-oxide,
1,2-dimethylphosphorane-1-oxide,
1,3-dimethylphosphorane-1-oxide,
1-methyl-2-ethylphosphorane-1-oxide,
2-methyl-1-ethylphosphorane-1-oxide,
1-methylphosphinan-1-oxide,
1-ethylphosphinan-1-oxide, and the like.

Among the phosphine oxides exemplified above, as the specific compound according to the present invention,
Trimethylphosphine oxide,
Triethylphosphine oxide,
Tri-n-butylphosphine oxide,
Tricyclohexylphosphine oxide,
Tri (2,2,2-trifluoroethyl) phosphine oxide,
Triperfluoroethylphosphine oxide,
Triallylphosphine oxide,
Triphenylphosphine oxide is particularly preferred.

  Even when the compound represented by the general formula (1) is an organophosphorus compound represented by p + q of 0, the combination with the specific carbonate described below has high capacity and excellent characteristics over a long period of time. Thus, it is possible to provide a non-aqueous electrolyte secondary battery having a particularly high discharge capacity maintenance rate.

  In addition, there is no restriction | limiting in the molecular weight of a specific compound, Although it is arbitrary unless the effect of this invention is impaired remarkably, Usually, 80 or more, Preferably it is 90 or more. Moreover, although there is no restriction | limiting in particular in an upper limit, Since viscosity tends to rise, Usually 400 or less, Preferably 300 or less is practical.

  Moreover, there is no restriction | limiting in particular also in the manufacturing method of a specific compound, It is possible to select and manufacture a well-known method arbitrarily.

  Any one of the specific compounds described above may be contained alone in the non-aqueous electrolyte solution of the present invention, or two or more of them may be used in any combination and ratio.

  Moreover, there is no restriction | limiting in particular in the compounding quantity of the specific compound with respect to the non-aqueous electrolyte solution of this invention, Although it is arbitrary unless the effect of this invention is impaired remarkably, Usually 0.01% with respect to the non-aqueous electrolyte solution of this invention. It is desirable to contain at a concentration of not less than wt%, preferably not less than 0.1 wt%, and usually not more than 10 wt%, preferably not more than 5 wt%. Below the lower limit of this range, when the non-aqueous electrolyte solution of the present invention is used in a non-aqueous electrolyte secondary battery, the non-aqueous electrolyte secondary battery is less likely to exhibit a sufficient cycle characteristic improving effect. There is. On the other hand, when the upper limit of this range is exceeded, the reactivity in the non-aqueous electrolyte increases, and the battery characteristics of the non-aqueous electrolyte secondary battery may deteriorate.

[I-2. (Specific carbonate)
The specific carbonate according to the present invention is a carbonate having at least one of an unsaturated bond and a halogen atom. That is, the specific carbonate according to the present invention may have only an unsaturated bond, may have only a halogen atom, or may have both an unsaturated bond and a halogen atom.

  The carbonate having an unsaturated bond (this is abbreviated as “unsaturated carbonate” as appropriate) is any carbonate that has a carbon-carbon unsaturated bond such as a carbon-carbon double bond or a carbon-carbon triple bond. There is no restriction | limiting, Arbitrary unsaturated carbonates can be used. In addition, the carbonate which has an aromatic ring shall also be contained in the carbonate which has an unsaturated bond.

  Examples of unsaturated carbonates include vinylene carbonate derivatives, ethylene carbonate derivatives substituted with a substituent having an aromatic ring or a carbon-carbon unsaturated bond, phenyl carbonates, vinyl carbonates, allyl carbonates, and the like. .

Specific examples of vinylene carbonate derivatives include
Vinylene carbonate,
Methyl vinylene carbonate,
4,5-dimethyl vinylene carbonate,
Phenyl vinylene carbonate,
4,5-diphenyl vinylene carbonate and the like.

Specific examples of ethylene carbonate derivatives substituted with a substituent having an aromatic ring or a carbon-carbon unsaturated bond include:
Vinyl ethylene carbonate,
4,5-divinylethylene carbonate,
Phenylethylene carbonate,
4,5-diphenylethylene carbonate and the like.

Specific examples of phenyl carbonates include
Diphenyl carbonate,
Ethyl phenyl carbonate,
Methyl phenyl carbonate,
and t-butylphenyl carbonate.

Specific examples of vinyl carbonates include
Divinyl carbonate,
And methyl vinyl carbonate.

Specific examples of allyl carbonates include
Diallyl carbonate,
And allyl methyl carbonate.

  Among these unsaturated carbonates, as the specific carbonate, vinylene carbonate derivatives, ethylene carbonate derivatives substituted with a substituent having an aromatic ring or a carbon-carbon unsaturated bond are preferable, and in particular, vinylene carbonate, 4,5 -Diphenyl vinylene carbonate, 4,5-dimethyl vinylene carbonate, and vinyl ethylene carbonate are more preferably used because they form a stable interface protective film.

  On the other hand, the carbonate having a halogen atom (this is appropriately abbreviated as “halogenated carbonate”) is not particularly limited as long as it has a halogen atom, and any halogenated carbonate can be used. .

  Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom or a chlorine atom is preferable, and a fluorine atom is particularly preferable. The number of halogen atoms contained in the halogenated carbonate is not particularly limited as long as it is 1 or more, but is usually 6 or less, preferably 4 or less. When the halogenated carbonate has a plurality of halogen atoms, they may be the same as or different from each other.

  Examples of halogenated carbonates include ethylene carbonate derivatives, dimethyl carbonate derivatives, ethyl methyl carbonate derivatives, diethyl carbonate derivatives and the like.

Specific examples of ethylene carbonate derivatives include
Fluoroethylene carbonate,
Chloroethylene carbonate,
4,4-difluoroethylene carbonate,
4,5-difluoroethylene carbonate,
4,4-dichloroethylene carbonate,
4,5-dichloroethylene carbonate,
4-fluoro-4-methylethylene carbonate,
4-chloro-4-methylethylene carbonate,
4,5-difluoro-4-methylethylene carbonate,
4,5-dichloro-4-methylethylene carbonate,
4-fluoro-5-methylethylene carbonate,
4-chloro-5-methylethylene carbonate,
4,4-difluoro-5-methylethylene carbonate,
4,4-dichloro-5-methylethylene carbonate,
4- (fluoromethyl) -ethylene carbonate,
4- (chloromethyl) -ethylene carbonate,
4- (difluoromethyl) -ethylene carbonate,
4- (dichloromethyl) -ethylene carbonate,
4- (trifluoromethyl) -ethylene carbonate,
4- (trichloromethyl) -ethylene carbonate,
4- (fluoromethyl) -4-fluoroethylene carbonate,
4- (chloromethyl) -4-chloroethylene carbonate,
4- (fluoromethyl) -5-fluoroethylene carbonate,
4- (chloromethyl) -5-chloroethylene carbonate,
4-fluoro-4,5-dimethylethylene carbonate,
4-chloro-4,5-dimethylethylene carbonate,
4,5-difluoro-4,5-dimethylethylene carbonate,
4,5-dichloro-4,5-dimethylethylene carbonate,
4,4-difluoro-5,5-dimethylethylene carbonate,
4,4-dichloro-5,5-dimethylethylene carbonate and the like.

Specific examples of dimethyl carbonate derivatives include
Fluoromethyl methyl carbonate,
Difluoromethyl methyl carbonate,
Trifluoromethyl methyl carbonate,
Bis (fluoromethyl) carbonate,
Bis (difluoro) methyl carbonate,
Bis (trifluoro) methyl carbonate,
Chloromethyl methyl carbonate,
Dichloromethyl methyl carbonate,
Trichloromethyl methyl carbonate,
Bis (chloromethyl) carbonate,
Bis (dichloro) methyl carbonate,
And bis (trichloro) methyl carbonate.

