KR100858418B1 - Gel-typed Solid Electrolyte for Secondary Battery - Google Patents

Abstract

The present invention provides a gel solid electrolyte, wherein a lithium salt-containing electrolyte is contained in the form of a gel in a substrate obtained by polymerization of a mixture of an oligomer of Formula 1 and a monomer of Formula 2 below.

(1)

(One)

(2)

(2)

Wherein n is an integer from 2 to 30.

In addition, the gel solid electrolyte according to the present invention can prevent the swelling phenomenon of the battery and improve the high temperature storage characteristics while preventing the degradation of the rate characteristics and cycle characteristics caused by using the gel type electrolyte solution.

Description

Gel-type solid electrolyte for secondary battery {Gel-typed Solid Electrolyte for Secondary Battery}

1 is a graph showing the heating conditions of the battery cell of Example 1 and Comparative Example 4 according to the present invention in Experimental Example 3;

2 is a graph showing the change in battery cell thickness in Experimental Example 3.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gel solid electrolyte for secondary batteries formed by polymerization of a mixture of different monomers and oligomer compounds, and more particularly, to poly (ethylene glycol) diarylate in the form of oligomers. And 1,3-butylene glycol dimethyl acrylate (1,3-butylene glycol dimethacyclate) in the form of a monomer mixed with the polymerization to prepare, while preventing degradation of the rate characteristics and cycle characteristics in a conventional gel-type solid electrolyte, At the same time, the present invention relates to a gel solid electrolyte for secondary batteries, which prevents swelling of the battery and improves high temperature storage characteristics.

Recently, secondary batteries capable of charging and discharging have been widely used as energy sources of wireless mobile devices. Among them, lithium secondary batteries are widely used due to advantages such as high energy density, discharge voltage, and output safety.

A lithium secondary battery may be classified into a lithium ion battery containing a liquid electrolyte as it is, a lithium ion polymer battery containing a liquid electrolyte in a gel-like form, and a lithium polymer battery of a solid electrolyte, depending on the form of the electrolyte. In particular, lithium-ion polymer batteries have many advantages, such as low leakage potential of liquid electrolyte, high safety, and ultra-thin and light weight of the battery. However, due to the low mobility of lithium ions, the resistance inside the battery is high, which is disadvantageous for large current discharge, and has a disadvantage in that the volume energy density is lower than that of the lithium ion battery, and the manufacturing process is relatively complicated, resulting in high manufacturing cost.

In this regard, as will be described in detail later, the present invention proposes a method for solving the above-mentioned problems of battery performance by using a specific gel-type solid electrolyte that is thermally polymerized by mixing different types of oligomers and monomers.

On the other hand, some techniques for producing a gel solid electrolyte by thermal polymerization of a monomer and a polymer are known.

For example, in Korean Patent Registration No. 052527, a precursor including an interpenetrating polymer network (IPN) and an electrolyte mixed with a polymerized polymer and a reactive monomer is injected into a battery cell, and then heated and polymerized to prepare a gel polymer electrolyte. The technique is disclosed.

However, the patent uses a monomer (methyl methacrylate) and a polymer (polymethyl methacrylate) based on the same compound, and only the content of adjusting the properties of the electrolyte by adjusting the mixing ratio thereof is disclosed, There is no mention of any technique using monomers and oligomers.

As described above, when preparing a gel-type solid electrolyte using a mixture of monomers and polymers based on the same compound, the electrochemical properties of the materials are similar to each other, thereby reducing the performance of the battery exhibited in the conventional gel-type solid electrolyte. The problem was found to be unpredictable.

Therefore, there is a high need for a technology that can fundamentally solve these problems.

The present invention aims to solve the problems of the prior art as described above and the technical problems that have been requested from the past.

After in-depth research and various experiments, the inventors have surprisingly found that when a gel solid electrolyte is prepared by thermal polymerization using a specific oligomer and a specific monomer as a combination of heterogeneous materials, surprisingly, the rate characteristics and cycles caused by conventional electrolytes are surprising. It was confirmed that the deterioration of the characteristics can be significantly suppressed, the swelling phenomenon of the battery can be prevented at the same time, and the high temperature storage characteristics are improved. The present invention has been completed based on this finding.

Therefore, the gel solid electrolyte according to the present invention is characterized in that a lithium salt-containing electrolyte is contained in the form of a gel in a substrate obtained by polymerization of a mixture of an oligomer represented by the following formula (1) and a monomer represented by the following formula (2).

