TW200409394A - Gel electrolyte secondary battery and its manufacturing method - Google Patents

Abstract

This invention is to improve battery characteristics of a gel electrolyte secondary battery and provide its manufacturing method. Since a precursor solution becomes easier to interpenetrate in a separator and an electrode when butyric acid is contained in the precursor solution of a gel electrolyte, a manufacturing process of the gel electrolyte secondary battery is improved. Furthermore, when the butyric acid is contained in the gel electrolyte, a gel electrolyte secondary battery with superior battery performance can be provided.

Description

200409394 Description of the invention: [Technical Field] The present invention relates to a gel electrolyte secondary battery using a gel-like substance as an electrolyte and a method for manufacturing the same. In more detail, the present invention relates to an improvement of a gel electrolyte secondary battery and a manufacturing method thereof for the purpose of providing a high-performance lithium polymer secondary battery. [Prior technology] At present, the electrolytes of lithium primary batteries or lithium secondary batteries sold on the market use lithium salts dissolved in organic solvents (electrolytes for lithium batteries). However, it is easy for organic solvents to occur outside the battery. Leakage or volatilization, etc. have poor long-term reliability, and the electrolyte is scattered during the sealing process. In order to improve the leakage resistance, safety, and long-term storage, the use of ion-conducting polymers (gel electrolytes) with high ion conductivity as the electrolyte has attracted attention as a means to solve the above-mentioned problems. . For example, Japanese Unexamined Patent Publication No. 58-75779, Japanese Unexamined Patent Publication No. 59-149601, and U.S. Patent No. 4,792,504 have proposed a gel electrolyte that absorbs an electrolyte for a lithium battery into a solid state of a gel-like substance. The electrolytes reported for batteries that have been reported so far can be roughly divided into (1) non-bridged thermoplastic polymers, (2) oligopolymers with bridged groups, (3) non-bridged polymers and bridged polymers Three types of combination. However, there are many improvements to these gel electrolytes, which are being researched and developed from various angles. Here, the electrolyte having the weakness of (1)-(3) gel electrolyte is overcome, that is, the polymer chain has at least ethylene oxide (EO) units or propylene oxide (PO) units, and its ends and / Or a polyfunctional propionate having a propylene group in its side chain, 200409394 or a polyfunctional methacrylate having a methacrylic group, mixed with an electrolyte for a lithium battery as a precursor solution, and subjecting it to light, heat, Gel electrolytes obtained from bridges such as electron beams are attracting attention. Its advantage is that the precursor solution of the gel electrolyte has a secondary hydrocarbon-based oxygen structure with high compatibility with the general electrolytic solution, so the electrolyte after the bridge has good retention. Examples include better effects on load characteristics and low temperature characteristics. . For example, in Japanese Patent Application Laid-Open No. 1 1-176452, a tetrafunctional terminal propane-denatured hypoalkylene oxypolymer as a gel electrolyte precursor is described, and a gel obtained by bridging it with electron beam irradiation is disclosed. Electrolyte solid battery cycle characteristics. In addition, in Japanese Patent Application Laid-Open No. 2001-210380, in order to prevent the use of monofunctional, difunctional, and trifunctional acrylates as gel electrolyte precursors, and gel bridges obtained by irradiation with ultraviolet rays; and battery use The decomposition of the gel electrolyte revealed a polymer battery including graphite particles with amorphous carbon adhered on the surface as a negative electrode. The battery of this publication is the one in which the precursor solution is immersed in the positive electrode, the negative electrode, and the separator, and integrated after bridging. In the manufacturing process of the battery, a separator is inserted between the positive electrode and the negative electrode, and it is laminated in a rolled shape or a plurality of layers and packed into the battery exterior material, and then injected into the electrolyte solution of the gel electrolyte. However, it is found that the precursor solution is difficult to penetrate the separator and the electrode, especially the negative electrode. In the past, electrolytes for lithium secondary batteries containing γ-butyrolactone (γ-BL) tended to have difficulty in penetrating electrodes with low porosity. In recent years, with the increase in energy density, voids inside the battery have become extremely small. Therefore, when the precursor solution containing γ-BL is to be immersed in the spacer and the electrode, only the surface of these is impregnated. Therefore, even a 200409394 bridge cannot form a good ion conductor. Therefore, the utilization efficiency of the active material becomes low, the charge-discharge reaction will become local, and the battery characteristics will be significantly reduced. Secondly, problems are also found in the bridging method. In the case of ultraviolet radiation, the transmission of electricity and internal permeability is also a problem. That is, the range in which ultraviolet rays can be irradiated is limited to the vicinity of the seal, and it is difficult to penetrate the inside of the electrode and the separator. Therefore, the precursor solution is 'inadequate' and the remaining precursor solution is left unreacted. The result is that it will stand when the battery is used; ά ’s effect ’and bring bad effects on battery characteristics: sub-radiation, springs, and shots, although there are fewer transmission problems such as ultraviolet radiation, bridging becomes difficult when thickened. Further, due to the device and the reason, it is difficult to increase the size of Γ, and as a result, the cost will increase. The method of bridging girls, (: ultraviolet or electron beam irradiation is not suitable for a large number of solutions, · solution two :. The other 10,000 'thermal bridge also has the heat of electrolyte salts :: hair installation, thermal polymerization initiator and battery composition The reactivity, and also the issue of: the heat resistance of the laminate are mainly based on the temperature characteristics. ', Λ 5 active material of the positive and negative electrodes and the gel, γ, and the surface resistance of η is significant. Er Jiao Wu * Jian "Problems and methods that will not exist in the industry can obtain battery characteristics of the previous electrolyte system [Inventive Content]