Specific examples of ethyl methyl carbonate derivatives include
2-fluoroethyl methyl carbonate,
Ethyl fluoromethyl carbonate,
2,2-difluoroethyl methyl carbonate,
2-fluoroethyl fluoromethyl carbonate,
Ethyl difluoromethyl carbonate,
2,2,2-trifluoroethyl methyl carbonate,
2,2-difluoroethyl fluoromethyl carbonate,
2-fluoroethyl difluoromethyl carbonate,
Ethyl trifluoromethyl carbonate,
2-chloroethyl methyl carbonate,
Ethyl chloromethyl carbonate,
2,2-dichloroethyl methyl carbonate,
2-chloroethyl chloromethyl carbonate,
Ethyl dichloromethyl carbonate,
2,2,2-trichloroethyl methyl carbonate,
2,2-dichloroethyl chloromethyl carbonate,
2-chloroethyl dichloromethyl carbonate,
And ethyl trichloromethyl carbonate.

Specific examples of diethyl carbonate derivatives include
Ethyl- (2-fluoroethyl) carbonate,
Ethyl- (2,2-difluoroethyl) carbonate,
Bis (2-fluoroethyl) carbonate,
Ethyl- (2,2,2-trifluoroethyl) carbonate,
2,2-difluoroethyl-2′-fluoroethyl carbonate,
Bis (2,2-difluoroethyl) carbonate,
2,2,2-trifluoroethyl-2′-fluoroethyl carbonate,
2,2,2-trifluoroethyl-2 ′, 2′-difluoroethyl carbonate,
Bis (2,2,2-trifluoroethyl) carbonate,
Ethyl- (2-chloroethyl) carbonate,
Ethyl- (2,2-dichloroethyl) carbonate,
Bis (2-chloroethyl) carbonate,
Ethyl- (2,2,2-trichloroethyl) carbonate,
2,2-dichloroethyl-2'-chloroethyl carbonate,
Bis (2,2-dichloroethyl) carbonate,
2,2,2-trichloroethyl-2′-chloroethyl carbonate,
2,2,2-trichloroethyl-2 ′, 2′-dichloroethyl carbonate,
And bis (2,2,2-trichloroethyl) carbonate.

  Among these halogenated carbonates, carbonates having fluorine atoms are preferred, ethylene carbonate derivatives having fluorine atoms are more preferred, and in particular, fluoroethylene carbonate, 4- (fluoromethyl) -ethylene carbonate, 4,4-difluoroethylene carbonate. 4,5-difluoroethylene carbonate is more preferably used because it forms an interface protective film.

  Furthermore, as the specific carbonate, a carbonate having both an unsaturated bond and a halogen atom (this is appropriately abbreviated as “halogenated unsaturated carbonate”) can also be used. There is no restriction | limiting in particular as a halogenated unsaturated carbonate, As long as the effect of this invention is not impaired remarkably, arbitrary halogenated unsaturated carbonates can be used.

Examples of halogenated unsaturated carbonates include vinylene carbonate derivatives, ethylene carbonate derivatives substituted with a substituent having an aromatic ring or a carbon-carbon unsaturated bond, phenyl carbonates, vinyl carbonates, allyl carbonates, and the like. Can be mentioned.

Specific examples of vinylene carbonate derivatives include
Fluorovinylene carbonate,
4-fluoro-5-methylvinylene carbonate,
4-fluoro-5-phenyl vinylene carbonate,
Chlorovinylene carbonate,
4-chloro-5-methylvinylene carbonate,
4-chloro-5-phenyl vinylene carbonate, etc. are mentioned.

Specific examples of ethylene carbonate derivatives substituted with a substituent having an aromatic ring or a carbon-carbon unsaturated bond include:
4-fluoro-4-vinylethylene carbonate,
4-fluoro-5-vinylethylene carbonate,
4,4-difluoro-4-vinylethylene carbonate,
4,5-difluoro-4-vinylethylene carbonate,
4-chloro-5-vinylethylene carbonate,
4,4-dichloro-4-vinylethylene carbonate,
4,5-dichloro-4-vinylethylene carbonate,
4-fluoro-4,5-divinylethylene carbonate,
4,5-difluoro-4,5-divinylethylene carbonate,
4-chloro-4,5-divinylethylene carbonate,
4,5-dichloro-4,5-divinylethylene carbonate,
4-fluoro-4-phenylethylene carbonate,
4-fluoro-5-phenylethylene carbonate,
4,4-difluoro-5-phenylethylene carbonate,
4,5-difluoro-4-phenylethylene carbonate,
4-chloro-4-phenylethylene carbonate,
4-chloro-5-phenylethylene carbonate,
4,4-dichloro-5-phenylethylene carbonate,
4,5-dichloro-4-phenylethylene carbonate,
4,5-difluoro-4,5-diphenylethylene carbonate,
4,5-dichloro-4,5-diphenylethylene carbonate and the like.

Specific examples of phenyl carbonates include
Fluoromethylphenyl carbonate,
2-fluoroethyl phenyl carbonate,
2,2-difluoroethyl phenyl carbonate,
2,2,2-trifluoroethyl phenyl carbonate,
Chloromethylphenyl carbonate,
2-chloroethyl phenyl carbonate,
2,2-dichloroethyl phenyl carbonate,
2,2,2-trichloroethyl phenyl carbonate, etc. are mentioned.

Specific examples of vinyl carbonates include
Fluoromethyl vinyl carbonate,
2-fluoroethyl vinyl carbonate,
2,2-difluoroethyl vinyl carbonate,
2,2,2-trifluoroethyl vinyl carbonate,
Chloromethyl vinyl carbonate,
2-chloroethyl vinyl carbonate,
2,2-dichloroethyl vinyl carbonate,
2,2,2-trichloroethyl vinyl carbonate, etc. are mentioned.

Specific examples of allyl carbonates include
Fluoromethylallyl carbonate,
2-fluoroethyl allyl carbonate,
2,2-difluoroethyl allyl carbonate,
2,2,2-trifluoroethyl allyl carbonate,
Chloromethylallyl carbonate,
2-chloroethyl allyl carbonate,
2,2-dichloroethyl allyl carbonate,
2,2,2-trichloroethyl allyl carbonate, etc. are mentioned.

  Among the above-mentioned examples of the halogenated unsaturated carbonate, as the specific carbonate, vinylene carbonate, vinylethylene carbonate, fluoroethylene carbonate, 4,5-difluoroethylene carbonate, and their derivatives are highly effective when used alone. It is particularly preferable to use one or more selected from the group consisting of:

  In addition, there is no restriction | limiting in particular in the molecular weight of a specific carbonate, Although it is arbitrary unless the effect of this invention is impaired remarkably, Usually, 50 or more, Preferably it is 80 or more, Usually, 250 or less, Preferably it is 150 or less. If the molecular weight is too large, the solubility of the specific carbonate in the non-aqueous electrolyte solution is lowered, and the effects of the present invention may not be sufficiently exhibited.

  Moreover, there is no restriction | limiting in particular in the manufacturing method of specific carbonate, It is possible to select and manufacture a well-known method arbitrarily.

  Also about the specific carbonate demonstrated above, in the non-aqueous electrolyte solution of this invention, any 1 type may be contained independently, and 2 or more types may be used together by arbitrary combinations and ratios.

  Moreover, there is no restriction | limiting in the compounding quantity of the specific carbonate with respect to the non-aqueous electrolyte solution of this invention, Although it is arbitrary unless the effect of this invention is impaired remarkably, Usually 0.01 weight with respect to the non-aqueous electrolyte solution of this invention. % Or more, preferably 0.1% by weight or more, more preferably 0.3% by weight or more, and usually 70% by weight or less, preferably 50% by weight or less, more preferably 40% by weight or less. Is desirable. Below the lower limit of this range, when the non-aqueous electrolyte solution of the present invention is used in a non-aqueous electrolyte secondary battery, the non-aqueous electrolyte secondary battery is less likely to exhibit a sufficient cycle characteristic improving effect. In addition, when the ratio of the specific carbonate is too large, when the non-aqueous electrolyte of the present invention is used for a non-aqueous electrolyte secondary battery, the high-temperature storage characteristics and trickle charge of the non-aqueous electrolyte secondary battery There is a tendency for the characteristics to decrease, and in particular, the amount of gas generation increases, and the discharge capacity retention rate may decrease.