(1)

(One)

(2)

(2)

Wherein n is an integer from 2 to 30.

In general, the gel solid electrolyte has a disadvantage of weak mechanical properties. Therefore, in recent years, studies have been conducted to improve mechanical properties and electrical conductivity using copolymers. However, when the oligomer compound is used alone, there is a problem that the physical properties are not easily controlled and a large amount is used. On the other hand, when the monomer is used alone, deterioration of cycle characteristics and desired mechanical properties are obtained. There is a problem that can not be. Therefore, the present invention solves these problems at once by mixing and polymerizing the compound in the oligomer state and the compound in the monomer state. Furthermore, by using the oligomer of Formula 1 and the monomer of Formula 2 as a combination of heterogeneous materials, the gel solid electrolyte of an optimum state is obtained by complementary complementary to the electrochemical and mechanical properties of each material.

In the gel solid electrolyte according to the present invention, when preparing a base material containing lithium-containing electrolyte in the form of a gel, the oligomer and monomer are mixed in a ratio of 1:10 to 10: 1 by weight. desirable. If the mixing ratio is 1:10 or less, the battery resistance is increased due to an increase in the content of the monomer of Formula 1, which leads to a decrease in battery capacity and deterioration in cycle characteristics. On the other hand, if the mixing ratio is 10: 1 or more, since the content of the oligomer of Formula 2 is increased, it is not preferable to control the physical properties and to increase the total amount of the mixture to obtain the desired level of physical properties.

In order to minimize the above problems while maintaining the performance of the battery, the mixing ratio of the oligomer and the monomer is more preferably 4: 6 to 6: 4.

In the lithium ion polymer secondary battery, since the electrolyte is contained in a gel type rather than in a liquid state, in order for the electrolyte to be uniformly applied to the electrode, the ratio of the polymer is important as a substrate composed of the electrolyte and a mixture of the oligomer and the monomer. That is, when the ratio of the polymer is too low, the problem of the swelling phenomenon and the high temperature storage characteristics of the battery, which occur when the liquid electrolyte is used, may still occur, and it is difficult to manufacture a substrate having a predetermined thickness. . On the contrary, when the content of the polymer is too high, not only the problem of deterioration of battery performance due to the reduced mobility of lithium ions, but also the viscosity increases, making it difficult to apply uniformly to the corresponding site. Therefore, the mixture of the oligomer and the monomer is preferably included in 1 to 5% by weight based on the total weight of the electrolyte.

In Formula 1, n is 2 to 30, as defined above, and when n is 1, the effect of using the oligomer and the monomer is canceled, and when n is too large, the ratio of double bonds in the reactant is reduced, so that the desired The polymerization may not proceed at such a level. N may preferably be 5 to 20.

The polymer as a substrate in the gel solid electrolyte in the present invention can be prepared by a method known in the art. For example, first, a predetermined amount of an initiator, the oligomer, and the monomer are added to an electrolyte solution containing lithium salt, mixed, and then injected into a battery cell. After sealing the injection port of such a battery cell, the polymerization is carried out by heating at 40 to 80 ° C. for 1 to 20 hours to obtain an electrolyte containing a lithium salt-containing electrolyte solution in the form of a gel. As the initiator, azo-based compounds and peroxy-based compounds may be used. Specifically, 2,2'-Azobis (2,4-dimethyl valronitrile), 2,2'-Azobis (isobutyronitrile), Di- (4 -tertbutylcyclohexyl) -peroxydicarbonatearmyl peroxypivalate may be used.

The lithium salt is a material in which lithium ions are dissociated in a non-aqueous electrolyte solution and dissociate lithium ions. For example, LiCl, LiBr, LiI, LiClO ₄ , LiBF ₄ , LiB ₁₀ Cl ₁₀ , LiPF ₆ , LiCF ₃ SO ₃ , and LiCF ₃ CO _{2, LiAsF 6, LiSbF 6,} LiAlCl 4, CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, lithium tetraphenyl borate, imide, etc. This can be used.

