JP2003272702A - Electrolyte material for lithium secondary battery and lithium secondary battery using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrolyte material for a lithium secondary battery with a light load to environment. <P>SOLUTION: This electrolyte material for the lithium secondary battery contains lithium bis(dicarboxylic acid) borate represented by general formula 9. Since halogen elements are not contained, the electrolyte material with the light load to environment is obtained. Since two carboxylic acids coordinated to boron have specified structure, the degree of dissociation of lithium is large, and the stable electrolyte material is obtained. (In the formula, R<SB>1</SB>, R<SB>2</SB>are each hydrogen, a 1-3C alkyl). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolyte material used in a lithium secondary battery that utilizes the absorption / desorption phenomenon of lithium ions, and a lithium secondary battery using the same.

[0002]

2. Description of the Related Art Lithium secondary batteries that utilize the absorption and desorption phenomenon of lithium have a high energy density.
With the miniaturization of mobile phones, personal computers, etc., they have become widely used in the fields of communication equipment and information related equipment. Also in the field of automobiles, development of electric vehicles is urgently required due to resource problems and environmental problems, and lithium secondary batteries are also considered as a power source for these electric vehicles.

Lithium secondary batteries currently in practical use
Is generally a lithium transition metal composite oxide in the positive electrode active material.
And a negative electrode using a carbon material as the negative electrode active material
And a non-aqueous electrolyte solution in which an electrolyte material is dissolved in an organic solvent
Which has a high voltage of 4V class
Mainstream. And the electrolysis that constitutes the electrolytic solution
The material is dissolved in an organic solvent to generate lithium ions.
As a LiBF _Four, LiPF₆, LiClO_Fouretc
Is often used.

[0004]

Generally, in a lithium secondary battery, an electrolyte solution is used only in a very small amount to impregnate an electrode. Therefore, it is difficult to collect the electrolytic solution when processing the used lithium secondary battery.
Therefore, it is considered that after the use of the lithium secondary battery, the electrolytic solution is incinerated together with other constituent members such as a separator.

Electrolyte materials such as LiBF ₄ currently used contain halogen elements such as fluorine and chlorine. Therefore, when the electrolytic solution containing the electrolyte material is incinerated, dioxin may be generated, which causes environmental pollution.

The present invention has been made to solve the above problems, and an object of the present invention is to provide an electrolyte material for a lithium secondary battery, which has a low environmental load.

[0007]

The electrolyte material for a lithium secondary battery of the present invention has the general formula

[0008]

[Chemical 5]

Lithium bis (dicarboxylic acid) represented by
It is characterized by including a baud rate. As shown in the above formula (1), the lithium bis (dicarboxylic acid) borate contains no halogen element. in this way,
By using a non-halogen boron-based lithium salt as the electrolyte material, the generation of dioxins is small even when the battery is used and then incinerated. That is, the environmental load is reduced.

On the other hand, the present inventor paid attention to the resonance effect (M-effect) in the benzene ring and the electron transfer effect (E-effect) due to the resonance effect, and if these effects were utilized, it was more stable and It was found that an electrolyte material having a large degree of dissociation of lithium ions can be obtained. That is,
Focusing on the two dicarboxylic acids coordinated to the boron of the lithium bis (dicarboxylic acid) borate, the dicarboxylic acids are each cyclically coordinated. In addition, the two carbons bonded to the carbon in the carboxyl group of each dicarboxylic acid are bonded by a double bond. Therefore, the anion in the lithium bis (dicarboxylic acid) borate is stabilized by the resonance effect due to this double bond. Further, due to the presence of the carbon double bond, the electron of the boron atom is attracted. When electrons are attracted, the boron atom becomes electron deficient. As the boron atom becomes electron-deficient, it becomes easier to receive an electron from the lithium atom.
The dissociation degree of lithium ions increases.

As described above, the electrolyte material for a lithium secondary battery according to the present invention is a material having a low electrolyte load and a high electrolyte capacity. Further, by dissolving the electrolyte material for a lithium secondary battery of the present invention in an organic solvent to form an electrolytic solution, an electrolytic solution having a low environmental load and a high electric conductivity can be formed.

