JP2005228631A - Electrolytic solution for secondary battery, and secondary battery using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lithium secondary battery, having the properties of an outstanding energy density, electromotive force, and the like, as well as superior cycle life time and safety. <P>SOLUTION: An electrolytic solution for secondary batteries is used in which a sulfonate compound is contained in an aprotic solvent. Alternatively, an electrolytic solution for secondary batteries is used, in which a sulfonate compound or a vinylene carbonate is further contained in the electrolytic solution. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an electrolyte for a secondary battery and a secondary battery using the same.

  Non-aqueous electrolyte lithium ion or lithium secondary batteries using carbon materials, oxides, lithium alloys or lithium metals for the negative electrode and lithium-containing transition metal composite oxides for the positive electrode can realize high energy density. It is attracting attention as a power source for notebook computers. In this secondary battery, it is known that a surface film, a protective film, or a film called SEI or a film is formed on the surface of the electrode. Since this surface film has a great influence on charge / discharge efficiency, cycle life, and safety, it is known that control of the surface film is indispensable for improving the performance of the electrode. For carbon materials and oxide materials, it is necessary to reduce the irreversible capacity, and for lithium metal and alloy negative electrodes, it is necessary to solve the problem of safety due to reduction in charge / discharge efficiency and generation of dendrites.

  Various techniques have been proposed as a technique for solving these problems. For example, it has been proposed to suppress the formation of dendrite by providing a film layer made of lithium fluoride or the like using a chemical reaction on the surface of lithium metal or lithium alloy.

Patent Document 1 discloses a technique in which a lithium negative electrode is exposed to an electrolytic solution containing hydrofluoric acid, and the negative electrode is reacted with hydrofluoric acid to cover the surface with a lithium fluoride film. Hydrofluoric acid is produced by the reaction of LiPF ₆ and a small amount of water. On the other hand, a surface film of lithium hydroxide or lithium oxide is formed on the surface of the lithium negative electrode by natural oxidation in air. When these react, a surface film of lithium fluoride is formed on the negative electrode surface. However, this lithium fluoride film is formed by utilizing the reaction between the electrode interface and the liquid, and side reaction components are likely to be mixed into the surface film, and it may be difficult to obtain a uniform film. . Also, there may be cases where the surface film of lithium hydroxide or lithium oxide is not uniformly formed or there is a part where lithium is exposed. In these cases, a uniform thin film cannot be formed. In addition, there is a safety problem due to the reaction of lithium with water or hydrogen fluoride. Moreover, when reaction is inadequate, unnecessary compound components other than a fluoride remain, and bad influences, such as causing the fall of ion conductivity, are considered. Furthermore, in the method of forming a fluoride layer using such a chemical reaction at the interface, there are cases where the selection range of available fluorides and electrolytes may be limited, and a stable surface film is formed with high yield. It was difficult.

  In Patent Document 2, a mixed gas of argon and hydrogen fluoride and an aluminum-lithium alloy are reacted to obtain a lithium fluoride surface film on the negative electrode surface. However, when a surface film is preliminarily present on the surface of the lithium metal, particularly when a plurality of types of compounds are present, the reaction tends to be non-uniform and it may be difficult to form a lithium fluoride film uniformly. It was. In this case, it is difficult to obtain a lithium secondary battery having sufficient cycle characteristics.

  Patent Document 3 discloses a technique for forming a surface film structure mainly composed of a substance having a rock salt type crystal structure on the surface of a lithium sheet having a uniform crystal structure, that is, a (100) crystal plane preferentially oriented. It is disclosed. By carrying out like this, it is said that uniform precipitation dissolution reaction, ie, charge / discharge of a battery, can be performed, dendrite precipitation of lithium metal can be suppressed, and the cycle life of the battery can be improved. It is stated that the substance used for the surface film preferably has a halide of lithium, and it is preferable to use a solid solution of LiF with at least one selected from LiCl, LiBr, and LiI. Specifically, in order to form a solid solution film of at least one of LiCl, LiBr, and LiI and LiF, a lithium sheet with a (100) crystal plane preferentially oriented formed by pressing (rolling) is used. A negative electrode for a non-aqueous electrolyte battery is created by immersing in an electrolyte containing at least one of chlorine molecules or chlorine ions, bromine molecules or bromine ions, iodine molecules or iodine ions, and fluorine molecules or fluorine ions. . In the case of this technology, a rolled lithium metal sheet is used, and since the lithium sheet is easily exposed to the atmosphere, a film derived from moisture and the like is easily formed on the surface, and the presence of active sites becomes uneven, which is the purpose. In some cases, it is difficult to produce a stable surface film, and the effect of suppressing dentlite is not always sufficiently obtained.