As said electrolyte solution, it is N-methyl- 2-pyrrolidinone, a propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, gamma-butyl, for example. Lactone, 1,2-dimethoxy ethane, tetrahydroxy franc, 2-methyl tetrahydrofuran, dimethylsulfoxide, 1,3-dioxolon, formamide, dimethylformamide, dioxolon, acetonitrile Nitromethane, methyl formate, methyl acetate, triester phosphate, trimethoxy methane, dioxoron derivatives, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivatives, Aprotic organic solvents such as tetrahydrofuran derivatives, ethers, methyl pyroionate and ethyl propionate can be used.

In addition, for the purpose of improving charge / discharge characteristics, flame retardancy, etc., for example, pyridine, triethyl phosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, Nitrobenzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyrroles, 2-methoxy ethanol, aluminum trichloride and the like may be added. have. In some cases, in order to impart nonflammability, halogen-containing solvents such as carbon tetrachloride and ethylene trifluoride may be further included, and carbon dioxide gas may be further included to improve high temperature storage characteristics.

The present invention also provides a lithium ion polymer secondary battery comprising the gel solid electrolyte. In general, a lithium ion polymer secondary battery is manufactured by configuring a lithium salt-containing electrolyte in the form of a gel in an electrode assembly having a separator interposed between a positive electrode and a negative electrode.

The positive electrode is prepared by, for example, applying a mixture of a positive electrode active material, a conductive agent, and a binder onto a positive electrode current collector, followed by drying and pressing. If necessary, a filler may be further added to the mixture.

The positive electrode current collector is generally made of 3 to 500 μm thick. Such a positive electrode current collector is not particularly limited as long as it has high conductivity without causing chemical changes in the battery. For example, the surface of stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel Surface treated with carbon, nickel, titanium, silver or the like can be used. The current collector may form fine irregularities on its surface to increase the adhesion of the positive electrode active material, and may be in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.

The positive electrode active material may be a layered compound such as lithium cobalt oxide (LiCoO ₂ ), lithium nickel oxide (LiNiO ₂ ), or a compound substituted with one or more transition metals; Li _{1 + x} Mn _{2 - x} O ₄ (Where x is 0 to 0.33), lithium manganese oxides such as LiMnO ₃ , LiMn ₂ O ₃ , LiMnO _2, and the like; Lithium copper oxide (Li ₂ CuO ₂ ); Vanadium oxides such as LiV ₃ O ₈ , LiFe ₃ O ₄ , V ₂ O ₅ , Cu ₂ V ₂ O ₇ and the like; Ni-site type lithium nickel oxide represented by the formula LiNi _1-x M _x O ₂ , wherein M = Co, Mn, Al, Cu, Fe, Mg, B, or Ga, and x = 0.01 to 0.3; Formula LiMn _2-x M _x O ₂ (wherein M = Co, Ni, Fe, Cr, Zn or Ta and x = 0.01 to 0.1) or Li ₂ Mn ₃ MO ₈ (wherein M = Fe, Co, Lithium manganese composite oxide represented by Ni, Cu or Zn); LiMn ₂ O _{4 in} which a part of Li in the formula is substituted with alkaline earth metal ions; Disulfide compounds; Fe ₂ (MoO ₄ ) ₃ and the like, but are not limited to these.

The conductive agent is typically added in an amount of 1 to 50 wt% based on the total weight of the mixture including the positive electrode active material. Such a conductive agent is not particularly limited as long as it has conductivity without causing chemical change in the battery. Examples of the conductive agent include graphite such as natural graphite and artificial graphite; Carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and summer black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.

The binder is a component that assists in bonding the active material and the conductive agent to the current collector, and is generally added in an amount of 1 to 50 wt% based on the total weight of the mixture including the positive electrode active material. Examples of such binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene , Polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butylene rubber, fluorine rubber, various copolymers and the like.

The filler is optionally used as a component for inhibiting the expansion of the positive electrode, and is not particularly limited as long as it is a fibrous material without causing chemical change in the battery, for example, olefinic polymers such as polyethylene, polypropylene; Fibrous materials, such as glass fiber and carbon fiber, are used.

The negative electrode is manufactured by coating and drying a negative electrode material on a negative electrode current collector, and if necessary, the components as described above may be further included.

The negative electrode current collector is generally made of 3 to 500 μm thick. Such a negative electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery. For example, the surface of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver, and the like, aluminum-cadmium alloy, and the like can be used. In addition, like the positive electrode current collector, fine concavities and convexities may be formed on the surface to enhance the bonding strength of the negative electrode active material, and may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.