Concentrated on the above pE] HS and carefully reviewed; 'Γ good secondary battery characteristics and manufacturing methods butyric acid, ": found in the gel electrolyte before the drive solution contains a negative electrode, so the solution will easily penetrate into the separator According to the invention, the electrode and the electrode are used to complete the present invention / fabrication method and further improve the battery characteristics. According to the present invention, 200409394 provides a gel electrolyte secondary battery, which is characterized by containing: The positive electrode and the negative electrode of the active material; and the gel electrolyte disposed between the positive electrode and the negative electrode; wherein the gel electrolyte contains butyric acid at a concentration of 5 to 5500 ppm. According to the present invention, a gel electrolyte 2 is provided. A method for manufacturing a secondary battery. The gel electrolyte secondary battery includes: a positive electrode and a negative electrode containing an active material capable of inserting / removing lithium ions; and a gel electrolyte disposed between the positive electrode and the negative electrode. The gel electrolyte is made of butyric acid at a concentration of 5 to 550 ppm in the presence of butyric acid by bridging the polymer of the gel electrolyte raw material. [Embodiment] Since butyric acid includes both a hydrophobic alkyl group (-CH2CH2CH3) and a hydrophilic carboxyl group (-COOH), for example, there is a hydrophobic material such as a carbon element material for a negative electrode active material, and The effect of affinity of the hydrophilic materials of the electrolyte for secondary batteries contained in the gel electrolyte with each other. This effect does not disappear even after the bridging process. It has been determined that the presence of butyric acid in the gel electrolyte improves the battery characteristics. Either n-butyric acid or isobutyric acid is effective as butyric acid. However, the melting point of n-butyric acid is -5.2 ° C, and the melting point of isobutyric acid is -46.1 ° C, so a low temperature below 0 ° C is considered. In terms of characteristics, isobutyric acid is preferred. As a gel electrolyte, a gel electrolyte previously used in lithium polymer batteries can be applied. In addition, electrolysis for lithium secondary batteries used in lithium polymer batteries It also has an effect. As a method for quantifying the content of butyric acid in a gel electrolyte, for example, a solvent such as tetrahydrofuran or n-hexane can be used for 200409394 to extract the electrolyte containing butyric acid from the gel electrolyte. Phase chromatography or liquid Chromatographic measurement. The content of butyric acid in the gel electrolyte is 5 to 550 ppm, preferably 10 to 500 ppm. When the content is lower than 5 ppm, the affinity between the active substance and the gel electrolyte is not sufficiently improved, so It is difficult to obtain good battery characteristics. On the other hand, when the content is higher than 550 ppm, the decomposition reaction of butyric acid accompanying the charge and discharge reaction starts to reduce the charge and discharge efficiency. Therefore, among the good battery characteristics, low temperature characteristics will be difficult to obtain. For this reason, the melting point of n-butyric acid is considered to be -5.2 ° C. The preferred content is 10 to 500 ppm which can improve all battery characteristics. The gel electrolyte is a lithium salt, a non-aqueous solvent, and contains butyric acid. Polymer cross-linked body; wherein the polymer comprises a polymer having at least a trifunctional acrylate having an ethylene oxide (EO) unit or a propylene oxide (PO) unit of P0 / EO = 0 to 5 Or copolymers, and polymers or copolymers of monofunctional acrylic acid with PO / Έ〇 = 0 ~ 5 having EO units or PO units are preferred. As a method for analyzing the gel electrolyte, a known method such as gel permeation chromatography or ultrathreshold chromatography can be applied. For example, the former measurement is applicable to bridges having average molecular weight distributions of 200 to 3,000 and 7,000 to 9,000. In the present invention, by mixing a polymer or copolymer of a trifunctional propionate with a polymer or copolymer of a monofunctional acrylate, the battery characteristics are not lowered, and it is found that improvement can be made. By mixing, the flexibility of the gel electrolyte will be increased, which will ease the expansion and contraction of the bridge, which can prevent the gel electrolyte from occurring near the cycle, and the gel electrolyte near the electrode can be prevented from being broken or broken. In addition, when monofunctional acrylate is used instead of monofunctional acrylate, in order to obtain the same effect, it is necessary to mix more than 200409394 than monofunctional acrylate. As a result, the holding power of the liquid is reduced, which is not suitable for battery electrolytes. . The mechanical strength index of the gel electrolyte can be exemplified by tensile strength, which is preferably 0.05 to 25 MPa. The non-aqueous solution of the electrolyte solution for the lithium secondary battery is more preferably composed of EC and γ-BL, and contains a third solvent selected from the group consisting of diethyl carbonate (DEC), methyl ethyl carbonate (MEC), One or more solvents of vinyl carbonate (VC), and the volume ratio of EC is 10-50%. This is for the following reasons. When the volume ratio of EC is less than 10%, it is difficult to densely coat the surface of graphite particles with a protective film, so graphite particles will react with γ-BL, which may cause reduction in cycle characteristics. On the other hand, when the volume ratio of EC is greater than 50%, the viscosity of the precursor solution becomes high, and it is difficult to penetrate the barrier layer and the electrode even if butyric acid is added. Therefore, since the gel electrolyte cannot be formed sufficiently between the separator and the electrode after the bridge, good battery characteristics cannot be obtained. In addition, in order to improve low-temperature characteristics, at least γ-BL is preferably present at a volume ratio of 10 to 90% for the entire non-aqueous solvent. A more preferred range is 30 to 70% by volume. When the volume ratio of γ-BL is less than 10%, it is difficult to obtain sufficient low temperature characteristics. On the other hand, when the volume ratio of γ-BL is more than 90%, it becomes difficult to cover the surface of the carbon element with a dense protective film, and graphite particles and γ-BL will react, which may cause a reduction in cycle characteristics. In order to improve the permeability of the electrode active material falling into the precursor or the interior of the interlayer substrate, the volume ratio of DEC and MEC to the entire non-aqueous solvent is preferably 10 to 40%. It is because the viscosity of DEC or MEC is lower than that of EC and γ-BL, which has the effect of reducing the viscosity of the precursor solution. ◦ The volume ratio of DEC or MEC is less than 10%. When the volume ratio is greater than 40%, it is not good because it will be difficult to suppress the oxidative decomposition of the gel electrolyte under high temperature environments, which will cause deformation of the exterior material.

In addition, VC is preferably added to the total weight of the electrolyte solution for a lithium secondary battery at a weight ratio of 1 to 10 / °. When added in this proportion, in addition to forming the protective film of EC on the surface of the carbon element, it is easy to form a thin and dense protective film by VC, which can suppress the generation of gas and control the deformation of the exterior material. When the weight ratio of vC is less than 1%, it will be difficult to form a thin and dense protective film, and the possibility of external materials and laughter due to gas generation will increase. On the other hand, the weight ratio of vc is greater than 10 /. In this case, it is difficult to suppress the oxidative decomposition of the gel electrolyte in a high-temperature environment and cause deformation of the exterior material, which is not preferable. As the non-aqueous solvent other than the above, the same cyclic carbons as EC can be used, for example, isopropyl ester, butyl isobutyl ester, or the same cyclic and acid g as γ-BL, chain esters, Examples include dimethyl carbonate. Lithium salts, such as lithium perchlorate, lithium tetrafluoroborate, and phosphoric acid 6

