JPH11162508A - Manufacture of electrolyte and manufacture of secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrolyte with high yield that has a long cycle life and contains small impurities by reacting an organic silane compound containing silicon and carbon with a fluorine compound in a solvent containing a nonaqueous solvent as a main constituent. SOLUTION: An electrolyte formed from a salt of an organic fluorine and silicon compound containing silicon, fluorine and carbon elements is produced by reacting an organic silane compound containing at least silicon and carbon elements in a solvent containing a nonaqueous solvent as a main constituent. This electrolyte is placed in the battery housing of a secondary battery. Because the electrolyte hardly absorbs water content by itself, when it is used for a secondary battery, in particular a secondary battery utilizing an intercalation and a deintercalation reaction of lithium ions for charging and discharging, the water content in the electrolyte can easily be controlled with low density. Consequently, the reaction between a metal such as lithium or the like deposited by charge reaction and the water content is suppressed, so that the cycle life of the nonaqueous secondary battery can be prolonged.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a secondary battery, in particular, a secondary battery utilizing intercalation and deintercalation reactions of lithium ions for charging and discharging. The present invention relates to a method for producing an electrolyte which provides a secondary battery having a long cycle life.

[0002]

2. Description of the Related Art Recently, since the amount of CO2 gas contained in the atmosphere is increasing, it is predicted that global warming will occur due to the greenhouse effect. For this reason, it has become difficult to construct a new thermal power plant that emits a large amount of CO2 gas. Therefore, as an effective use of the power generated by generators such as thermal power plants, nighttime power is stored in secondary batteries installed in ordinary households, and this is used during the daytime when power consumption is high, and the load is leveled. The so-called road leveling has been proposed. In addition, development of a secondary battery having a high energy density is expected as a secondary battery essential for electric vehicles that does not emit air pollutants. Furthermore, for the power supply of portable devices such as book-type personal computers, word processors, video cameras, and mobile phones, there is an urgent need to develop small, lightweight, and high-performance secondary batteries.

[0003] Such a small, lightweight and high-performance secondary battery uses a lithium intercalation compound which deintercalates lithium ions from the interlayer in a reaction during charging as a positive electrode material and uses metallic lithium as a negative electrode. A rocking chair-type so-called "lithium ion", which uses a secondary battery used for lithium-ion and a carbon material typified by graphite, which can intercalate lithium ions between six-membered ring network plane layers formed of carbon atoms, as a negative electrode material The development of a "battery" is being promoted. (In the specification of the present application, a secondary battery using lithium ion intercalation and deintercalation reactions by charge and discharge will be referred to as a "lithium ion battery" using a carbon material as a negative electrode. And lithium secondary batteries).

However, a high-capacity lithium secondary battery using metallic lithium for the negative electrode has a very short charge-discharge cycle life and has not reached a practical level. According to the study of the present inventors, the main cause of the extremely short charge / discharge cycle life of a lithium secondary battery using metallic lithium as a negative electrode is that metallic lithium reacts with impurities such as moisture in an electrolyte or an organic solvent. An insulating film is formed, and as a result, lithium metal grows in a dendrite (dendritic) shape by repeated charge and discharge, causing an internal short circuit between the negative electrode and the positive electrode, or the dissociated electrolyte becomes a polymerization initiator. It is presumed that the organic solvent in the electrolytic solution is polymerized, the impedance inside the battery is increased, and the repetition of charge and discharge promotes the decomposition of the electrolytic solution, leading to a long life.

Further, when the above-mentioned lithium dendrite grows and the negative electrode and the positive electrode are short-circuited, the energy of the battery is consumed in a short time due to the short-circuit, so that heat is generated or the solvent of the electrolytic solution is consumed. Decomposition and generation of gas may increase the internal pressure or damage the battery.

On the other hand, in the above-mentioned "lithium ion battery", a negative electrode composed of a carbon material having a graphite structure can theoretically intercalate only a maximum of 1/6 lithium atoms per carbon atom. A secondary battery with a high energy density comparable to a lithium primary battery when used as a material has not been realized. If an attempt is made to intercalate more than the theoretical amount of lithium into the carbon material negative electrode of a "lithium ion battery" during charging, lithium metal precipitates on the carbon material negative electrode surface, and the above-mentioned lithium metal is used for the negative electrode. As in the case of batteries, metallic lithium reacts with impurities such as water in the electrolyte and organic solvents to form an insulating film, which grows in dendrites (dendrites) by repeated charge / discharge cycles, and between the negative and positive electrodes. Causes an internal short circuit and extends the life. Thus, it exceeds the theoretical capacity of graphite anodes. "
Lithium-ion batteries do not have sufficient cycle life for practical use.

[0007] Therefore, in lithium secondary batteries, it is strongly desired to increase the energy density and extend the cycle life.

To achieve this, Japanese Patent Application Laid-Open No. 9-823 discloses
No. 59 discloses that in a lithium secondary battery, an electrolyte made of a salt of an organic fluorine silicon compound is used to reduce performance deterioration due to repeated charge / discharge and prolong cycle life.

[0009]

SUMMARY OF THE INVENTION The present invention relates to a high-performance electrolyte for providing a secondary battery having a long cycle life, in particular, a secondary battery utilizing a lithium ion intercalation reaction and a deintercalation reaction for charging and discharging. It is an object of the present invention to produce a high-performance electrolyte useful for improving performance due to repetition of charge and discharge and improving cycle life in a battery with few impurities and high yield.

[0010]

According to the present invention, there is provided a method comprising reacting an organic silane compound containing at least a silicon element and a carbon element with a fluorine compound in a solvent containing a non-aqueous solvent as a main component. An object of the present invention is to provide a method for producing an electrolyte comprising a salt of an organic fluorine silicon compound containing an element and a carbon element.

Further, the present invention relates to a method of manufacturing a secondary battery in which at least a positive electrode, a negative electrode, and a separator are housed in a battery housing, wherein a lithium ion intercalation reaction and a deintercalation reaction are used for charging and discharging. hand,
An organic fluorinated silicon compound containing a silicon element, a fluorine element, and a carbon element by a method having a step of reacting an organic silane compound containing at least a silicon element and a carbon element with a fluorine compound in a solvent containing the above non-aqueous solvent as a main component It is intended to provide a method for producing a secondary battery in which an electrolyte comprising a salt of the above is obtained and the electrolyte is disposed in a battery housing.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION In the method for producing an electrolyte of the present invention,
By reacting an organic silane compound and a fluorine compound in a solvent containing a non-aqueous solvent as a main component, it has become possible to produce an electrolyte with a small amount of impurities and a high yield. This is because a non-aqueous solvent as a main component contains a small amount of anions such as hydroxyl ions. It is considered that the rate of competition reaction of the elements decreases, and the substitution reaction of elemental fluorine proceeds preferentially, so that generation of impurities can be reduced. In addition, since a solvent containing a non-aqueous solvent as a main component has a small amount of ions originally present in the solvent, interaction between fluorine ions and other ions hardly occurs, and the above-described substitution reaction is caused by an increase in free fluorine ions. Is considered to occur efficiently, and the yield increases. Further, when an aprotic solvent is used as a solvent mainly containing a non-aqueous solvent, anions in the solvent can be almost eliminated, so that impurities can be further reduced. Also, if it is a non-aqueous solvent that dissolves the organosilane compound and the fluorine compound,
Since the concentration of the monomolecular organic silane compound and the fluorine ion is further increased, the substitution reaction is more efficiently performed and the yield can be increased.