The negative electrode material may be, for example, carbon such as hardly graphitized carbon or graphite carbon; Li _x Fe ₂ O ₃ (0 ≦ _x ≦ 1), Li _x WO ₂ (0 ≦ _x ≦ 1), Sn _x Me _{1 - x} Me _y O _z (Me: Mn, Fe, Pb, Ge; Me: Al Metal complex oxides such as B, P, Si, Group 1, Group 2, Group 3 elements of the periodic table, halogen, 0 <x ≦ 1; 1 ≦ y ≦ 3; 1 ≦ z ≦ 8); Lithium metal; Lithium alloys; Silicon-based alloys; Tin-based alloys; SnO, SnO ₂ , PbO, PbO ₂ , Pb ₂ O ₃ , Pb ₃ O ₄ , Sb ₂ O ₃ , Sb ₂ O ₄ , Sb ₂ O ₅ , GeO, GeO ₂ , Bi ₂ O ₃ , Bi ₂ O ₄ , and metal oxides such as Bi ₂ O ₅ ; Conductive polymers such as polyacetylene; Li-Co-Ni-based materials and the like can be used.

The secondary battery according to the present invention may have a cylindrical can, a rectangular can, or a shape embedded in a battery case of a laminate sheet including a metal layer and a resin layer. As a preferable example, a rectangular can can be used. For example, an electrolyte in which a mixture of the oligomer of Formula 1 and the monomer of Formula 2 is added is added to the rectangular can with an electrode assembly and sealed, and then 40 to 80. It is possible to prepare a desired rectangular lithium ion polymer battery by heating to 1 ° C. for 1 to 20 hours to induce curing by polymerization. Since decompression occurs in this process, the phenomenon in which the battery is swelled due to the gas generated during the charge / discharge of the battery may be prevented in advance.

Hereinafter, the present invention will be further described with reference to Examples, but the scope of the present invention is not limited thereto.

Example 1

95% by weight of LiCoO ₂ , 2.5% by weight of Super-P (conductor) and 2.5% by weight of PVdF (binder) were added to NMP (N-methyl-2-pyrrolidone) as a cathode active material to prepare a cathode mixture slurry. A positive electrode was prepared by coating, drying, and pressing one surface of the aluminum foil, respectively.

95% by weight of artificial graphite, 2.5% by weight of Super-P (conductor) and 2.5% by weight of PVdF (binder) were added to NMP as a solvent to prepare a negative electrode mixture slurry, and then coated on one surface of copper foil, The negative electrode was prepared by drying and pressing.

An electrode assembly was prepared by laminating the positive electrode and the negative electrode using Celgard ^TM as a separator, and then inserted into a battery cell.

1,3-butylene glycol dimethacyclate (Mw = 226) 1.75 wt%, poly [ethylene glycol] diarylate (Mw = 700, degree of polymerization = 13) 1.75 wt% and 2,2 Azobis (2,4-dimethyl valronitrile) 0.1 as initiator Weight percent was added to the electrolyte (1 M LiPF ₆ , VC 1.5 weight percent, PS 0.5 weight percent, EC / EMC / DEC = 4/3/3).

The mixed electrolyte solution was injected through the injection hole of the battery cell in which the electrode assembly was embedded, the injection hole of the battery cell was sealed, and then polymerized at 60 ° C. for 12 hours to prepare a lithium ion polymer secondary battery.

Comparative Example 1

A secondary battery was manufactured in the same manner as in Example 1, except that 1,3-butylene glycol dimethacyclate was not added and poly [ethylene glycol] was added to the electrolyte as a diarylate 5.5% by weight.

Comparative Example 2

A secondary battery was manufactured in the same manner as in Example 1, except that 1,3-butylene glycol dimethacyclate was added to the electrolyte at 2.5 wt% without adding poly [ethylene glycol] diarylate.

Comparative Example 3

1.75 wt% poly [ethylene glycol] diarylate, trimethylopropane triacrylate instead of 1,3-butylene glycol dimethacyclate monomer

A secondary battery was manufactured in the same manner as in Example 1, except that 1.75 wt% was added to the electrolyte.

[Comparative Example 4]

A secondary battery was manufactured in the same manner as in Example 1, except that only an electrolyte solution was added without adding a monomer and an oligomer.

Experimental Example 1

For the battery cells prepared in Example 1 and Comparative Examples 1 to 4, the potential change according to the battery capacity during charge / discharge was measured and shown in Table 1 below.