[I-3. Ratio of specific compound to specific carbonate)
In the nonaqueous electrolytic solution of the present invention, the ratio of the specific compound and the specific carbonate is also arbitrary, but the relative weight ratio of both expressed by “weight of the specific compound / weight of the specific carbonate” is usually 0.0001 or more, Preferably, it is 0.001 or more, more preferably 0.01 or more, and usually 1000 or less, preferably 100 or less, more preferably 10 or less. If the relative weight ratio is too low or too high, it may be difficult to obtain a synergistic effect.

  When the specific compound and the specific carbonate are contained in the non-aqueous electrolyte solution, the charge / discharge cycle characteristics of the non-aqueous electrolyte secondary battery using the non-aqueous electrolyte solution can be improved. Although the details of this reason are not clear, it is estimated as follows. That is, the specific compound contained in the non-aqueous electrolyte and the specific carbonate react together to form a good protective coating layer on the surface of the negative electrode active material, thereby suppressing side reactions and suppressing cycle deterioration. It is inferred that Although details are unknown, it is speculated that the presence of the specific compound and the specific carbonate in the electrolyte simultaneously contributes to improving the properties of the protective film in some form.

[I-4. Nonaqueous solvent)
As the nonaqueous solvent contained in the nonaqueous electrolytic solution of the present invention, any solvent can be used as long as the effects of the present invention are not significantly impaired. In addition, a non-aqueous solvent may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

Examples of commonly used non-aqueous solvents include
Cyclic carbonate,
Chain carbonate,
Chain and cyclic carboxylic acid esters,
Chain and cyclic ethers,
Phosphorus-containing organic solvent,
And sulfur-containing organic solvents.

Although there is no restriction | limiting in particular in the kind of cyclic carbonate, As an example of what is normally used, except the carbonate corresponding to the above-mentioned specific carbonate,
Ethylene carbonate,
Propylene carbonate,
And butylene carbonate.

  Among these, ethylene carbonate and propylene carbonate are preferable in that they have a high dielectric constant, so that the solute is easily dissolved and the cycle characteristics are good when a non-aqueous electrolyte secondary battery is obtained. Therefore, the nonaqueous electrolytic solution of the present invention preferably contains ethylene carbonate and / or propylene carbonate as a nonaqueous solvent in addition to the carbonate corresponding to the above-mentioned specific carbonate.

In addition, the type of chain carbonate is not particularly limited, but as an example of what is usually used, except for carbonates corresponding to the above-mentioned specific carbonate,
Dimethyl carbonate,
Ethyl methyl carbonate,
Diethyl carbonate,
Methyl-n-propyl carbonate,
Ethyl-n-propyl carbonate,
And di-n-propyl carbonate.

  Therefore, the non-aqueous electrolyte solution of the present invention includes, as a non-aqueous solvent, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl-n-propyl carbonate, ethyl-n-propyl, in addition to the carbonate corresponding to the above-mentioned specific carbonate. It is preferable to include at least one selected from the group consisting of carbonate and di-n-propyl carbonate. Among these, diethyl carbonate, methyl-n-propyl carbonate, and ethyl-n-propyl carbonate are preferable. In particular, diethyl carbonate is preferable in terms of good cycle characteristics when a non-aqueous electrolyte secondary battery is used.

Furthermore, there are no particular restrictions on the type of chain carboxylic acid ester, but examples of commonly used ones include:
Methyl acetate,
Ethyl acetate,
Acetic acid-n-propyl,
Acetic acid-i-propyl,
N-butyl acetate,
I-butyl acetate,
Tert-butyl acetate,
Methyl propionate,
Ethyl propionate,
N-propyl propionate,
Propionate-i-propyl,
Propionate-n-butyl,
Propionate-i-butyl,
And propionate-t-butyl.
Among these, ethyl acetate, methyl propionate, and ethyl propionate are more preferable.

In addition, there is no particular limitation on the type of cyclic carboxylic acid ester, but as an example of what is usually used,
γ-butyrolactone,
γ-valerolactone,
and δ-valerolactone.
Among these, γ-butyrolactone is more preferable.

Furthermore, there is no particular limitation on the type of chain ether, but examples of commonly used ones include:
Dimethoxymethane,
Dimethoxyethane,
Diethoxymethane,
Diethoxyethane,
Ethoxymethoxymethane,
And ethoxymethoxyethane.
Among these, dimethoxyethane and diethoxyethane are more preferable.

In addition, the type of cyclic ether is not particularly limited, but as an example of what is usually used,
Tetrahydrofuran,
2-methyltetrahydrofuran etc. are mentioned.

Furthermore, the type of the phosphorus-containing organic solvent is not particularly limited, but examples of commonly used ones include
Trimethyl phosphate,
Triethyl phosphate,
Phosphate esters such as triphenyl phosphate;
Trimethyl phosphite,
Triethyl phosphite,
Phosphites such as triphenyl phosphite;
Trimethylphosphine oxide,
Triethylphosphine oxide,
Phosphine oxides such as triphenylphosphine oxide; and the like.

In addition, although there is no particular limitation on the type of sulfur-containing organic solvent, as an example of what is usually used,
Ethylene sulfite,
1,3-propane sultone,
1,4-butane sultone,
Methyl methanesulfonate,
Busulfan,
Sulfolane,
Sulfolene,
Dimethyl sulfone,
Diphenylsulfone,
Methylphenylsulfone,
Dibutyl disulfide,
Dicyclohexyl disulfide,
Tetramethylthiuram monosulfide,
N, N-dimethylmethanesulfonamide,
N, N-diethylmethanesulfonamide and the like can be mentioned.

  Among these, it is preferable to use ethylene carbonate and / or propylene carbonate, which are cyclic carbonates, and it is preferable to use these in combination with a chain carbonate.

  Thus, when using a cyclic carbonate and a chain carbonate as a non-aqueous solvent, the preferred content of the chain carbonate in the non-aqueous solvent in the non-aqueous electrolyte solution of the present invention is usually 30% by weight or more, Preferably it is 50 weight% or more, and is 95 weight% or less normally, Preferably it is 90 weight% or less. On the other hand, the preferred content of the cyclic carbonate in the non-aqueous solvent in the non-aqueous electrolyte of the present invention is usually 5% by weight or more, preferably 10% by weight or more, and usually 50% by weight or less, preferably 40%. % By weight or less. If the proportion of the chain carbonate is too small, the viscosity of the non-aqueous electrolyte solution of the present invention may increase, and if the proportion of the chain carbonate is too large, the dissociation degree of the lithium salt that is the electrolyte decreases, The electrical conductivity of the non-aqueous electrolyte solution of the invention may decrease.

[I-5. Electrolytes〕
There is no restriction | limiting in the electrolyte used for the non-aqueous electrolyte of this invention, A well-known thing can be arbitrarily employ | adopted if it is used as an electrolyte for the target non-aqueous electrolyte secondary battery. When the nonaqueous electrolytic solution of the present invention is used for a lithium secondary battery, a lithium salt is usually used as an electrolyte.