Also, when a compound which already has a fluorine element as a substituent of a silicon element is used as the organic silane compound, the non-aqueous solvent contains a small amount of other anions similarly to the above, so that fluorine ion is eliminated. It is considered that the generation of impurities hardly occurs and the generation of impurities is suppressed.

The thus obtained electrolyte composed of a salt of an organic fluorine silicon compound containing at least a silicon element, a fluorine element, and a carbon element is difficult to adsorb moisture on the electrolyte itself. When used as an electrolyte of a secondary battery that uses intercalation and deintercalation reactions for charging and discharging, it is easier to control the water content in the electrolyte to a low concentration. As a result, the reaction between the metal such as lithium precipitated by the charging reaction and moisture can be suppressed, so that the cycle life of the nonaqueous secondary battery can be extended. Further, since the above-mentioned electrolyte has a low catalytic activity as a polymerization reaction initiator and suppresses the polymerization of the solvent in the electrolyte, the charge / discharge cycle life of a non-aqueous secondary battery using this electrolyte can be extended.

In the production method of the present invention, in the step of reacting an organic silane compound containing at least a silicon element and a carbon element with a fluorine compound in a solvent containing a non-aqueous solvent as a main component, for example, the following formula (1) or It is considered that the reaction process (2) proceeds.

[0016]

In the above formula, R _n SiX _4-n and R _n SiF _4-n are organic silane compounds, wherein R is an alkyl group, an aryl group, an alkenyl group, an alkynyl group or the like, and X is a halogen halogen group. , A hydroxyl group, an alkoxy group, an acyloxy group, an arenoxy group, an amino group, hydrogen, and the like (when there are a plurality of R or X, each may have a different group in the above group). MF is a fluorine compound, and M is a metal (ion), an ammonium group, or the like. n is 1 to 3, and m is 1 or 2.

As for R _n SiF _4-n used in the formula (2), an organic silane compound and a fluorine compound are reacted in a solvent containing a non-aqueous solvent as a main component, and the reaction of the following formula (3) is carried out. Allow to proceed and prepare.

[0019]

As described above, according to the method of the present invention, in the step of reacting an organic silane compound and a fluorine compound in a solvent containing a non-aqueous solvent as a main component, for example, the above-mentioned reactions (1) to (3) are advanced, finally silicon element, the fluorine element, for example a lithium salt represented by the salts of organic fluorine silicon compound containing carbon element (formula Mm [R _n SiF _{4-n + m],} sodium salt, potassium salt, ammonium salt , Quaternary ammonium salts), and mixtures thereof. Such an element made of a salt of an organic fluorine silicon compound containing at least a silicon element, a fluorine element, and a carbon element, the electrolyte itself is unlikely to adsorb moisture as described above, and was thus used as an electrolyte of a lithium secondary battery. In this case, the reaction between the metal such as lithium precipitated by the charging reaction and moisture can be suppressed, so that the cycle life of the nonaqueous secondary battery can be extended.

The salt of an organofluorine silicon compound having an aryl group such as a phenyl group can be easily dissolved in an organic solvent, so that an electrolyte having a higher ionic conductivity can be obtained. In such a lithium secondary battery, the internal impedance can be reduced, a larger current can flow, and the charge / discharge cycle life becomes longer.

Next, an embodiment of the method for producing an electrolyte of the present invention will be described. In this embodiment, basically,
An organic silane compound and a fluorine compound are stirred and reacted in a solvent containing a non-aqueous solvent as a main component to synthesize a target organic fluorine silicon compound. FIG. 1 shows a specific example of a manufacturing process.
This will be described in detail with reference to FIG.

First, dry air, more preferably dry nitrogen or an inert gas, is charged into a closed vessel equipped with a reflux device and a stirring device, and a solvent containing a fluorine compound and a non-aqueous solvent as main components is filled in the container. And agitated (Step A), and the organic silane compound was added little by little (Step B). Then, stirring was continued (Step C). In a solvent containing a non-aqueous solvent as a main component, at least a silicon element and a carbon element were added. And the reaction of a fluorine compound with, for example, the above-described formulas (1) to (3). After the above reaction, the synthesized product is extracted, concentrated, and dried by a conventional method (Step D), and more preferably, a purification step (Step E) is further performed to obtain an electrolyte comprising a salt of an organic fluorine silicon compound.

At this time, it is preferable to keep the temperature constant by heating or cooling the reaction vessel, and it is preferable to control the temperature at 100 ° C. or less. When a compound having a high substitution reactivity such as a halogen group or an alkoxy group as a substituent of a silicon element is used as the organic silane compound, it is more preferable to cool to room temperature or lower in the first half of the reaction and raise the temperature in the second half of the reaction. Addition of organic silane compound (dropping)
When the organic silane compound is a solid or a gas, it is dissolved in a solvent containing a non-aqueous solvent used for the reaction as a main component when the organic silane compound is a liquid, and when the organic silane compound is a liquid, the solution is added dropwise little by little. (Step B ′).

When the organic silane compound and the fluorine compound are reacted in a solvent containing a non-aqueous solvent as a main component (particularly, Steps B to
C) The fluorine compound may be used in an amount corresponding to the synthesis of a salt of the organofluorine silicon compound with respect to the organosilane compound, but the use of an excess amount of the fluorine compound is preferable because the yield is good. The preferred amount is 100% to 300%, more preferably 100% to 200% by mole ratio to the organic silane compound. The amount of the solvent containing a non-aqueous solvent as a main component is not particularly limited. However, when an organic silane compound or a fluorine compound in which the substitution reaction proceeds rapidly, it is preferable to increase the amount of the solvent. Of the organic silane compound is 1 mol / k
g.

Further, when the reaction conditions are adjusted so that the number of fluorine elements as substituents of the silicon element of the salt of the synthesized organic fluorine silicon compound is 3 or less per silicon element, the concentration and the drying after the reaction are reduced. Thermal decomposition of the organofluorine silicon compound is suppressed, which is preferable in terms of yield and impurities.

