JP6583809B2 - Non-aqueous electrolyte and lithium ion secondary battery - Google Patents

Description

  The present invention relates to an electrolytic solution for an electrochemical device and a lithium ion secondary battery.

  Conventionally, low molecular weight or high molecular weight organic gelling agents have been used in various industrial fields to solidify organic liquids. As low molecular weight organic gelling agents, for example, low molecular weight compound groups having hydrogen-bonding functional groups such as amino groups, amide groups, and urea groups in the molecule are known, such as cosmetics, cosmetics, and sludge treatments. It is suitably used in the field. On the other hand, examples of the high molecular weight organic gelling agent include a group of polymer compounds having a three-dimensional network structure in the molecule. For example, polyether compounds are well known. There are many examples of studies on high molecular weight organic gelling agents, which are being developed in various fields.

  On the other hand, low molecular weight organic gelling agents are relatively slowly developed compared to high molecular weight ones, and there are few known types of gelling agents. As low molecular weight organic gelling agents, for example, dialkyl urea derivatives (see, for example, Patent Document 1) and perfluoroalkyl derivatives (see, for example, Patent Documents 2 to 3 and Non-Patent Document 1) are known.

JP-A-8-231942 International Publication No. 2007/083843 International Publication No. 2009/078268

J. et al. Fluorine. Chem. 111, 47-58 (2001)

  At present, electrochemical devices using organic liquids are used in various applications, and typical examples thereof include lithium ion secondary batteries mainly used for rechargeable batteries of portable devices. Further, in recent years, there has been a demand for energy saving due to increasing interest in the environment, and there are increasing expectations for various electrochemical devices using organic liquids that can contribute to this demand. However, when applying an organic liquid electrolyte to an electrochemical device, further improvement of its safety is a major issue. For example, lithium ion secondary batteries are expected to be widely used for automotive applications in the near future, and higher battery safety (non-leakage, flame retardancy, dendride suppression, etc.) is required. Therefore, for example, development of a polymer (gel) battery, a battery using an ionic liquid or a fluoro solvent as an electrolytic solution, and the like is underway. However, at present, the battery safety and battery characteristics (charge / discharge characteristics, low temperature operation, high temperature durability, etc.) are in a trade-off relationship. A polymer (gel) battery is expected from the viewpoint of battery size reduction and increased freedom of form in addition to battery safety, but existing dry polymer batteries cannot be said to have high battery characteristics. In addition, although the gel polymer battery has an effect of improving battery characteristics (particularly rate characteristics) as compared with the dry polymer battery, it does not reach the battery using the existing non-aqueous liquid electrolyte.

  At present, there are few research examples of electrolytes and secondary batteries using low molecular weight organic gelling agents, which are not sufficient. For example, Patent Document 2 proposes an electrolytic solution using a low molecular weight organic gelling agent, but there is still room for improvement in battery performance even when this electrolytic solution is used.

  This invention is made | formed in view of the said situation, and it aims at providing the electrolyte solution and lithium ion secondary battery for electrochemical devices which are excellent also in a battery characteristic, and also implement | achieve high safety | security.

  In order to achieve the above-mentioned object, the present inventors examined the possibility of applying low molecular weight organic gelling agents including those described in the above-mentioned patent documents to an electrolytic solution and a lithium ion secondary battery. As a result, it was found that a specific low molecular weight organic gelling agent having a perfluoroalkyl group is useful as an electrolytic solution and can form a gel electrolyte having high performance as a gel. Furthermore, when producing a secondary battery using this electrolyte solution, it discovered that it was compatible with high discharge capacity and high safety, and came to complete this invention.

That is, the present invention is as follows.
[1] An electrolytic solution for an electrochemical device containing a nonaqueous solvent, an electrolyte, and a compound represented by the following general formula (1).
Rf-X-Ar-OCO-Ar'-OR (1)
(In the formula (1), Rf represents a functional group having a substituted or unsubstituted perfluoroalkyl group having 2 to 18 carbon atoms in the main chain, and R represents a substituted or unsubstituted carbon group having 1 to 8 carbon atoms in the main chain. X represents a sulfur atom, oxygen atom, SO group or SO ₂ group, and Ar and Ar ′ are each independently substituted or unsubstituted having 5 to 20 ring atoms. An aromatic group or an alicyclic group.)
[2] The electrolytic solution according to [1], wherein Rf is a group represented by the following general formula (2).
Rf'-R'- (2)
(In Formula (2), Rf ′ represents a substituted or unsubstituted perfluoroalkyl group having 2 to 14 carbon atoms in the main chain, and R ′ is a single bond or a substituted or unsubstituted carbon atom having 1 to 8 carbon atoms in the main chain. Of the divalent hydrocarbon group.)
[3] Ar and Ar ′ are each independently a substituted or unsubstituted phenylene group, biphenylene group, terphenylene group, naphthylene group, anthranylene group, or pyridylene group, according to [1] or [2] Electrolytic solution.
[4] The electrolytic solution according to [1] or [2], wherein Ar and Ar ′ are each independently a substituted or unsubstituted phenylene group, biphenylene group, or naphthylene group.
[5] The electrolyte solution according to any one of [1] to [4], wherein X is a sulfur atom, an SO group, or an SO ₂ group.
[6] Any of [1] to [4], wherein Ar and Ar ′ are each independently a substituted or unsubstituted phenylene group or biphenylene group, and X is an S atom or an SO ₂ group. The electrolyte solution as described in any one.
[7] The electrolyte solution according to any one of [1] to [6], wherein the electrolyte solution is a gelled gel electrolyte.
[8] A lithium ion secondary battery comprising a positive electrode containing a positive electrode active material, a negative electrode containing a negative electrode active material, and the electrolyte solution according to any one of [1] to [7].
[9] The lithium ion secondary battery according to [8], wherein the positive electrode active material includes a lithium-containing compound.
[10] The negative electrode active material contains at least one material selected from the group consisting of metallic lithium, a carbon material, a material containing an element capable of forming an alloy with lithium, and a lithium-containing compound. [8] Or the lithium ion secondary battery as described in [9].

  ADVANTAGE OF THE INVENTION According to this invention, the electrolyte solution for electrochemical devices and a lithium ion secondary battery which are excellent also in a battery characteristic and also implement | achieve high safety | security can be provided.

Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail.
The electrolyte solution of the present embodiment includes a non-aqueous solvent, an electrolyte, and a compound represented by the following general formula (1) (hereinafter also simply referred to as “perfluoro group-containing compound” or “compound (1)”). It contains.
Rf-X-Ar-OCO-Ar'-OR (1)
Here, in the formula, Rf represents a functional group having a substituted or unsubstituted perfluoroalkyl group having 2 to 18 carbon atoms in the main chain, and R represents a substituted or unsubstituted carbon group having 1 to 8 carbon atoms in the main chain. Represents a monovalent hydrocarbon group, X represents a sulfur atom, oxygen atom, SO group or SO ₂ group, and Ar and Ar ′ each independently represents a substituted or unsubstituted group having 5 to 20 ring atoms. An aromatic group or an alicyclic group is shown.
Moreover, the lithium ion secondary battery of this embodiment is equipped with the positive electrode containing a positive electrode active material, the negative electrode containing a negative electrode active material, and the electrolyte solution of this embodiment.
Since it is configured as described above, the electrolytic solution and the lithium ion secondary battery of the present embodiment are excellent in battery characteristics and at the same time can realize high safety.