  In addition, when a carbon material such as graphite or hard carbon capable of occluding and releasing lithium ions is used as the negative electrode, a technique for improving capacity and charge / discharge efficiency has been reported.

  In patent document 4, the negative electrode which coat | covered the carbon material with aluminum is proposed. Thereby, reductive decomposition on the carbon surface of solvent molecules solvated with lithium ions is suppressed, and deterioration of cycle life is suppressed. However, since aluminum reacts with a small amount of water, the capacity may decrease rapidly when the cycle is repeated.

  Patent Document 5 proposes a negative electrode in which the surface of a carbon material is covered with a thin film of a lithium ion conductive solid electrolyte. Thereby, it is said that the decomposition | disassembly of the solvent which arises when using a carbon material can be suppressed, and especially the lithium ion secondary battery which can use a propylene carbonate can be provided. However, cracks generated in the solid electrolyte due to changes in stress during insertion and desorption of lithium ions may lead to deterioration of characteristics. Further, due to non-uniformity such as crystal defects of the solid electrolyte, a uniform reaction cannot be obtained on the negative electrode surface, leading to deterioration of cycle life.

  Further, in Patent Document 6, the negative electrode is made of a material containing graphite, the electrolytic solution is mainly composed of cyclic carbonate and chain carbonate, and 0.1 to 4% by weight of 1,3 in the electrolytic solution. -Secondary batteries containing propane sultone and / or 1,4-butane sultone are disclosed. Here, 1,3-propane sultone or 1,4-butane sultone contributes to the formation of a passive film on the surface of the carbon material, and the active and highly crystallized carbon material such as natural graphite or artificial graphite is a passive film. It is considered that the coating has an effect of suppressing the decomposition of the electrolyte without impairing the normal reaction of the battery.

In Patent Document 7, by adding an aromatic compound to the electrolyte solvent, the deterioration of the capacity when the secondary battery is repeatedly charged and discharged over a long period of time is suppressed by preventing oxidation of the electrolyte solvent. This is a technique for preventing the decomposition of the solvent by preferentially oxidatively decomposing the aromatic compound. However, when this additive is used, the positive electrode surface is not coated, so that the effect of improving the cycle characteristics may not be sufficient. Patent Document 8 describes a technique for improving cycle characteristics when a high-voltage positive electrode is used by adding a nitrogen-containing unsaturated cyclic compound to an electrolytic solution. However, although nitrogen-containing unsaturated cyclic compounds improve the charge / discharge efficiency of the negative electrode, they generally do not improve the charge / discharge efficiency of the positive electrode.
JP-A-7-302617 JP-A-8-250108 Japanese Patent Laid-Open No. 11-288706 Japanese Patent Laid-Open No. 5-234583 JP-A-5-275077 JP 2000-3724 A JP 2003-7334 A JP 2003-115324 A

However, the above prior art has the following common problems.
The surface film generated on the electrode surface is deeply related to charge / discharge efficiency, cycle life, and safety depending on its properties, but there is no method for controlling the film for a long time. For example, when a surface film made of lithium halide or a glassy oxide is formed on a layer made of lithium or an alloy thereof, although a certain degree of dentite suppression effect can be obtained during initial use, In some cases, the surface film deteriorates and the function as a protective film decreases. This is because a layer made of lithium or an alloy thereof changes in volume by occlusion / release of lithium, whereas a film made of lithium halide or the like located on the upper side hardly changes in volume. This is thought to be due to the generation of internal stress at the interface. By generating such internal stress, it is considered that a part of the surface film made of lithium halide or the like is particularly damaged, and the dendrite suppressing function is lowered.