The lithium secondary battery of the present invention is a lithium secondary battery comprising a positive electrode, a negative electrode, and an electrolytic solution prepared by dissolving an electrolytic material in an organic solvent, wherein the electrolytic material is represented by the above formula (1). It is characterized in that it contains the indicated lithium bis (dicarboxylic acid) borate. That is, by including the above electrolyte material of the present invention, the lithium secondary battery of the present invention becomes a lithium secondary battery having a low environmental load and good battery performance.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The electrolyte material for a lithium secondary battery of the present invention, the electrolyte solution for a lithium secondary battery using the same, and the lithium secondary battery will be described in detail below. Note that the embodiment to be described is only one embodiment, the electrolyte material for a lithium secondary battery of the present invention, the electrolyte solution for a lithium secondary battery using the same, and the lithium secondary battery are limited to the following embodiments. Not something. The present invention can be implemented in various forms including various modifications and improvements based on the knowledge of those skilled in the art, including the following embodiments.

<Electrolyte Material for Lithium Secondary Battery> The electrolyte material for lithium secondary battery of the present invention contains the lithium bis (dicarboxylic acid) borate represented by the above formula (1). As shown in the above formula (1), if the two carbons bonded to the carbon in the carboxyl group of each dicarboxylic acid coordinated with boron are bonded with a double bond, the kind thereof is It is not limited. For example,
formula

[0015]

[Chemical 6]

Lithium bis (citraconic acid) represented by
Baud rate, formula

[0017]

[Chemical 7]

Lithium bis (maleic acid) borate, lithium bis (cis 1,2 dimethyl ethylene 1,2 dicarboxylic acid) borate, lithium bis (cis 1,2 diethyl 1,2 dicarboxylic acid) borate, lithium bis ( Cis 1 ethyl ethylene 1,2 dicarboxylic acid)
Examples include baud rate. These may be used alone or in combination of two or more. Among them, lithium bis (citraconic acid) borate and lithium bis (maleic acid) borate are easily dissolved in a mixed solvent of ethylene carbonate and diethyl carbonate, which is generally used as an electrolytic solution for lithium secondary batteries. Is preferred.

The method for producing the lithium bis (dicarboxylic acid) borate is not particularly limited.
The present inventor has conducted extensive studies and has established a simple and high-yield synthetic method for lithium bis (dicarboxylic acid) borate. Hereinafter, a method for producing lithium bis (dicarboxylic acid) borate will be described.

This production method comprises a first raw material preparing step for preparing a first raw material containing lithium tetraalkoxy borate, a second raw material preparing step for preparing a second raw material containing a predetermined dicarboxylic acid, and a first raw material. The second raw material is reacted to exchange the alkoxy group of lithium tetraalkoxy borate with the dicarboxylic acid to synthesize lithium bis (dicarboxylic acid) borate.

The lithium tetraalkoxy borate (LiB (OR) ₄ ) used as the first raw material is not particularly limited in its alkoxy group (—OR).
The alkoxy group is preferably a methoxy group because it has a low electron donating property and the exchange reaction described below easily proceeds. For example, it is preferable to use lithium tetramethoxyborate (LiB (OCH ₃ ) ₄ ). Also,
The first raw material is not particularly limited as long as it contains lithium tetraalkoxy borate. For example, lithium tetraalkoxy borate can be added to a predetermined solvent to prepare a lithium tetraalkoxy borate solution. In this case, the solvent is preferably one in which at least one of lithium tetraalkoxy borate and dicarboxylic acid used as the second raw material is dissolved. In particular, since the dicarboxylic acid used as the second raw material is easily dissolved and can be used as the organic solvent in the electrolytic solution for a lithium secondary battery, it is preferable to use a mixture of ethylene carbonate and diethyl carbonate, respectively. . The amount of the solvent is not particularly limited, and may be about 100 to 200 mL with respect to 0.2 mol of lithium tetraalkoxy borate.

The dicarboxylic acid to be exchanged with the alkoxy group of lithium tetraalkoxy borate may be appropriately selected according to the desired lithium bis (dicarboxylic acid) borate. For example, when synthesizing lithium bis (citraconic acid) borate, citraconic acid may be used as the dicarboxylic acid. When synthesizing lithium bis (maleic acid) borate, maleic acid may be used as the dicarboxylic acid. The second raw material is not particularly limited as long as it contains the above dicarboxylic acid. For example, dicarboxylic acid can be added to a predetermined solvent to prepare a dicarboxylic acid solution. in this case,
As with the above, the solvent used is not particularly limited,
For the reasons described above, ethylene carbonate and diethyl carbonate can be mixed and used.
The amount of solvent may be about 100 to 200 mL with respect to 0.4 mol of dicarboxylic acid.