TABLE 1

As shown in Table 1, the battery cells of Comparative Examples 1, 2, and 3 at the initial charge / discharge have a charge capacity of 878.6, 884.9, and 870.1 mAh, respectively, and the cell thicknesses of the charge are 5.21, 4.57, and 4.48 mm. Whereas the capacity is 767.2, 801.7 and 691.5 mAh, the battery cell of Example 1 can be confirmed that the charging capacity is 890.4 mAh, the cell thickness at the time of charging is 4.33mm and the discharge capacity is 804.6 mAh, the secondary battery according to the present invention It can be seen that the swelling of the thickness is remarkably small.

In the experimental results, the battery cell of Comparative Example 4 has a low cell thickness at the same level as that of Example 1, but the battery cell of Comparative Example 4 is based on a liquid electrolyte battery system, so it is based on a solid electrolyte battery system. Compared with the batteries of Example 1 and Comparative Examples 1 to 3, the liquid electrolyte has a high possibility of leakage of liquid, and thus has a disadvantage of relatively low battery safety. This fact can be confirmed also in Experimental example 3, etc. after this.

Experimental Example 2

For each of the battery cells prepared in Example 1 and Comparative Example 4 was measured in the battery capacity according to the rate of discharge (rate) is shown in the following 2.

TABLE 2

As shown in Table 2, it can be seen that although Example 1 is a polymer electrolyte cell system, it has a rate characteristic comparable to that of Comparative Example 4, which is a liquid electrolyte cell system.

Experimental Example 3

In order to confirm the safety at high temperatures for the battery cells prepared in Example 1 and Comparative Example 4, the change in the cell thickness was observed while heating these battery cells under the same conditions as in FIG. The results are shown in FIG. In FIG. 2, a black line means a battery cell of Comparative Example 4 and a red line means a battery cell of Example 1. FIG.

As shown in FIG. 2, the battery of Comparative Example 4 was expanded to about 671 um based on the initial cell thickness, whereas the battery of Example 1 was only expanded to about 118 um based on the initial cell thickness, Example 1 It can be seen that the cell thickness expansion degree of the battery was significantly small at high temperature exposure.

The present invention provides a substrate of a gel solid electrolyte by polymerization of a heterogeneous oligomer and monomer mixture, thereby preventing swelling of the battery while preventing degradation of rate characteristics and cycle characteristics caused by a conventional gel solid electrolyte, and at a high temperature. There is an effect that can improve the storage characteristics.

Those skilled in the art to which the present invention pertains will be able to perform various applications and modifications within the scope of the present invention based on the above contents.

Claims (9)

A lithium salt-containing electrolyte solution is included in the form of a gel in a substrate obtained by polymerization of a mixture of an oligomer of Formula 1 and a monomer of Formula 2, and a mixing ratio of the oligomer and monomer is 1: 10 to 10: Gel-type solid electrolyte, characterized in that 1:

(One)

(2) Wherein n is an integer from 2 to 30. delete The gel solid electrolyte of claim 1, wherein the mixing ratio of the oligomer and the monomer is 4: 6 to 6: 4 by weight. The gel solid electrolyte of claim 1, wherein the mixture of the oligomer and the monomer is included in an amount of 1 to 5 wt% based on the total weight of the electrolyte. The gel solid electrolyte of claim 1, wherein n is 5 to 20 in Chemical Formula 1. The method of claim 1, wherein the mixture of the oligomer and monomer is added to the electrolyte solution together with the thermal polymerization initiator, and then heated to 40 to 80 ℃ after assembly of the battery to induce a polymerization reaction for the formation of a gel containing a lithium salt-containing electrolyte solution. Gel solid electrolyte, characterized in that. A lithium ion polymer secondary battery comprising the gel solid electrolyte according to any one of claims 1 and 3 to 6. 8. The lithium ion polymer secondary battery of claim 7, wherein the gel solid electrolyte is embedded in a cylindrical can, a square can, or a battery case of a laminate sheet including a metal layer and a resin layer. The method of claim 8, wherein the gel solid electrolyte is formed by a polymerization reaction by adding an electrolyte solution to which a mixture of an oligomer of Formula 1 and a monomer of Formula 2 is added to a rectangular can together with an electrode assembly, sealing the can, and heating. After completion of the reaction, the inside of the can is a lithium ion polymer secondary battery, characterized in that the pressure is reduced.

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