It is known that lithium salts can be used in combination of two or more kinds. The lithium salt is dissolved by the selected non-aqueous solvent to prepare an electrolytic solution. The lithium salinity corresponding to the non-aqueous solvent is 0.8 to 2 5 m; 1/1 is preferable. When the salt concentration is higher than 0.8, it is impossible to get the ion transmission necessary to obtain the discharge characteristics at high load. When the 2.5 ° mol / 1 is high, the cost of lithium salt is increased, because = It rises again and it is difficult to penetrate into the electrode. Further, it is necessary to dissolve the lithium salt: it is not suitable for industry because it is not suitable for a long time. In addition, the non-aqueous solvents and lithium salts used in the preparation of the precursor solution are not limited to the above-mentioned sons. 0 -12- 200409394 About the self-cup, the non-amorphous / and sexual substances attached to the clay can be listed in graphite The particle surface is made of an elemental material (hereinafter referred to as surface amorphous graphite). solution. The special D | J solid and cymbal graphite can inhibit gel electrolyte or butyric acid. It inhibits the decomposition of butyric acid during charge and discharge. It can easily control the butyral battery. Swelling and :: There is no decomposition reaction. The generation of gas caused by the letter of the battery caused by the battery short circuit, leakage, etc., can be improved by = amorphous graphite based on a highly crystalline graphite material as the core material, borrowing :: " 广 去A method such as a liquid phase method, a solid phase method, and the like can be used to obtain amorphous carbon adhered to the surface of the stone i. = In non-graphite graphite, it must have a certain size because it is attached to amorphous carbon, which is related to the specific surface area measured by the dark method. Among them, the ratio of the area of f to 1-5 is better. The surface area of the dagger is greater than W / g = the contact area of the butyric acid or the non-aqueous solvent contained in the gel electrolyte is also large, which is not good because it is easy to produce such decomposition reactions. Further, it is because of the former 2 solution The increase of the adsorption amount of the polymerization initiator to the surface of the negative electrode, " " will hinder the bridge of the precursor solution or reduce the initial charge and discharge efficiency, so ==. When the specific surface area is less than lm2 / g, 'the contact area with the electrolyte changes Small: The electrochemical reaction speed will be slower, and the load characteristics of the battery will be reduced, so it is not good. As the highly crystalline graphite material used as the core material, the former can be used as the highly crystalline graphite material as the core material. In the light wide-angle diffraction method, the (002) plane average interplanar spacing (d〇〇2) is 0.335 ~ 〇34〇, and ~ [a is preferably more than 10 nm. When d⑼2 is greater than 0.340 nm, or When Lc and La are less than 10 positions, due to insufficient crystallinity as a core material, When using it to make the surface amorphous stone black 13 200409394, the capacitance of lithium dissolved out of mV) will be insufficient, and the nearby potential portion (Li's potential reference system is 0 ~ 300) is not good. The X-ray wide-angle diffraction method is commonly used to determine the crystal size (U, La). For example, "Experimental Technology for Carbon Element Materials 1, P · ~ 63 'Edited by Carbon Tt Element Materials Society (Science and Technology Corporation), , The recorded party

For example, Lai Lu is at the end of the time domain, and Lai Xiaonu uses the field "powdering". For the sample, add about 15% of the χ-light standard high-purity stone powder 2 as an internal standard material, add and mix, and load the sample into Container, κ graphite early color detector uses the monochromatic CuKa rays as the light source, and measures the wide-angle X-ray diffraction curve by the reflex diffraction detector method. In the correction of the curve, ride the so-called stochastic, bias factor, The absorption factors, atomic scatter factors, etc. are not corrected, and the following simple method is used.

That is, by extending the baseline corresponding to the (002) diffraction curve, a modified diffraction curve of the (002) plane can be obtained. Then, the diffraction curve is corrected to use the so-called half value β, which is half the height of the learned value, to size the crystals in the c-axis direction. Calculated by LC = (K · λ) / (β · ⑽㊀). Here, λ is 1.5418A, and θ is a diffraction angle. La can also be measured in the same place. For the peak intensity ratio near Raman Raman, the peak intensity ratio (hereinafter referred to as r value) near 136 ° is preferably 0.5 or less (more preferably 0.4 or less). When the R value exceeds 0.5, the crystallinity of the surface is insufficient due to insufficient crystallinity of the core material, and the capacitance of the nearby potential portion due to the dissolution of lithium will be insufficient, which is unfavorable. In addition, although the crystallinity of the attached part is not particularly limited, but by using the crystallinity that is lower than that of the core material, that is, the larger the R, R value, etc., -14-200409394 can be obtained as the surface non- Effect of crystalline graphite. In X-ray diffraction, due to the large number of properties of the material, it may not be possible to show a large difference when the surface layer is thin. For example, at this time, R measured by Raman measurement that can measure surface properties The value will be valid. For low-crystalline carbon materials, dQG2 is preferably greater than 0.34 nm, and R value is greater than 0.5 (more preferably greater than 0.4). These are based on the same CVD conditions of the carbon element materials attached to the surface or the firing conditions of various raw materials, and only the surface carbon element materials are made similarly. The physical properties can be determined indirectly by measuring their physical properties. Next, the gel electrolyte in a gel electrolyte secondary battery contains butyric acid at a concentration of 5 to 550 ppm, and is manufactured by bridging a polymer as an electrolyte raw material in the presence of butyric acid. Gel electrolytes are polymers or copolymers containing trifunctional acrylates with PO / EO 20 to 5 having at least ethylene oxide (EO) units or propylene oxide (PO) units in the polymer chain, A polymer or copolymer with a monofunctional propionate having EO / PO units of PO / E0 = 0 ~ 5, preferably in the presence of an electrolyte for lithium batteries, a polymerization initiator, and butyric acid . Butyric acid contains 5 to 550 ppm in the gel electrolyte after bridging, and the amount of butyric acid added in the production is adjusted. The amount of butyric acid to be added to the precursor solution in manufacturing should be added more than the butyric acid concentration contained in the gel electrolyte after bridging. The amount of butyric acid added is preferably in the range of 9 to 560 ppm based on the total weight of the precursor solution. When the butyric acid content is less than 9 ppm, the electrolyte cannot be incorporated into the separator and the electrode ', and the effect cannot be obtained in the manufacturing process. On the other hand, if the content of butyric acid is more than 560 ppm, there is no problem in the manufacturing process, but the battery characteristics may be damaged after bridging. A more preferable addition amount is 15 to 50.0 μm. The raw material of the second gel s electrolyte is tri-functional polyether polyalcohol polyacrylic acid (a polymer or copolymer of tri-methyl sulfonium) as the main body. It has: "Polyether moiety shown in the general formula T", and the polymer is formed by three-dimensional bridge formation ', and it is preferable that the polymerization site is polyfunctional. Its typical giant; U-molecular weight polymer; although it is a polymer, a gel electrolysis temporary matrix is formed after bridging. Trivalent alcohol such as propane is used as the starting material; here, it is obtained by polymerizing E0 alone or in addition to p0. [化 1] 〇Η 〇Η ch-o ^ a ^ c ~ c = ch2 CH, · 〇Ί-C = CH, II I w (Ap A2, A3 means at least more than £ 0 units, and any Including 3 PO units and 2½ residues, the number of cations and E〇 is within the range of p0 / E0u, and EO + PO-35.) The average molecular weight of the polymer or copolymer of trifunctional acrylic acid It is better to be within the range of 7, 000 ^ 9,000. When the average molecular weight is less than 7, _ will produce a liquid retention solution [生 《问 _, greater than 9, and coffee must be taken for a very long time because of its dissolution. It is not universally used in Wang industry, and f is not good. Especially when the gel electrolyte contains an electrolyte: 'Because the polymer or copolymer of triauryl acrylate is more monofunctional and diaerial,' it is easier to produce a three-dimensional bridge structure, due to high mechanical strength and retention -16- 200409394 The ionic conductivity of the gel electrolyte will be high, and it is better as an electrolyte for batteries. The monofunctional acrylate has a polyether portion and the polymer is formed in a one-dimensional bridge structure. It is preferable that the polymerization site is monofunctional. Its typical giant single system esterifies the terminal hydroxyl group of polyetherpolyol with acrylic acid. Polyether polyols are derived from monovalent alcohols such as methanol, ethanol, and propanol, and are obtained by polymerizing EO alone or by adding PO. [Chemical 2]