For carbon materials such as graphite, charges due to decomposition of solvent molecules or anions appear as irreversible capacity components, which may lead to a decrease in initial charge / discharge efficiency. Further, the composition, crystal state, stability, etc. of the film produced at this time have a great influence on the subsequent efficiency and cycle life.
In the case of a secondary battery having a high voltage of 4.5 V or more using a lithium-containing transition metal composite oxide for the positive electrode, decomposition of solvent molecules may occur on the positive electrode. Invited.

As described above, studies have been made to improve the charge / discharge efficiency and cycle life by forming a film on the electrode for the secondary battery, but sufficient battery characteristics have not been obtained yet.
The present invention has been made in view of the above situation, and by containing a predetermined sulfonic acid ester compound in an aprotic solvent, it has excellent characteristics such as energy density and electromotive force, and is charged and discharged. The object is to obtain a lithium secondary battery excellent in efficiency, cycle life and safety.

  According to the present invention, when a secondary battery is produced by applying an aprotic electrolyte solution containing at least a sulfonic acid ester compound represented by the general formula (1) to an aprotic solvent, the charge / discharge efficiency is obtained. Excellent cycle characteristics. That is, this invention relates to the electrolyte solution for secondary batteries containing an aprotic solvent and the sulfonic acid ester compound shown by following General formula (1) at least.

(In the general formula (1), n = 1 to 5, m = 1 to 5, and R ₁ and R ₂ are each independently a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms or fluoroalkylene. And may be branched.)
Furthermore, in the present invention, the sulfonic acid ester compound is preferably a compound represented by the following general formula (2).

(However, in the said General formula (2), it is n = 2-10, R is a substituted or unsubstituted C1-C5 alkylene group or fluoroalkylene group, and may branch.)
Furthermore, in the present invention, the sulfonic acid ester compound is preferably a compound represented by the following general formula (3).

(In the general formula (3), R ₁ and R ₂ are each independently a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms or a fluoroalkylene group.)
Furthermore, in the present invention, the sulfonic acid ester compound is preferably a compound represented by the following general formula (4).

(However, in the general formula (4), x and y are each independently 1 to 5).
Furthermore, in the present invention, the sulfonic acid ester compound is preferably a compound represented by the following general formula (5).

(However, in the said General formula (5), x is 1-5 and n is 2-10.)
Furthermore, in the present invention, it is preferable that the electrolyte solution for a secondary battery further includes a compound having one or more sulfonyl groups.
Furthermore, in the present invention, the compound having a sulfonyl group is preferably a compound represented by at least the following general formula (6).

(In the general formula (6), Q represents an oxygen atom, a methylene group or a divalent group represented by —CH ₂ —S—, and A represents a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms. , A carbonyl group, a sulfinyl group, a substituted or unsubstituted fluoroalkylene group having 1 to 6 carbon atoms, or an ether group and an alkylene group or fluoroalkylene group having 2 to 6 carbon atoms, and B represents a substituted or unsubstituted alkylene group Represents a group, a substituted or unsubstituted fluoroalkylene group, or an oxygen atom, which may be branched.)
Here, the fluoroalkylene group is one in which part or all of the hydrogen atoms bonded to the carbon atom are substituted with fluorine atoms.

  According to the present invention, an electrolytic solution for a secondary battery in which an aprotic solvent contains a sulfonic acid ester compound, or a secondary battery in which the electrolytic solution further contains a sulfonic acid ester compound or vinylene carbonate different from the above. By using the electrolytic solution for use, it is possible to obtain a lithium secondary battery having excellent characteristics such as energy density and electromotive force, and having excellent cycle life and safety.

  The electrolytic solution for a secondary battery of the present invention is characterized in that a compound represented by the following general formula (1) is contained in an aprotic solvent.

(In the general formula (1), n = 1 to 5, m = 1 to 5, and R ₁ and R ₂ are each independently a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms or fluoroalkylene. And may be branched.)
Here, the fluoroalkylene group is one in which part or all of the hydrogen atoms bonded to the carbon atom are substituted with fluorine atoms.
In addition, when R ₁ and R ₂ of the sulfonate compound represented by the general formula (1) are substituted alkylene groups or fluoroalkylene groups, the substituents in R ₁ and R ₂ are each independently A sulfonyl group, a sulfinyl group or an alkoxy group is preferred. When R ₁ and R ₂ have these substituents, the film formed on the electrode can have a low resistance.
By having such an electrolytic solution, it is possible to form a film on the electrode surface, and to obtain a lithium secondary battery having excellent characteristics such as energy density and electromotive force, and having excellent cycle life and safety. it can.