The reaction between the first raw material and the second raw material may be carried out by mixing both the prepared raw materials. The mixing ratio of the first raw material and the second raw material may be such that the dicarboxylic acid is 2 equivalents with respect to 1 equivalent of lithium tetraalkoxy borate. The reaction conditions for the above reaction are not particularly limited. In order to accelerate the reaction, for example, reflux may be performed under heating, and by-products may be removed by distillation, extraction or the like. Furthermore, it is desirable to purify the reaction product by vacuum drying or the like.

<Electrolytic Solution for Lithium Secondary Battery> The electrolytic solution for a lithium secondary battery of the present invention is obtained by dissolving the electrolyte material of the present invention in an organic solvent. In addition to the above electrolyte material, a radical scavenger, a surfactant, a flame retardant, or the like may be added to form an electrolytic solution. The concentration of the electrolyte material in the electrolytic solution is 0.5M because it increases the ionic conductivity.
It is desirable to set it to 1.5 M or less. This is because when the concentration of the electrolyte material is less than 0.5 M, the ionic conductivity is small and a sufficient capacity cannot be obtained, and when it exceeds 1.5 M, the viscosity of the electrolytic solution becomes high and the ionic conductivity increases. This is because the conductivity becomes small.

As the organic solvent for dissolving the above electrolyte material, an aprotic organic solvent having no ability to donate hydrogen ions is used. For example, a cyclic carbonate, a chain carbonate, a cyclic ester, a cyclic ether, a chain ether, a phosphazene compound, or a phosphoric acid compound may be used alone or in combination of two or more. Examples of the cyclic carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate and the like, examples of the chain carbonate include dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate, and examples of the cyclic ester include γ-butyrolactone and γ. -Valerolactone and the like, tetrahydrofuran as an example of the cyclic ether,
2-Methyltetrahydrofuran and the like, examples of chain ethers include dimethoxyethane, ethylene glycol dimethyl ether and the like, examples of phosphazene compounds include hexaethoxytricyclophosphazene, tripropoxyphosphazophosphonyl dipropoxide, and phosphoric acid. Examples of the compound include trioctyl phosphate, tributyl phosphate and the like. Any one of these may be used alone, or two or more of them may be mixed and used.

Further, the organic solvent is required to have a high dielectric constant in order to promote the dissociation of lithium ions in the electrolyte material and a low viscosity in order not to hinder the movement of lithium ions. However, since there is no suitable organic solvent having both properties of high dielectric constant and low viscosity, it is general to use a mixture of an organic solvent of high dielectric constant and an organic solvent of low viscosity. For example, it is desirable to use ethylene carbonate as a high dielectric constant solvent and diethyl carbonate as a low viscosity solvent, respectively. High electrical conductivity can be obtained by mixing these. The mixing ratio of ethylene carbonate and diethyl carbonate is preferably in the range of 8: 2 to 2: 8 by volume ratio. When the mixing ratio of ethylene carbonate becomes small, the dissociation of lithium ions in the electrolyte material is not sufficiently performed, and the conductivity of lithium ions decreases. On the other hand, when the mixing ratio of diethyl carbonate decreases, the viscosity of the electrolytic solution increases and the conductivity of lithium ions also decreases. Further, since ethylene carbonate is a solid at room temperature, if the mixing ratio of ethylene carbonate is large, it may be solidified in the battery. In consideration of these, in order to make the battery reaction proceed more smoothly, the mixing ratio of ethylene carbonate and diethyl carbonate is preferably in the range of 7: 3 to 3: 7 by volume, and is 5: 5. It is more preferable.

<Lithium Secondary Battery> The lithium secondary battery of the present invention is a secondary battery provided with an electrolytic solution in which the above electrolyte material is dissolved in an organic solvent. Other than the electrolyte material, other constituent elements are particularly The present invention is not limited to this, and an ordinary lithium secondary battery that already exists may be used. Hereinafter, each component will be described.