〇Η

II IR—A4 — C — C = CH2 (R is a hydrogen atom or a methyl group, and A4 is a divalent compound that has at least three ethylene oxide units (EO) and arbitrarily contains propylene oxide units (PO). The number of residues, PO and EO is in the range of PO / EOO ~ 5, and EO + P〇 ^ 35.) The average molecular weight of the polymer or copolymer of monofunctional acrylate is preferably in the range of 200 ~ 3,000. When the average molecular weight is less than 200, gelation is difficult, and when the average molecular weight is more than 3,000, it takes a very long time to dissolve, which is not suitable for industrial use, so it is not good. Because the polymer or copolymer of monofunctional acrylic acid ester has a linear one-dimensional structure, it has poor liquid retention compared with bifunctional or trifunctional ones, so the ionic conductivity of the gel electrolyte cannot be fully obtained. Although the amount of the electrolyte in the precursor solution of the gel electrolyte, the gel electrolyte is formed after bridging, and a continuous phase is formed in the electrolyte, but it is better that the electrolyte is not separated and oozed out after time. For example, when a trifunctional acrylate and a monofunctional acrylate polymer or copolymer are mixed, the weight ratio of the macromonomer to the electrolyte is set to a range of 3: 97 ~ 15: 85. Achieving Shangcheng > B aa > \ Purpose. When the weight ratio of the macromonomer is greater than 丨 5%, the ion conductivity will be changed; ^ ¥ ',' In addition, on the other hand, when the weight ratio of the macromonomer is less than 3%, it will be difficult to gel, and Μ p and hydration will increase. At the beginning of the dose, gelation does not result in sufficient mechanical strength, and there is also the problem of leakage of the electrolyte when time passes. In one step, the amount of the polymer or copolymer of early ear energy acrylate is added, and the weight ratio in the flooding solution is preferably 0.5 to 7%. The weight ratio of monofunctional acrylic ", wood & At 0 ° C, the gel electrolyte will not be able to achieve a three-dimensional bridge structure, so its ionic conductivity will not be able to satisfy the battery characteristics. In addition, when the absolute amount of the macromonomer in the precursor solution is small, it becomes difficult to gelate. It is expected that when the weight ratio of the polymer or copolymer of monofunctional acrylic acid is less than that, please lose the effect of mixing. The ash method solves the above problem. u / The viscosity of the precursor solution of the gel electrolyte of the present invention is preferably 50 mPa · S or less. When the anode active material layer and the anode active material layer can be simply impregnated, the lower the viscosity of the precursor solution, the better. The precursor solution viscosity is affected by the mixing ratio of macromonomer and non-aqueous solvent, lithium salt concentration, and temperature. In addition, as a means for reducing the viscosity, although the temperature of the precursor solution is considered to be increased, it is preferable that the polymerization initiator and the non-aqueous solvent be hardly affected, and it is preferable to perform it below. In order to improve the efficiency and speed of impregnation, it is also possible to perform wind impregnation and true six impregnation. As a bridging method, in addition to the heating method, use of ultraviolet rays, electron rays, and visible light, etc., is used. It is also important to use a polymerization starter when necessary. Especially for | & Μ J In the method of bridging the outer line, it is better to add a polymerization initiator of several% or less. Examples of the polymerization initiator include: 200409394 t-hexylperoxyvaleric acid (Π) hour half-life temperature machine, activation energy 28.3 kcai / mol), t-butyl peroxyvaleric acid, 00 hours half-life temperature 54 ° C, activation energy 28.6 kcal / mol), etc .; di-3,5,5-di Methylhexanone peroxide (10-hour half-life temperature step, 29.7 kcal / mol at live-time energy), Laurel peroxide 1000-hour half-life temperature 61 it, chemical energy 29.9 kcal / mol), stearyl peroxide 100-hour half-life temperature 62 · t :, activation energy 30.3 kcal / mol), -toluene, benzene oxide (10-hour half-life

Phase temperature: 73.1 ° C, activation energy: 30.6 kcal / m i), isobutyrium peroxide (10 hours, half-life temperature: 33 it, activation energy: 26_5 kcal / mol), etc.