  Here, for example, the coating is formed by combining a negative electrode and a positive electrode having lithium as an active material with a separator interposed therebetween, and after being inserted into a battery outer package, impregnated with an electrolytic solution containing a compound represented by the general formula (1), It can be formed by charging the battery after sealing or sealing the battery outer package.

  The compound represented by the general formula (1) is preferably contained in the electrolytic solution in an amount of 0.01 to 10% by mass. If it is less than 0.01% by mass, the film formation on the electrode surface is not sufficiently effective. Exceeding 10% by mass is not preferable because it not only dissolves but also increases the viscosity of the electrolyte. In the present invention, a sufficient film effect can be obtained by adding 0.05 to 5% by mass, more preferably 0.1 to 5% by mass.

  Representative examples of the sulfonic acid ester compound represented by the general formula (1) are illustrated below, but the present invention is not limited thereto.

  These compounds represented by the general formula (1) can be obtained, for example, by applying the production methods described in US Pat. No. 4,950,768 and JP-B-5-44946.

  FIG. 1 shows a schematic structure of an example of a battery according to the present invention. A positive electrode current collector 11, a layer 12 containing a positive electrode active material composed of any of oxides or sulfur compounds capable of inserting and extracting lithium ions, conductive polymers, stabilized radical compounds, or a mixture thereof; lithium A carbon material or oxide that occludes and releases ions; a metal that forms an alloy with lithium; a layer 13 containing a negative electrode active material made of lithium metal itself or a mixture thereof; a negative electrode current collector 14; It is comprised from the liquid 15 and the porous separator 16 containing this. Here, the sulfonic acid ester compound represented by the general formula (1) is contained in the electrolytic solution 15 containing a lithium salt as an electrolyte.

  As the positive electrode current collector, aluminum, stainless steel, nickel, titanium, or an alloy thereof can be used. As the negative electrode current collector, copper, stainless steel, nickel, titanium, or an alloy thereof can be used.

  Aprotic Solvent The electrolytic solution in the present invention is cyclic such as propylene carbonate (hereinafter referred to as PC), ethylene carbonate (hereinafter referred to as EC), butylene carbonate (BC), vinylene carbonate (VC) and the like. Carbonates, dimethyl carbonate (hereinafter referred to as DMC), diethyl carbonate (hereinafter referred to as DEC), chain carbonates such as ethyl methyl carbonate (EMC) and dipropyl carbonate (DPC), methyl formate, Aliphatic carboxylic acid esters such as methyl acetate and ethyl propionate, γ-lactones such as γ-butyrolactone, chain ethers such as 1,2-ethoxyethane (DEE) and ethoxymethoxyethane (EME), tetrahydrofuran, Such as 2-methyltetrahydrofuran Cyclic ethers, dimethyl sulfoxide, 1,3-dioxolane, formamide, acetamide, dimethylformamide, dioxolane, acetonitrile, propylnitrile, nitromethane, ethyl monoglyme, phosphoric acid triester, trimethoxymethane, dioxolane derivatives, sulfolane, methylsulfolane, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, propylene carbonate derivative, tetrahydrofuran derivative, ethyl ether, 1,3-propane sultone, anisole, N-methylpyrrolidone, fluorinated carboxylate, etc. These aprotic organic solvents can be used alone or in combination of two or more.

  1,3-propane sultone, 1,4-butane sultone, and the like can be further dissolved in the electrolytic solution in which the compound represented by the general formula (1) is dissolved. The concentration of the compound represented by the general formula (1) when these substances are dissolved in the electrolytic solution is not particularly limited, but is preferably 0.01 to 10% by mass with respect to the entire electrolytic solution. When the amount is less than 0.01% by mass, the effect of the additive does not spread over the entire electrode surface, and when the amount exceeds 10% by mass, the viscosity of the electrolyte increases and the liquid resistance increases. At this time, 0.01-10 mass% of the sulfonic acid ester compound contained in the whole electrolyte solution is preferable. When the amount is less than 0.01% by mass, the effect of the additive does not spread over the entire electrode surface, and when the amount exceeds 10% by mass, the viscosity of the electrolyte increases and the liquid resistance increases.