Specific examples of electrolytes include
LiClO ₄ ,
LiAsF ₆ ,
LiPF ₆ ,
Li ₂ CO ₃ ,
Inorganic lithium salts such as LiBF ₄ ;
LiCF ₃ SO ₃ ,
LiN (CF ₃ SO ₂ ) ₂ ,
LiN (C ₂ F ₅ SO ₂ ) ₂ ,
Lithium 1,3-hexafluoropropane disulfonylimide,
Lithium 1,2-tetrafluoroethanedisulfonylimide,
LiN (CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ),
LiC (CF ₃ SO ₂ ) ₃ ,
LiPF ₄ (CF ₃ ) ₂ ,
LiPF ₄ (C ₂ F ₅ ) ₂ ,
LiPF ₄ (CF ₃ SO ₂ ) ₂ ,
LiPF ₄ (C ₂ F ₅ SO ₂ ) ₂ ,
LiBF ₂ (CF ₃ ) ₂ ,
LiBF ₂ (C ₂ F ₅ ) ₂ ,
LiBF ₂ (CF ₃ SO ₂ ) ₂ ,
Fluorine-containing organic lithium salts such as LiBF ₂ (C ₂ F ₅ SO ₂ ) ₂ ;
Lithium bis (oxalato) borate,
Lithium tris (oxalato) phosphate,
Lithium salt containing dicarboxylic acid complex such as lithium difluorooxalatoborate;
KPF ₆ ,
NaPF ₆ ,
NaBF ₄ ,
Sodium salt or potassium salt such as NaCF ₃ SO ₃ ;

Of these, LiPF ₆ , LiBF ₄ , LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , and lithium 1,2-tetrafluoroethanedisulfonylimide are particularly preferable. LiPF ₆ and LiBF ₄ are preferred.

Moreover, electrolyte may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio. In particular, when two types of specific inorganic lithium salts are used in combination, or when an inorganic lithium salt and a fluorine-containing organic lithium salt are used in combination, gas generation during trickle charging is suppressed, or deterioration after high-temperature storage is suppressed. Therefore, it is preferable. In particular, the combination and the LiPF ₆ and LiBF _4, and an inorganic lithium salt such as _{LiPF 6, LiBF 4, LiCF 3} SO 3, LiN (CF 3 SO 2) 2, LiN (C 2 F 5 SO 2) _2, etc. It is preferable to use in combination with a fluorine-containing organic lithium salt.

Furthermore, when LiPF ₆ and LiBF ₄ are used in combination, it is preferable that LiBF ₄ is usually contained at a ratio of 0.01 wt% or more and 20 wt% or less with respect to the entire electrolyte. LiBF ₄ has a low degree of dissociation, and if the ratio is too high, the resistance of the electrolytic solution may be increased.

On the other hand, when inorganic lithium salts such as LiPF ₆ and LiBF ₄ are used in combination with fluorine-containing organic lithium salts such as LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , and LiN (C ₂ F ₅ SO ₂ ) ₂ The ratio of the inorganic lithium salt in the entire electrolyte is preferably in the range of usually 70 wt% or more and 99 wt% or less. In general, the fluorine-containing organic lithium salt has a large molecular weight as compared with the inorganic lithium salt, and if the ratio is too high, the ratio of the solvent in the entire electrolyte solution may decrease and the resistance of the electrolyte solution may be increased.

The concentration of the lithium salt in the non-aqueous electrolyte of the present invention is arbitrary as long as the effects of the present invention are not significantly performed, but usually 0.5 mol · dm ⁻³ or more, preferably 0.6 mol · dm ^−3. or more, more preferably 0.8 mol · dm ^-3 or more, and usually 3 mol · dm ^-3 or less, preferably 2 mol · dm ^-3 or less, and more preferably 1.5 mol · dm ^-3 or less of. If this concentration is too low, the electrical conductivity of the non-aqueous electrolyte may be insufficient. If the concentration is too high, the electrical conductivity will decrease due to an increase in viscosity, and the non-aqueous electrolyte of the present invention will be used. The performance of the existing non-aqueous electrolyte secondary battery may deteriorate.

[I-6. Additive〕
The nonaqueous electrolytic solution of the present invention preferably contains various additives as long as the effects of the present invention are not significantly impaired. A conventionally well-known thing can be arbitrarily used as an additive. In addition, an additive may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the additive include an overcharge inhibitor and an auxiliary agent for improving capacity maintenance characteristics and cycle characteristics after high temperature storage.

As a specific example of the overcharge inhibitor,
Biphenyl,
Alkylbiphenyl,
Terphenyl,
Partially hydrogenated terphenyl,
Cyclohexylbenzene,
t-butylbenzene,
t-amylbenzene,
Diphenyl ether,
Aromatic compounds such as dibenzofuran;
2-fluorobiphenyl,
o-cyclohexyl fluorobenzene,
partially fluorinated product of the aromatic compound such as p-cyclohexylfluorobenzene;
2,4-difluoroanisole,
2,5-difluoroanisole,
2,6-difluoro Aniso Lumpur, fluorinated anisole compound and the like; and the like.

  In addition, these overcharge inhibitors may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

  When the non-aqueous electrolyte of the present invention contains an overcharge inhibitor, its concentration is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.1% by weight or more based on the whole non-aqueous electrolyte, It is desirable to set it in the range of 5% by weight or less. By including an overcharge inhibitor in the non-aqueous electrolyte, it is possible to suppress the rupture / ignition of the non-aqueous electrolyte secondary battery due to overcharging, and the safety of the non-aqueous electrolyte secondary battery is improved. preferable.

On the other hand, as a specific example of the auxiliary agent for improving capacity maintenance characteristics and cycle characteristics after high temperature storage,
Succinic acid,
Maleic acid,
Dicarboxylic acid anhydrides such as phthalic acid;
Erythritan carbonate,
Spin Robys (dimethylene carbonate), carbonate compounds other than those corresponding to a specific carbonate and the like;
Ethylene sulfite,
1,3-propane sultone,
1,4-butane sultone,
Methyl methanesulfonate,
Busulfan,
Sulfolane,
Sulfolene,
Dimethyl sulfone,
Diphenylsulfone,
Methylphenylsulfone,
Dibutyl disulfide,
Dicyclohexyl disulfide,
Tetramethylthiuram monosulfide,
N, N-dimethylmethanesulfonamide,
Sulfur-containing compounds such as N, N-diethylmethanesulfonamide;
1-methyl-2-pyrrolidinone,
1-methyl-2-piperidone,
3-methyl-2-oxazolidinone,
1,3-dimethyl-2-imidazolidinone,
Nitrogen-containing compounds such as N-methylsuccinimide;
Heptane,
Octane,
Hydrocarbon compounds such as cycloheptane;
Fluorobenzene,
Difluorobenzene,
Fluorine-containing aromatic compounds such as benzotrifluoride; and the like.

  In addition, these adjuvants may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  When the non-aqueous electrolyte of the present invention contains an auxiliary agent, the concentration thereof is arbitrary as long as the effects of the present invention are not significantly impaired, but usually 0.1 wt% or more and 5 wt. % Or less is preferable.

[II. Non-aqueous electrolyte secondary battery]
The non-aqueous electrolyte secondary battery of the present invention, that is, the lithium secondary battery includes a negative electrode and a positive electrode capable of occluding and releasing lithium ions, and a non-aqueous electrolyte, and the negative electrode includes Si atoms, Sn atoms, and Pb atoms. While containing the negative electrode active material which has at least 1 type of atom chosen from a group, nonaqueous electrolyte solution is the above-mentioned nonaqueous electrolyte solution of this invention, It is characterized by the above-mentioned.

[II-1. Battery configuration)
The non-aqueous electrolyte secondary battery of the present invention is the same as the conventionally known non-aqueous electrolyte secondary battery except for the negative electrode and the non-aqueous electrolyte. Usually, the non-aqueous electrolyte of the present invention is the same as the non-aqueous electrolyte secondary battery. A positive electrode and a negative electrode are laminated via an impregnated porous film (separator), and these are housed in a case (exterior body). Therefore, the shape of the non-aqueous electrolyte secondary battery of the present invention is not particularly limited, and may be any of a cylindrical shape, a square shape, a laminate shape, a coin shape, a large size, and the like.

[II-2. Non-aqueous electrolyte)
As the non-aqueous electrolyte, the above-described non-aqueous electrolyte of the present invention is used. In addition, in the range which does not deviate from the meaning of this invention, it is also possible to mix and use other nonaqueous electrolyte solution with respect to the nonaqueous electrolyte solution of this invention.