For the positive electrode, a positive electrode active material capable of inserting and extracting lithium ions is mixed with a conductive material and a binder, and a suitable solvent is added to form a paste-like positive electrode mixture. It can be formed by coating and drying on the surface of a current collector made of, and compressing to increase the electrode density if necessary. In this case, application, drying, pressing and the like may be performed according to ordinary methods.

The positive electrode active material is not particularly limited, and for example, a lithium transition metal composite oxide can be used. Examples of the lithium-transition metal composite oxide include a lithium cobalt composite oxide and a lithium nickel composite oxide having a layered rock salt structure with a basic composition of LiCoO ₂ and LiNiO ₂ , from the viewpoint that a secondary battery of 4 V class can be formed. Alternatively, it is preferable to use a lithium manganese composite oxide having a spinel structure having a basic composition of LiMn ₂ O ₄ . Of these lithium-transition metal composite oxides, one type may be used alone, or two or more types may be mixed and used.

In particular, it is desirable to use a layered rock salt structure lithium nickel composite oxide having a basic composition of LiNiO _{2 from} the viewpoint that it is cheaper than LiCoO ₂ and can form a secondary battery having a large capacity. The basic composition means a typical composition of each of the above composite oxides, and in addition to the one represented by the above composition formula, for example, a lithium site or a transition metal site may be another type such as Al or Fe, or It also includes compositions such as those in which two or more elements are partially replaced. Further, it is not necessarily limited to a stoichiometric composition, and for example, a non-stoichiometric composition in which a cation atom such as lithium or a transition metal, which is inevitably produced in production, is deficient or an oxygen atom is deficient. Also includes things.

The conductive material is for ensuring the electric conductivity of the positive electrode, and for example, one or a mixture of two or more kinds of carbon substance powders such as carbon black, acetylene black, graphite and the like should be used. You can The binder plays a role of binding the active material particles and the conductive material particles together, and for example, a fluorine-containing resin such as polytetrafluoroethylene, polyvinylidene fluoride, or fluororubber, or a thermoplastic resin such as polypropylene or polyethylene is used. be able to. An organic solvent such as N-methyl-2-pyrrolidone can be used as a solvent for dispersing the active material, the conductive material, and the binder.

The negative electrode facing the positive electrode can be formed by sheet-forming metal lithium, which is the negative-electrode active material, or by pressing the sheet-shaped one onto a current collector net of nickel, stainless steel or the like. Instead of metallic lithium, a lithium alloy or a lithium compound can be used as the negative electrode active material.

As another form of the negative electrode, the negative electrode can be formed by using a carbon material capable of absorbing and desorbing lithium ions as the negative electrode active material. Examples of carbon substances that can be used include graphitic materials such as natural graphite, spherical or fibrous artificial graphite, easily graphitizable carbon such as coke, and carbonaceous materials such as non-graphitizable carbon such as a phenol resin fired body. Can be mentioned. In this case, the negative electrode active material is mixed with a binder, and a suitable solvent is added to form a paste of the negative electrode mixture,
It can be formed by coating on the surface of a metal foil current collector such as copper, drying and then pressing. In this case, coating, drying, pressing and the like may be carried out according to ordinary methods. When a carbon material is used as the negative electrode active material, like the positive electrode, a fluorine-containing resin such as polyvinylidene fluoride can be used as the negative electrode binder, and an organic solvent such as N-methyl-2-pyrrolidone can be used as the solvent.

The separator sandwiched between the positive electrode and the negative electrode separates the positive electrode and the negative electrode and holds the electrolytic solution, and a thin microporous film such as polyethylene or polypropylene can be used.

The lithium secondary battery composed of the above-mentioned components can have various shapes such as a cylindrical type, a laminated type and a coin type. Regardless of which shape is adopted, a separator is sandwiched between the positive electrode and the negative electrode to form an electrode body. Then, the positive electrode current collector and the negative electrode current collector are connected to the positive electrode terminal and the negative electrode terminal that communicate with the outside by using a current collecting lead or the like, and the electrode body is impregnated with an electrolytic solution containing the electrolyte material of the present invention. Seal the battery case to complete the lithium secondary battery.