t-butyl peroxyneodecanoate (10-hour half-life temperature 46 °, activation energy 26.8 kcal / mol), U, 3,3-tetramethylbutyl peroxyneodecanoate (10-hour half-life temperature 41 C, activation energy 27.2 kcal / mol), t-hexyl peroxyneodecanoate (10-hour half-life temperature 44t :, activation energy 34.8 kcal / mol), α, α, di (neodecanyl peroxy) di Cumene (10 hour half-life temperature 35.9 it, activation energy 25.5 kcal / mol), α-cumyl peroxide neodecanoate (10 hour half-life temperature 38 C, activation energy 27.2 kcal / mol), etc. Alkyl peroxides; and monomethoxybutyl percarbonate (10 hour half-life temperature 43 ° C, activation energy 34.1 kcal / mol), bis (4-t-butylcyclohexyl) peroxide Carbonate (10-hour half-life temperature 44 ° C, activation energy 30.2 kcal / mol), Dipropyl peroxycarbonate (10-hour half-life temperature 40 · 3, activation energy 27.2 kcal / mol)-isopropyl peroxide Carbonic acid vinegar (10-hour half-life temperature 45 t, activation energy 30.4 kcal / mol), Bucyclohexyl small methylethyl peroxide neodecanoic acid (10-hour half-life temperature 41.4t: Activation energy 27.8 kCal / m2i • 19- 200409394 ethoxyethyl peroxycarbonate (丨 0-hour half-life temperature 43 • 丨. C, activation of this 30 · kcal / mol), one (2- Ethylhexylperoxy) dicarbonate (hour and a half yuan) / degree 43.6 C, activation energy 3 1 · 1 kcal / mol), bis (3-methyl-3-methoxybutylperoxy) Dicarbonates (10-hour half-life temperature 46.7 °, activation energy 27 · 1 kcal / mol), etc. percarbonates, etc. These polymerization initiators can be used singly or in combination. From the positive electrode, gel electrolyte, and negative electrode In the completed secondary battery, the 10-hour half-life temperature of the polymerization initiator is from about 400c to the thermal blocking temperature of the fiber used in the spacer, and the hardening point temperature of the resin 4 used in the layered packaging. A polymerization initiator in the range up to that point is preferable. Specifically, a starter having an hour half-life temperature of 40 ° C or more and 90 ° or less is preferable. When it is less than 40 C, the polymerization starter is unstable, so it is not good. When the temperature is 9 ° C or higher, it is easy to produce non-aqueous solvents during heat treatment. In order to achieve the invention, the above-mentioned ones are ^ butylperoxy neodecanoate, t-hexylperoxy neodecanoate, and butyl peroxide. The three types of shoulder polymerization initiators, such as oxidized terpentyl oxide, are suitable for use because they do not adversely affect the precursor solution (butyric acid or electrode components). The combination starter is a polymer or copolymer of a trifunctional acrylate, a polymer or copolymer of a monofunctional acrylate is added, and the total weight of the electrolyte for a lithium secondary battery is represented by “卜 ppn ^ | 加It is better. The amount of jealousy agent is as small as possible, because it can reduce the reaction during charge and discharge: the decomposition of the agent. However, when the amount of the starter is too small, the polymerization reaction cannot be fully generated. Macromonomers have the possibility of remaining, so it is not good .: -20- 200409394 As mentioned above, the amount of the polymerization initiator added to the total weight of the macromonomer and the non-aqueous solution is in the range of ^, ⑻ handsome. It is more preferable, among which ⑻⑻ ～ 丨 force㈧ppm is more preferable. The following describes the secondary battery using the above-mentioned gel electrolyte. The battery is manufactured by the following steps. A) Manufacturing of the negative electrode An example of a method for manufacturing the negative electrode is described below. The binding agent is dissolved in a mortar with a solution of age to separate the negative electrode material. The "Department of Science uses a kneading machine, a pulverizer, a paint disperser, and a drill temple." Both H ^ & In the state of "Powder", it is prepared into a paste. If the paste is coated on the current collector 0r. ^ T is enough to be a poise, and it will be dried at 40 ~ 100 c. Then it will be dried at about 15 (rc, In order to achieve a specific density of active materials, we use a punch press to compress, use, grasp, handle, and wind add. In compression molding, it is usually used to flush urine. These presses are pressurized ^ Material, rotation method, temperature, 41,,, v Used for the welding of the electrodeless coating part to remove moisture and remove the water at about 150 ° C, and become tired & cat soil ^ Λ ii iT ^ minus i The dry person can be used as the negative electrode. The fhm of the battery can be used, and the lithium ion cell known as the negative electrode material can be used. The carbon element material is preferred. 乂 4 乂 is about 0.1 ~ 150 μηι is better ~ 耆Although the agent can use polytetramethylene (PVdF) ^, rat ethylene (PTFE) and polyvinylidene fluoride α ^ temple, but it is not limited to these. ,, the amount of the Ministry, 佶 社-士 丨, vermiculite ratio for activity The weight of the substance is 100, and the agent is 1 to 30 weight parts of the a pool, preferably from $ imam. For the manufacture of high-energy density electricians, the substance is extremely dense. The degree is 丨. In order to improve the adhesion during production, i is better. In addition, 'negative electrode treatment is better. ， °° The temperature before and after the melting point of the sword is heated.' 21 »200409394 b) Positive electrode production method An example is described below. The binding agent is dissolved in a mortar with a solvent to disperse the active substance. The dispersing treatment is generally carried out by using an pulverizer, a pulverizer, and a coating agent to disperse the active substance, the conductive agent, and the binding agent in a homogeneous dispersion. Drills, etc., into a paste. Apply this paste to the current collector of gold history and wither 40 ~ 100. (: Dried dry 4 and put it on the bottom, go to "C"仃 heat treatment and

The special active material 嶋 'is compression-molded using a punch. Yu Zengchengcheng Kai J often uses roller punches. There are no special restrictions on the quality of the pressing surface of these punches. After that, Tian Yaogong, the material of the electrode electrode, was set to 15 ° to remove water. . The left and right under reduced pressure serve as the positive electrode. • As the positive electrode active material, LiCo〇2, LiNi〇2, UMn〇2, or · 2 or a series of LiAi-xTx〇2 (where A is Fe, Co, Ni, and Mη <any of ; T represents a transition metal, a metal of group 4B, or a group SB. Υ, and I ^ Mπ2 04 and other known cathode materials for lithium-ion batteries. Although Xun Xun Xun can use carbon elements such as acetylene black or graphite powder, but It is not limited to these. Although PTFE, pvdF, etc. can be used as the binding agent, it is not limited to these. The mixing ratio is 1 to 50 parts by weight of the active material, and the conductive agent is 1 to 50% by weight, and the binding agent is 1 to 30. The weight part is better. In order to manufacture a high energy density battery, the density of the tongue material of the positive electrode is preferably 2 · 8 g / cm3 or more, and more preferably 3.0 g / cm3 or more. In addition, in order to improve the adhesion of the positive electrode, It is better to perform heat treatment after the melting point of the binding agent can be post-processed. -22- 200409394 The positive electrode and the negative electrode are basically various active materials that are fixed with the binding agent and are laminated on the metal foil that becomes the current collector. The material and shape of the current collector are not limited. For the positive electrode, the negative electrode active material, and the electrode, For the solution, chemically and electrochemically stable conductors can be used. The material of the metal foil is aluminum, stainless steel, copper, nickel, etc. In consideration of electrochemical stability, ductility, and economy, aluminum foil for positive electrodes and copper for negative electrodes A foil is preferred. In addition to the metal foil, the shape of the positive electrode and negative electrode current collectors may include a mesh, a perforated sheet, and the like. C) The precursor solution of the gel electrolyte may be prepared as follows, for example. The non-aqueous solvent of EC + Y-BL was mixed with the third solvent, and the lithium salt was dissolved to prepare a 4 $ electrolyte for a secondary battery. A trifunctional acrylate polymer or copolymer (TA) having an average molecular weight of 7,000 to 9,000 and a monofunctional acrylate polymer or copolymer having an average molecular weight of 200 to 3,000 are added to the electrolyte, and a specific amount of polymerization is started. Agent and butyric acid to obtain a precursor solution. d) The battery is assembled between the positive electrode and the negative electrode obtained as described above, so that the person who arranges the separator (electrode group) is turned into a roll shape, inserted into a bag made of A1 layered resin film as an exterior material, and injected into c) Prepare the precursor solution and seal the bag. The battery was bridged by heating at 40 to 90 ° C for 20 minutes to 100 hours to complete the battery. The shape of the electrode group may be directly used as a rolled shape, or may be flattened by compressing it in the radial direction. As a method of forming the electrode group into a roll shape, a conventionally known method can be used. As the compression method, a conventional method of performing multi-stage compression at a desired pressure can be used. -23-200409394 In order to maintain the gel electrolyte barrier, non-woven synthetic trees such as fat fibers, broken glass fibers, and natural fibers can be listed for stability. Polychlorinated vinyl chloride: ’is also used. The quality of non-woven fabrics is better. These synthetic resins do not dissolve the additional barriers due to heat at the time of the contract and the money. The second pool is called heat from the point of view of safety. The use of these functions is good. Although the thickness of the layer is not particularly limited, the thickness can be constant, = liquid, which can be guaranteed and prevent short circuit between the positive electrode and the negative electrode. Qin .. 5_ is better. Such ;: use, 1 coffee:, ~ :. ： /-3, but with only one side to keep the battery inside low:: It is better to prevent the short circuit strength inside the pen pool. In addition, the secondary battery can also be manufactured by integrating the cathode solution with the positive electrode solution, heating and bridging, and integrating and impregnating the precursor. However, the former: "Insert the external interface of the external material into a non-adherent interface" is formed by bridging ... "The negative connection can reduce the internal resistance of the battery. Therefore, compared with the latter method, the number of positive electrodes / separators / negative electrodes is more complex. The weight is the largest, and note: C) After preparing the precursor solution and sealing the bag containing the material for the second night, the appearance of the battery is except for the layered type and resin shown above. For example, cylindrical or :: ：: The outer material can be a gold electrode group inserted into the can, so that the can and the electrode group:… will become the shape of a roll and seal through the insulating packaging material = Q ° Insulate the sealing plate from the can by dropping the precursor. Batteries can be sealed and sealed, or the battery can be made by bridging the heat through the airtight connection. -24- At this time, you can use I + + full element jl, Wang "Anyu valve as the sealing plate. Yu An Wang Several pieces, for example, make two PTC elements. AA ,,,% &quot; Wan Fuwu, fuse, bimetal, ^ p, and female full valve, as a countermeasure for the internal pressure rise of the battery can, can Use the method of marking the cracks between the gas, the method of rising within the I, or the electricity, and also about Crack overcharge sealing plate marked "L: marked with lines of other methods. In addition, using group entry, you can also ... In the case of a hard-band battery, the positive or negative electrode is a battery. For p # T # y, hunting is bridged by heating to make e), i: layer can be made of synthetic resin-based non-woven fabrics. The content of butyric acid in Tongsheng Electrolyte The content of butyric acid in the gel electrolyte is extracted with a solvent, and the extraction is performed; the gel is electrolyzed and the gel is electrolyzed. Specifically,

