KR20040080529A - Nonaqueous electrolyte and lithium battery using the same - Google Patents

Abstract

PURPOSE: A nonaqueous electrolyte solution and a lithium battery employing the electrolyte solution are provided, to inhibit swelling even at a high temperature for reducing the deformation due to the thickness of a battery, thereby improving the reliance of a battery. CONSTITUTION: The nonaqueous electrolyte solution comprises a lithium salt, an organic solvent and a compound represented by the formula 1, wherein R1, R2, R3 and R4 are independently H, a halogen atom, OH, a cyano group, an amino group, a nitro group, a carboxyl group, a substituted or unsubstituted alkyl group of C1-C20, a substituted or unsubstituted heteroalkyl group of C1-C100, a substituted or unsubstituted alkenyl group of C2-C20, a substituted or unsubstituted heteroalkenyl group of C2-C20, a substituted or unsubstituted alkoxy group of C1-C20, a substituted or unsubstituted aryl group of C6-C30, a substituted or unsubstituted heteroaryl group of C3-C30, a substituted or unsubstituted aralkyl group of C7-C30, or a substituted or unsubstituted heteroaralkyl group of C4-C30; R5 is H, a halogen atom, OH, a cyano group, an amino group, a nitro group, a carboxyl group, a substituted or unsubstituted alkyl group of C1-C20, a substituted or unsubstituted heteroalkyl group of C1-C100, a substituted or unsubstituted alkenyl group of C2-C20, a substituted or unsubstituted heteroalkenyl group of C2-C20, a substituted or unsubstituted aryl group of C6-C30, a substituted or unsubstituted heteroaryl group of C3-C30, a substituted or unsubstituted aralkyl group of C7-C30, a substituted or unsubstituted heteroaralkyl group of C4-C30, or -O-SiR7R8R9; R6 is H, a halogen atom, OH, a cyano group, an amino group, a nitro group, a carboxyl group, a substituted or unsubstituted alkyl group of C1-C20, a substituted or unsubstituted heteroalkyl group of C1-C100, a substituted or unsubstituted alkenyl group of C2-C20, a substituted or unsubstituted heteroalkenyl group of C2-C20, a substituted or unsubstituted aryl group of C6-C30, a substituted or unsubstituted heteroaryl group of C3-C30, a substituted or unsubstituted aralkyl group of C7-C30, a substituted or unsubstituted heteroaralkyl group of C4-C30, or -SiR7R8R9; and n and m are independently an integer of 1-1,000,000.

Description

Non-aqueous electrolyte and lithium battery employing the same {Nonaqueous electrolyte and lithium battery using the same}

The present invention relates to a non-aqueous electrolyte and a lithium battery employing the same, and more particularly, to a non-aqueous electrolyte and a lithium battery employing the same, even if the battery is left at a high temperature.

Recently, as the electronic equipment becomes smaller and lighter due to the development of advanced electronic devices, the use of portable electronic devices is gradually increasing. Therefore, the necessity of a battery having high energy density characteristics used as a power source for such an electronic device is increasing, and research on lithium batteries has been actively conducted.

A lithium battery is a battery manufactured by forming a separator, an electrolyte, and an electrolyte that provides a migration path between lithium ions between a cathode and an anode, and when the lithium ions are inserted / deinserted from the cathode and the anode, Electric energy is generated by the reduction reaction. However, if the battery is overcharged due to charger malfunction, etc., and the voltage rises rapidly, excess lithium is precipitated at the cathode and excess lithium is inserted at the anode, so that the cathode of the cathode / anode is thermally unstable. When the organic solvent of the electrolyte is decomposed to cause a sudden exothermic reaction, a situation such as thermal runaway occurs suddenly, causing a serious damage to safety.

In order to solve such a problem, many attempts have been made to suppress the overcharging of lithium batteries by changing the composition of the electrolyte or adding an additive to the electrolyte. For example, U.S. Patent No. 5,580,684 adds trimethyl phosphate, tri (trifluoroethyl) phosphate, tri (2-chloroethyl) phosphate, etc. to the electrolyte as a phosphate ester substance to increase the self-extinguishing of the electrolyte. In this case, US Pat. No. 5,776,627 adds thiophene, biphenyl, furan, and the like to polymerize the battery when the battery is abnormal, thereby preventing the movement of lithium. A method of increasing the safety of a battery by opening the vent easily is disclosed.