After the reaction between the organosilane compound and the fluorine compound, a step of exchanging the cation of the obtained salt of the organofluorine silicon compound with another ionic species is carried out (step F). It is preferable because impurity salts having different ionization numbers of the organic fluorine silicon compound salt formed in the reaction stage of the compound can be reduced. In particular, in steps A to D (or E), an ammonium ion, (C4
An organic fluorine silicon compound salt having a quaternary ammonium ion such as H ₉ ) ₄ N ⁺ as a cation is obtained, and the cation is exchanged in step F with an alkali metal ion such as Li ⁺ , Na ⁺ , and K ⁺ . An organic fluorine silicon compound salt can be obtained after efficiently reducing impurity salts having different ionization numbers. Above all, the case of exchanging with Li ⁺ ions is more preferable because impurities can be reduced most.

The exchange reaction of ionic species in the step F proceeds according to the following reaction formula (4).

[0029] Here, M ′ = Li, Na, K and the like.

After the above-described ion exchange reaction, the synthesized product is extracted, concentrated and dried by a conventional method (Step G), and more preferably, a purification step (Step H) is further performed to obtain an ion-exchanged organofluorine silicon compound. An electrolyte consisting of a salt is obtained.

As the method of ion exchange, a conventional ion exchange means can be used, but a method of directly exchanging with a cation exchange resin or a membrane, exchanging hydrogen with a cation exchange resin or a membrane, and then exchanging with a desired cation. In the method of neutralizing and exchanging, and the method of cation exchanging by mixing ionic strength or precipitation with a salt containing the target ion in a solvent, reduction of impurity salts having different ionization numbers is performed more efficiently. This is preferable.

Next, each material used in the reaction between the organosilane compound and the fluorine compound in the above-described series of steps will be described in detail.

(Solvent Having Non-Aqueous Solvent as Main Component) The solvent used in the production method of the present invention is a non-aqueous solvent, that is, a solvent having a solvent other than water as a main component, and contains only a trace amount of water. Use things. The content of the non-aqueous solvent in the solvent is preferably 95% by weight or more, and the use of a solvent containing no water is more preferable because the generation of impurities is further reduced.

It is preferable to use a solvent capable of dissolving an organosilane compound containing a silicon element and a carbon element and a fluorine compound, since an electrolyte can be obtained in a higher yield.
As the solvent capable of dissolving the organic silane compound and the fluorine compound, a solvent having a large relative dielectric constant is preferable, and when the relative dielectric constant is 3 or more (when the solvent temperature is 20 ° C.), the organic silane compound and the fluorine compound can be dissolved. In particular, a compound containing a fluorine element having poor solubility in an organic solvent can generally be dissolved in a larger amount, so that the yield of an electrolyte as a synthetic product is increased, which is preferable. The relative dielectric constant is a value obtained by comparing the dielectric constant of an insulator such as a solvent with the dielectric constant 1 in a vacuum, and is represented by the following equation.

Ε = C / C ₀ (ε: relative permittivity, C:
Capacitance when insulator is put in capacitor, C0:
Capacitance when vacuum is applied without putting any insulator in the capacitor)

Further, it is more preferable to use an aprotic solvent in which the solvent has a small amount of other anions that cause a competitive reaction with fluorine ions in the electrolyte synthesis reaction step, since generation of impurities is suppressed. Preferred aprotic solvents that can be used include ethers, ketones, esters, amides, nitriles, amines, halogen compounds, nitro compounds, sulfur compounds. More preferred specific examples include diethyl ether, diisopropyl ether, tetrahydrofuran, tetrahydropyran,
2-methoxyethane, diethylene glycol dimethyl ether, acetone, ethyl methyl ketone, cyclohexanone, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, dimethyl carbonate, formamide, N,
N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, acetonitrile, propionitrile,
Slicinonitrile, benzonitrile, ethylenediamine, triethyleneamine, aniline, pyridine, piperidine, morpholine, methylene chloride, chloroform, 1,
2-dichloroethane, chlorobenzene, 1-bromo-2
-Chloroethane, nitromethane, nitrobenzene, o-
Nitrotoluene, dimethylsulfoxide, sulfolane and the like can be mentioned. These solvents can be used either as a single solution or as a mixed solution of two or more.

(Organic silane compound) The organic silane compound containing at least a silicon element and a carbon element used in the present invention has at least one silicon element, and at least one carbon element is bonded to the silicon element. Which has one silicon element and has four substituents bonded to the silicon element (in the present invention, a group bonded to the silicon element is referred to as a substituent). Silane compounds (for example, the aforementioned R _n SiX _4-n ) are preferable in terms of improving yield because of their good reactivity.

Further, when the organic silane compound is silicon
Of these substituents, those having 1-3 substituents which are liable to undergo a substitution reaction with fluorine ions are preferable, and those having an elemental fluorine as a substituent are more preferable. Examples of the substituent (X in the above formula) which easily causes a substitution reaction with a fluorine ion include a halogen group such as -Cl, -Br, -I, -OH.
_{Hydroxyl, -OCH 3, -OC 2 H 5} , an alkoxy group such as _{-OC 4 H 9, -OCOCH 3,} -OCOC 2 H 5 , etc. acyloxy _{group, -OC 6 H 5, -OC 6} H 4 CH 3 , -OC ₁₀ H ₇
Allenoxy groups such as -NR ¹ H, -NR ¹ R ² (R ¹ ,
R ² : an alkyl group); and —H (hydrogen).

Further, the organic silane compound has, as the remaining substituent (R in the above formula), a substituent which is less likely to cause a substitution reaction with a fluorine ion, in addition to the above-mentioned substituent which tends to cause a substitution reaction with a fluorine ion. It is preferable because during the substitution reaction, the solubility in an organic solvent can be maintained favorably and the reaction proceeds efficiently. Examples of the fluorine ion and substitution reaction caused hardly substituents R, although carbon element to silicon element include the substituents directly attached, -CH _3, -
C ₂ H _5, alkyl groups such as _{-C 4 H 9, -C 6 H} 5, -C 6 H 4
Aryl groups such as CH ₃ and —C ₁₀ H ₇ are preferable because they hardly react with fluorine ions and fluorine ions are effectively used for substitution reactions, and phenyl groups are more preferable in terms of solubility.

When the substituents are -C ₂ H ₃ , -C ₄ H ₇ , -C ₂
In the case of an alkenyl group or an alkynyl group having an unsaturated bond such as a double bond or a triple bond in a substituent such as H, -C ₃ H ₃ , the compound having this substituent is reacted with a fluorine compound, This substituent can be used by performing a previous reaction such as an addition reaction.

(Fluorine Compound) The fluorine compound used in the present invention is a compound capable of generating fluorine ions (for example, the above-mentioned MF), for example, hydrogen fluoride, fluorine gas, xenon fluoride, tetrafluoride Inorganic and organic fluorine compounds such as sulfur, perchloryl fluoride, cesium fluoride sulfate, hypofluorites, N-fluoroammoniums, fluoride salts and the like can be used, but from the viewpoint of handling and safety, tetraethyl fluoride, tetra More preferred are quaternary ammonium fluoride salts such as butyl fluoride, and fluoride salts such as ammonium fluoride, lithium fluoride, sodium fluoride and potassium fluoride. Among them,
Ammonium fluoride salt (in particular NH ₄ F and the general formula R ³ ₄ N
F (a quaternary ammonium salt represented by R ³ : alkyl group) is more preferable because of its particularly good solubility in non-aqueous solvents.

The method for producing an electrolyte according to the present invention has been described above. A secondary battery is produced by a usual formulation using the thus synthesized electrolyte. Hereinafter, one embodiment of a lithium secondary battery using the electrolyte synthesized by the production method of the present invention,
This will be described with reference to FIGS. 3, 4, and 5. FIG.

FIG. 3 is a sectional view schematically showing the structure of a secondary battery. In the secondary battery 300 shown in FIG.
And a positive electrode 302 opposedly disposed via an electrolyte or electrolyte solution (electrolyte solution) 303 and a separator 304,
These members are housed in the battery housing 307. The salt of the organic fluorine silicon compound synthesized by the method of the present invention is used for the electrolyte 303. The negative electrode 301 is connected to the input / output terminal 305, and the positive electrode 302 is connected to the input / output terminal 306.
Connect to

(Method of Using Electrolyte) The method of using the electrolyte (303) synthesized by the method of the present invention in a secondary battery includes the following three methods. (1) A method used as it is. (2) A method of using as a solution dissolved in a solvent. (3) A method in which a gelling agent such as a polymer is added to a solution to be used as an immobilized one.

Generally, an electrolytic solution obtained by dissolving an electrolyte in a solvent is used by being retained in a porous separator. It is desirable that the electrolyte synthesized by the production method of the present invention be sufficiently dehydrated and deoxidized by heating under reduced pressure.

Examples of the solvent for the electrolyte include acetonitrile, benzonitrile, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, dimethylformamide, tetrahydrofuran, nitrobenzene, dichloroethane, diethoxyethane, 1,2-dimethoxyethane, chlorobenzene, and the like. γ-butyrolactone, dioxolane, sulfolane, nitromethane, dimethylsulfide, dimethylsulfoxide, methyl formate, 3-methyl-2-oxazolidinone, 2-methyltetrahydrofuran, 3-propylsidone, sulfur dioxide, phosphoryl chloride, thionyl chloride, sulfuryl chloride ,
Alternatively, a mixture of these can be used.

The solvent may be dehydrated with, for example, activated alumina, molecular sieve, phosphorus pentoxide, calcium chloride, or the like, or may be distilled in an inert gas in the presence of an alkali metal to remove impurities and dehydrate. Good to do.

To prevent the electrolyte solution from leaking, it is preferable to form a gel. As the gelling agent, it is desirable to use a polymer that absorbs the solvent of the electrolytic solution and swells.
As such a polymer, polyethylene oxide, polyvinyl alcohol, polyacrylamide and the like are used. The electrolyte obtained in the present invention is particularly used as an electrolyte in a lithium secondary battery, and as described above, a reaction between a metal such as lithium precipitated by a charging reaction and moisture can be suppressed. Can be extended.

Hereinafter, each member when the secondary battery shown in FIG. 1 is a lithium secondary battery will be described.

(Positive Electrode) The positive electrode (301) used in the lithium secondary battery is composed of a current collector, a positive electrode active material, a conductive auxiliary material, a binder, and the like. This positive electrode is manufactured by molding a mixture of a positive electrode active material, a conductive auxiliary material, and a binder material on the surface of a current collector.

As the positive electrode active material, a transition metal oxide, a transition metal sulfide, a lithium-transition metal oxide, or a lithium-transition metal sulfide is generally used. As the transition metal element of the transition metal oxide or transition metal sulfide, for example,
Which is an element having a d-shell or f-shell partially
Sc, Y, Lanthanoid, Actinoid, Ti, Zr, Hf, V,
Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh,
Ir, Ni, Pd, Pt, Cu, Ag, Au. In particular, Ti, V, Cr, Mn, Fe, Co, Ni, and Cu, which are the first transition series metals, are preferably used.

Examples of the conductive auxiliary agent used for the positive electrode include graphite, amorphous carbon called carbon black such as Ketjen black and acetylene black, and fine metal powder such as nickel. Examples of the binder used for the positive electrode include polyolefins such as polyethylene and polypropylene, and fluororesins such as polyvinylidene fluoride and tetrafluoroethylene polymers.

The positive electrode current collector plays a role of efficiently supplying a current consumed in the electrode reaction at the time of charging or collecting a current generated at the time of discharging. Therefore, as a material for forming the current collector of the positive electrode, high conductivity, and,
A material inert to the battery reaction is desirable. Preferred materials include nickel, stainless steel, titanium, aluminum, copper, platinum, palladium, gold, zinc, various alloys,
And the above-mentioned two or more composite metals. As the shape of the current collector, for example, a plate shape, a foil shape, a mesh shape, a sponge shape, a fiber shape, a punching metal, an expanded metal, and the like can be adopted. (Negative Electrode) In the negative electrode (302) used for the lithium secondary battery, a carbon material including graphite, a lithium metal, a lithium alloy, and a metal element forming an alloy with lithium are used as a negative electrode active material serving as a lithium ion host material. And a transition metal oxide having a positive electrode active material and an electromotive force. When the shape of the negative electrode active material is powder, a negative electrode is manufactured by using a binder or by sintering to form a negative electrode active material layer on the current collector. When the negative electrode active material powder has low conductivity, it is necessary to appropriately mix a conductive auxiliary material, as in the formation of the positive electrode active material layer. As the current collector and the conductive auxiliary material, those used for the positive electrode can be similarly used.

(Separator) The separator (304) has a role of preventing a short circuit between the negative electrode and the positive electrode. In addition, the electrolyte (30
In some cases, it has a role to hold 3).

The separator must have pores through which lithium ions can move, and must be insoluble and stable in the electrolytic solution. Therefore, as the separator, for example, a nonwoven fabric such as glass, polyolefin such as polypropylene or polyethylene, a fluororesin, or a material having a micropore structure is suitably used. Further, a metal oxide film having fine pores or a resin film in which a metal oxide is compounded can be used. In particular, when a metal oxide film having a multilayered structure is used, the dendrite hardly penetrates, which is effective in preventing a short circuit. When a fluororesin film which is a flame retardant material, or a glass or metal oxide film which is a nonflammable material is used, safety can be further improved.

(Battery Shape and Structure) The shape of the secondary battery is based on the structure shown in FIG. 3, specifically, for example, a flat shape, a cylindrical shape, a rectangular parallelepiped shape, a sheet shape and the like. The structure of the members in the battery includes, for example, a single-layer structure, a multilayer structure, and a spiral structure. Among them, the spiral cylindrical battery has a feature that the electrode area can be increased by winding the separator between the negative electrode and the positive electrode with the separator interposed therebetween, and a large current can flow during charging and discharging. Further, a rectangular parallelepiped or sheet type battery has a feature that the storage space of a device for storing the battery can be effectively used.

Hereinafter, the shape and structure of the battery will be described in more detail with reference to FIGS. FIG. 4 is a cross-sectional view of a single-layer flat (coin-shaped) battery, and FIG. 5 is a cross-sectional view of a spiral cylindrical battery. These lithium batteries have basically the same configuration as that of FIG. 3, and include a negative electrode, a positive electrode, an electrolyte / separator, a battery housing, an output terminal,
Etc.

4 and 5, reference numerals 400 and 500 denote negative electrode current collectors, 401 and 501 denote negative electrode active materials, and 403 and 50, respectively.
3 is a positive electrode active material, 405 and 505 are negative electrode terminals (negative electrode caps), 406 and 506 are positive electrode cans, 407 and 507 are separators holding an electrolyte, 410 and 510 are insulating packings, and 511 is an insulating plate. In the flat structure lithium secondary battery illustrated in FIG. 4, the positive electrode including the positive electrode active material 403 and the negative electrode including the negative electrode active material 401 and the negative electrode current collector 400 are formed using the silicon element, the fluorine element,
The laminated body laminated via at least a separator 407 holding an electrolyte made of a salt of an organic fluorine silicon compound containing at least a carbon element has a positive electrode can 406 from the positive electrode side.
The negative electrode side (negative electrode cap) 40
5. The other part in the positive electrode can is provided with, for example, an insulating material (insulating packing 4).
10).

In the cylindrical lithium secondary battery shown in FIG. 5, a positive electrode containing a positive electrode active material 503 and a negative electrode active material 501
Having an electrolyte comprising a salt of an organic fluorine silicon compound containing at least a silicon element, a fluorine element and a carbon element synthesized as described above between anodes
, And a multilayer body having a cylindrical structure wound around a predetermined axis in a multiplex manner is accommodated in the positive electrode can 506 from the side surface and one bottom surface side. The other bottom surface (upper surface) side of the laminate is covered with a negative electrode terminal (negative electrode cap) 505. An insulator is disposed in the other part of the positive electrode can (insulating packing 510). Hereinafter, an example of a method of assembling the battery shown in FIGS. 4 and 5 will be described. (1) A separator (407, 5) is provided between the negative electrode active material layer (401, 501) and the formed positive electrode active material layer (403, 503).
07), and assembled into the positive electrode can (406, 506). (2) After injecting the electrolyte, the negative electrode cap (405, 50
5) and the insulating packing (410, 510) are assembled. (3) The battery is completed by caulking the above (2).

In addition, the material preparation of the above-mentioned lithium battery,
It is desirable that the battery be assembled in dry air from which moisture has been sufficiently removed or in a dry inert gas.

(Insulation Packing) Gasket (410, 5
As the material of 10), for example, fluorine resin, polyamide resin, polysulfone resin, and various rubbers can be used.
As a method for sealing the battery, a method such as glass sealing, adhesive, welding, soldering, or the like is used in addition to "caulking" using insulating packing as shown in FIGS.

As the material of the insulating plate in FIG. 5, various organic resin materials and ceramics are used.

(Outer can) The outer can of the battery is
6, 506) and a negative electrode cap (405, 505). As a material for the outer can, stainless steel is preferably used. In particular, a titanium clad stainless steel plate, a copper clad stainless steel plate, a nickel plated steel plate and the like are frequently used.

In the embodiment shown in FIGS. 4 and 5, the positive electrode can (406,
Since 506) also serves as a battery housing, the above stainless steel is preferable. However, when the positive electrode can does not double as the battery housing, as the material of the battery housing, a metal such as zinc other than stainless steel, a plastic such as polypropylene, or a composite material of metal or glass fiber and plastic is used. .

(Safety Valve) The lithium secondary battery is provided with a safety valve as a safety measure when the internal pressure of the battery increases. Although not shown in FIGS. 4 and 5, as the safety valve, for example, rubber, a spring, a metal ball, a rupture foil, or the like can be used.

Hereinafter, the present invention will be described in detail with reference to examples. The present invention is not limited to these examples. In the description, parts and% are based on weight.

Example 1 (Synthesis of Organic Fluorine Silicon Compound Salt) First, dry nitrogen gas was charged into a reaction vessel of a three-necked flask equipped with a reflux device, a stirrer, and a dropping funnel. In this three-necked flask, tetra-n-butylammonium fluoride (n-Bu) ₄ NF from which water was removed by vacuum drying at 50 ° C.
(Purity 99%) 10.4 parts (0.04 mol) and 100 parts of diethyl ether (purity 99.5%) dried with Molecular Sieve 3A were added, and the mixture was stirred until tetra n-butylammonium fluoride was melted. The water content of diethyl ether after drying with molecular sieve was measured with a Karl Fischer moisture meter, and was 0.5
%, And the relative dielectric constant of diethyl ether after drying with molecular sieve was measured using an Impedance Analyzer (H
(Manufactured by Company P) and found 4.3 (20 ° C.).

Next, 5.5 parts (0.02 mol) of triphenylchlorosilane Ph ₃ SiCl from which water was removed by vacuum drying at 50 ° C. was dissolved in 100 parts of the same dry diethyl ether as above, and this solution was subjected to the above reaction. The container was placed in the dropping funnel.

The above reaction vessel was cooled to 0 ° C. with an ice bath, and the solution in the dropping funnel was gradually added dropwise to the vessel while stirring the vessel. After the addition, the mixture was stirred at 0 ° C. for 1 hour, and then heated to 50 ° C. and further stirred for 2 hours.

After completion of the reaction, the solvent diethyl ether was concentrated by a rotary evaporator and dried, and then the obtained crystals were washed with cold water to remove by-product tetra-n-butylammonium chloride, and the desired triphenyl Tetra n-butylammonium difluorosilicate (n-
Bu) ₄ N [Ph ₃ SiF ₂ ] was obtained.

(Ion exchange of organofluorine silicon compound salt)
The triphenyldifluorosilicate tetra n obtained above
-Butyl ammonium salt and lithium tetrafluoroborate LiBF ₄ (purity 98%) were dissolved in acetone, stirred for 2 hours, then concentrated on a rotary evaporator, and dried.
Thereafter, the obtained crystals are washed with cold water to remove tetra-n-butylammonium tetrafluoroborate as a by-product, and the intended lithium triphenyldifluorosilicate Li
[Ph ₃ SiF ₂ ] was obtained.

Comparative Example 1 (Synthesis of Organic Fluorine Silicon Compound Salt) Instead of the dry diethyl ether used in Example 1,
Except for using a mixed aqueous solution of water (10%: 90%),
The same treatment as in Example 1 was performed, and triphenyldifluorosilicate tetra-n-butylammonium salt (n-Bu) ₄ N
[Ph ₃ SiF ₂ ] was obtained.

Example 2 (Synthesis of Organic Fluorine Silicon Compound Salt) In the same manner as in Example 1, first, dry nitrogen gas was charged into a reaction vessel of a three-necked flask equipped with a reflux device, a stirrer, and a dropping funnel. . In this three-necked flask, tetraethylammonium fluoride Et was dried at 50 ° C. under vacuum to remove water.
9.0 parts (0.06 mol) of ₄ NF (99% purity) and 80 parts of dimethyl sulfoxide (99% purity) dried with Molecular Sieve 3A were added, and the mixture was stirred until tetraethylammonium fluoride was melted. The water content of dimethyl sulfoxide after drying with molecular sieve was measured with a Karl Fischer moisture meter.
0.05%, and the relative dielectric constant of dimethyl sulfoxide after drying with molecular sieve
It was 48.9 (20 degreeC) when it measured with e Analyzer.

Next, vacuum drying was diphenyldichlorosilane Ph ₂ SiCl ₂ 5.1 parts of water was removed by at 50 ° C. The (0.02 mol), dissolved in the same dry dimethylsulfoxide 80 parts of the above, this The solution was placed in the dropping funnel of the reaction vessel.

Thereafter, the desired tetraethylammonium diphenyltrifluorosilicate was prepared in the same manner as in Example 1.
Et ₄ N [Ph ₂ SiF ₃ ] was obtained.

(Ion exchange of organofluorine silicon compound salt)
Tetraethylammonium diphenyltrifluorosilicate and lithium perchlorate LiClO obtained above
4 (98% purity) was dissolved in acetone, stirred for 2 hours, concentrated on a rotary evaporator, and dried. After that, the obtained crystals were washed with cold water to remove by-product tetraethylammonium perchlorate. Of lithium diphenyltrifluorosilicate Li [Ph ₂ SiF ₃ ] was obtained.

Comparative Example 2 (Synthesis of Organic Fluorine Silicon Compound Salt) Example 2 was repeated except that a mixed aqueous solution of dimethyl sulfoxide / water (30%: 70%) was used instead of the dried dimethyl sulfoxide used in Example 2. The same treatment as described above was performed, and diphenyltrifluorosilicate tetraethylammonium salt Et ₄ N [Ph
₂ SiF ₃ ] was obtained.

Example 3 (Synthesis of Organic Fluorine Silicon Compound Salt) As in Example 1, first, dry nitrogen gas was charged into a reaction vessel of a three-necked flask equipped with a reflux device, a stirrer, and a dropping funnel. . In the three-necked flask, ammonium fluoride NH ₄ F (purity 97) was dried at 50 ° C. under vacuum to remove water.
%) 3.7 parts (0.1 mol) and acetonitrile (purity 99.5%) 10 dried with molecular sieve 3A
0 parts were added and the mixture was stirred until the ammonium fluoride was dissolved. The water content of acetonitrile after drying with the molecular sieve 3A was measured with a Karl Fischer moisture meter, and was 0.1%. The relative dielectric constant of the acetonitrile after drying with the molecular sieve was Impeda.
It was 37.5 (20 ° C.) as measured with a nce analyzer.

Next, phenylmethyldimethoxysilane PhMeSi (O
3.6 parts (0.02 mol) of Me) ₂ was dissolved in 80 parts of the same dry acetonitrile as described above, and the solution was placed in a dropping funnel of the reaction vessel.

Thereafter, in the same manner as in Example 1, the target ammonium phenylmethyltrifluorosilicate NH ₄ [P
hMeSiF ₃ ] was obtained.

(Ion exchange of organofluorine silicon compound salt)
Ammonium phenylmethyltrifluorosilicate and lithium hexafluorophosphate LiPF obtained above
₆ (purity 99%) was dissolved in acetonitrile, stirred for 2 hours, concentrated by a rotary evaporator and dried, and the obtained crystals were washed with cold water to remove ammonium hexafluorophosphate as a by-product. Lithium phenylmethyltrifluorosilicate Li [PhMeSiF
₃ ] was obtained.

Comparative Example 3 (Synthesis of Organic Fluorine Silicon Compound Salt) The procedure of Example 3 was repeated except that a mixed aqueous solution of acetonitrile / water (50%: 50%) was used instead of the dried acetonitrile used in Example 3. The same treatment was performed to obtain ammonium phenylmethyltrifluorosilicate NH ₄ [PhMeSiF ₃ ].

Example 4 (Synthesis of Organic Fluorine Silicon Compound Salt) As in Example 1, first, dry nitrogen gas was charged into a reaction vessel of a three-necked flask equipped with a reflux device, a stirrer, and a dropping funnel. . In the three-necked flask, ammonium fluoride NH ₄ F (purity 97) was dried at 50 ° C. under vacuum to remove water.
%) And 120 parts of chlorobenzene (purity: 99.5%) dried with a molecular sieve and stirred until the ammonium fluoride was dissolved. The water content of chlorobenzene after drying with the molecular sieve 3A was measured with a Karl Fischer moisture meter and found to be 0.005%, and the relative dielectric constant of the chlorobenzene after drying with the molecular sieve was measured by Impedanc.
It was 5.6 (20 ° C.) as measured by e Analyzer.

Next, phenyltriethoxysilane PhSi (OEt) ₃ from which water has been removed by vacuum drying at 50 ° C.
4.8 parts (0.02 mol) were dissolved in 50 parts of the same dried chlorobenzene, and the solution was placed in the dropping funnel of the reaction vessel.

Thereafter, in the same manner as in Example 1, the target ammonium phenylpentafluorosilicate (NH ₄ ) ₂ [P
hSiF ₅ ] was obtained.