Encapsulate the shellfish π in tetrahydrofuran (TH sonication 24 hours after the sonication with r / Hexane Temple / cereal, and use the excess liquid to extract, use the gas phase to extract the treatment. The value obtained by the above-mentioned extraction The weight of butyric acid is quantified by lower or liquid decantation. The content. The butyrate n is isomorphic, and the butyric acid and butyric acid in the extract can be obtained. The amount is the butyric acid in the gel electrolyte. In addition, the weight of the butyric acid (mg) / the weight of the extraction liquid ω In addition, in the present invention (g) is a small value n in the amount of butyric acid added, the content will change the battery's tolerance, Consumption at the time of bridge, sleeve, and out-of-sleeve handling. The charge-discharge operation test is performed up to V ^ u 疋 value to make the battery voltage reach 4 · 〖~ 4 · 2 Electric ° Battery voltage reaches 4〗 ~ 4 2 From the post-charging time to reading f π soil, and then charge with a fixed voltage to make a total of 2.7 ~ 3 · 0 V;, and charge until the battery is discharged. Discharge is to make the battery voltage reach this point and perform it at a fixed current value. -25- 200409394 In addition, battery evaluations were carried out in a glove box under the inactive atmosphere μ, | Kongyuedou 5. The inactive gas It is better to use ordinary argon, nitrogen, etc. [Examples] Although the following describes the lack of the present invention, only examples and comparative examples, and its effects will be specifically described, the present invention is not limited to 1 &lt; male examples. Let the batteries of Examples 1 to 19 and Comparative Examples 1 to 2 both have a private battery capacitance of about 0.8 Ah and blend the positive and negative electrodes. (Example 1) The battery of Example 1 was made by the following procedure. A) Negative electrode The surface amorphous graphite (average particle diameter i2 '= 0.336 nm, thief = 0.35, and specific surface area BU 2 ^) produced on the carbon element material was used. The binding agent pvdF is dissolved in the soluble methyl _2_ slightly ketone ketone (NMp) in the transfer to make the surface amorphous stone soil knife. Wan, knife handle using a 2-axis star-walking mixing mixer, The carbon element material and the binding agent are prepared into a paste in a state of being uniformly dispersed. The negative electrode is composed of a carbon element material i⑻ weight part, and then a weight part. Put the Wen paste into a copper foil with a thickness of about 20 μm, and place it on the plate. c fake drying. Thereafter, heat treatment was performed at about 15 ° C for 12 hours, and the density of the active material reached 1.5 gW. The compaction was performed using a roller press in the atmosphere, and nickel coating (50 ° F, wire was welded to the uncoated portion. Thereafter, A negative electrode was used which was dried under reduced pressure at about 150t for 12 hours in order to remove moisture, and was used as a negative electrode. In addition, j was used to measure the average interplanar spacing (d⑽2) and the size of the mouth (Lc, La) by X-ray wide-angle diffraction. For the method, a method known in the past can be used, for example, "Experimental Techniques of Obstructive Materials; ρ 55 ~ 63, edited by the Society of Carbon Element Materials (Science and Technology-26-200409394 Technology Company)" or JP 61-11 1907 The method described. The shape factor K (two Lc · β · cose / λ; β: half-value width, Θ: 〇1002 angle, λ: X-ray wavelength) of the crystal size is determined. The average particle size is 0-9. The diameter is measured using a laser diffraction particle size distribution meter (SALD1100, manufactured by Shimadzu Corporation), and the peak value of the particle size distribution is taken as the average particle diameter. B) The cathode is made of lithium cobalt oxide CoCo2 (average particle diameter of 10 μηι) as the active material. ). Dissolve PVdF in NMP in a mortar to make the above activity The conductive substance is dispersed with the conductive agent acetylene black (AB). In the dispersing process, a two-axis star-type mixing and kneading machine is used to prepare the active material, the conductive agent, and the binding agent in a uniformly dispersed state to prepare a paste. The composition is 100 parts by weight of LiCo〇2, AB5 by weight, and PVdF5 by weight. This paste is applied to an aluminum foil having a thickness of about 20 μm, and dried at 50 to 70 ° C and then 150 ° After the heat treatment in C, compression molding is performed. Compression molding is performed by using a roller punch in the atmosphere to achieve an active material density of about 3.0 g / cm3. Nickel foil (50 μηι) leads are fused to the uncoated portion. Further, use is to remove Moisture and dry at about 150 ° C under reduced pressure as the positive electrode. C) The solution of the precursor solution before the gel electrolyte was prepared at EC + γ-BL + EMC (volume ratio 24:56:20), and LiBF4 was 2.5 mol / 1 was dissolved at a concentration, and VC 2 wt% was added thereto to prepare an electrolyte solution for a lithium secondary battery. The electrolyte solution was 97 wt%, TA 2.4 wt% with an average molecular weight of 7,500 to 9,000, and 0.6% by weight of a polymer or copolymer (GX) of monofunctional propionate having an average molecular weight of 200 to 300. Add t-butyl peroxyneodecanoate (BPN) 250 ppm, t-butyl pervalerate (BPP) 250 ppm, and 15 ppm butyric acid as polymerization initiators to obtain precursor solutions. 200409394 fluid. d) Assembly of the battery Between the positive electrode and the negative electrode obtained above, a polyethylene microporous membrane (thickness: 25 μm, air permeability: 380 sec / cm3) was used as a separator substrate, and rolled up in a full roll. The rolled body is compressed in the radial direction to become flat. Compression is carried out at a desired pressure by 5-stage compression. The electrode group formed into a roll shape is inserted into a bag made of an A1 layered resin film as an exterior material, and the precursor solution is filled with c), and the bag is sealed. This was bridged by heating at 60 ° C for 72 hours to complete the battery. (Example 2) The battery of Example 2 was produced by the following procedure. a) In the manufacture of the negative electrode, except for changing the surface amorphous graphite (average particle size 18 μηι, dQ () 2 = 0.336 nm, R value = 0.5, specific surface area 1 ~ 2 m2 / g), and the composition of the negative electrode is changed to carbon element Except for 100 parts by weight of the material and 8 parts by weight of PVdF, the negative electrode was produced in the same manner as in Example 1. b) Production of the positive electrode Repeated the same operation as in Example 1 to produce the positive electrode. c) Preparation of gel electrolyte precursor solution at EC + y-BL + DEC (volume ratio 20: 50 ·· 30), LiPF6 was dissolved to a concentration of 2.0 mol / 1, and VC 3 wt% was added to this An electrolyte for a lithium secondary battery is prepared. 95 wt% of the foregoing electrolyte was mixed with 2.5 wt% of TA having an average molecular weight of 7,000 to 9,000 and 2.5 wt% of GX having an average molecular weight of 200 to 300. Next, BPN 200 ppm, BPP 300 ppm, and butyric acid 51 200409394 ppm as polymerization initiators were added to obtain a precursor solution. d) Battery assembly The battery was fabricated in the same manner as in Example 1 except that the polyethylene microporous membrane (thickness 25 μm, air permeability 480 sec / cm3) and the bridging conditions under heating were changed to 70 ° C for 70 hours. . (Example 3) The battery of Example 3 was produced by the following procedure. a) In the preparation of the negative electrode, the surface amorphous graphite (average particle size 25 μΐΉ, ¢ 1 () () 2 = 0.336 nm, R value = 0.25, specific surface area 1 ~ 2 m2 / g), and the composition of the negative electrode are changed. A negative electrode was produced in the same manner as in Example 1 except for 100 parts by weight of the carbon element material and 9 parts by weight of PVdF9. b) Production of positive electrode The same operation as in Example 1 was repeated to produce a positive electrode. c) Preparation of gel electrolyte precursor solution at EC + γ-BL + MEC (volume ratio 25:55:20), LiBF4 was dissolved to a concentration of 1.8 mol / 1, and VC 3 wt% was added to prepare Electrolyte for lithium secondary batteries. In the aforementioned electrolytic solution, 97 wt%, TA 2.4 wt% with an average molecular weight of 7,500 to 9,000, and GX 0.6 wt% with an average molecular weight of 200 to 300 were mixed. Secondly, BPP as a polymerization initiator at 150 ppm, t-hexyl pivalate (HPP) at 150 ppm, and butyric acid at 102 ppm can be used to obtain a precursor solution. d) Battery assembly A battery was fabricated in the same manner as in Example 2 except that the bridge condition by heating was changed to 80 ° C for 65 hours. -29- 200409394 (Example 4) The battery of Example 4 was produced by the following procedure. a) Production of negative electrode The same operation as in Example 1 was repeated to make a negative electrode. b) Fabrication of a positive electrode &lt; The same operation as in Example 1 was repeated to produce a positive electrode.