Also similar to the above methods, US Pat. No. 5,763,119, 1,2-dimethoxy-4-bromo-benzene, US Pat. No. 5,709,968, 2-chloro-p-xylene and 4-chloro-anisole, US Pat. 5,858,573 discloses a method for improving battery safety by adding 2,7-diacetyl thianthrene and the like, respectively.

However, such additives may polymerize under normal operating conditions of the battery, or may generate a large amount of gas by oxidative decomposition to increase the swelling phenomenon of the battery. There are a number of problems such as deterioration of the characteristics, which has not yet been put into practical use.

SUMMARY OF THE INVENTION The present invention has been made in an effort to provide a non-aqueous electrolyte solution in which a swelling phenomenon caused by decomposition of an electrolyte solution when left at a high temperature is suppressed.

Another object of the present invention is to provide a lithium battery employing the non-aqueous electrolyte.

In order to achieve the above technical problem, the present invention provides a non-aqueous electrolyte further comprising a compound of formula (1) as a non-aqueous electrolyte containing a lithium salt and an organic solvent.

Wherein R ₁ , R ₂ , R ₃ , and R ₄ are each independently a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an amino group, a nitro group, a carboxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, 1 carbon atom Substituted or unsubstituted heteroalkyl group having from 100 to 100 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted heteroalkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms , Substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, or substituted or unsubstituted C 4 to 30 carbon atoms A substituted heteroaralkyl group,

R ₅ is a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an amino group, a nitro group, a carboxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 100 carbon atoms, 2 to 20 carbon atoms Substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted heteroalkenyl group, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, An aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 4 to 30 carbon atoms, or Indicates,

R ₆ is a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an amino group, a nitro group, a carboxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 100 carbon atoms, and 2 to 20 carbon atoms Substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted heteroalkenyl group, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, An aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 4 to 30 carbon atoms, or ,

R ₇ , R ₈ and R ₉ are a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an amino group, a nitro group, a carboxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom 1 to 20 Heteroalkyl group, substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted heteroalkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or substituted with 6 to 30 carbon atoms, or An unsubstituted aryl group, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, or a substituted or unsubstituted heteroaralkyl group having 4 to 30 carbon atoms,

M and n each independently represent an integer of 1 to 1,000,000.

It is preferable that the mixed weight ratio of the compound of Formula 1 and an electrolyte solution containing a lithium salt and an organic solvent is 1: 0.0001 to 1.0.

This invention also provides the lithium battery which employ | adopted the said electrolyte solution.

Hereinafter, the present invention will be described in more detail.

In the case of a lithium battery, when the battery is left at a high temperature, a phenomenon in which the battery swells, that is, a swelling phenomenon, inevitably occurs. Such swelling causes deformation of the battery thickness, which is a problem in the reliability of the battery. To this end, when the compound containing the siloxane group according to the present invention is added to the electrolyte solution, the swelling phenomenon of the electrolyte solution as described above can be suppressed.

The non-aqueous electrolyte solution used in the present invention is obtained by further adding a compound containing a siloxane group to a conventional electrolyte solution containing a lithium salt and an organic solvent, and the compound containing the siloxane group in such electrolyte solution suppresses decomposition of the electrolyte solution. This makes it possible to suppress the swelling phenomenon.

The compound added to the non-aqueous electrolyte solution of the present invention has a structure represented by the following general formula (1).

[Formula 1]

Wherein R ₁ , R ₂ , R ₃ , and R ₄ are each independently a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an amino group, a nitro group, a carboxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, 1 carbon atom Substituted or unsubstituted heteroalkyl group having from 100 to 100 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted heteroalkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms , Substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, or substituted or unsubstituted C 4 to 30 carbon atoms A substituted heteroaralkyl group,

R ₅ is a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an amino group, a nitro group, a carboxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 100 carbon atoms, 2 to 20 carbon atoms Substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted heteroalkenyl group, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, An aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 4 to 30 carbon atoms, or Indicates,

R ₆ is a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an amino group, a nitro group, a carboxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 100 carbon atoms, and 2 to 20 carbon atoms Substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted heteroalkenyl group, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, An aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 4 to 30 carbon atoms, or ,

R ₇ , R ₈ and R ₉ are a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an amino group, a nitro group, a carboxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom 1 to 20 Heteroalkyl group, substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted heteroalkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or substituted with 6 to 30 carbon atoms, or An unsubstituted aryl group, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, or a substituted or unsubstituted heteroaralkyl group having 4 to 30 carbon atoms,

M and n each independently represent an integer of 1 to 1,000,000.

Preferred compounds of the compound of Formula 1 have the structure of Formula 2 below.