[0036]

[Example] Based on the above-described embodiment, lithium bis (citraconic acid) borate, lithium bis (maleic acid)
Two types of lithium secondary batteries were prepared using each baud rate as an electrolyte material. In addition, as a comparative example, a lithium secondary battery was manufactured using lithium bis (succinic acid) borate as an electrolyte material. Then, the charge / discharge characteristics of each lithium secondary battery were evaluated. Hereinafter, synthesis of each electrolyte material, production of a lithium secondary battery, and evaluation of charge / discharge characteristics will be described in order.

<Synthesis of Electrolyte Material> (1) Example 1: Synthesis of lithium bis (citraconic acid) borate Lithium bis (citraconic acid) borate was synthesized from lithium tetramethoxyborate. Lithium tetramethoxyborate (LiB (OCH ₃ ) ₄ ) 2
8.6 g (corresponding to 0.2 mol) and citraconic acid (HO
53.3g of _{OC (H 3 C) C =} CHCOOH) (0.4
mol equivalent) was added to a mixed solvent (200 mL) of ethylene carbonate and diethyl carbonate. The mixing ratio of ethylene carbonate and diethyl carbonate in the mixed solvent was 1: 1 by volume. Then, reflux was performed at a temperature of 90 to 100 ° C. for 22 hours.
After completion of the reaction, the mixed solvent was removed by distillation under reduced pressure to obtain a dark brown solid substance. This solid material is heated at 100 ° C for 24 hours
Vacuum dried for an hour. From the results of elemental analysis and infrared absorption spectroscopy, it was confirmed that the solid substance had a lithium bis (citraconic acid) borate.
When the lithium secondary battery described below was manufactured, the reaction solution was used as it was as the electrolytic solution without removing the mixed solvent after the reflux in the above synthesis.

(2) Example 2: Synthesis of lithium bis (maleic acid) borate A lithium bis (maleic acid) borate was synthesized from lithium tetramethoxy borate. In the synthesis method of the above (1), maleic acid (H
46.4 g (0.4 mo of OOCHC = CHCOOH)
l) It was synthesized in the same manner as in (1) above except that it was used. In addition, in the same manner as above, when the lithium secondary battery was produced, the mixed solvent was not removed after the reflux, and the reaction solution was used as it was as the electrolytic solution.

(3) Comparative example: lithium bis (succinic acid)
From the synthetic lithium tetramethoxy baud rate of the baud rate, the formula

[0040]

[Chemical 8]

A lithium bis (succinic acid) borate represented by: was synthesized. In the synthesis method of (1) above, succinic acid (HOOC (CH ₂ ) ₂ CO is used instead of citraconic acid.
OH) was used, except that 47.2 g (0.4 mol) was used.
It was synthesized in the same manner as (1) above. In addition, in the same manner as above, when the lithium secondary battery was produced, the mixed solvent was not removed after the reflux, and the reaction solution was used as it was as the electrolytic solution.

<Preparation of Lithium Secondary Battery> Using each of the above-mentioned electrolyte materials, that is, using the reaction solution after the reaction in the synthesis of each of the above-mentioned electrolyte materials as it is as an electrolyte solution,
Three types of lithium secondary batteries were prepared. In each lithium secondary battery, all constituent elements other than the electrolyte material were the same.

First, the positive electrode is made of LiNiO _{2 as} an active material.
Of artificial graphite powder as a conductive material and 5 parts by weight of polyvinylidene fluoride as a binder are mixed with 85 parts by weight of N., and an appropriate amount of N-methyl-2-pyrrolidone is added as a solvent to form a paste. A positive electrode mixture material was prepared. Then
Using a roll coater,
A 20 μm thick aluminum foil current collector was applied on both sides, dried, and compressed by a roll press to prepare a sheet-shaped positive electrode. In addition, this sheet-shaped positive electrode is 54 mm × 450 m
It was cut into a size of m and used.

For the negative electrodes facing each other, artificial graphite was used as an active material. 5 parts by weight of polyvinylidene fluoride as a binder is mixed with 95 parts by weight of artificial graphite powder as a negative electrode active material, and an appropriate amount of N-methyl-2-pyrrolidone is added as a solvent to prepare a paste-like negative electrode mixture. Was prepared. Next, this paste-like negative electrode mixture was applied onto both surfaces of a copper foil current collector having a thickness of 10 μm using a roll coater, dried, and compressed by a roll press to prepare a sheet-like negative electrode. In addition,
This sheet-shaped negative electrode was cut into a size of 56 mm × 500 mm and used.