  Representative examples of the sulfonic acid ester compound represented by the general formula (6) are illustrated below, but the present invention is not limited thereto.

  The cycle characteristics can be further improved by adding or mixing at least one of vinylene carbonate and derivatives thereof in the electrolytic solution. These substances can be used alone or in combination. When the vinylene carbonate or a derivative thereof is used as an additive, the effect can be obtained by adding 0.01 to 10% by mass in the electrolytic solution. Moreover, when using as a liquid solvent, an effect is acquired by including 1-5 mass%.

The electrolyte can include a lithium salt. The lithium salt, the lithium salt, lithium imide _{salt, LiPF 6, LiAsF 6, LiAlCl} 4, LiClO 4, LiBF 4, LiSbF 6 , and the like. Of these, LiPF ₆ and LiBF ₄ are particularly preferable. By including these lithium salts, a high energy density can be achieved.

  The electrolyte further has at least one selected from the group consisting of 1,3-propane sultone, 1,4-butane sultone, sulfolane, alkanesulfonic acid anhydride, cyclic disulfonic acid ester compound, γ-sultone compound, and sulfolene compound. Is preferred. These substances are considered to contribute to the formation of a passive film on the negative electrode surface, and to have an effect of suppressing the decomposition of the electrolyte without impairing the normal reaction of the battery by covering the negative electrode surface with a passive film. The content of these substances in the electrolytic solution is preferably 0.1 to 4% by mass.

The negative electrode of the secondary battery according to the present invention is made of a material that can occlude and release lithium, such as lithium metal, a lithium alloy, or a carbon material or an oxide.
As the carbon material, graphite that occludes lithium, amorphous carbon, diamond-like carbon, carbon nanotube, carbon nanohorn, or a composite thereof can be used.

  Further, as the oxide, any of silicon oxide, tin oxide, indium oxide, zinc oxide, lithium oxide, phosphoric acid, boric acid, or a composite thereof may be used, and it is particularly preferable to include silicon oxide. . The structure is preferably in an amorphous state. This is because silicon oxide is stable and does not cause a reaction with other compounds, and the amorphous structure does not lead to deterioration due to nonuniformity such as crystal grain boundaries and defects. As a method for forming the layer having the negative electrode active material, a method such as an evaporation method, a CVD method, or a sputtering method can be used.

  The lithium alloy is composed of lithium and a metal capable of forming an alloy with lithium. For example, it is composed of a binary or ternary or higher alloy of a metal such as Al, Si, Pb, Sn, In, Bi, Ag, Ba, Ca, Hg, Pd, Pt, Te, Zn, La, and lithium. As the lithium metal or lithium alloy, an amorphous alloy is particularly preferable. This is because the amorphous structure hardly causes deterioration due to non-uniformity such as crystal grain boundaries and defects.

  Lithium metal or lithium alloy is formed by an appropriate method such as a melt cooling method, a liquid quenching method, an atomizing method, a vacuum deposition method, a sputtering method, a plasma CVD method, a photo CVD method, a thermal CVD method, a sol-gel method, etc. Can do. By using these materials as the negative electrode active material, a secondary battery having a high energy density can be obtained.

In the present invention, as the positive electrode active material, a composite oxide that is Li _b ZO ₂ (wherein Z represents at least one transition metal), for example, Li _b CoO ₂ , Li _b NiO ₂ , Li _b Mn ₂ O ₄ , Li _b MnO ₃ , Li _b Ni _d Cr _1-d O ₂ (where 0 <b <1, 0 <d <1), or organic sulfur compound, conductive polymer, organic A radical compound or the like can be used. Alternatively, a lithium-containing composite oxide having a plateau at 4.5 V or more at the metal lithium counter electrode potential can be used. Examples of the lithium-containing composite oxide include spinel-type lithium manganese composite oxide, olivine-type lithium-containing composite oxide, and reverse spinel-type lithium-containing composite oxide. The lithium-containing composite oxide is, for example, a general formula Li _a (A _x Mn _2−x ) O ₄ (where 0 <x <2, 0 <a <1.2. A is Ni, Co, Fe , At least one selected from the group consisting of Ti, Cr and Cu.). By using these materials as the positive electrode active material, a secondary battery having a high energy density can be obtained.