[II-3. Negative electrode)
The negative electrode in the non-aqueous electrolyte secondary battery of the present invention is made of a group consisting of Si (silicon) atoms, Sn (tin) atoms and Pb (lead) atoms (these may be hereinafter referred to as “specific metal elements”). A negative electrode active material having at least one selected atom is contained.

  Examples of the negative electrode active material having at least one atom selected from a specific metal element include a single metal of any one specific metal element, an alloy composed of two or more specific metal elements, one or more specific metals Examples thereof include an alloy composed of an element and other one or more metal elements, and a compound containing one or two or more specific metal elements. By using these simple metals, alloys or metal compounds as the negative electrode active material, the capacity of the battery can be increased.

  Examples of compounds containing one or more specific metal elements include composite compounds such as carbides, oxides, nitrides, sulfides, and phosphides containing one or more specific metal elements. .

  Moreover, the compound which these complex compounds combined with several elements, such as a metal simple substance, an alloy, or a nonmetallic element, can also be mentioned as an example. More specifically, for example, in Si and Sn, an alloy of these elements and a metal that does not operate as a negative electrode can be used. In addition, for example, in Sn, a complex compound containing 5 to 6 kinds of elements in combination with a metal that acts as a negative electrode other than Sn, Si, Sn, and Pb, a metal that does not operate as a negative electrode, and a nonmetallic element is also included. Can be used.

  Among these negative electrode active materials, since the capacity per unit weight is large when a battery is made, any single element of a specific metal element, an alloy of two or more specific metal elements, an oxide of a specific metal element In particular, Si and / or Sn simple metals, alloys, oxides, carbides, nitrides, and the like are preferable from the viewpoint of capacity per unit weight and environmental load.

In addition, although the capacity per unit weight is inferior to that of using a single metal or an alloy, the following compounds containing Si and / or Sn are also preferable because of excellent cycle characteristics.
The element ratio of Si and / or Sn to oxygen is usually 0.5 to 1.5, preferably 0.7 to 1.3, more preferably 0.9 to 1.1, and Si and / or Sn. Oxide.
-The element ratio of Si and / or Sn and nitrogen is usually 0.5 to 1.5, preferably 0.7 to 1.3, more preferably 0.9 to 1.1, and Si and / or Sn. Nitride.
The element ratio of Si and / or Sn to carbon is usually 0.5 to 1.5, preferably 0.7 to 1.3, more preferably 0.9 to 1.1, and Si and / or Sn. carbide.

  In addition, any one of the above-described negative electrode active materials may be used alone, or two or more thereof may be used in any combination and ratio.

  The negative electrode in the non-aqueous electrolyte secondary battery of the present invention can be produced according to a conventional method. Specifically, as a manufacturing method of the negative electrode, for example, a method in which a negative electrode active material added with a binder or a conductive material is roll-formed as it is to form a sheet electrode, or a compression-molded pellet electrode and The above negative electrode is usually applied to a negative electrode current collector (hereinafter also referred to as “negative electrode current collector”) by a method such as a coating method, a vapor deposition method, a sputtering method, or a plating method. A method of forming a thin film layer (negative electrode active material layer) containing an active material is used. In this case, by adding a binder, a thickener, a conductive material, a solvent, etc. to the above-mentioned negative electrode active material to form a slurry, applying this to the negative electrode current collector, drying, and pressing to increase the density A negative electrode active material layer is formed on the negative electrode current collector.

  Examples of the material of the negative electrode current collector include steel, copper alloy, nickel, nickel alloy, and stainless steel. Of these, copper foil is preferred from the viewpoint of easy processing into a thin film and cost.

  The thickness of the negative electrode current collector is usually 1 μm or more, preferably 5 μm or more, and is usually 100 μm or less, preferably 50 μm or less. If the thickness of the negative electrode current collector is too thick, the capacity of the entire battery may be too low, and conversely, if it is too thin, handling may be difficult.

  In addition, in order to improve the binding effect with the negative electrode active material layer formed on the surface, the surface of these negative electrode current collectors is preferably subjected to a roughening treatment in advance. Surface roughening methods include blasting, rolling with a rough roll, polishing cloth with a fixed abrasive particle, grinder, emery buff, wire brush equipped with steel wire, etc. Examples thereof include a mechanical polishing method, an electrolytic polishing method, and a chemical polishing method.

  Further, in order to reduce the weight of the negative electrode current collector and improve the energy density per weight of the battery, a perforated negative electrode current collector such as an expanded metal or a punching metal can be used. In this type of negative electrode current collector, the weight can be changed to white by changing the aperture ratio. Further, when a negative electrode active material layer is formed on both surfaces of this type of negative electrode current collector, the negative electrode active material layer is further less likely to peel due to the rivet effect through the hole. However, when the aperture ratio becomes too high, the contact area between the negative electrode active material layer and the negative electrode current collector becomes small, and thus the adhesive strength may be lowered.

  The slurry for forming the negative electrode active material layer is usually prepared by adding a binder, a thickener and the like to the negative electrode material. In addition, the “negative electrode material” in this specification refers to a material in which a negative electrode active material and a conductive material are combined.

  The content of the negative electrode active material in the negative electrode material is preferably 70% by weight or more, particularly 75% by weight or more, and usually 97% by weight or less, particularly 95% by weight or less. When the content of the negative electrode active material is too small, the capacity of the secondary battery using the obtained negative electrode tends to be insufficient, and when the content is too large, the content of the binder or the like is relatively insufficient. The strength of the negative electrode tends to be insufficient. When two or more negative electrode active materials are used in combination, the total amount of the negative electrode active materials may be set to satisfy the above range.

  Examples of the conductive material used for the negative electrode include metal materials such as copper and nickel; carbon materials such as graphite and carbon black. These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio. In particular, it is preferable to use a carbon material as the conductive material because the carbon material acts as an active material. It is preferable that the content of the conductive material in the negative electrode material is usually 3% by weight or more, particularly 5% by weight or more, and usually 30% by weight or less, particularly 25% by weight or less. When the content of the conductive material is too small, the conductivity tends to be insufficient. When the content is too large, the content of the negative electrode active material and the like is relatively insufficient, and thus the battery capacity and strength tend to decrease. Note that when two or more conductive materials are used in combination, the total amount of the conductive materials may satisfy the above range.

  As the binder used for the negative electrode, any material can be used as long as it is a material safe with respect to the solvent and the electrolytic solution used at the time of producing the electrode. Examples thereof include polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, styrene / butadiene rubber / isoprene rubber, butadiene rubber, ethylene / acrylic acid copolymer, and ethylene / methacrylic acid copolymer. These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio. The content of the binder is usually 0.5 parts by weight or more, particularly 1 part by weight or more, and usually 10 parts by weight or less, particularly 8 parts by weight or less, with respect to 100 parts by weight of the negative electrode material. When the content of the binder is too small, the strength of the obtained negative electrode tends to be insufficient. When the content is too large, the content of the negative electrode active material and the like is relatively insufficient, and thus the battery capacity and conductivity tend to be insufficient. It becomes. In addition, when using two or more binders together, what is necessary is just to make it the total amount of a binder satisfy | fill the said range.

  Examples of the thickener used for the negative electrode include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, and casein. These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio. The thickener may be used as necessary, but when used, the thickener content in the negative electrode active material layer is usually in the range of 0.5 wt% or more and 5 wt% or less. Is preferred.

  The slurry for forming the negative electrode active material layer is prepared by mixing a conductive agent, a binder, and a thickener as necessary with the negative electrode active material, and using an aqueous solvent or an organic solvent as a dispersion medium. The As the aqueous solvent, water is usually used, and an organic solvent such as alcohols such as ethanol and cyclic amides such as N-methylpyrrolidone is used in combination within a range of 30% by weight or less with respect to water. You can also. As the organic solvent, usually, cyclic amides such as N-methylpyrrolidone, linear amides such as N, N-dimethylformamide and N, N-dimethylacetamide, and aromatic carbonization such as anisole, toluene and xylene Examples thereof include alcohols such as hydrogens, butanol and cyclohexanol, among which cyclic amides such as N-methylpyrrolidone, linear amides such as N, N-dimethylformamide and N, N-dimethylacetamide are preferable. . Any one of these may be used alone, or two or more may be used in any combination and ratio.

  The obtained slurry is applied onto the above-described negative electrode current collector, dried, and then pressed to form a negative electrode active material layer. The method of application is not particularly limited, and a method known per se can be used. The drying method is not particularly limited, and a known method such as natural drying, heat drying, or reduced pressure drying can be used.

The electrode structure when the negative electrode active material is made into an electrode by the above method is not particularly limited, but the density of the active material present on the current collector is preferably 1 g · cm ⁻³ or more, more preferably 1. 2 g · cm ⁻³ or more, more preferably 1.3 g · cm ⁻³ or more, and the upper limit is 2 g · cm ⁻³ or less, preferably 1.9 g · cm ⁻³ or less, more preferably 1.8 g · cm ^{−. It is 3} or less, more preferably 1.7 g · cm ⁻³ or less. Exceeding this range may destroy active material particles, leading to an increase in initial irreversible capacity and deterioration of high current density charge / discharge characteristics due to reduced permeability of the non-aqueous electrolyte near the current collector / active material interface. . On the other hand, if it is lower, the conductivity between the active materials is lowered, the battery resistance is increased, and the capacity per unit volume may be lowered.

[II-4. (Positive electrode)
The positive electrode in the non-aqueous electrolyte secondary battery of the present invention contains a positive electrode active material in the same manner as a normal non-aqueous electrolyte secondary battery.

Examples of the positive electrode active material include transition metal oxides, composite oxides of transition metals and lithium (lithium transition metal composite oxides), transition metal sulfides, inorganic compounds such as metal oxides, lithium metals, lithium alloys or These complexes are mentioned. Specifically, transition metal oxides such as MnO, V ₂ O ₅ , V ₆ O ₁₃ and TiO ₂ ; LiCoO ₂ or lithium cobalt composite oxide whose basic composition is LiCoO ₂ , LiNiO ₂ or basic composition of LiNiO ₂ Lithium nickel composite oxide, LiMn ₂ O ₄ or LiMnO ₂ or lithium manganese composite oxide whose basic composition is LiMn ₂ O ₄ or LiMnO ₂ , lithium nickel manganese cobalt composite oxide, lithium nickel cobalt aluminum composite oxide, etc. And lithium transition metal composite oxides; transition metal sulfides such as TiS and FeS; and metal oxides such as SnO ₂ and SiO ₂ . Among them, lithium transition metal composite oxide, specifically, LiCoO ₂ or lithium cobalt composite oxide whose basic composition is LiCoO ₂ , LiNiO ₂ or lithium nickel composite oxide whose basic composition is LiNiO ₂ , LiMn ₂ O Lithium manganese composite oxide, lithium nickel manganese cobalt composite oxide, or lithium nickel cobalt aluminum composite oxide having ₄ or LiMnO ₂ or a basic composition of LiMn ₂ O ₄ or LiMnO ₂ achieves both high capacity and high cycle characteristics. Since it is obtained, it is used suitably. In addition, lithium transition metal composite oxide is a part of cobalt, nickel or manganese, Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, etc. Substitution with a metal is preferable because the structure can be stabilized. Any one of these positive electrode active materials may be used alone, or two or more thereof may be used in any combination and ratio.

  The positive electrode in the non-aqueous electrolyte secondary battery of the present invention can be produced according to a conventional method. Specifically, as a method for producing the positive electrode, for example, a method in which the above-described positive electrode active material added with a binder or a conductive material is directly roll-molded to form a sheet electrode, or compression-molded to obtain a pellet electrode. A method for forming a positive electrode active material layer by applying an active material on a positive electrode current collector (hereinafter sometimes referred to as a “positive electrode current collector”), and vapor deposition on the positive electrode current collector Examples include a method of forming the above-described thin film layer (positive electrode active material layer) containing a positive electrode active material by a method such as sputtering, plating, or the like. Usually, a positive electrode active material layer is formed using a coating method. Form.

  When using the coating method, add a binder, thickener, conductive material, solvent, etc. to the positive electrode active material described above to form a slurry, apply this to the positive electrode current collector, dry it, and press to increase the density. By doing so, a positive electrode active material layer is formed on the positive electrode current collector.

  Examples of the material of the positive electrode current collector include aluminum, titanium, tantalum, and alloys containing one or more of these. Of these, aluminum and its alloys are preferable.

  The thickness of the positive electrode current collector is usually 1 μm or more, preferably 5 μm or more, and usually 100 μm or less, preferably 50 μm or less. If the thickness of the positive electrode current collector is too thick, the capacity of the entire battery will be too low. Conversely, if it is too thin, handling may be difficult.

  In addition, in order to improve the binding effect with the positive electrode active material layer formed on the surface, it is preferable that the surface of these positive electrode current collectors is roughened in advance. Surface roughening methods include blasting, rolling with a rough roll, polishing cloth with a fixed abrasive particle, grinder, emery buff, wire brush equipped with steel wire, etc. Examples thereof include a mechanical polishing method, an electrolytic polishing method, and a chemical polishing method.

  Further, in order to reduce the weight of the positive electrode current collector and improve the energy density per weight of the battery, a perforated positive electrode current collector such as an expanded metal or a punching metal can be used. This type of positive electrode current collector can be freely changed in weight by changing its aperture ratio. In addition, when a positive electrode active material layer is formed on both surfaces of this type of positive electrode current collector, the positive electrode active material layer is further unlikely to peel due to the rivet effect through this hole. However, when the aperture ratio becomes too high, the contact area between the positive electrode active material layer and the positive electrode current collector becomes small, and thus the adhesive strength may be lowered.

  The positive electrode active material layer usually contains a conductive material in order to increase conductivity. There are no particular restrictions on the type of conductive material, but specific examples include metal materials such as copper and nickel, graphite such as natural graphite and artificial graphite, carbon black such as acetylene black, and amorphous such as needle coke. Examples thereof include carbon materials such as carbon. In addition, these substances may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  The proportion of the conductive material in the positive electrode active material layer is usually 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 1% by weight or more, and usually 50% by weight or less, preferably 30%. % By weight or less, more preferably 15% by weight or less. If the proportion of the conductive material is too low, the conductivity may be insufficient, and conversely if it is too high, the battery capacity may be reduced.

  The binder used for manufacturing the positive electrode active material layer is not particularly limited, and in the case of a coating method, any material that is stable with respect to the liquid medium used at the time of electrode manufacturing may be used. Specific examples include polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamide, cellulose, resin polymers such as nitrocellulose, SBR (styrene butadiene rubber), NBR (acrylonitrile butadiene rubber), fluorine rubber, Rubber polymers such as isoprene rubber, butadiene rubber, ethylene / propylene rubber, styrene / butadiene / styrene block copolymer and hydrogenated products thereof, EPDM (ethylene / propylene / diene terpolymer), styrene / ethylene / Thermoplastic elastomeric polymers such as butadiene / ethylene copolymer, styrene / isoprene styrene block copolymer and hydrogenated products thereof, syndiotactic-1,2-polybutadiene, polyvinyl acetate, ethylene Fluorine-based polymers such as vinyl acid copolymers, soft resinous polymers such as propylene / α-olefin copolymers, polyvinylidene fluoride, polytetrafluoroethylene, fluorinated polyvinylidene fluoride, and polytetrafluoroethylene / ethylene copolymers Examples thereof include a polymer and a polymer composition having ion conductivity of alkali metal ions (particularly lithium ions). These substances may be used alone or in combination of two or more in any combination and ratio.

  The ratio of the binder in the positive electrode active material layer is usually 0.1% by weight or more, preferably 1% by weight or more, more preferably 5% by weight or more, and usually 80% by weight or less, preferably 60% by weight or less. More preferably, it is 40% by weight or less, and most preferably 10% by weight or less. If the proportion of the binder is too low, the positive electrode active material cannot be sufficiently retained and the positive electrode has insufficient mechanical strength, which may deteriorate battery performance such as cycle characteristics. It may lead to a decrease in conductivity.

  The liquid medium for forming the slurry may be any type of solvent that can dissolve or disperse the positive electrode active material, the conductive agent, the binder, and the thickener used as necessary. There is no particular limitation, and either an aqueous solvent or an organic solvent may be used.

Examples of the aqueous medium, e.g., water, and a mixture Solvent etc. of alcohol and water. Examples of the organic medium include aliphatic hydrocarbons such as hexane; aromatic hydrocarbons such as benzene, toluene, xylene, and methylnaphthalene; heterocyclic compounds such as quinoline and pyridine; ketones such as acetone, methyl ethyl ketone, and cyclohexanone. Esters such as methyl acetate and methyl acrylate; amines such as diethylenetriamine and NN-dimethylaminopropylamine; ethers such as diethyl ether, propylene oxide and tetrahydrofuran (THF); N-methylpyrrolidone (NMP) Amides such as dimethylformamide and dimethylacetamide; aprotic polar solvents such as hexamethylphosphalamide and dimethylsulfoxide.

In particular, when an aqueous medium is used, it is preferable to make a slurry using a thickener and a latex such as styrene-butadiene rubber (SBR). Thickener is usually used to adjust the viscosity of the slurry. The thickener is not particularly limited, and specific examples include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein, and salts thereof. These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and ratios. When a thickener is further added, the ratio of the thickener to the active material is 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 0.6% by mass or more. The upper limit is 5% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less. Below this range, applicability may be significantly reduced. If it exceeds, the ratio of the active material in the positive electrode active material layer may decrease, and there may be a problem that the capacity of the battery decreases and a problem that the resistance between the positive electrode active materials increases.

  The viscosity of the slurry is not particularly limited as long as it is a viscosity that can be applied onto the current collector, and may be appropriately adjusted by changing the amount of the solvent used when preparing the slurry so that the viscosity can be applied. .

The resulting slurry was applied on a positive electrode collector described above, after drying, by pressing, a positive electrode active material layer is formed. The method of application is not particularly limited, and a method known per se can be used. Drying techniques also particularly limited Lena bur can be used natural drying, heat drying, a known method vacuum drying.

  The positive electrode active material layer obtained by coating and drying is preferably consolidated by a hand press, a roller press or the like in order to increase the packing density of the positive electrode active material.

Density of the positive electrode active material layer is preferably 1.5 g · cm ^-3 or more, more preferably 2 g · cm ^-3 or higher, still more preferably 2.2 g · cm ^-3 or more, and the upper limit is preferably 3 .5g · cm ^-3 or less, more preferably 3 g · cm ^-3 or less, more preferably in the range of 2.8 g · cm ^-3 or less. If this range is exceeded, the permeability of the non-aqueous electrolyte solution to the vicinity of the current collector / active material interface may decrease, and the charge / discharge characteristics at a high current density may decrease. On the other hand, if it is lower, the conductivity between the active materials may be reduced, and the battery resistance may be increased.

[II-5. (Separator)
Usually, a separator is interposed between the positive electrode and the negative electrode in order to prevent a short circuit. In this case, the nonaqueous electrolytic solution of the present invention is usually used by impregnating the separator.

  There is no restriction | limiting in particular about the material and shape of a separator, As long as the effect of this invention is not impaired remarkably, a well-known thing can be employ | adopted arbitrarily. Among these, it is preferable to use a porous sheet or a nonwoven fabric that is formed of a material that is stable with respect to the nonaqueous electrolytic solution of the present invention and has excellent liquid retention.

  As a material for the separator, for example, polyolefin such as polyethylene and polypropylene, polytetrafluoroethylene, polyethersulfone, glass filter and the like can be used. Of these, glass filters and polyolefins are preferred, and polyolefins are more preferred. These materials may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  Although the thickness of a separator is arbitrary, it is 1 micrometer or more normally, Preferably it is 5 micrometers or more, More preferably, it is 10 micrometers or more, and is 50 micrometers or less normally, Preferably it is 40 micrometers or less, More preferably, it is 30 micrometers or less. If the separator is too thin, the insulation and mechanical strength may decrease. If the separator is too thick, not only the battery performance such as rate characteristics may decrease, but also the energy density of the entire non-aqueous electrolyte secondary battery. May decrease.

  Furthermore, when a porous material such as a porous sheet or nonwoven fabric is used as the separator, the porosity of the separator is arbitrary, but is usually 20% or more, preferably 35% or more, more preferably 45% or more, Usually, it is 90% or less, preferably 85% or less, more preferably 75% or less. If the porosity is too small, the membrane resistance increases and the rate characteristics tend to deteriorate. On the other hand, if it is too large, the mechanical strength of the separator is lowered and the insulating property tends to be lowered.

  Moreover, although the average pore diameter of a separator is also arbitrary, it is 0.5 micrometer or less normally, Preferably it is 0.2 micrometer or less, and is 0.05 micrometer or more normally. If the average pore diameter is too large, a short circuit is likely to occur, and if it is too small, the membrane resistance may increase and the rate characteristics may deteriorate.

[II-6. (Exterior body)
The non-aqueous electrolyte secondary battery of the present invention is usually configured by housing the non-aqueous electrolyte, the negative electrode, the positive electrode, the separator, and the like in an exterior body. There is no restriction | limiting in this exterior body, As long as the effect of this invention is not impaired remarkably, a well-known thing can be employ | adopted arbitrarily.

  Specifically, the material of the exterior body is arbitrary, but usually, for example, nickel-plated iron, stainless steel, aluminum or an alloy thereof, nickel, titanium, or the like is used.

  The shape of the exterior body is also arbitrary, and may be any of a cylindrical shape, a square shape, a laminate shape, a coin shape, a large size, and the like.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to description of a following example, unless the summary is exceeded.

[Examples 1-42 and Comparative Examples 1-17]
Non-aqueous electrolyte secondary batteries were assembled and evaluated according to the following procedures, and the results obtained are shown in Tables 1-6.

(Production of negative electrode)
<Production of Silicon Alloy Negative Electrode: Examples 1-42 and Comparative Examples 1-6>
As the negative electrode active material, 73.2 parts by weight of silicon, which is a non-carbon material, 8.1 parts by weight of copper, and 12.2 parts by weight of artificial graphite powder (trade name “KS-6” manufactured by Timcal) were used. And 54.2 parts by weight of an N-methylpyrrolidone solution containing 12 parts by weight of poly (vinylidene fluoride) (hereinafter abbreviated as “PVDF”) and 50 parts by weight of N-methylpyrrolidone, The mixture was made into a slurry. The obtained slurry was uniformly applied onto a 18 μm thick copper foil as a negative electrode current collector, and once naturally dried, it was finally dried under reduced pressure at 85 ° C. overnight. Then, it pressed so that an electrode density might be set to about 1.5 g * cm ^<-3 >, and it punched in the disk shape of diameter 12.5mm, and set it as the negative electrode (silicon alloy negative electrode).

<Production of Graphite Negative Electrode: Comparative Examples 7 to 17>
As an anode active material, 100 parts by weight of artificial graphite powder (trade name “KS-6” manufactured by Timcal) was used, and 83.5 parts by weight of an N-methylpyrrolidone solution containing 12 parts by weight of PVDF was added thereto. 50 parts by weight of methylpyrrolidone was added and mixed with a disperser to form a slurry. The obtained slurry was uniformly applied onto a 18 μm thick copper foil as a negative electrode current collector, and once naturally dried, it was finally dried under reduced pressure at 85 ° C. overnight. Then, it pressed so that an electrode density might be set to about 1.5 g * cm ^<-3 >, and it punched in the disk shape of diameter 12.5mm, and set it as the negative electrode (graphite negative electrode).