The positive electrode and each negative electrode were wound with a polyethylene separator having a thickness of 25 μm and a width of 58 mm interposed between them to form a roll-shaped electrode body. And
The electrode body is used as an 18650 type cylindrical battery case (outer diameter 18
mmφ, length 65 mm), the above electrolytic solutions were injected, the battery case was sealed, and a cylindrical lithium secondary battery was produced. The thus-produced secondary batteries were made into lithium secondary batteries of Examples 1 and 2 and Comparative Example using each electrolyte material.

<Evaluation of Charging / Discharging Characteristics> The charging / discharging characteristics of each secondary battery were evaluated by charging / discharging each of the secondary batteries of Examples 1 and 2 and Comparative Example. Charge and discharge at 20 ℃,
3. Charging upper limit voltage at a constant current with a current density equivalent to 0.02C.
After charging to 1 V, discharging was performed to a discharge lower limit voltage of 3.0 V with a constant current having a current density equivalent to 0.02 C. The current density when discharging the reference capacity of each secondary battery in 1 hour (current density in 1-hour rate discharge) is 1C. FIG. 1 shows the voltage change during charge / discharge of each secondary battery.

As is clear from FIG. 1, the secondary batteries of Examples 1 and 2 were capable of charging / discharging up to around 3 to 4.1V. In other words, lithium bis (citraconic acid)
It is understood that a 4V class battery can be constructed when a baud rate or lithium bis (maleic acid) baud rate is used as the electrolyte material. As described above, it was confirmed that the electrolyte material of the present invention has excellent electrolyte ability. On the other hand, the lithium secondary battery of the comparative example could not be discharged because the voltage at the end of charging was 3 V or less (not shown). That is, it was found that lithium bis (succinic acid) borate in which a dicarboxylic acid having no carbon bonded by a double bond is coordinated with boron is not suitable as an electrolyte material.

[0048]

The electrolyte material for a lithium secondary battery of the present invention contains the lithium bis (dicarboxylic acid) borate represented by the above formula (1). Since it does not contain halogen elements, it becomes an electrolyte material with a low environmental impact. Further, since the two dicarboxylic acids coordinated to boron have a predetermined structure, the degree of dissociation of lithium ions is large and the electrolyte material is stable. By using such an electrolyte material, the electrolytic solution for a lithium secondary battery of the present invention becomes an electrolytic solution having a low environmental load and a high electric conductivity. Moreover, since the lithium secondary battery of the present invention is configured to include the electrolyte material of the present invention, it is a lithium secondary battery having a small environmental load and good battery performance.

[Brief description of drawings]

FIG. 1 shows voltage changes during charge and discharge of each secondary battery of Example 1 and Example 2.

Continued front page    (72) Inventor Yoshio Ukyo             Aichi Prefecture Nagachite Town Aichi District             Local 1 Toyota Central Research Institute Co., Ltd. F-term (reference) 4H048 AA03 AB78 AB91 VA50 VA77                 5H029 AJ12 AK03 AL07 AM03 AM05                       AM07 BJ02 BJ14 BJ27 EJ11                       HJ02

Claims (5)

[Claims] 1. A general formula: An electrolyte material for a lithium secondary battery containing a lithium bis (dicarboxylic acid) baud rate represented by: 2. The lithium bis (dicarboxylic acid) borate has the formula: The electrolyte material for a lithium secondary battery according to claim 1, which is a lithium bis (citraconic acid) baud rate represented by: 3. The lithium bis (dicarboxylic acid) borate has the formula: The electrolyte material for a lithium secondary battery according to claim 1, which is a lithium bis (maleic acid) baud rate represented by: 4. An electrolytic solution for a lithium secondary battery, wherein the electrolyte material for a lithium secondary battery according to claim 1 is dissolved in an organic solvent. 5. A lithium secondary battery comprising a positive electrode, a negative electrode, and an electrolytic solution in which an electrolytic material is dissolved in an organic solvent, wherein the electrolytic material has the general formula: A lithium secondary battery containing a lithium bis (dicarboxylic acid) baud rate represented by: