JP2011150820A - Additive material for lithium-ion secondary battery electrolyte - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an additive material for producing a non-aqueous electrolyte achieving both of improvement in flame retardancy and battery performance in the non-aqueous electrolyte, especially in the electrolyte for a lithium-ion battery. <P>SOLUTION: Boric-acid ester containing fluorine is shown in a general formula (1), in which R<SB>1</SB>, R<SB>2</SB>, and R<SB>3</SB>may be the same or different 1-10C alkyl group or fluorine-containing alkyl group. At least one of R<SB>1</SB>, R<SB>2</SB>, and R<SB>3</SB>is the fluorine-containing alkyl group. The additive material containing the boric-acid ester containing fluorine to improve its self-extinguishing characteristic is added to the non-aqueous electrolyte. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a nonaqueous electrolytic solution, particularly a nonaqueous electrolytic solution containing a fluorine-containing boric acid ester used as a modifier for a lithium ion secondary battery electrolytic solution.

Non-aqueous electrolyte secondary batteries, particularly lithium ion secondary batteries, are widely used as storage batteries for consumer devices such as notebook personal computers and mobile phones.
In these lithium-based batteries, due to the high operating voltage, an aqueous solution cannot be used basically, and a nonaqueous solvent having a wide electrochemically stable potential range (potential window) is used.

  However, non-aqueous solvents used in lithium secondary batteries, such as ethylene carbonate and dimethyl carbonate, have volatility and flammability, and the electrodes have been short-circuited during use so far due to problems during production, etc. There is an accident that the battery burns by igniting the electrolyte.

  On the other hand, in recent years, lithium ion secondary batteries have attracted attention as power sources for electric vehicles and hybrid vehicles, solar power generation, hydroelectric power generation, etc. In order to satisfy these performances, further enlargement, There is a demand for higher capacity (see Non-Patent Document 1, for example).

  However, as batteries increase in size, non-aqueous electrolytes that do not pose a risk of fire are desired for further safety, and technology using non-aqueous electrolytes that have flame retardancy or self-extinguishing properties has attracted attention. (Non-Patent Document 2).

  As a method for making the non-aqueous electrolyte flame-retardant, addition of a phosphoric acid ester known as a flame retardant for resin materials has been studied (for example, see Patent Documents 1 and 2).

  However, in order to use a non-aqueous electrolyte in an electric vehicle or the like, not only safety but also high battery performance is required, but the non-aqueous electrolyte containing these phosphate esters is the charge / discharge efficiency of the battery, It was not always satisfactory in terms of battery performance such as energy density and battery life.

On the other hand, boron compounds generally have high Lewis acidity, and it is known that when added to the electrolyte of a non-aqueous secondary battery, ion conductivity and ion solubility are improved.
For example, a method for improving large current charge / discharge characteristics of a lithium secondary battery by adding a small amount of tris (pentafluorophenyl) borane or tris (2H-hexafluoroisopropyl) borate has been proposed (for example, Patent Document 3). , Patent Document 4 and Patent Document 5).
In these Examples of Patent Documents 3 to 5, an example in which tris (2H-hexafluoroisopropyl) borate (HFPB) is added at a maximum of 12 wt% is shown.

Furthermore, such boron compounds have also been reported to improve the dissociation properties of Li salts with small ionic radii (for example, LiF, LiCl, CF ₃ COOLi, etc.) and enable charge / discharge in non-aqueous electrolyte secondary batteries. (See, for example, Patent Document 6, Patent Document 7, Patent Document 8, and Non-Patent Document 3).

JP-A-8-22839 JP-A-11-260401 JP 2008-198499 A JP 2008-198542 A JP 2009-43597 A US Pat. No. 6,022,463 US Pat. No. 6,352,798 Special table 2008-543002

Fuji Keizai, 2008 Battery-related market research 1st volume 2008 NTS Co., Ltd., Electron and ion functional chemistry series vol. 3. Next-generation lithium secondary battery Journal of the Electrochemical Society, 151 (9), A1429, 2004.