Wherein R ₁ , R ₂ , R ₃ , and R ₄ are each independently a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms , A substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms,

R ₅ is a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and carbon atoms An aralkyl group of 7 to 30, or Indicates,

R ₆ is a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and carbon atoms An aralkyl group of 7 to 30, or ,

R ₇ , R ₈ and R ₉ are a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, or a substituted or substituted carbon group having 1 to 20 carbon atoms or An unsubstituted alkoxy group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms,

M and n each independently represent an integer of 1 to 1,000,000.

As described above, the compound of Formula 1 having a siloxane group in a molecule may be added as an additive to improve high temperature swelling characteristics to a conventional electrolyte solution including a lithium salt and an organic solvent, and the content of the compound of Formula 1 and a lithium salt It can be used so that the mixing weight ratio of the electrolyte solution consisting of and an organic solvent is 1: 0.0001 to 1.0. When the content of the compound of Formula 1 exceeds the above range, there is a problem of lowering the capacity characteristics and lifetime characteristics of the battery. When the content of the compound is less than the above range, the effect of improving the swelling characteristics is insignificant. There is a problem and is undesirable.

Hereinafter, a method of manufacturing a lithium ion battery electrolyte according to the present invention will be described.

As a high temperature swelling enhancement additive, a compound having a Si-O group, which is a siloxane group, in a molecule is mixed with an electrolyte solution consisting of a lithium salt and an organic solvent, such as the compound of Formula 1, to prepare a lithium ion battery electrolyte composition.

In the above-described lithium ion battery electrolyte composition for improving the swelling characteristic, the weight ratio of the compound of Formula 1, which is a material for improving the swelling characteristic, and the electrolyte is preferably 1: 0.0001 to 1.0. If the swelling characteristic improving material exceeds the above range with respect to the content of the electrolyte, a problem of deteriorating the capacity characteristics and the life characteristics of the battery occurs. If the swelling characteristic improving material is less than the above range, the swelling characteristics are not improved, which is not preferable. .

In the lithium ion battery electrolyte composition for improving the swelling characteristics described above, any organic solvent constituting the electrolyte may be used as long as it is commonly used in lithium batteries. Specific examples thereof include propylene carbonate, ethylene carbonate, dimethyl carbonate, methylethyl carbonate, diethyl carbonate, tetrahydrofuran, 2-methylhydrofuran, diethoxyethane, methyl formate, ethyl formate and gamma butyrotactone. Use one or more selected from the group. The content of the organic solvent is 90 to 99.9 parts by weight based on 100 parts by weight of the electrolyte.

In addition, the lithium salts constituting the electrolyte include lithium perchlorate (LiClO ₄ ), lithium tetrafluoroborate (LiBF ₄ ), lithium hexafluorophosphate (LiPF ₆ ), lithium trifluoride methanesulfonate (LiCF ₃ SO ₃ ), and lithium bistrifluoro One or more selected from the group consisting of methanesulfonylamide (LiN (CF ₃ SO ₂ ) ₂ ) is used. The content of the lithium salt is 0.1 to 10 parts by weight based on 100 parts by weight of the electrolyte.

Hereinafter, a method of manufacturing a lithium battery using the electrolyte prepared according to the above method will be described.

The cathode and the anode are each prepared in accordance with conventional methods used in the manufacture of lithium batteries. First, a cathode active material composition is prepared by mixing a cathode active material, a conductive agent, a binder, and a solvent. The cathode active material composition is directly coated and dried on an aluminum current collector to prepare a cathode electrode plate. Alternatively, the cathode active material composition may be cast on a separate support, and then a film obtained by peeling from the support may be laminated on an aluminum current collector to manufacture a cathode electrode plate.

In this case, a lithium metal composite oxide, a transition metal compound, a sulfur compound, and the like are used as the cathode active material, and in particular, LiCoO ₂ , LiMn _x O _2x , LiNi _1-x Mn _x O _2x (x = 1, 2), Ni _1- It is preferable to use _xy Co _x Mn _y O ₂ or the like.

Carbon black compounds are used as the conductive agent, and vinylidene fluorite / hexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene and the like A mixture and a styrene butadiene rubber-based polymer are used, and N-methylpyrrolidone, acetone, water and the like can be used as a solvent. In this case, the content of the cathode active material, the conductive agent, the binder, and the solvent may be used at levels commonly used in lithium batteries.