[Production of positive electrode]
As a positive electrode active material, 85 parts by weight of LiCoO ₂ (“C5” manufactured by Nippon Kagaku Kogyo Co., Ltd.) was used, and 6 parts by weight of carbon black (trade name “Denka Black” manufactured by Denki Kagaku Kogyo Co., Ltd.), polyvinylidene fluoride KF-1000 ( 9 parts by weight of Kureha Chemicals trade name “KF-1000”) was added and mixed, and dispersed with N-methyl-2-pyrrolidone to form a slurry. The obtained slurry was uniformly applied on a 20 μm-thick aluminum foil as a positive electrode current collector so as to be 90% of the theoretical capacity of the negative electrode used, dried at 100 ° C. for 12 hours, and then 12. A positive electrode was punched into a 5 mm disk.

(Preparation of non-aqueous electrolyte)
In the columns of [Examples] and [Comparative Examples] in Tables 1 to 7 below, the compounds described in the columns of [Specific carbonate], [Other compounds], and [Specific compounds] are described in the same column. In addition, LiPF ₆ was dissolved as an electrolyte salt so as to have a concentration of 1 mol · dm ⁻³ , and a non-aqueous electrolyte solution (non-aqueous electrolyte solutions of Examples 1-42 and Comparative Examples 1-17) Was prepared.

[Production of coin cell]
Using the above positive electrode and negative electrode and the non-aqueous electrolyte prepared in each Example and Comparative Example, coin-type cells (non-aqueous electrolytes 2 of Examples 1 to 42 and Comparative Examples 1 to 17 were prepared in the following procedure. Secondary battery). That is, the negative electrode was placed through a polyethylene separator impregnated with an electrolytic solution on a positive electrode accommodated in a stainless steel can body also serving as a positive electrode conductor. The can body and a sealing plate serving also as a negative electrode conductor were caulked and sealed via an insulating gasket to produce a coin-type cell. As the negative electrode, the above-described silicon alloy negative electrode or graphite negative electrode was selected and used according to the description in the column of [Negative electrode] in the columns of [Examples] and [Comparative Examples] in Tables 1 to 7 below. .

[Evaluation of coin cell (discharge capacity and discharge capacity maintenance rate)]
About the coin-type cell (Examples 1-42 and the nonaqueous electrolyte secondary battery of Comparative Examples 1-17) obtained by the said procedure, discharge capacity and discharge capacity maintenance factor were evaluated in the following procedures. That is, using each coin-type cell, a constant current and constant voltage charge with a charge end voltage of 4.2 V-3 mA, a charge end current of 0.15 μA, and a constant current of a discharge end voltage of 3.0 V-3 mA under the condition of 25 ° C. 50 cycles of charge and discharge were performed with one discharge as one cycle. At this time, the discharge capacities of the first cycle and the tenth cycle were measured, and the discharge capacity retention ratio in each cycle was calculated by the following formula.

The discharge capacities of the first and tenth cycles and the discharge capacity retention rate (%) obtained for the coin-type cells of each Example and Comparative Example are shown in the [Battery Evaluation] column of Tables 1 to 7 below. . In Tables 1 to 7 below, the value of the discharge capacity is shown as the capacity per unit weight (mAh · g ⁻¹ ) of the negative electrode active material. “Wt%” represents “wt%”.

  From the results in Tables 1 to 7, the following is clear.

  Examples 1-42 using the non-aqueous electrolyte containing the compound shown by the specific compound and the specific carbonate are Comparative Example 6 using the non-aqueous electrolyte containing neither the specific compound nor the specific carbonate. In comparison, the discharge capacity retention rate is greatly improved.

  On the other hand, Comparative Examples 3 to 5 using the non-aqueous electrolyte containing only the specific compound do not show an improvement in the discharge capacity retention rate relative to Comparative Example 6. Comparative Examples 1 and 2 using a non-aqueous electrolyte containing only a specific carbonate do not greatly affect Examples 1 to 42, although capacity maintenance is improved.

  On the other hand, Comparative Examples 7-17 used only a carbon material as a negative electrode active material, and the non-aqueous electrolyte solution of Comparative Example 7 does not contain any specific compound or specific carbonate, and the non-aqueous system of Comparative Examples 8-10. The electrolyte solution contains only the specific compound, the non-aqueous electrolyte solution of Comparative Example 11 contains only the specific carbonate, and the non-aqueous electrolyte solutions of Comparative Examples 12 to 17 contain the specific compound and the specific carbonate.

  Compared with Comparative Examples 7 to 17 in which the negative electrode active material is only a carbon material, Examples 1-42 in which the negative electrode active material is a silicon alloy have a higher discharge capacity. Moreover, when a negative electrode active material is a carbon material, although the improvement of the discharge capacity maintenance factor by non-aqueous electrolyte solution containing specific carbonate is recognized from contrast of Comparative Examples 7-17, it is because it contains only a specific compound. The effect or the synergistic effect by including a specific compound and a specific carbonate is not recognized.

  The non-aqueous electrolyte secondary battery of the present invention is excellent in long-term charge / discharge cycle characteristics, so that it is a notebook computer, pen-inserted personal computer, mobile personal computer, electronic book player, cellular phone, portable fax machine, portable copy, portable printer. , Headphone stereo, video movie, LCD TV, handy cleaner, portable CD, minidisc, transceiver, electronic notebook, calculator, memory card, portable tape recorder, radio, backup power supply, motor, lighting equipment, toy, game device, clock, It can be used for electric bicycles, electric scooters, electric cars, etc. as well as power supplies such as strobes, cameras, and power load leveling.

Claims (9)

It comprises a lithium ion and a negative electrode and a positive electrode capable of occluding and releasing a non-aqueous electrolyte, a non-aqueous electrolyte used in the nonaqueous electrolyte secondary battery comprising a negative electrode active material negative electrode having a Si atom ,
Vinylene carbonate derivatives or ethylene carbonate derivatives substituted with a substituent having a carbon-carbon unsaturated bond 0.01% by weight to 5% by weight, and carbonates having fluorine atoms 0.01% by weight to 50% by weight A nonaqueous electrolytic solution comprising at least one of the following and at least one organic phosphorus compound represented by the following general formula (1):

(In general formula (1),
p and q each independently represent an integer of 0 or 1,
R ¹ , R ² and R ³ each independently represents a hydrocarbon group having 1 to 6 carbon atoms which may have a halogen atom. Further, any two of R ¹ , R ² and R ³ may be bonded to each other to form a ring structure. ) The non-aqueous electrolyte solution according to claim 1, wherein p + q is 1 or 2 in the general formula (1). The non-aqueous electrolyte solution according to claim 1, wherein p + q is 0 in the general formula (1). The concentration of the compound represented by the general formula (1) in the nonaqueous electrolytic solution is 0.01 wt% or more and 10 wt% or less, according to any one of claims 1 to 3. The non-aqueous electrolyte described. The concentration of the compound represented by the general formula (1) in the nonaqueous electrolytic solution is 0.01 wt% or more and 5 wt% or less, according to any one of claims 1 to 4, The non-aqueous electrolyte described. The above vinylene carbonate derivatives or ethylene carbonate derivatives substituted with a substituent having a carbon-carbon unsaturated bond, or the above-mentioned carbonate having a fluorine atom is vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate, and difluoroethylene. The nonaqueous electrolytic solution according to any one of claims 1 to 5, wherein the nonaqueous electrolytic solution is one or more carbonates selected from the group consisting of carbonates and derivatives thereof. The nonaqueous electrolytic solution according to any one of claims 1 to 6, further comprising ethylene carbonate and / or propylene carbonate. It further comprises at least one carbonate selected from the group consisting of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl-n-propyl carbonate, ethyl-n-propyl carbonate, and di-n-propyl carbonate. The non-aqueous electrolyte solution according to any one of claims 1 to 7. A negative electrode and a positive electrode capable of inserting and extracting lithium ions and a non-aqueous electrolyte solution,
With negative electrode contains a negative electrode active material having a Si atom,
The non-aqueous electrolyte secondary battery, wherein the non-aqueous electrolyte is the non-aqueous electrolyte according to any one of claims 1 to 8.