<Electrolyte>
The electrolytic solution according to this embodiment contains (i) a nonaqueous solvent, (ii) an electrolyte, and (iii) a perfluoro group-containing compound.

<Nonaqueous solvent>
(I) As a nonaqueous solvent, an aprotic solvent is mentioned, for example, Aprotic polar solvent is preferable. Specific examples thereof include, but are not limited to, ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, trans-2,3-butylene carbonate, cis-2,3-butylene carbonate, 1,2-pentylene carbonate. , Trans-2,3-pentylene carbonate, cis-2,3-pentylene carbonate, trifluoromethylethylene carbonate, fluoroethylene carbonate, cyclic carbonate represented by 4,5-difluoroethylene carbonate, γ-butyrolactone, γ -Lactone represented by valerolactone; cyclic sulfone represented by sulfolane; cyclic ether represented by tetrahydrofuran and dioxane; methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, Chain carbonates typified by tilpropyl carbonate, methyl isopropyl carbonate, dipropyl carbonate, methyl butyl carbonate, dibutyl carbonate, ethyl propyl carbonate, methyl trifluoroethyl carbonate; nitriles typified by acetonitrile and propionitrile; typified by dimethyl ether A chain carboxylic acid ester represented by methyl propionate; a chain ether carbonate compound represented by dimethoxyethane. These are used singly or in combination of two or more.

  In particular, when the electrolytic solution is used for a lithium ion secondary battery or a lithium ion capacitor, the nonaqueous solvent is composed of a cyclic aprotic polar solvent and a nitrile solvent from the viewpoint of increasing the ionization degree of the lithium salt that contributes to charging and discharging. It is preferable to include one or more solvents selected from the group, and it is more preferable to include one or more cyclic carbonates typified by ethylene carbonate and propylene carbonate. Cyclic aprotic polar solvents and nitrile solvents have a high dielectric constant and tend to act effectively to aid ionization of the lithium salt and increase gelation ability.

An ionic liquid can also be used as the nonaqueous solvent. An ionic liquid is a liquid composed of ions obtained by combining an organic cation and an anion.
Examples of organic cations include, but are not limited to, imidazolium ions such as dialkylimidazolium cations and trialkylimidazolium cations, tetraalkylammonium ions, alkylpyridinium ions, dialkylpyrrolidinium ions, and dialkylpiperidinium ions. .

The anions that serve as counter ions for these organic cations are not limited to the following. For example, PF ₆ anions, PF ₃ (C ₂ F ₅ ) ₃ anions, PF ₃ (CF ₃ ) ₃ anions, BF ₄ anions, BF ₂ (CF ₃ ) ₂ anion, BF ₃ (CF ₃ ) anion, bisoxalate borate anion, Tf (trifluoromethanesulfonyl) anion, Nf (nonafluorobutanesulfonyl) anion, bis (fluorosulfonyl) imide anion, bis ( A trifluoromethanesulfonyl) imide anion, a bis (pentafluoroethanesulfonyl) imide anion, or a dicyanoamine anion can be used.

<Electrolyte>
(Ii) The electrolyte is not particularly limited as long as it is used as a normal nonaqueous electrolyte in the electrolytic solution, and any electrolyte may be used. Note that “gel electrolyte” described later indicates a gelled (gel-like) electrolytic solution, and is a concept different from “electrolyte” in this section. When the electrolytic solution is used in a lithium ion secondary battery and a lithium ion capacitor, a lithium salt is used as an electrolyte. Specific examples of the lithium salt include, but are not limited to, for example, LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , Li ₂ SiF ₆ , LiOSO ₂ C _k F _{2k + 1} [k is an integer of 1 to 8]. LiN (SO ₂ C _k F _{2k + 1} ) ₂ [k is an integer of 1 to 8], LiPF _n (C _k F _{2k + 1} ) _6-n [n is an integer of 1 to 5, k is 1 to 8 LiBF _n ((C _k F _{2k + 1} ) _4-n [n is an integer of 1 to 3, k is an integer of 1 to 8], lithium bis represented by LiB (C ₂ O ₄ ) ₂ (Oxalate) borate, lithium difluoro (oxalate) borate represented by LiBF ₂ (C ₂ O ₄ ), lithium tetrafluoro (oxalate) phosphate represented by LiPF ₄ (C ₂ O ₄ ), LiPO ₂ F ₂ , Li ₂ PO ₃ F.

Moreover, the lithium salt represented by the following general formula (2a), (2b), or (2c) can also be used.
LiC (SO ₂ R ¹¹ ) (SO ₂ R ¹² ) (SO ₂ R ¹³ ) (2a)
LiN (SO ₂ OR ¹⁴ ) (SO ₂ OR ¹⁵ ) (2b)
LiN (SO ₂ R ¹⁶ ) (SO ₂ OR ¹⁷ ) (2c)
Here, in the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ may be the same or different from each other, and are a C 1-8 perfluoroalkyl group. Indicates.

These lithium salts are used singly or in combination of two or more. Among these lithium salts, LiPF ₆ , LiBF ₄ , LiN (SO ₂ C _k F _{2k + 1} ) ₂ [k is an integer of 1 to 8] from the viewpoint of improving gelation ability in addition to battery characteristics and stability. LiB (C ₂ O ₄ ) ₂ is preferred, and LiPF ₆ and LiBF ₄ are more preferred.
The lithium salt is preferably contained in the electrolytic solution at a concentration of 0.1 to 3 mol / liter, more preferably 0.5 to 2 mol / liter.

<Perfluoro group-containing compound>
(Iii) The perfluoro group-containing compound acts, for example, as a gelling agent or as a safety improving additive such as a flame retardant, and is represented by the above general formula (1), either alone or in combination. Two or more types are used in combination.

Compound (1) is composed of a perfluoroalkyl (oligomethylene) group, two aromatic rings or alicyclic rings (carbon ring excluding the aromatic ring), and an OCO group (a group represented by —OCO—). It can also be called the compound which has. In the general formula (1), X represents a sulfur atom, an oxygen atom, an SO group (a group represented by —SO—) or an SO ₂ group (a group represented by —SO ₂ —). A compound having a sulfur atom or an SO group is superior in handleability and is easier to synthesize. A compound having an oxygen atom or an SO ₂ group is further excellent in achieving both gelling performance and battery characteristics. In addition, having an OCO group together with the group represented by X has a gelling ability (the amount of gelling agent necessary for gelling the electrolytic solution, the heating temperature necessary for dissolving the gelling agent in the electrolytic solution), It is more advantageous to achieve various performances such as battery characteristics (long-term charge / discharge cycle characteristics, storage characteristics, temperature characteristics) and safety (thermal runaway suppression, overcharge runaway suppression) at the same time.