曽 c) Preparation of precursor solution of gel electrolyte in EC + γ-BL + DEC (volume ratio 30:60:10), LiClO4 was dissolved to a concentration of 1.5 # mol / 1, and VC 2 was added to this wt% to prepare an electrolyte for secondary batteries. 93 wt% of the foregoing electrolyte was mixed with 3.5 wt% of TA having an average molecular weight of 7,500 to 9,000 and 3.5 wt% of a monofunctional acrylate polymer or copolymer (MA) having an average molecular weight of 2,800 to 3,000. Next, 300 ppm of BPN as a polymerization initiator and 254 ppm of butyric acid were added to obtain a precursor solution. d) Battery assembly A battery was fabricated in the same manner as in Example 1 except that the bridging condition by heating was changed to 65 ° C for 71 hours. Xin (Example 5) The battery of Example 5 was produced by the following procedure. (α) Production of negative electrode The same operation as in Example 2 was repeated to make a negative electrode. b) Production of positive electrode The same operation as in Example 1 was repeated to produce a positive electrode. c) The precursor solution of the gel electrolyte is prepared in EC + y-BL + MEC (volume ratio 30:40:30), LiBF4 is dissolved at a concentration of 2_25 -30- 200409394 mol / l, and this is a strong point VC was 1.5 wt% to prepare an electrolyte for secondary batteries. In the foregoing electrolyte solution, 96 wt%, 3.0 wt% of D-A with an average molecular weight of 7,000 to 9,000, and 1.0 wt% of MA with an average molecular weight of 2,800 to 3,000 were mixed. Next, 200 ppm of BPP as a polymerization initiator and 452 ppm of butyric acid were added to obtain a precursor solution. d) Battery assembly A battery was fabricated in the same manner as in Example 2 except that the bridging condition by heating was changed to 60 ° C for 72 hours. (Example 6) The battery of Example 6 was produced by the following procedure. a) Production of negative electrode The same operation as in Example 3 was repeated to make a negative electrode. b) Production of positive electrode The same operation as in Example 1 was repeated to produce a positive electrode. c) Preparation of gel electrolyte precursor solution at EC + y-BL + MEC (volume ratio 25:55:20), LiBF4 was dissolved to a concentration of 1_75 mol / 1, and VC 3 wt% was added to prepare An electrolyte for a clock secondary battery. In the aforementioned electrolytic solution, 97 wt%, TA 2.4 wt% having an average molecular weight of 7,000 to 9,000, and MA 0.6 wt% having an average molecular weight of 2,800 to 3,000 were mixed. Next, 300 ppm of HPP as a polymerization initiator and 503 ppm of butyric acid were added to obtain a precursor solution. d) Assembly of the battery A battery was produced in the same manner as in Example 2 except that the bridging condition by heating was changed to 80 ° C for 60 hours. 200409394 (Example 7) The battery of Example 7 was produced by the following procedure. a) Production of negative electrode The same operation as in Example 1 was repeated to make a negative electrode. b) Production of positive electrode The same operation as in Example 1 was repeated to produce a positive electrode. c) Preparation of gel electrolyte precursor solution in EC + y-BL + MEC (volume ratio 24:56:20), LiBF4 was dissolved to a concentration of 2.0 mol / 1, and VC 3 wt% was added to prepare Electrolyte for lithium secondary batteries. In the aforementioned electrolytic solution, 96 wt%, TA 3 wt% having an average molecular weight of 7,500 to 9,000, and GX 1.0 wt% having an average molecular weight of 200 to 300 were mixed. Next, BPN 200 ppm, BPP 200 ppm, and butyric acid 9 ppm as polymerization initiators were added to obtain a precursor solution. d) Assembly of battery A battery was produced in the same manner as in Example 1. (Example 8) The battery of Example 8 was produced by the following procedure. a) Production of negative electrode The same operation as in Example 2 was repeated to make a negative electrode. b) Production of positive electrode The same operation as in Example 1 was repeated to produce a positive electrode. c) Preparation of precursor solution of gel electrolyte A precursor solution was prepared in the same manner as in Example 2 except that the addition amount of butyric acid was changed to 13 ppm. -32- 200409394 d) Assembly of battery The battery was fabricated in the same manner as in Example 2. (Example 9) The battery of Example 9 was fabricated in the following procedure. a) Production of negative electrode The same operation as in Example 3 was repeated to make a negative electrode. b) Fabrication of the positive electrode The same procedure as in Example 1 was used to fabricate the positive electrode. c) Gel electrolysis &gt; &amp; 胛 贝 &lt; Then the preparation of the driver solution was the same as that in Example 3 except that the precursor solution of a butyrate a was changed to 5 Uppm. d) The assembly and implementation of the battery Example 3 Phase @ground battery. (Example 10) The battery of Example 10 was produced by the following steps. a) Fabrication of Negative Electrode The same operation as in Example 1 was repeated to fabricate a negative electrode. b) Fabrication of the positive electrode The same operation as in Example 丨 was repeated to produce the positive electrode. c) Preparation of the precursor solution of the gel electrolyte, except that the addition of K 1 to 550 ppm was changed to 550 ppm, and the precursor solution was prepared in the same manner as in Example 4. d) Assembly of battery A battery was produced in the same manner as in Example 4. -33- 200409394 (Example 11) The battery of Example 11 was produced by the following procedure. a) Production of negative electrode The same operation as in Example 2 was repeated to make a negative electrode. b) Production of positive electrode The same operation as in Example 1 was repeated to produce a positive electrode. c) Preparation of gel electrolyte precursor solution at EC + y-BL + MEC (volume ratio 25:55:20), LiBF4 was dissolved to a concentration of 1.8 mol / 1, and VC 3 wt% was added to prepare Electrolyte for lithium secondary batteries. In the aforementioned electrolytic solution, 96 wt%, TA 4 wt% having an average molecular weight of 7,500 to 9,000 was mixed. Next, BPN 150 ppm, BPP 150 ppm, and butyric acid 100 ppm as polymerization initiators were added to obtain a precursor solution. d) Assembly of battery A battery was produced in the same manner as in Example 6. (Example 12) The battery of Example 12 was produced by the following procedure. a) Production of negative electrode The same operation as in Example 3 was repeated to make a negative electrode. b) Production of positive electrode The same operation as in Example 1 was repeated to produce a positive electrode. c) Preparation of gel electrolyte precursor solution at EC + y-BL + DEC (volume ratio 20:60:20), LiBF4 was dissolved to a concentration of 1.8 mol / 1, and VC 3 wt% was added to prepare Electrolyte for lithium secondary batteries. A polymer or copolymer (DA) having an average molecular weight of 7,500 to 9,000-34-200409394 TA 2.5% by weight and an average molecular weight of 3,500 to 4,500 bifunctional acrylic acid (DA) at 97 wt% in the foregoing electrolyte solution. ) 1.5 wt ° / 〇. [化 3] 〇 〇