  In the positive electrode according to the present invention, these active materials are dispersed and kneaded in a solvent such as N-methyl-2-pyrrolidone (NMP) together with a conductive material such as carbon black and a binder such as polyvinylidene fluoride (PVDF). It can be obtained by a method such as coating on a substrate such as an aluminum foil.

  The lithium secondary battery according to the present invention includes a negative electrode and a positive electrode laminated in a dry air or inert gas atmosphere via a separator, or after winding the laminated one, the lithium secondary battery is accommodated in a battery can or a synthetic resin A battery can be manufactured by sealing with a flexible film made of a laminate with a metal foil. In addition, as a separator, porous films, such as polyolefin, such as a polypropylene and polyethylene, a fluororesin, are used.

  The shape of the secondary battery according to the present invention is not particularly limited, and examples thereof include a cylindrical shape, a square shape, a coin shape, and a laminate shape.

(Example 1)
(Production of battery)
The positive electrode current collector 11 has an aluminum foil having a thickness of 20 μm, the positive electrode active material in the positive electrode 12 is LiMn ₂ O ₄ , and the negative electrode 13 has a negative electrode current collector 14 deposited on a 10 μm thick copper foil. The metal / electrolyte solution 15 used EC and a DEC mixed solvent (volume ratio: 30/70) as a solvent, and 1 mol / L LiPF ₆ was dissolved in the solvent. As an additive, 0.5% by mass of Compound No. 1 was added and dissolved. And the negative electrode and the positive electrode were laminated | stacked through the separator 16 which consists of polyethylene, and the coin-type secondary battery was produced.

(Charge / discharge cycle test)
At a temperature of 20 ° C., the charge rate was 0.05 C, the discharge rate was 0.1 C, the charge end voltage was 4.2 V, the discharge end voltage was 3.0 V, and the utilization factor (discharge depth) of the lithium metal negative electrode was 33%. The capacity retention rate (%) is a value obtained by dividing the discharge capacity (mAh) after 100 cycles by the discharge capacity (mAh) at the 10th cycle. The results obtained in the cycle test are shown in Table 1 below.

(Example 2)
Instead of the additive shown in Example 1, Compound No. 8 was used to form a battery. Except for this, a battery was prepared and evaluated in the same manner as in Example 1. The results of examining the cycle characteristics in the same manner as in Example 1 are shown in Table 1.

(Comparative Example 1)
A battery similar to that of Example 1 was prepared except that the compound represented by the general formula (1) was not added to the electrolytic solution, and the results of examining the cycle characteristics as in Example 1 are shown in Table 1.

  The capacity retention ratios in Examples 1 and 2 are much higher than those in Comparative Example 1. This is presumably because the irreversible reaction was suppressed by the stabilization of the surface film present at the interface between the negative electrode surface and the electrolyte and the high ionic conductivity of the film.

(Example 3)
Table 2 shows the results of producing a battery similar to that of Example 1 except that the negative electrode active material is composed of a graphite material, and examining cycle characteristics (however, measurement was performed up to 300 cycles) as in Example 1.

Example 4
Use PC, EC, and DEC mixed solvent (volume ratio: 20/20/60) instead of EC and DEC mixed solvent (volume ratio: 30/70) as electrolyte solvent, and use amorphous carbon as the negative electrode active material. Except for the above, a battery was produced in the same manner as in Example 1, and the cycle characteristics (however, measured up to 300 cycles) were examined as in Example 1, and the results are shown in Table 2.

(Comparative Example 2)
A battery of Comparative Example 3 was produced in the same manner as Example 3 except that no additive was added. The battery was evaluated in the same manner as in Example 1.

(Comparative Example 3)
A battery of Comparative Example 3 was produced in the same manner as Example 4 except that no additive was added. The battery was evaluated in the same manner as in Example 1.