  Ar and Ar ′ each independently represent a substituted or unsubstituted divalent aromatic group or alicyclic group having 5 to 20 ring atoms, and Ar and Ar ′ may be the same or different from each other. Also good. The divalent aromatic group is a cyclic divalent group exhibiting so-called “aromaticity”. The divalent aromatic group (aromatic hydrocarbon group) may be a monocyclic group or a heterocyclic group. A divalent alicyclic group (alicyclic hydrocarbon group) has a single bond between carbons and may or may not have a non-conjugated multiple bond between carbons. It is a divalent group. These divalent aromatic groups or alicyclic groups may be substituted with a substituent or may be unsubstituted. The substituent is selected from the viewpoints of easily allowing the introduction of a perfluoroalkyl (oligomethylene) thio group and the introduction of a hydrocarbon oxy group when synthesizing the compound (1), or the compound (1) serving as a gelling agent. It is selected from the viewpoint of optimizing the melting point and gelling ability.

  Among divalent aromatic groups, a monocyclic group has 5 to 20 ring-forming atoms, may be substituted with a substituent, and is unsubstituted or unsubstituted. Also good. Specific examples thereof include, but are not limited to, divalent having a ring represented by a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, an anthranylene group, a phenanthrylene group, a pyrenylene group, a chrysenylene group, and a fluoranthenylene group. The group of is mentioned. In addition, the monocyclic group may have two or more of the above-described divalent groups within the range of 5 to 20 ring-forming atoms. Here, two or more divalent groups may be the same as or different from each other. When using a monocyclic group, from the viewpoint of ease of synthesis and ease of gelation, a substituted or unsubstituted phenylene group, biphenylene group, terphenylene group, naphthylene group, and anthranylene group may be used. It is preferable to use any one of a substituted or unsubstituted phenylene group, biphenylene group and naphthylene group.

  Among the divalent aromatic groups, the heterocyclic group has 5 to 20 ring-forming atoms, and is not limited to the following. For example, a pyrrolene group, a furylene group, a thiophenylene group, a triazolen group, an oxa group Examples thereof include divalent groups having a ring represented by a diazolene group, a pyridylene group, and a pyrimidylene group. Further, the heterocyclic group may have two or more of the above-described divalent groups within the range of 5 to 20 ring forming atoms. Here, two or more divalent groups may be the same as or different from each other.

  Furthermore, Ar and Ar ′ may be a group having both the above monocyclic group and heterocyclic group within the range of 5 to 20 ring-forming atoms.

  The alicyclic group has 5 to 20 ring-forming atoms and is not limited to the following, but examples thereof include a divalent group having a ring represented by a cyclopentane group, a cyclohexane group, and a cyclooctane group. .

  Among these, from the viewpoint of more effectively and reliably achieving the effects of the present embodiment, a substituted or unsubstituted phenylene group, biphenylene group, terphenylene group, naphthylene group, anthranylene group, or pyridylene group is preferable, and substituted or unsubstituted. Of these, a phenylene group, a biphenylene group or a naphthylene group is more preferred, and a substituted or unsubstituted phenylene group or biphenylene group is more preferred. From the viewpoint of easy availability of raw materials and easy synthesis, a phenylene group is preferable, and a biphenylene group is preferable from the viewpoint of showing high gelling ability with a small amount of use.

  Moreover, as said substituent, although not limited to the following, For example, the alkyl group represented by the methyl group and the ethyl group, and a halogen atom are mentioned.

  Furthermore, when Ar and Ar ′ are different from each other, the gelling ability (the amount of gelling agent necessary for gelation of the electrolyte, the heating temperature necessary for dissolving the gelling agent in the electrolyte), battery characteristics (long-term It is advantageous because various performances such as charge / discharge cycle characteristics, storage characteristics, temperature characteristics) and safety (heat runaway suppression, overcharge runaway suppression) can be easily controlled according to the purpose.

R represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms in the main chain. R may be a monovalent aliphatic hydrocarbon group, and may further have a monovalent aromatic hydrocarbon group such as a phenyl group as a substituent. When the monovalent hydrocarbon group is a monovalent aliphatic hydrocarbon group, it may be branched or unbranched (linear). When the monovalent hydrocarbon group has a monovalent aromatic hydrocarbon group as a substituent, the aromatic hydrocarbon group may or may not have a substituent.
Examples of the unsubstituted monovalent hydrocarbon group include, but are not limited to, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, n-pentyl group, neopentyl group, n-hexyl group, C1-C8 branched or linear alkyl groups, such as n-heptyl group and n-octyl group, are mentioned.

In the compound (1), Ar and Ar ′ are each independently a phenylene group or a biphenylene group, and X is preferably a sulfur atom or an SO ₂ group, and any one of Ar and Ar ′ is a phenylene group, More preferably, the other is a biphenylene group and X is a sulfur atom or an SO ₂ group. With such a structure, it is possible to have a higher level in terms of ease of synthesis, gelation ability, battery characteristics, and safety.

Rf represents a group containing a monovalent perfluoroalkyl group or a substituted or unsubstituted 2 to 18 carbon atoms in the main chain. The number of carbon atoms in the main chain of Rf is preferably 4 to 16, and more preferably 4 to 10. By making the carbon number within the above range, the compound (1) is easy to synthesize, exhibits high gelling ability, and is excellent in handleability.

Rf is the following formula (2):
Rf'-R'- (2)
It is preferable that it is group represented by these. Here, Rf 'is a monovalent perfluoroalkyl group or a substituted or unsubstituted carbon atoms 2 to 14 backbone, R' is a single bond, or backbone carbon atoms of 1 to 8 substituted or unsubstituted A substituted divalent hydrocarbon group, preferably a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms in the main chain, and more preferably an unsubstituted alkylene group having 1 to 8 carbon atoms in the main chain; preferable. Moreover, the carbon number of the main chain of R ′ is more preferably 2 to 6, and further preferably 2 to 4. By using a structure having both a perfluoroalkyl group and an alkylene group, it is possible to achieve both higher gelling ability and handleability. From the same viewpoint, it is more preferable that Rf ′ has more carbon atoms than R ′.

  As described above, the compound (1) has at least two aromatic groups and alicyclic groups. Having a plurality of aromatic groups or alicyclic groups is excellent in that the gelling ability is increased even if the perfluoroalkyl chain is relatively short. Since the perfluoroalkyl group becomes difficult to obtain as the alkyl chain in the perfluoroalkyl group becomes longer, the perfluoroalkyl group becomes a gel even if the alkyl chain of the perfluoroalkyl group is short. This is an advantage of the compound (1). is there. Compound (1) has X and an ester moiety. By combining these portions as a group for connecting an aromatic group and another group, the strength of the gel to be formed and the sol-gel temperature can be easily handled as a battery. Furthermore, the compound (1) has a relatively simple structure and is excellent from the viewpoints of ease of synthesis and availability of synthetic raw materials.

  Although the manufacturing method of the compound (1) of this embodiment is not specifically limited, For example, it is compoundable with the following scheme or the scheme according to it. In more detail, it can be synthesized by the method described in the examples. Moreover, the code | symbol same as the said General formula (1) among the code | symbols in each formula is synonymous with the thing in the general formula (1), and when each formula has the same code | symbol mutually, those code | symbols mutually It is synonymous.

First, a compound represented by the following general formula (1a) is sulfided or etherified with a compound represented by the following general formula (1b) in the presence of an alkali metal compound such as K ₂ CO _{3 in} a solvent such as acetone. To obtain a compound represented by the following general formula (1c).
H—X ¹ —Ar—OH (1a)
RfZ ¹ (1b)
^{Rf-X 1 -Ar-OH (} 1c)
Here, in the above formula, X ¹ represents an oxygen atom or a sulfur atom, and Z ¹ represents a halogen atom such as an iodine atom (the same applies hereinafter).

When X ¹ in the compound represented by the general formula (1c) is a sulfur atom, the compound is oxidized (sulfonylated or sulfoxidized) with an oxidizing agent such as hydrogen peroxide in the presence of a catalyst such as acetic acid. Thus, a compound represented by the following general formula (1d) is obtained.
^{Rf-X 2 -Ar-OH (} 1d)
Here, in the formula (1d), X ² represents a group represented by —SO ₂ — or —SO—.

Further, a compound represented by the following general formula (1e) (carboxylic acid compound) is chlorinated using thionyl chloride or the like to obtain a compound represented by the following general formula (1f).
RO-Ar'-COOH (1e)
RO-Ar'-COCl (1f)

  Next, anhydrous toluene is added to the compound represented by the above general formula (1c) or (1d), and the compound is reacted with the compound represented by the above general formula (1f) dissolved in anhydrous pyridine to give the compound (1). obtain.

  Compound (1) can gel the non-aqueous solvent in the present embodiment, preferably by adding a small amount of about 20% by mass or less. The compound (1) is added to a non-aqueous solvent, dissolved by heating, and the resulting solution is gelled by returning to room temperature. Compound (1) is an aprotic polar solvent having a high dielectric constant suitable for an electrolytic solution, for example, propylene, with a small addition of, for example, 0.3 to 20% by mass, preferably about 0.4 to 15% by mass. It is possible to gel a cyclic carbonate represented by carbonate and butylene carbonate; a lactone represented by γ-butyrolactone and γ-valerolactone; a cyclic sulfone represented by sulfolane; a nitrile represented by acetonitrile.

  The perfluoro group-containing compound in the present embodiment is used alone or in combination of two or more of the above compound (1).

  The mixing ratio of the perfluoro group-containing compound and the non-aqueous solvent is arbitrary, but from the viewpoint of further improving the gelling ability and handleability, the perfluoro group-containing compound: non-aqueous solvent is 0 on a mass basis. : 1: 99.9 to 20:80, and more preferably 0.5: 99.5 to 15:85. When the ratio of the perfluoro group-containing compound is 0.1% by mass or more with respect to 100% by mass of the mixture, the gel-sol phase transition point becomes high and the gel becomes stronger. If it exists, the viscosity of electrolyte solution will become lower and it will become a gel which is easier to handle.

  The mixing ratio of the nonaqueous solvent, the electrolyte and the perfluoro group-containing compound can be selected according to the purpose, but the electrolyte is preferably 0.1 to 3 mol / liter, more preferably 0.5 to The perfluoro group-containing compound is a mass-based perfluoro group-containing compound: non-aqueous solvent, preferably 0.1: 99.9 to 20:80, more preferably 2 mol / liter of the mixed liquid. It is preferable to add 0.3: 99.7 to 10:90. By preparing the electrolytic solution with such a composition, all of battery characteristics, handleability and safety can be further improved.

In addition, it does not specifically limit as a manufacturing method of the electrolyte solution of this embodiment, The electrolyte solution of this embodiment can be manufactured by mixing the nonaqueous solvent mentioned above, electrolyte, and a perfluoro group containing compound suitably. it can. The mixing order of the non-aqueous solvent, the electrolyte, and the compound (1) is not particularly limited, and various orders can be selected. For example, a mother electrolyte in which a predetermined amount of electrolyte is dissolved in a nonaqueous solvent may be prepared, and then compound (1) may be introduced into the mother electrolyte. The liquid obtained by introducing the compound (1) is heated to 70 to 150 ° C. to make a uniform solution, and then cooled to room temperature, whereby the electrolytic solution of this embodiment can be prepared.
Alternatively, the non-aqueous solvent and the compound (1) are mixed, the temperature is raised to 70 to 150 ° C. to dissolve the compound (1), the temperature is lowered, and then the electrolyte is dissolved, whereby the electrolytic solution of the present embodiment is obtained. It may be prepared.
Furthermore, it is also possible to prepare the electrolytic solution of this embodiment by mixing all the compounds simultaneously.

  In addition, in the range which does not inhibit the desired effect of this embodiment, the electrolyte solution of this embodiment may contain gelling agents other than compound (1) in addition to compound (1) as a gelling agent. Good.

  The electrolytic solution of the present embodiment is preferably a gelled electrolyte, that is, a gel electrolyte, from the viewpoint of achieving both battery characteristics and safety. Here, the gel electrolyte is different from the “electrolyte” of the present embodiment described above, and indicates a gel electrolyte of an originally liquid electrolyte solution by the action of the perfluoro group-containing compound in the present embodiment. The distinction as to whether or not it is a gel electrolyte can be determined, for example, by performing “evaluation of gelling ability of electrolytic solution” described in Examples below.

<Positive electrode>
A positive electrode will not be specifically limited if it acts as a positive electrode of a lithium ion secondary battery, A well-known thing may be used. The positive electrode preferably contains one or more materials selected from the group consisting of materials capable of inserting and extracting lithium ions as the positive electrode active material. Examples of such materials include, but are not limited to, composite oxides represented by the following general formulas (6a) and (6b), metal chalcogenides having a tunnel structure and a layered structure, and metal oxides. .
Li _x MO ₂ (6a)
Li _y M ₂ O ₄ (6b)
Here, in the formula, M represents one or more metals selected from transition metals, x represents a number from 0 to 1, and y represents a number from 0 to 2.

More specifically, although not limited to the following, for example, lithium cobalt oxide typified by LiCoO ₂ ; lithium manganese oxide typified by LiMnO ₂ , LiMn ₂ O ₄ , Li ₂ Mn ₂ O ₄ ; LiNiO ₂ Li _z MO ₂ (M represents two or more elements selected from the group consisting of Ni, Mn, Co, Al, and Mg, and z is more than 0.9 and less than 1.2. And a lithium-containing composite metal oxide represented by LiFePO ₄ and an iron phosphate olivine represented by LiFePO ₄ . The positive electrode active material is not limited to the following, but, for example, S, MnO ₂ , FeO ₂ , FeS ₂ , V ₂ O ₅ , V ₆ O ₁₃ , TiO ₂ , TiS ₂ , MoS ₂ and NbSe ₂ are representative. Examples thereof include oxides of metals other than lithium. Furthermore, conductive polymers represented by polyaniline, polythiophene, polyacetylene, and polypyrrole are also exemplified as the positive electrode active material.

In addition, it is preferable that the positive electrode active material contains a lithium-containing compound because a higher voltage and a higher energy density tend to be obtained. Such a lithium-containing compound is not limited to the following as long as it contains lithium, and is, for example, a composite oxide containing lithium and a transition metal element; a phosphate compound containing lithium and a transition metal element And a metal silicate compound containing lithium and a transition metal element (for example, Li _t M _u SiO ₄ , M is as defined in the above formula (6a), t is a number from 0 to 1, u is a number from 0 to 2. Are shown). From the viewpoint of obtaining a higher voltage, lithium, cobalt (Co), nickel (Ni), manganese (Mn), iron (Fe), copper (Cu), zinc (Zn), chromium (Cr), vanadium ( V) and composite oxides containing at least one transition metal element selected from the group consisting of titanium (Ti) and phosphate compounds are preferred.

More specifically, the lithium-containing compound is preferably a metal oxide having lithium, a metal chalcogenide having lithium, and a metal phosphate compound having lithium. For example, the lithium-containing compounds are represented by the following general formulas (7a) and (7b), respectively. The compound which is made is mentioned.
^{_{Li v M I O 2 (7a}} )
Li _w M ^II PO ₄ (7b)
Here, in the formula, M ^I and M ^II each represent one or more transition metal elements, and the values of v and w vary depending on the charge / discharge state of the battery, but usually v is 0.05 to 1.10, w Indicates a number from 0.05 to 1.10.

  The compound represented by the general formula (7a) generally has a layered structure, and the compound represented by the general formula (7b) generally has an olivine structure. In these compounds, for the purpose of stabilizing the structure, a part of the transition metal element is substituted with Al, Mg, other transition metal elements or included in the crystal grain boundary, a part of the oxygen atom And those substituted with a fluorine atom or the like. Furthermore, what coat | covered the other positive electrode active material to at least one part of the positive electrode active material surface is mentioned.

  A positive electrode active material is used individually by 1 type or in combination of 2 or more types.

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

Although a positive electrode is not limited to the following, for example, it is obtained as follows. That is, first, a positive electrode mixture-containing paste is prepared by dispersing, in a solvent, a positive electrode mixture obtained by adding a conductive additive, a binder, or the like to the positive electrode active material as necessary. Next, this positive electrode mixture-containing paste is applied to a positive electrode current collector and dried to form a positive electrode mixture layer, which is pressurized as necessary to adjust the thickness, thereby producing a positive electrode.
Here, the solid content concentration in the positive electrode mixture-containing paste is preferably 30 to 80% by mass, and more preferably 40 to 70% by mass.
The positive electrode current collector is not limited to the following, but is constituted by, for example, a metal foil such as an aluminum foil or a stainless steel foil.

<Negative electrode>
A negative electrode will not be specifically limited if it acts as a negative electrode of a lithium ion secondary battery, A well-known thing may be used. The negative electrode preferably contains at least one material selected from the group consisting of a material capable of inserting and extracting lithium ions as a negative electrode active material and metallic lithium. In addition to metallic lithium, such materials include, but are not limited to, for example, amorphous carbon (hard carbon), artificial graphite, natural graphite, graphite, pyrolytic carbon, coke, glassy carbon, organic polymer compounds Examples thereof include carbon materials typified by fired bodies, mesocarbon microbeads, carbon fibers, activated carbon, graphite, carbon colloid, carbon black and the like. Among these, the coke is not limited to the following, and examples thereof include pitch coke, needle coke, and petroleum coke. Further, the fired body of the organic polymer compound is obtained by firing and polymerizing a polymer material such as a phenol resin or a furan resin at an appropriate temperature. In the present embodiment, a battery employing metallic lithium as the negative electrode active material is also included in the lithium ion secondary battery.

  Further, examples of the material capable of inserting and extracting lithium ions include a material containing an element capable of forming an alloy with lithium. This material may be a single metal or semi-metal, an alloy or a compound, and may have at least a part of one or more of these phases. .

  In the present specification, the “alloy” includes an alloy having one or more metal elements and one or more metalloid elements in addition to an alloy composed of two or more metal elements. In addition, the alloy may have a nonmetallic element as long as the alloy has metallic properties as a whole. In the alloy structure, a solid solution, a eutectic (eutectic mixture), an intermetallic compound, or two or more of these coexist.

  Examples of such metal elements and metalloid elements include, but are not limited to, titanium (Ti), tin (Sn), lead (Pb), aluminum, indium (In), silicon (Si), and zinc (Zn). ), Antimony (Sb), bismuth (Bi), gallium (Ga), germanium (Ge), arsenic (As), silver (Ag), hafnium (Hf), zirconium (Zr), and yttrium (Y).

  Among these, metal elements and metalloid elements of Group 4 or 14 in the long-period periodic table are preferable, and titanium, silicon, and tin are particularly preferable.

  Examples of tin alloys include, but are not limited to, for example, silicon, magnesium, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, Examples thereof include those having one or more elements selected from the group consisting of antimony and chromium.

  Examples of the alloy of silicon include, but are not limited to, for example, tin, magnesium, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, Examples thereof include those having one or more elements selected from the group consisting of antimony and chromium.

  The titanium compound, tin compound, and silicon compound are not limited to the following, but include, for example, those having oxygen (O) or carbon (C). In addition to titanium, tin, or silicon, the second compound described above is used. It may have a constituent element.

  The negative electrode active material in the present embodiment is one or more selected from the group consisting of lithium metal, carbon material, a material containing an element capable of forming an alloy with lithium, and a lithium-containing compound from the viewpoint of battery capacity and handleability. It is preferable to contain these materials. Of these, the lithium-containing compound may be the same as that described for the positive electrode.

  A negative electrode active material is used individually by 1 type or in combination of 2 or more types.

  The number average particle diameter (primary particle diameter) of the negative electrode active material is preferably 0.1 μm to 100 μm, more preferably 1 μm to 10 μm. The number average particle size of the negative electrode active material is measured in the same manner as the number average particle size of the positive electrode active material.

Although a negative electrode is not limited to the following, for example, it is obtained as follows. That is, first, a negative electrode mixture-containing paste is prepared by dispersing, in a solvent, a negative electrode mixture prepared by adding a conductive additive or a binder to the negative electrode active material, if necessary. Next, the negative electrode mixture-containing paste is applied to a negative electrode current collector and dried to form a negative electrode mixture layer, which is pressurized as necessary to adjust the thickness, thereby producing a negative electrode.
Here, the solid content concentration in the negative electrode mixture-containing paste is preferably 30 to 80% by mass, and more preferably 40 to 70% by mass.
Although a negative electrode electrical power collector is not limited to the following, For example, metal foils, such as copper foil, nickel foil, aluminum foil, or stainless steel foil, etc. are comprised.

  In the production of the positive electrode and the negative electrode, the conductive aid used as necessary is not limited to the following, and examples thereof include carbon black typified by graphite, acetylene black, and ketjen black, carbon fiber, and the like. The number average particle size (primary particle size) of the conductive assistant is preferably 0.1 μm to 100 μm, more preferably 1 μm to 10 μm, and is measured in the same manner as the number average particle size of the positive electrode active material. Examples of the binder include, but are not limited to, PVDF, PTFE, polyacrylic acid, styrene butadiene rubber, and fluorine rubber.

<Separator>
In the lithium ion secondary battery of this embodiment, it is preferable to provide a separator between the positive electrode and the negative electrode from the viewpoint of providing safety such as prevention of short circuit between the positive and negative electrodes and shutdown. The separator is preferably an insulating thin film having high ion permeability and excellent mechanical strength.

  Although the material of the separator used for this embodiment is not limited to the following, For example, a ceramic, glass, resin, and a cellulose are mentioned. The resin may be a synthetic resin or a natural resin (natural polymer), and may be an organic resin or an inorganic resin. This is preferable because it tends to be excellent. The organic resin is not limited to the following, but from the viewpoint of further ensuring the shutdown performance at the time of abnormality, further facilitating film formation, and further improving the degree of freedom in molecular design (affinity with other members). Examples thereof include heat-resistant resins such as polyolefin, polyester, polyamide, liquid crystal polyester, and aramid. From the viewpoint of high heat resistance, ceramic and glass are preferable, and from the viewpoint of handleability and heat resistance, polyester, polyamide, liquid crystal polyester, aramid, and cellulose are preferable. Further, from the viewpoint of cost and processability, polyolefin is preferable. Among these materials, when a resin is employed, a resin that is a homopolymer may be used, a copolymer resin may be used, or a mixture of a plurality of types of resins and an alloy may be used.

  Further, the separator may be a laminated body in which films made of a plurality of materials are laminated. When the separator is a laminate, the material of each layer may be the same or different. In the case of manufacturing a separator of a laminated body, it may be formed by sequentially forming a layer on another layer, that is, by sequentially multilayering, and a plurality of films prepared separately are bonded together. Thus, a laminate may be produced, or each layer may be formed simultaneously and laminated in-line.

  Although the form of the separator used in this embodiment is not limited to the following, for example, a synthetic resin microporous film manufactured by forming a synthetic resin film, a fiber obtained by spinning a synthetic resin or a natural resin, a glass fiber, or a ceramic fiber Examples thereof include processed woven fabrics, non-woven fabrics, knitted fabrics, papermaking, and films prepared by arranging fine particles of synthetic resin and glass.

  The separator according to the present embodiment is made of a component other than the above, for example, an organic filler, an inorganic filler, an organic particle, or an inorganic particle on the surface and / or inside of the separator from the viewpoints of film reinforcement, charge / discharge assist, heat resistance improvement, and the like. May be included.

<Production method of battery>
The lithium ion secondary battery of this embodiment is produced by a known method using the above-described electrolyte solution, positive electrode, negative electrode, and optionally a separator. For example, a plurality of positive electrodes in which a positive electrode and a negative electrode are wound in a laminated state with a separator interposed therebetween to be formed into a laminate having a wound structure, or they are alternately laminated by bending or laminating a plurality of layers. Or a laminate in which a separator is interposed between the electrode and the negative electrode. Next, the laminated body is accommodated in a battery case (exterior), the electrolytic solution according to the present embodiment is injected into the case, and the laminated body is immersed in the electrolytic solution and sealed. The lithium ion secondary battery can be manufactured. Alternatively, an electrolyte membrane containing a gelled electrolyte solution is prepared in advance, and a positive electrode, a negative electrode, an electrolyte membrane, and optionally a separator are formed by bending or stacking as described above, and then placed in the battery case. A lithium ion secondary battery can also be produced by housing. The shape of the lithium ion secondary battery of the present embodiment is not particularly limited, and for example, a cylindrical shape, an elliptical shape, a rectangular tube shape, a button shape, a coin shape, a flat shape, a laminate shape, and the like are suitably employed.

  The electrolytic solution (electrolytic solution for electrochemical device) and the lithium ion secondary battery of the present embodiment have high safety (for example, flame retardancy and liquid retention) and high battery characteristics (for example, long-term durability and high rate). The lithium ion secondary battery has high battery characteristics (for example, charge / discharge characteristics, low temperature operability, high temperature durability, etc.) and high safety (suppression of lithium dendrite). Is also realized. For example, even when the electrolyte solution of the present embodiment includes four or more kinds of the nonaqueous solvent and the electrolyte, the low molecular weight perfluoro group-containing compound added in the present embodiment is a property of the nonaqueous solvent and the electrolyte. It is difficult to damage. Therefore, the electrolytic solution and the lithium ion secondary battery of the present embodiment can exhibit high safety without deteriorating high battery characteristics derived from the nonaqueous solvent and the electrolyte. Further, since the electrolyte solution of the present embodiment contains a low-molecular weight perfluoro group-containing compound, it is possible to prevent leakage of the electrolyte solution to the outside of the battery, as well as the lithium ion secondary battery of the present embodiment. In addition, the risk of inconvenience and combustion due to lithium dendrite can be further reduced.

  As mentioned above, although the form for implementing this invention was demonstrated, this invention is not limited to the said embodiment. The present invention can be variously modified without departing from the gist thereof. For example, the electrolytic solution of the present embodiment can be applied not only to a lithium ion secondary battery but also to other electrochemical devices, for example, various innovative secondary batteries using lithium, and an electrolytic solution of a lithium ion capacitor.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. Various characteristics and safety of the electrolytic solution and the lithium ion secondary battery were measured and evaluated as follows.

(I) Evaluation of gelling ability of electrolyte solution By preparing an electrolyte solution in a glass sample bottle and leaving it at 25 ° C for 2 hours, the sample bottle is turned upside down, and the fluidity at that time is confirmed visually. The gelation ability was evaluated. The evaluation criteria are as follows.
○: It does not flow.
X: Flows.

(Ii) Evaluation of stability of gel property of electrolytic solution Whether the electrolytic solution prepared in “(i) Evaluation of gelling ability of electrolytic solution” is allowed to stand at 25 ° C. for 3 days to maintain the gel property It was confirmed visually. The evaluation criteria are as follows.
○: The gel property of the same level as that immediately after preparation is maintained.
(Triangle | delta): It is the gel which a part liquid exuded.
X: The gel property is lost and the liquid is uniform. Alternatively, the liquid and the solid are separated.

(Iii) Electrical conductivity measurement of electrolyte solution An electrolyte solution was prepared in a glass sample bottle and connected to an electrical conductivity meter “CM-30R” (trade name) manufactured by Toa DK Corporation. The cell for electrical conductivity measurement “CT-57101B” (trade name) was inserted into a sample bottle containing an electrolytic solution and heated to 75 ° C. Thereafter, the temperature of the sample bottle was lowered to 30 ° C. while the electric conductivity measurement cell was inserted, and the electric conductivity of the electrolytic solution at 30 ° C. was measured.

(Iv) Discharge capacity measurement The discharge capacity at a specific discharge current was measured to evaluate the discharge characteristics of the lithium ion secondary battery. As a lithium ion secondary battery for measurement, a small battery with 1C = 6 mA was prepared and used. For the measurement, a charge / discharge device ACD-01 (trade name) manufactured by Asuka Electronics Co., Ltd. and a thermostat PLM-63S (trade name) manufactured by Futaba Kagaku Co., Ltd. were used. After charging at a constant current of 6 mA and reaching 4.2 V, charging was performed at a constant voltage of 4.2 V for a total of 3 hours. Then, the discharge capacity when discharging to 3.0 V with a constant current was measured. The discharge capacity was measured by setting the discharge current to 6 mA and 18 mA. The battery ambient temperature at this time was set to 25 ° C.

(V) Safety test (combustion test)
An electrolyte component combustion test was performed to evaluate battery safety. First, 1 mL of an electrolytic solution heated to 110 ° C. was absorbed onto a 13 mm × 125 mm × 2 mm glass filter paper, and then the glass filter paper was cooled to 25 ° C. to prepare a sample. Set the sample at the specified position of “mcm-2” (trade name), a multi-calorie meter manufactured by Toyo Seiki Co., Ltd., and perform a horizontal combustion test of UL94HB. Time required for ignition (ignition time) The time required for the flame to propagate from the ignition to the edge of the filter paper (elapsed time) and the time from ignition to extinguishing (burning time) were measured.

Example 1
(1) Preparation of electrolyte solution Ethylene carbonate and methyl ethyl carbonate are mixed at a mass ratio of 1: 2, and the mixture is gelled by adding LiPF ₆ to 1 mol / L. No electrolyte solution (A) was prepared. A compound represented by the following formula (3), which is a gelling agent, is added to the electrolyte solution (A) so as to be 1% by mass with respect to the total amount of the electrolyte solution, and heated to 95 ° C. After uniformly mixing, the temperature was lowered to 25 ° C. to obtain an electrolytic solution (a). The electrolyte solution (a) was a gel electrolyte that was sufficiently gelled.

(Example 2)
LiClO ₄ was added to γ-butyrolactone so as to be 1 mol / L to prepare an electrolyte solution (B) that was not gelled. The compound represented by the above formula (3), which is a gelling agent, is added to the electrolytic solution (B) so as to be 4% by mass with respect to the total amount of the electrolytic solution, and heated to 95 ° C. to be uniform. Then, the temperature was lowered to 25 ° C. to obtain an electrolytic solution (b).

Example 3
Ethylene carbonate, propylene carbonate, and γ-butyrolactone were mixed at a mass ratio of 1: 1: 2, and LiBF ₄ was added to the mixture so as to be 1.5 mol / L and gelled. An electrolytic solution (C) not formed was prepared. A compound represented by the above formula (3) is added to the electrolyte solution (C) as a gelling agent so as to be 7% by mass with respect to the total amount of the electrolyte solution, and heated to 105 ° C. uniformly. After mixing, the temperature was lowered to 25 ° C. to obtain an electrolytic solution (c).

(Comparative Example 1)
An electrolytic solution (f) was obtained in the same manner as in the preparation of the electrolytic solution (a) in Example 1 except that the gelling agent was not added.

(Comparative Example 2)
An electrolytic solution (g) was obtained in the same manner as in the preparation of the electrolytic solution (b) in Example 2 except that the gelling agent was not added.

(Comparative Example 3)
An electrolytic solution (h) was obtained in the same manner as in the preparation of the electrolytic solution (c) in Example 3 except that no gelling agent was added.

(Comparative Example 4)
10% by mass of a polyurethane composed of a diol compound having a molecular weight of 1000 and an OH value of 110 mgKOH / g and an isocyanate is added to the electrolytic solution (C), and the polyurethane solution is made to absorb the electrolytic solution (C). i) (hereinafter referred to as electrolyte solution (i)) was obtained. The resulting polyurethane gel electrolyte (i) had a thickness of 30 μm.

(Comparative Example 5)
Ethylene carbonate and methyl ethyl carbonate were mixed at a mass ratio of 1: 2, thereby preparing a non-gelled mixed solvent (D). The compound represented by the above formula (3) is added to the mixed solvent (D) as a gelling agent so as to be 10% by mass with respect to the total amount of the electrolytic solution, and heated to 105 ° C. uniformly. After mixing, the temperature was lowered to 25 ° C. to obtain an electrolytic solution (j). The electrolyte solution (j) was a gel electrolyte that was sufficiently gelled.

Example 4
(2) Production of positive electrode Lithium cobalt acid (LiCoO ₂ ) having a number average particle diameter of 5 μm as a positive electrode active material, graphite carbon powder having a number average particle diameter of 3 μm as a conductive additive, and polyvinylidene fluoride (PVdF) as a binder. Mixed at a mass ratio of 85: 10: 5. N-methyl-2-pyrrolidone was added to the obtained mixture so as to have a solid content of 60% by mass and further mixed to prepare a slurry solution. This slurry-like solution was applied to one side of an aluminum foil having a thickness of 20 μm, and the solvent was dried and removed, followed by rolling with a roll press. The rolled product was punched into a disk shape having a diameter of 16 mm to obtain a positive electrode.

(3) Production of negative electrode Mesocarbon microbeads having a number average particle diameter of 5 μm as a negative electrode active material and diene rubber as a binder (glass transition temperature: −5 ° C., number average particle diameter upon drying: 120 nm, dispersion medium: water And a solid content concentration of 40 mass%) were mixed so that the solid content concentration of the negative electrode active material was 60 mass% while adjusting the viscosity with carboxymethylcellulose to prepare a slurry-like solution. The slurry solution was applied to one side of a 10 μm thick copper foil, and the solvent was removed by drying, followed by rolling with a roll press. The rolled product was punched into a disk shape having a diameter of 16 mm to obtain a negative electrode.

(4) Battery assembly A laminate in which the positive electrode and the negative electrode produced as described above are superposed on both sides of a separator made of polyethylene (film thickness: 25 μm, porosity: 50%, pore diameter: 0.1 μm to 1 μm) It was inserted into a disk type battery case. Next, 0.5 mL of the electrolyte solution (a) heated to 110 ° C. was injected into the battery case, and the laminate was immersed in the electrolyte solution (a). Then, the battery case was sealed and a lithium ion secondary battery (small size) Battery). The lithium ion secondary battery was held at 110 ° C. for 1 hour and then cooled to 25 ° C. to obtain a battery (a).

(Comparative Example 6)
A battery (f) was obtained in the same manner as in Example 4 except that the electrolytic solution (f) was used instead of the electrolytic solution (a).

(Comparative Example 7)
A laminate in which a positive electrode and a negative electrode produced in the same manner as in Example 4 were superimposed on both sides of the electrolyte solution (i) was inserted into a SUS disk type battery case. Next, without immersing the laminate in the electrolyte, the battery case was sealed to produce a lithium ion secondary battery. This lithium ion secondary battery was held at 70 ° C. for 1 hour, and then cooled to 25 ° C. to obtain battery (i).

  The compound represented by the above formula (3) was synthesized as follows.

(Synthesis of Compound (3a))
First, the compound (3a) which is a phenol derivative was obtained with the following scheme.

Specifically, first, in a 250 mL round bottom flask, 20.4 g (42.19 mmol) of 2- (perfluorohexyl) ethyl iodide and 5.32 g (42.19 mmol) of 4-mercaptophenol were added to 50 mL of acetone. Then, 5.83 g (42.19 mmol) of potassium carbonate was added and refluxed. After confirming disappearance of the raw materials by high performance liquid chromatography, cyclopentyl methyl ether, water, and 1N hydrochloric acid were added thereto. The aqueous phase was removed, and the remaining organic phase was washed with water and saturated brine. The washed organic phase was dried using anhydrous magnesium sulfate, magnesium sulfate was removed using fold filtration, and the resulting solution was concentrated under reduced pressure. The residue obtained by concentration was purified by column chromatography (filler: silica gel, developing solvent: chloroform) to obtain 19.13 g (40.51 mmol) of a colorless solid compound (3a). The melting point of the obtained compound (3a) was 68 to 70 ° C., and the yield was 96%. Moreover, the compound (3a) was identified with the nuclear magnetic resonance apparatus (The JEOL Co., Ltd. make, brand name "JMN-LA500". The following is same). The results are shown below.
IR (KBr): ν = 3381, 1580, 1228-1276 cm ^-1
1 H NMR (500 MHz, CDCl ₃ ): δ = 2.25-2.35 (2H, m), 3.00 (2H, m), 5.00 (1H, s), 6.82 (2H, d, J = 9.2 Hz), 7.38 (2H , d, J = 9.2 Hz) ppm

Next, a compound (3) was obtained by the following scheme.

Specifically, first, 8 mL of thionyl chloride was added to 1.83 g (6.77 mmol) of 4′-butoxy-4-biphenylcarboxylic acid in a 100 mL eggplant flask, and a calcium chloride tube was attached for 1 hour at 60 ° C. , Heated and stirred. Thereafter, excess thionyl chloride was removed under reduced pressure to obtain a colorless solid. Thereto was added 10 mL of anhydrous toluene. On the other hand, compound (3a) (3.20 g, 6.77 mmol) was dissolved in 10 mL of anhydrous pyridine, and this was added dropwise to the 100 mL eggplant flask and heated and stirred at 70 ° C. for 3 hours. The solvent was removed under reduced pressure, and the resulting residue was purified by column chromatography (filler: silica gel, developing solvent: chloroform) to obtain 3.80 g (5.40 mmol) of a colorless solid compound (3). It was. The yield of the obtained compound (3) was 77%. Further, the compound (3) was identified by an infrared spectrophotometer (manufactured by Shimadzu Corporation, trade name “IR Prestige-21”, the same applies hereinafter) and a nuclear magnetic resonance apparatus. The results are shown below.
IR (KBr): ν = 1728.2, 1186.22, 1143.8 cm ^-1
1 H NMR (500 MHz, CDCl ₃ ): δ = 0.99 (3 H, t, J = 7.3 Hz), 1.53 (2H, m), 1.81 (2H, m), 2.42 (2H, m), 3.13 (2H, m), 4.03 (2H, t, J = 6.7 Hz), 7.01 (2H, d, J = 8.5 Hz), 7.23 (2H, d, J = 8.5 Hz), 7.45 (2H, d, J = 8.5 Hz) , 7.60 (2H, d, J = 8.5 Hz), 7.70 (2H, d, J = 8.5 Hz), 8.22 (2H, d, J = 8.5 Hz) ppm

  With respect to the electrolytic solutions (a) to (c) and (f) to (j) of Examples 1 to 3 and Comparative Examples 1 to 5, gelation ability, gel stability, and electrical conductivity were evaluated or measured. . The results are shown in Table 1. Moreover, about the battery (a), (f), and (i) of Example 4 and Comparative Examples 6 and 7, the discharge capacity was measured and the cycle characteristics were evaluated. The results are shown in Table 2. Furthermore, a safety test was performed on the electrolytic solutions (a), (f), and (i) of Example 1 and Comparative Examples 1 and 4. The results are shown in Table 3.

  The electrolytic solution of the present invention can also be applied to lithium ion secondary batteries, various innovative secondary batteries using lithium, and lithium ion capacitors. Therefore, the present invention has industrial applicability in these fields.

Claims (10)

An electrolytic solution for an electrochemical device comprising a nonaqueous solvent, an electrolyte, and a compound represented by the following general formula (1).
Rf-X-Ar-OCO-Ar'-OR (1)
(In the formula (1), Rf represents a functional group having a substituted or unsubstituted perfluoroalkyl group having 2 to 18 carbon atoms in the main chain, and R represents a substituted or unsubstituted carbon group having 1 to 8 carbon atoms in the main chain. X represents a sulfur atom, oxygen atom, SO group or SO ₂ group, and Ar and Ar ′ are each independently substituted or unsubstituted having 5 to 20 ring atoms. An aromatic group or an alicyclic group.) The electrolytic solution according to claim 1, wherein Rf is a group represented by the following general formula (2).
Rf'-R'- (2)
(In Formula (2), Rf ′ represents a substituted or unsubstituted perfluoroalkyl group having 2 to 14 carbon atoms in the main chain, and R ′ is a single bond or a substituted or unsubstituted carbon atom having 1 to 8 carbon atoms in the main chain. Of the divalent hydrocarbon group.)   3. The electrolytic solution according to claim 1, wherein Ar and Ar ′ are each independently a substituted or unsubstituted phenylene group, biphenylene group, terphenylene group, naphthylene group, anthranylene group, or pyridylene group.   3. The electrolytic solution according to claim 1, wherein Ar and Ar ′ are each independently any one of a substituted or unsubstituted phenylene group, a biphenylene group, or a naphthylene group. 5. The electrolytic solution according to claim 1, wherein X is a sulfur atom, an SO group, or an SO ₂ group. The Ar and Ar ′ are each independently a substituted or unsubstituted phenylene group or biphenylene group, and the X is an S atom or an SO ₂ group. Electrolyte.   The electrolyte solution according to claim 1, wherein the electrolyte solution is a gelled gel electrolyte. A positive electrode containing a positive electrode active material;
A negative electrode containing a negative electrode active material;
The electrolyte solution according to any one of claims 1 to 7,
A lithium ion secondary battery comprising:   The lithium ion secondary battery according to claim 8, wherein the positive electrode active material includes a lithium-containing compound.   The negative electrode active material contains at least one material selected from the group consisting of metallic lithium, a carbon material, a material containing an element capable of forming an alloy with lithium, and a lithium-containing compound. The lithium ion secondary battery as described.