As in the case of producing the cathode electrode plate described above, the anode active material, the conductive agent, the binder, and the solvent are mixed to prepare the anode active material composition, which is directly coated on a copper current collector or cast on a separate support, and the anode is peeled off from the support. An anode electrode plate can be obtained by laminating an active material film to a copper current collector. In this case, as the anode active material, lithium metal, carbon material, graphite material, or the like can be used. In the anode active material composition, the conductive agent, the binder, and the solvent may be used in the same manner as in the case of the cathode.

In some cases, a plasticizer may be further added to the cathode active material composition and the anode active material composition to form pores inside the electrode plate.

Subsequently, a separator made of an insulating resin having a mesh structure is inserted between the cathode and the anode, and the electrode structure is formed by winding or stacking the separator and then placing the separator in a battery case to assemble the battery. .

Herein, the separator can be used as long as it is commonly used in lithium batteries, and in particular, it is preferable that the separator has a low resistance to ion migration of the electrolyte and excellent electrolyte-moisture capability. More specifically, this is a material selected from glass fiber, polyester, teflon, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), and combinations thereof, which may be nonwoven or woven. More specifically, in the case of a lithium ion battery, a coilable separator made of a material such as polyethylene, polypropylene, or the like, such as polyethylene separator, polypropylene separator, polyethylene / polypropylene two-layer separator, polyethylene / poly A propylene / polyethylene three-layer separator or a polypropylene / polyethylene / polypropylene three-layer separator is used, and in the case of a lithium ion polymer battery, a separator having excellent organic electrolyte impregnation ability is used. It can be manufactured according to.

That is, a separator composition is prepared by mixing a polymer resin, a filler, and a solvent. The separator composition may be directly coated and dried on an electrode to form a separator film, or the separator composition may be cast and dried directly on a support, followed by lamination on the electrode to separate the separator film. Can be.

Although the polymer resin is not particularly limited, any material used for the binder of the electrode plate may be used without any limitation. Vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate and mixtures thereof can be used here. Among these, preference is given to using vinylidene fluoride-hexafluoropropylene copolymers having a hexafluoropropylene content of 8 to 25% by weight.

The separator is disposed between the cathode electrode plate and the anode electrode plate as described above to form an electrode assembly. Winding or folding such an electrode assembly and storing it in a cylindrical battery case or a square battery case, and then injecting the non-aqueous electrolyte solution of the present invention, a lithium ion battery is completed. Alternatively, the electrode assembly is stacked in a bi-cell structure, and then, the electrode assembly is impregnated with an organic electrolyte, and the resultant is placed in a pouch and sealed to complete a lithium ion polymer battery.

The lithium battery of the present invention is not particularly limited in form, and both lithium primary batteries and lithium secondary batteries can be used.

Hereinafter, the present invention will be described in detail with reference to the following examples, but the present invention is not limited only to the following examples.

<Example 1>

A cathode active material slurry was prepared by dissolving 94 g of LiCoO ₂ , 3 g of Super-P and 3 g of polyvinylidene fluoride (PVDF) in N-methyl-2-pyrrolidone. The cathode active material slurry was applied to an Al-foil having a width of 4.9 cm and a thickness of 147 μm, dried, rolled, and cut to a predetermined dimension to prepare a cathode.

89.8 g of mesocarbon fiber (MCF: Petoca), 0.2 g of oxalic acid, and 10 g of PVDF were dissolved in N-methyl-2-pyrrolidone to prepare an anode active material slurry. The anode active material slurry was applied on a copper foil having a width of 5.1 cm and a thickness of 178 μm, and then dried, rolled, and cut into predetermined dimensions to produce an anode.

A separator was placed between the cathode and the anode and wound to make an electrode assembly. The electrode assembly was placed in a battery case, and then a liquid electrolyte solution was injected under reduced pressure to complete the battery. Herein, the electrolyte solution is 0.05 g of poly [methylsiloxane-co-methyl (3-hydroxypropyl) siloxane] -graft-poly (ethylene glycol) methyl ether and 1.3 M LiPF ₆ EC: EMC: PC: FB (30). : 55: 5: 10 by volume) 2.3 g of a mixed solution consisting of 5 g of a solution was used.

Comparative Example 1

A cathode active material slurry was prepared by dissolving 94 g of LiCoO ₂ , 3 g of Super-P and 3 g of polyvinylidene fluoride (PVDF) in N-methyl-2-pyrrolidone. The cathode active material slurry was applied to an Al-foil having a width of 4.9 cm and a thickness of 147 μm, dried, rolled, and cut to a predetermined dimension to prepare a cathode.

89.8 g of mesocarbon fiber (MCF: Petoca), 0.2 g of oxalic acid, and 10 g of PVDF were dissolved in N-methyl-2-pyrrolidone to prepare an anode active material slurry. The anode active material slurry was applied on a copper foil having a width of 5.1 cm and a thickness of 178 μm, and then dried, rolled, and cut into predetermined dimensions to produce an anode.

A separator was placed between the cathode and the anode and wound to make an electrode assembly. The electrode assembly was placed in a battery case, and then a liquid electrolyte solution was injected under reduced pressure to complete the battery. As the electrolyte solution, 1.3 M 30: 55: 5: 10 volume ratio LiPF ₆ EC: EMC: PC: FB was used.

The battery performance of the lithium ion batteries prepared according to Example 1 and Comparative Example 1 and the swelling characteristics of the battery at 90 ° C. at high temperature were investigated. Table 1 shows data for Example 1 and Comparative Example 1. .

In order to evaluate the swelling characteristics of the lithium ion battery at high temperature, the batteries prepared according to Comparative Example 1 and Example 1 were fully charged and left in a 90 ° C. hot air oven for 4 hours, and the thicknesses before and after standing were measured.

Cell Performance and High Temperature Swelling Characteristics division Standard Charge / Discharge Characteristics (mAh) Rate discharge characteristics (mAh) High temperature leaving characteristic (mm) charge Discharge efficiency(%) 0.5C 1.0C 2.0C Before neglect After leaving Thickness increase (%) Example 1 720 719 99.9 710.3 709.2 681.5 3.62 4.37 20.7 Comparative Example 1 717 716 99.9 708.8 708 680.2 3.57 5.54 55.2

As can be seen from Table 1, in the case of the lithium ion battery of Example 1, when the electrolyte solution containing a compound containing a Si-O group, which is a siloxane group, is added as an electrolyte, the battery performance is obtained when the electrolyte solution of Comparative Example 1 is used. Compared with the battery characteristics, it showed more than equivalent level, and at the same time, the high temperature swelling characteristics were significantly improved compared with the conventional electrolyte solution.

The electrolyte including the compound of Formula 1 containing the siloxane group of the present invention and the lithium battery employing the same may improve the reliability of the battery because the swelling phenomenon is suppressed and the strain according to the thickness of the battery is reduced even when left at a high temperature.

Claims (14)

Electrolyte solution containing a lithium salt and an organic solvent; And a non-aqueous electrolyte comprising a compound of Formula 1 below: <Formula 1> Wherein R ₁ , R ₂ , R ₃ , and R ₄ are each independently a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an amino group, a nitro group, a carboxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, 1 carbon atom Substituted or unsubstituted heteroalkyl group having from 100 to 100 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted heteroalkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms , Substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, or substituted or unsubstituted C 4 to 30 carbon atoms A substituted heteroaralkyl group, R ₅ is a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an amino group, a nitro group, a carboxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 100 carbon atoms, 2 to 20 carbon atoms Substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted heteroalkenyl group, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, An aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 4 to 30 carbon atoms, or Indicates, R ₆ is a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an amino group, a nitro group, a carboxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 100 carbon atoms, and 2 to 20 carbon atoms Substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted heteroalkenyl group, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, An aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 4 to 30 carbon atoms, or , R ₇ , R ₈ and R ₉ are a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an amino group, a nitro group, a carboxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom 1 to 20 Heteroalkyl group, substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted heteroalkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or substituted with 6 to 30 carbon atoms, or An unsubstituted aryl group, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, or a substituted or unsubstituted heteroaralkyl group having 4 to 30 carbon atoms, M and n each independently represent an integer of 1 to 1,000,000. The non-aqueous electrolyte solution according to claim 1, wherein the compound of Formula 1 is a compound of Formula 2. <Formula 2> Wherein R ₁ , R ₂ , R ₃ , and R ₄ are each independently a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms , A substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, R ₅ is a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and carbon atoms An aralkyl group of 7 to 30, or Indicates, R ₆ is a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and carbon atoms An aralkyl group of 7 to 30, or , R ₇ , R ₈ and R ₉ are a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, or a substituted or substituted carbon group having 1 to 20 carbon atoms or An unsubstituted alkoxy group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, M and n each independently represent an integer of 1 to 1,000,000. The non-aqueous electrolyte solution according to claim 1, wherein a mixed weight ratio of the compound of Formula 1, an electrolyte solution containing a lithium salt, and an organic solvent is 1: 0.0001 to 1.0. The method of claim 1, wherein the organic solvent is propylene carbonate, ethylene carbonate, dimethyl carbonate, methylethyl carbonate, diethyl carbonate, tetrahydrofuran, 2-methylhydrofuran, diethoxyethane, methyl formate, ethyl formate and gamma Non-aqueous electrolyte solution, characterized in that at least one selected from the group consisting of butyrotactone. The non-aqueous electrolyte solution according to claim 1, wherein the organic solvent is 90 to 99.9 parts by weight based on 100 parts by weight of the electrolyte. The lithium salt of claim 1, wherein the lithium salt is lithium perchlorate (LiClO ₄ ), lithium tetrafluoroborate (LiBF ₄ ), lithium hexafluorophosphate (LiPF ₆ ), lithium trifluoride methanesulfonate (LiCF ₃ SO ₃ ), and lithium bistry. Non-aqueous electrolyte solution, characterized in that at least one selected from the group consisting of fluoromethanesulfonylamide (LiN (CF ₃ SO ₂ ) ₂ ). The non-aqueous electrolyte solution according to claim 1, wherein the lithium salt is present in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the electrolyte. Electrolyte solution containing a lithium salt and an organic solvent; And a lithium battery employing a non-aqueous electrolyte containing a compound of formula (1): <Formula 1> Wherein R ₁ , R ₂ , R ₃ , and R ₄ are each independently a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an amino group, a nitro group, a carboxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, 1 carbon atom Substituted or unsubstituted heteroalkyl group having from 100 to 100 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted heteroalkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms , Substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, or substituted or unsubstituted C 4 to 30 carbon atoms A substituted heteroaralkyl group, R ₅ is a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, an amino group, a nitro group, a carboxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 100 carbon atoms, 2 to 20 carbon atoms Substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted heteroalkenyl group, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, An aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 4 to 30 carbon atoms, or Indicates, R ₆ is a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an amino group, a nitro group, a carboxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 100 carbon atoms, and 2 to 20 carbon atoms Substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted heteroalkenyl group, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, An aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 4 to 30 carbon atoms, or , R ₇ , R ₈ and R ₉ are a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, an amino group, a nitro group, a carboxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon atom 1 to 20 Heteroalkyl group, substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted heteroalkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or substituted with 6 to 30 carbon atoms, or An unsubstituted aryl group, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, or a substituted or unsubstituted heteroaralkyl group having 4 to 30 carbon atoms, M and n each independently represent an integer of 1 to 1,000,000. The non-aqueous electrolyte solution according to claim 7, wherein the compound of Formula 1 is a compound of Formula 2. <Formula 2> Wherein R ₁ , R ₂ , R ₃ , and R ₄ are each independently a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms , A substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, R ₅ is a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and carbon atoms An aralkyl group of 7 to 30, or Indicates, R ₆ is a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and carbon atoms An aralkyl group of 7 to 30, or , R ₇ , R ₈ and R ₉ are a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, or a substituted or substituted carbon group having 1 to 20 carbon atoms or An unsubstituted alkoxy group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, M and n each independently represent an integer of 1 to 1,000,000. 8. The non-aqueous electrolyte solution according to claim 7, wherein a mixed weight ratio of the compound of Formula 1, an electrolyte solution containing a lithium salt, and an organic solvent is 1: 0.0001 to 1.0. 8. The method of claim 7, wherein the organic solvent is propylene carbonate, ethylene carbonate, dimethyl carbonate, methylethyl carbonate, diethyl carbonate, tetrahydrofuran, 2-methylhydrofuran, diethoxyethane, methyl formate, ethyl formate and gamma Non-aqueous electrolyte solution, characterized in that at least one selected from the group consisting of butyrotactone. The non-aqueous electrolyte solution according to claim 7, wherein the organic solvent has a content of 90 to 99.9 parts by weight based on 100 parts by weight of the electrolyte. 8. The method of claim 7, wherein the lithium salt is lithium perchlorate (LiClO ₄ ), lithium tetrafluoroborate (LiBF ₄ ), lithium hexafluorophosphate (LiPF ₆ ), lithium trifluoromethane sulfonate (LiCF ₃ SO ₃ ) and lithium bistry Non-aqueous electrolyte solution, characterized in that at least one selected from the group consisting of fluoromethanesulfonylamide (LiN (CF ₃ SO ₂ ) ₂ ). The non-aqueous electrolyte solution according to claim 7, wherein the content of the lithium salt is 0.1 to 10 parts by weight based on 100 parts by weight of the electrolyte.