  The results of Examples 3 and 4 and Comparative Examples 2 and 3 are shown in Table 2. Comparing the example with the comparative example, it can be seen that the capacity retention rate during the cycle is high in the example. From this result, even in the case where either graphite or amorphous carbon is used as the negative electrode active material in the secondary battery having the electrolytic solution containing the compound represented by the general formula (1), the same effect as in Example 1 is obtained. I found out that

(Example 5)
(Production of battery)
The production of the battery of this example will be described. 20 μm thick aluminum foil on the positive electrode current collector, LiMn ₂ O _{4 as} the positive electrode active material in the positive electrode, 20 μm thick lithium metal deposited as a negative electrode active material on the 10 μm thick copper foil of the negative electrode current collector, The electrolyte solution used EC and a DEC mixed solvent (volume ratio: 30/70) as a solvent, and 1 mol / L LiPF ₆ as a supporting electrolyte. As an additive, Compound No. 5 was added at a rate of 0.5% by mass in the electrolytic solution. 1 was used. Furthermore, 1% by mass of 1,3-propane sultone (hereinafter abbreviated as 1,3-PS) was contained in the electrolytic solution to prepare an electrolytic solution of Example 6.
And the negative electrode and the positive electrode were laminated | stacked through the separator which consists of polyethylene, and the secondary battery was produced.

(Charge / discharge cycle test)
Measurements were carried out in the same manner as described in Example 1. The obtained results are shown in Table 3 below.

(Example 6)
A battery was prepared and evaluated in the same manner as in Example 4 except that 1% by mass of 1,3-PS was added to the electrolytic solution of Example 4. The results of examining the cycle characteristics in the same manner as in Example 4 are shown in Table 3.

  The capacity retention ratios after the cycle test in Example 5 and Example 6 are higher than those in Example 1 or Example 4, respectively. This is probably because the addition of 1,3-PS suppressed the irreversible reaction due to the stabilization of the film present at the interface between the electrode surface and the electrolyte and the high ionic conductivity of the film.

(Example 7)
In this example, an electrolytic solution containing a compound represented by the general formula (1), 1,3-PS, and further vinylene carbonate (VC) as an additive is applied. A battery was prepared and evaluated in the same manner as in Example 4 except that 1% by mass of 1,3-PS and further vinylene carbonate (VC) were added to the electrolytic solution of Example 4. The results of examining the cycle characteristics in the same manner as in Example 4 are shown in Table 4.

  In the battery shown in Example 7, the capacity retention rate after the cycle test is further improved as compared with Example 6, that is, the compound represented by the general formula (1) and the general formula (1) It was confirmed that the cycle characteristics were improved by further adding VC to the electrolyte solution containing different sulfonic acid ester compounds.

(Examples 8 to 10)
A battery was prepared and evaluated in exactly the same manner as in Example 4 except that the concentration of the additive compound was changed. The results of examining the cycle characteristics in the same manner as in Example 4 are shown in Table 5.

  From Table 5, it can be seen that the compound concentration represented by the formula (1) has a more excellent effect at 0.1 to 5% by mass.

(Example 11)
In this example, compound No. 1 was used as an additive represented by general formula (1). 6 and using electrolyte mixture as PC, EC and DEC mixed solvent (volume ratio: 20/20/60) instead of PC, EC and DMC mixed volume (volume ratio: 20/20/60), positive electrode active material A battery similar to that of Example 6 was made and an experiment was performed except that a composite oxide (LiNi _0.5 Mn _1.35 Ti _0.15 O ₄ ) capable of obtaining a voltage of 4.5 V or higher was used.

The battery shown in Example 11 has an improved capacity retention rate after the cycle test as compared with Comparative Example 4, that is, a composite oxide capable of obtaining a voltage of 4.5 V or more as a positive electrode active material. When (LiNi _0.5 Mn _1.35 Ti _0.15 O ₄ ) was used, it was confirmed that the cycle characteristics were improved by using an electrolytic solution containing the compound represented by the general formula (1). As a result of peak splitting of the sulfur spectrum by XPS analysis of the positive electrode surface, it was confirmed that a substance having a peak in the vicinity of 164 eV was present. Compound No. Since it was not confirmed in Comparative Example 4 containing no 6, it is considered that a film unique to the sulfonate ester of the present invention was formed on the positive electrode.

(Comparative Example 4)
In Example 11, compound no. The same experiment as in Example 11 was performed except that 6 additive was not added.

It is a schematic block diagram of the secondary battery which concerns on this invention.