(Ion exchange of organofluorine silicon compound salt)
The ammonium phenylpentafluorosilicate obtained above was dissolved in acetonitrile, and the acetonitrile solution was passed through a column filled with cation exchange resin Diaion SK1B.
9%) and stirred for 2 hours. Thereafter, this solution was concentrated with a rotary evaporator, dried, and the intended lithium phenylpentafluorosilicate Li ₂ [PhSi
F ₅ ] was obtained.

Comparative Example 4 (Synthesis of Organic Fluorine Silicon Compound Salt) Instead of the dry chlorobenzene used in Example 4, water was used.
The same treatment as in Example 4 was performed to obtain ammonium phenylpentafluorosilicate (NH ₄ ) ₂ [PhSiF ₅ ].

Example 5 (Synthesis of Organic Fluorine Silicon Compound Salt) As in Example 1, first, dry nitrogen gas was charged into a reaction vessel of a three-necked flask equipped with a reflux device, a stirrer, and a dropping funnel. . In this three-necked flask, 2.6 parts (0.1 mol) of lithium fluoride (purity 98%) from which water was removed by vacuum drying at 50 ° C. and ethyl methyl ketone (purity 99.5%) were absorbed. 200 parts were added and stirred. In addition,
The water content of this ethyl methyl ketone was measured by a Karl Fischer moisture meter to be 3.5%, and the relative dielectric constant of the ethyl methyl ketone was measured using an Impedance Analyzer.
Was 18.9 (20 ° C.).

Next, 4.7 parts of ethyltriacetoxysilane EtSi (OCOCH ₃ ) ₃ dried at 50 ° C. (0.
02 mol) as it was in the dropping funnel of the reaction vessel.

Thereafter, in the same manner as in Example 1, the desired lithium salt of ethyl pentafluorosilicate Li ₂ [EtSiF ₅ ]
(The ion exchange step was not performed).

Comparative Example 5 (Synthesis of Organic Fluorine Silicon Compound Salt) In place of ethyl methyl ketone used in Example 5, water was used.
The same treatment as in Example 5 was performed to obtain lithium ethylpentafluorosilicate Li ₂ [EtSiF ₅ ].

Example 6 (Synthesis of Organic Fluorine Silicon Compound Salt) As in Example 1, first, dry nitrogen gas was charged into a reaction vessel of a three-necked flask equipped with a reflux device, a stirrer, and a dropping funnel. . In this three-necked flask, tetraethylammonium fluoride Et was dried at 50 ° C. under vacuum to remove water.
15.0 parts (0.10 mol) of ₄ NF (purity 99%) and 100 parts of diethyl ether (purity 99.5%) dried with Molecular Sieve 3A were added, and the mixture was stirred until tetraethylammonium fluoride was melted. The water content of diethyl ether after drying with molecular sieve was measured with a Karl Fischer moisture meter.
5%, and the relative dielectric constant of diethyl ether after drying with a molecular sieve was determined by Impedance.
4.3 (20 ° C.) when measured with an Analyzer
Met.

Next, vinyltriethoxysilane CH ₂ ＣＨCHSi (OC ₂ H
_{5) 3} 3.8 parts (0.02 mol), dissolved in 100 parts of the same dry diethyl ether as above was placed in the solution in the dropping funnel of the reaction vessel.

Thereafter, in the same manner as in Example 1, the target vinylpentafluorosilicate tetraethylammonium salt (E
t ₄ N) ₂ [CH ₂ ＣＨCHSiF ₅ ] was obtained.

(Ion exchange of organofluorine silicon compound salt)
The above-obtained tetraethylammonium vinylpentafluorosilicate and lithium perchlorate LiClO ₄
(Purity 98%) was dissolved in acetone, stirred for 2 hours, concentrated by a rotary evaporator, and dried. After that, the obtained crystals were washed with cold water to remove by-product tetraethylammonium perchlorate, and Lithium vinylpentafluorosilicate Li ₂ [CH ₂ CHSiF ₅ ] was obtained.

Comparative Example 6 (Synthesis of Organic Fluorine Silicon Compound Salt) Instead of the dry diethyl ether used in Example 6,
The same treatment as in Example 6 was performed except that a mixed aqueous solution of water (30%: 70%) was used to obtain lithium vinylpentafluorosilicate Li ₂ [CH ₂ ＣＨCHSiF ₅ ].

(Evaluation Method) Examples 1 to 6 and Comparative Examples 1 to
6, the yield and the amount of impurities were measured for the compound of organofluorine silicon obtained in Example 1, and Example 1 and Comparative Example 1,
The yield, the amount of impurities, and the amount of impurities after ion exchange were evaluated as described below by comparing the examples and the comparative examples as in Example 2 and Comparative Example 2, respectively.

As a result, as shown in Table 1, the yields of the organofluorine silicon compound salts obtained in the examples were all higher than those of the comparative examples, and the proportion of impurities was small.

[0099]

[Table 1] * 1 Yield The weight of the salt of the organofluorine silicon compound obtained in Example was
The determination was made in comparison with the comparative example as in the following calculation formula. Yield = weight of organofluorine silicon compound salt obtained in Example / weight of organofluorine silicon compound salt obtained in Comparative Example * 2 Impurity amount, * 3 Impurity amount after ion exchange The yield of the salt and the salt of the organofluorine silicon compound after ion exchange was measured using high performance liquid chromatography, and using p-toluenesulfonic acid tetra-n-butylammonium salt as an internal standard reagent, the yield was calculated as follows. The determination was made in comparison with the comparative example. Impurity amount = ((1−concentration of organofluorine silicon compound salt obtained in Example) / concentration of internal standard reagent)) /
((1−measured concentration of organofluorine silicon compound salt obtained in Comparative Example) / measured concentration of internal standard reagent) Impurity amount after ion exchange = ((1−organic concentration after ion exchange obtained in Example) Measurement concentration of fluorine silicon compound salt) /
Measurement concentration of internal standard reagent)) / ((1−concentration of organofluorine silicon compound salt obtained in Comparative Example) / measurement concentration of internal standard reagent)) Measurement concentration: of all components in high performance liquid chromatography measurement Each area% to the total area%

Using the lithium salt of the organofluorine silicon compound obtained in Examples 1 to 6, a coin-type secondary battery shown in FIG. 4 was prepared and charged and discharged. Hereinafter, a procedure for manufacturing each component of the battery and an assembly of the battery will be described.

Preparation of Electrolyte Solution The lithium salts of the organofluorine silicon compounds obtained in Examples 1 to 6 were each dissolved in a propylene carbonate solvent to prepare a 1 M (mol / l) electrolyte solution.