As described above, in order to improve the flame retardance of the non-aqueous electrolyte with a known flame retardant, battery performance such as charge / discharge characteristics and recycling characteristics must be sacrificed.
On the other hand, there is no known report about the boron-based compound that improves battery performance and exhibits flame retardancy, and the amount added is not an amount that exhibits flame retardancy. .
As described above, the improvement in the safety and performance of the batteries are contradictory, and it is necessary to select materials necessary for each.
However, as the size of batteries has increased, demands for battery performance such as safety and large current charge / discharge characteristics have been increasing, and materials that satisfy both of these performances have been demanded.

As a result of earnestly examining the improvement of battery performance, the present inventors have used a certain amount of a fluorine-based borate capable of improving the charge / discharge characteristics at a large current, so that the flame retardancy of the electrolyte solution, It has been found that self-extinguishing properties are exhibited, and the present invention has been completed.
Conventionally, it is known that charging and discharging characteristics and charging and discharging capacity are improved by adding a small amount of a fluorine-based borate ester, and charging and discharging characteristics and charging and discharging capacity are deteriorated when added in a large amount. However, the present inventors have found that if the addition is within a certain range, the charge / discharge characteristics and charge / discharge capacity are sacrificed to some extent, but the flame retardancy and self-extinguishing properties of the electrolyte are exhibited.

  That is, an object of the present invention is to provide a nonaqueous electrolytic solution containing a fluorinated boric acid ester that has both improved flame retardancy and improved battery performance in a nonaqueous electrolytic solution, particularly an electrolytic solution of a lithium ion secondary battery.

The present invention is described in detail below.
In the present invention, the fluorine-containing boric acid ester used in the electrolytic solution is represented by the following general formula (1)
(In the formula, R1, R2 and R3 may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms or a fluorine-containing alkyl group, and at least one of R1, R2 and R3 is a fluorine-containing alkyl group. It is a borate ester represented by

Examples of the alkyl group include 1 to 10 carbon atoms such as methyl, ethyl, branched, and linear propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. An alkyl group can be mentioned. Examples of the fluorine-containing alkyl group include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a tetrafluoroethyl group, a pentafluoroethyl group, an octafluorobutyl group, a nonafluorobutyl group, a dodecafluorohexyl group, and a trideca group. Examples thereof include fluorine-containing alkyl groups having 1 to 10 carbon atoms such as a fluorohexyl group, a hexadecafluorooctyl group, a heptadecafluorooctyl group, and an eicosafluorodecyl group.

Examples of such fluorinated boric acid esters include tris (2-monofluoroethyl) borate, tris (2,2-difluoroethyl) borate, tris (2,2,2-trifluoroethyl) borate, Tris borate (2,2,3,3-tetrafluoropropyl), tris borate (2,2,3,3,3-pentafluoropropyl), tris borate (hexafluoroisopropyl), tris borate (2 , 2,3,3,4,4,5,5-octafluoropentyl), tris borate (2,2,2,3,3,4,4,5,5-nonafluoropentyl), tris borate (2,2,3,3,4,5,5,6,6,7,7-dodecafluoroheptyl), tris borate (2,2,3,3,4,4,5,5,5) 6,6,7,7,8,8,9,9-hexadecafluorono ), Tris borate (2,2,3,3,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11-eicosadeca) Fluoroundecyl) and the like.

  Such a fluorinated boric acid ester is, for example, described in Journal of the Chemical Society, pages 2895-2897, (1985), or a method of synthesizing from boron trichloride, or Journal of the Electrochemical Society, Vol. 145 (8). , 2813-2818 (1998), a method of synthesizing from a borane-dimethyl sulfide complex is known.