Explanation of symbols

11 Positive Electrode Current Collector 12 Layer Containing Positive Electrode Active Material 13 Layer Containing Negative Electrode Active Material 14 Negative Electrode Current Collector 15 Nonaqueous Electrolyte Solution 16 Porous Separator

Claims (17)

An electrolytic solution for a secondary battery comprising an aprotic solvent and at least a sulfonic acid ester compound represented by the following general formula (1).

(In the general formula (1), n = 1 to 5, m = 1 to 5, and R ₁ and R ₂ are each independently a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms or fluoroalkylene. And may be branched.) 2. The electrolyte solution for a secondary battery according to claim 1, wherein the sulfonic acid ester compound is a compound represented by the following general formula (2).

(However, in the said General formula (2), it is n = 2-10, R is a substituted or unsubstituted C1-C5 alkylene group or fluoroalkylene group, and may branch.) The electrolyte solution for a secondary battery according to claim 1, wherein the sulfonic acid ester compound is a compound represented by the following general formula (3).

(In the general formula (3), R ₁ and R ₂ are each independently a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms or a fluoroalkylene group.) The electrolyte solution for a secondary battery according to claim 1, wherein the sulfonic acid ester compound is a compound represented by the following general formula (4).

(However, in the general formula (4), x and y are each independently 1 to 5). The electrolyte solution for a secondary battery according to claim 1, wherein the sulfonic acid ester compound is a compound represented by the following general formula (5).

(However, in the said General formula (5), x is 1-5 and n is 2-10.)   The electrolyte solution for a secondary battery according to any one of claims 1 to 5, wherein the electrolyte solution for a secondary battery further contains a compound having one or more sulfonyl groups. The electrolyte solution for a secondary battery according to claim 6, wherein the compound having a sulfonyl group is at least a compound represented by the following general formula (6).

(In the general formula (6), Q represents an oxygen atom, a methylene group or a divalent group represented by —CH ₂ —S—, and A represents a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms. , A carbonyl group, a sulfinyl group, a substituted or unsubstituted fluoroalkylene group having 1 to 6 carbon atoms or an ether group and an alkylene group or fluoroalkylene group having 2 to 6 carbon atoms, and B may be branched. Represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted fluoroalkylene group which may be branched, or an oxygen atom.)   The electrolyte for the secondary battery is further selected from the group consisting of 1,3-propane sultone, 1,4-butane sultone, sulfolane, alkanesulfonic acid anhydride, cyclic disulfonic acid ester compound, γ-sultone compound, and sulfolene compound. The electrolytic solution for a secondary battery according to any one of claims 1 to 7, further comprising at least one kind.   The secondary battery electrolyte solution according to any one of claims 1 to 8, wherein the secondary battery electrolyte solution further includes at least one of vinylene carbonate and a derivative thereof.   The aprotic solvent is at least selected from the group consisting of cyclic carbonates, chain carbonates, aliphatic carboxylic acid esters, γ-lactones, cyclic ethers, chain ethers, and fluorinated derivatives thereof. The electrolyte solution for secondary batteries according to any one of claims 1 to 9, comprising one kind of organic solvent. LIPF ₆ wherein the secondary battery electrolyte, as further lithium _{salt, LiBF 4, LiAsF 6, LiSbF} 6, LiClO 4, LiAlCl 4, LiN (C k F 2k + 1 SO 2) 2 and LiN (C _k F _{2k +1} SO ₂ ) (C _m F _{2m + 1} SO ₂ ) (k and m are each independently 1 or 2), and at least one selected from the group consisting of 1 to 10 is included. The electrolyte solution for secondary batteries of any one of these.   A secondary battery comprising a positive electrode, a negative electrode, and an electrolyte for a secondary battery, wherein the electrolyte for a secondary battery is the electrolyte for a secondary battery according to any one of claims 1 to 11. A secondary battery characterized by that.   The secondary battery according to claim 12, wherein the positive electrode has a lithium-containing composite oxide capable of inserting and extracting lithium.   The secondary battery according to claim 12 or 13, wherein the negative electrode has a metal material capable of forming an alloy with lithium metal or lithium as a negative electrode active material capable of inserting and extracting lithium.   The secondary battery according to claim 12, wherein the negative electrode has carbon as a negative electrode active material.   The secondary battery according to claim 15, wherein the carbon is graphite.   The secondary battery according to claim 15, wherein the carbon is amorphous carbon.

Images