Preparation of Positive Electrode 403 After lithium carbonate and cobalt carbonate were mixed at a molar ratio of 1: 2, the mixture was heat-treated in an air stream at 800 ° C. to prepare a lithium-cobalt oxide. A paste was prepared by adding 92% of this lithium-cobalt oxide, 3% of acetylene black carbon powder and 5% of polyvinylidene fluoride powder to N-methyl-2-pyrrolidone to prepare a current collector which is an expanded metal aluminum foil. And dried under reduced pressure at 150 ° C. to produce a positive electrode 403.

Preparation of Negative Electrode 402 A paste was prepared by adding 95% of natural graphite fine powder and 5% of polyvinylidene fluoride powder N-methyl-2-pyrrolidone heat-treated at 2000 ° C. in an argon gas stream to prepare a copper foil. After coating and drying the current collector, the negative electrode 402 was formed by drying at 150 ° C. under reduced pressure.

Separator A polyethylene microporous separator was used.

Battery Assembly A separator 407 containing an electrolyte was sandwiched between a negative electrode 402 and a positive electrode 403 in an argon gas atmosphere, and inserted into a titanium-clad stainless steel positive electrode can 406. The obtained positive electrode can 406 was covered with an insulating packing 410 made of polypropylene and a negative electrode cap 405 made of a stainless steel material clad with titanium, and caulked to obtain a lithium secondary battery.

FIG. 2 is a discharge curve at a discharge current of 0.4 mA of the secondary battery using the lithium salt of the organofluorine silicon compound of Example 1, and good charge / discharge performance was obtained. In addition, the lithium salt of the organofluorine silicon compound obtained in the other Examples also had good charge / discharge performance similar to that of Example 1.

[0107]

As described above, according to the method for producing an electrolyte of the present invention, the electrolyte for providing a lithium secondary battery having a long cycle life with little performance deterioration due to repeated charge and discharge is provided with a small amount of impurities and It becomes possible to produce in high yield.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating one embodiment of a manufacturing method of the present invention.

FIG. 2 is a diagram showing a discharge curve of a lithium secondary battery using an electrolyte obtained in an example of the present invention.

FIG. 3 is a cross-sectional view showing one embodiment of a structure of a lithium secondary battery using an electrolyte obtained by the production method of the present invention.

FIG. 4 is a cross-sectional view of a single-layer flat battery.

FIG. 5 is a sectional view of a spiral cylindrical battery.

[Explanation of symbols]

 301, 402 Negative electrode 302 Positive electrode 303 Electrolyte (electrolyte) 304 Separator 305 Negative terminal 306 Positive terminal 307 Battery housing 400, 500 Negative current collector 501 Negative active material 403, 503 Positive active material 505 Negative cap (negative terminal) 506 Positive can (Positive electrode terminal) 407, 507 Separator holding electrolyte 410, 510 Insulating packing 504 Positive electrode current collector 511 Insulating plate

Claims (18)

[Claims] 1. A method comprising reacting an organic silane compound containing at least a silicon element and a carbon element with a fluorine compound in a solvent containing a non-aqueous solvent as a main component. And a method for producing an electrolyte comprising a salt of an organic fluorine silicon compound containing a carbon element. 2. The method for producing an electrolyte according to claim 1, wherein the electrolyte is an electrolyte used for a secondary battery utilizing a charge / discharge of a lithium ion intercalation reaction and a deintercalation reaction. 3. The method for producing an electrolyte according to claim 1, wherein a salt of the organofluorine silicon compound is synthesized in the step of reacting the organosilane compound with the fluorine compound. 4. The method for producing an electrolyte according to claim 1, wherein the solvent containing the non-aqueous solvent as a main component is a solvent containing 95% by weight or more of the non-aqueous solvent. 5. The method for producing an electrolyte according to claim 1, wherein the solvent containing the non-aqueous solvent as a main component is a solvent capable of dissolving the organic silane compound and the fluorine compound. 6. The solvent containing a non-aqueous solvent as a main component has a relative dielectric constant of 3 or more when the temperature of the solvent is 20 ° C.
A method for producing the electrolyte according to the above. 7. The method for producing an electrolyte according to claim 1, wherein the non-aqueous solvent is an organic solvent. 8. The non-aqueous solvent is at least one or more aprotic solvents selected from ethers, ketones, esters, amides, nitriles, amines, halogen compounds, nitro compounds and sulfur compounds. The method for producing an electrolyte according to claim 6, which is a solvent. 9. The method according to claim 1, wherein the fluorine compound is a fluoride salt. 10. The method according to claim 9, wherein the fluoride salt is an ammonium fluoride salt. 11. The method for producing an electrolyte according to claim 10, wherein the organic silane compound is reacted with the ammonium fluoride salt to synthesize an ammonium salt of an organic fluorine silicon compound. 12. The method for producing an electrolyte according to claim 3, wherein a step of ion-exchanging a cation of the salt with an alkali metal cation is performed, using the synthesized salt of the organic fluorine silicon compound as an intermediate product. Method. 13. The method for producing an electrolyte according to claim 12, wherein the alkali metal cation is a lithium ion. 14. The ion-exchange step is a step of directly exchanging ions with a cation-exchange resin or a membrane, a step of exchanging hydrogen ions with a cation-exchange resin or a membrane, and then neutralizing and exchanging with a desired cation. 14. The method for producing an electrolyte according to claim 12, wherein the method is one or more steps selected from a step of mixing in a solvent with a salt containing ions to be subjected to cation exchange utilizing ionic strength or generation of precipitation. 15. The organic silane compound according to claim 1, wherein one or three substituents selected from a halogen group, a hydroxyl group, an alkoxy group, an acyloxy group, an arenoxy group, an amino group, and hydrogen are used as the four substituents of the silicon element. The method for producing an electrolyte according to claim 1, wherein the compound has a substituent selected from an alkyl group and an aryl group as the remaining substituents. 16. The method for producing an electrolyte according to claim 15, wherein the organic silane compound is an organic silane compound having at least one phenyl group as a substituent of a silicon element. 17. The electrolyte according to claim 1, wherein in the step of reacting the organic silane compound and the fluorine compound, the number of fluorine elements as a substituent of the silicon element in the salt of the organic fluorine silicon compound is adjusted to three or less. Production method. 18. A method for manufacturing a secondary battery, wherein at least a positive electrode, a negative electrode, and a separator are housed in a battery housing, wherein a lithium ion intercalation reaction and a deintercalation reaction are used for charging and discharging. Item 18. A method for manufacturing a secondary battery, comprising a step of disposing an electrolyte obtained by the method according to any one of Items 1 to 17 in a battery housing.