Next, the nonaqueous electrolytic solution containing the fluorinated boric acid ester of the present invention will be described.
Representative examples of organic solvents that are usually used as non-aqueous electrolytes include, for example, cyclic carbonates such as propylene carbonate, ethylene carbonate, butylene carbonate, and chloroethylene carbonate, γ-butyrolactone, γ-valerolactone, and propiolactone. Cyclic esters, chain carbonates such as dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, diphenyl carbonate, chain esters such as methyl acetate, methyl butyrate, tetrahydrofuran, 1,3-dioxane, dimethoxyethane, diethoxyethane, methoxyethoxyethane , Ethers such as methyl diglyme, nitriles such as acetonitrile and benzonitrile, dioxolane or a derivative thereof alone or a mixture of two or more thereof. wear.

As the electrolyte salt constituting the non-aqueous electrolyte solution, a lithium salt that is stable in a wide potential region used in a non-aqueous secondary battery can be used. Examples of the electrolyte salt include LiBF ₄ , LiPF ₆ , LiClO ₄ , LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiC (CF ₃ SO ₂ ). ₃ etc. are mentioned. These may be used alone or in combination of two or more. In order to improve the high rate charge / discharge characteristics of the battery, it is desirable that the concentration of the electrolyte salt in the non-aqueous electrolyte is in the range of 1 to 2.5 mol / L.

  In the present invention, in order to improve the flame retardancy and battery performance of the non-aqueous electrolyte secondary battery, the concentration of the fluorinated boric acid ester in the non-aqueous electrolyte is 10% by volume or more and 50% by volume or less. Desirably, it is preferably 15% by volume or more and 30% by volume or less.

  As mentioned earlier, boric acid esters containing fluorine atoms have high Lewis acidity and are known to improve battery performance by adding a small amount to the battery, even when the addition amount is less than 10% by volume. It is considered that this is effective in promoting ion dissociation and controlling resistance components between the electrode and the interface.

However, in the present invention, in order to achieve both the safety and high performance of the battery, the flame retarding effect of the electrolytic solution may not be sufficient at 15% by volume or less.
On the other hand, when boric acid ester in an amount exceeding 50% by volume is mixed, the flame retarding effect is sufficient, but the solubility of the electrolyte is lowered, and optimal battery performance may not be exhibited.
The non-aqueous secondary battery of the present invention uses an electrolytic solution having the above composition, and is a battery comprising at least a positive electrode, a negative electrode, and a separator.

  According to the method of the present invention, in a non-aqueous electrolyte secondary battery, in particular, an electrolyte of a lithium ion secondary battery, a non-aqueous electrolyte containing a fluorinated boric acid ester having both improved flame retardancy and battery performance is obtained. Can be provided.

It is a figure which shows the structure of a coin-type lithium ion secondary battery.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

1. Preparation of Electrolyte Solution As an electrolyte solvent, a solvent in which ethylene carbonate (hereinafter abbreviated as EC) and dimethyl carbonate (hereinafter abbreviated as DMC) were mixed at a volume ratio of 1: 1 was used. In a mixture of a predetermined amount of 2-trifluoroethyl) (hereinafter abbreviated as TFEB), 1.0 mol / L of lithium hexafluorophosphate (LiPF ₆ ) was dissolved as an electrolyte. As a comparative example, an electrolytic solution was prepared using the same amount of LiPF ₆ as an electrolyte in a mixed solvent obtained by mixing only a mixed solvent of EC and DMC, and further tris borate (trimethyl) containing no fluorine at a predetermined ratio.

2. Flame retardancy (self-extinguishing) test 0.5 g of electrolyte solution was dropped into 0.25 g of glass wool in a circular shape of about 2 cm. The glass wool in which this electrolyte solution was immersed was exposed to flame and ignited, and the presence or absence of ignition and the time until extinguishing when ignited were measured. This test was measured 5 times, and the average value of 3 points, excluding the upper and lower 2 points out of 5 times, was compared as the fire extinguishing time per 1 g (SET, sec / g).
The same flame retardant (self-digestibility) test was conducted using tris (2,2,3,3-tetrafluoropropyl) borate (TFPB) and tris (2H-hexafluoroisopropyl) borate (HFPB). The results are shown in Table-1.

3. Charging / discharging efficiency and cycle characteristics of the battery Lithium cobaltate (LiCoO ₂ ) was used as the positive electrode active material, and carbon black was used as the conductive additive, and polyvinylidene fluoride (PVDF) was used as the binder, LiCoO ₂ : carbon black: PVDF = 85: What was blended so as to be 7: 8 and slurried using 1-methyl-2-pyrrolidone was applied onto the aluminum current collector at a constant film pressure and dried to obtain a positive electrode.

A lithium metal foil was used as the negative electrode active material, and a negative electrode was obtained by pressure bonding to a copper current collector.
A glass filter was used as the separator.
EC: DMC was mixed at a volume ratio of 1: 1, and a predetermined amount of TFEB was added thereto. A solution obtained by dissolving LiPF ₆ in the mixed solvent to be 1.0 mol / L was used as the electrolyte.

A coin-type lithium ion secondary battery having the structure shown in FIG. 1 was prepared using the above components. Note that the battery is not limited to a coin type, and may be a cylindrical type.
The operating principle is that when charging is performed by applying a DC voltage between the current collectors 2 and 4, Li ions existing between the LiCoO ₂ layers of the positive electrode 3 pass through the electrolytic solution and deposit on the negative electrode 1. Li ions return between the LiCoO ₂ layers of the positive electrode 3 in a state where the stable chemical potential is low. This energy difference generates a voltage.

  Charging / discharging when the battery thus prepared was charged at a constant current of 25 ° C. with a current of 1.0 mA and an upper limit voltage of 4.2 V, and then discharged with a current of 1.0 mA to 3.0 V. Efficiency was measured. Such a charge / discharge cycle was repeated 200 times, and the ratio of the 200th discharge capacity to the initial discharge capacity was calculated as the cycle maintenance ratio.

  In addition, after charging a battery prepared in the same manner at a constant current of 25 mA and a constant current / constant voltage with a current of 10 mA and an upper limit voltage of 4.2 V, the battery was discharged to 3.0 V with a current of 30 mA. The discharge efficiency was measured. This test was repeated 200 times, and the 200th discharge capacity with respect to the initial charge / discharge efficiency was calculated as a high rate charge / discharge maintenance rate. The results are shown in Table 1.

It should be noted that tricycle (2,2,3,3-tetrafluoropropyl) borate (TFPB) and tris (2H-hexafluoroisopropyl) borate (HFPB) were used to maintain the same cycle maintenance rate and high rate charge / discharge maintenance. The results of the rate measurement are also shown in Table 1.

4). LiPF ₆ Solubility Test EC: 1 of DMC at a volume ratio of: 1 mixture was added TFEB from 10 volume% to up to 50 volume%, the LiPF ₆ dissolved by heating in the mixed solvent, the supernatant was crystallized out by cooling The saturation solubility of was measured by 19F-NMR. The results are shown in Table 2.

1 Negative electrode (lithium foil)
2 Current collector (Cu)
3 Positive electrode (LiCoO ₂ )
4 Current collector (Al)
5 Separator (glass filter)

Claims (5)

The following general formula (1)
(In the formula, R1, R2 and R3 may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms or a fluorine-containing alkyl group, and at least one of R1, R2 and R3 is a fluorine-containing alkyl group. An additive for an electrolytic solution of a lithium ion secondary battery containing the fluorinated boric acid ester shown in FIG. The additive for a lithium ion secondary battery electrolyte according to claim 1, wherein the fluorinated boric acid ester is tris (2,2,2-trifluoroethyl) borate. The additive for an electrolytic solution of a lithium ion secondary battery according to claim 1, wherein the fluorinated boric acid ester is tris (2,2,3,3-tetrafluoropropyl) borate. The additive for an electrolytic solution of a lithium ion secondary battery according to claim 1, wherein the fluorinated boric acid ester is tris borate (2H-hexafluoroisopropyl). 5. The lithium ion secondary according to claim 1, wherein the content of the fluorine-containing borate ester of the general formula (1) is mixed within a range of 15% by volume to 50% by volume with respect to the nonaqueous electrolytic solution. Additive for battery electrolyte.