II II ch2 = ch-c-〇-A5-C-CH two ch2 (A5 means that it has at least 3 EO units and arbitrarily contains divalent residues of PO units. The number of PO and EO is P0 / E0 = 0 to 5.) Next, BPN 150 ppm, BPP 150 ppm, and butyric acid 101 ppm as polymerization initiators are added to obtain a precursor solution. d) Battery assembly A battery was fabricated in the same manner as in Example 2. (Example 13) The battery of Example 13 was produced by the following procedure. a) Production of negative electrode The same operation as in Example 1 was repeated to make a negative electrode. b) Production of positive electrode The same operation as in Example 1 was repeated to produce a positive electrode. c) Preparation of gel electrolyte precursor solution at EC + y_BL + MEC (volume ratio 9:71:20), LiBF4 was dissolved to a concentration of 1.8moin, and VC 3 wt% was added to prepare lithium secondary battery. With electrolyte. In the aforementioned electrolytic solution, 96 wt%, TA 3 wt% having an average molecular weight of 7,500 to 9,000, and GX 1.0 wt% having an average molecular weight of 200 to 300 were mixed. Next, BPN 1 50 ppm, BPP 150 ppm, and butyric acid 500 ppm as polymerization initiators were added to obtain a precursor solution. 200409394 d) Battery assembly A battery was fabricated in the same manner as in Example 2. (Example 14) The battery of Example 14 was produced by the following procedure. a) Production of negative electrode The same operation as in Example 2 was repeated to make a negative electrode. b) Production of positive electrode The same operation as in Example 1 was repeated to produce a positive electrode. c) Preparation of gel electrolyte precursor solution at EC + y-BL + DEC (volume ratio 51:29:20), LiPF6 was dissolved to a concentration of 1.75 mol / 1, and VC 2.5 wt% was added to prepare Electrolyte for secondary batteries. In the aforementioned electrolytic solution, 96 wt%, TA 3 wt% having an average molecular weight of 7,500 to 9,000, and GX 1.0 wt% having an average molecular weight of 200 to 300 were mixed. Then, BPN 150 ppm, BPP 150 ppm, and butyric acid 500 ppm as polymerization initiators were added to obtain a precursor solution. d) Battery assembly A battery was fabricated in the same manner as in Example 2. (Example 15) The battery of Example 15 was produced by the following procedure. a) Production of negative electrode The same operation as in Example 3 was repeated to make a negative electrode. b) Production of positive electrode The same operation as in Example 1 was repeated to produce a positive electrode. c) Preparation of precursor solution for gel electrolyte 200409394 Dissolve LiBF4 at 1.5 mol / l concentration in EC + y-BL (volume ratio 35:65) to prepare an electrolyte for lithium secondary batteries. In the foregoing electrolyte solution, 96 wt ° / 〇, TK 3 wt% with an average molecular weight of 7,500 to 9,000, and GX 1.0 wt% with an average molecular weight of 200 to 300 were mixed. Next, BPN 150 ppm, BPP 150 ppm, and butyric acid 500 ppm as polymerization initiators were added to obtain a precursor solution. d) Battery assembly A battery was fabricated in the same manner as in Example 2.

(Example 16) The battery of Example 16 was produced by the following procedure. a) Production of negative electrode The same operation as in Example 2 was repeated to produce a negative electrode. b) Fabrication of the positive electrode The same operation as in Example 1 was repeated to produce a positive electrode. c) Preparation of precursor solution of gel electrolyte

In EC + y-BL + MEC (volume ratio 25:55:20), LiBF4 was dissolved to a concentration of 1.8 mol / 1, and 3% by weight of VC was added thereto to prepare an electrolyte for a lithium secondary battery. In the aforementioned electrolytic solution, 96 wt%, TA 3 wt% having an average molecular weight of 7,500 to 9,000, and GX 1.0 wt% having an average molecular weight of 200 to 300 were mixed. Next, a precursor solution was obtained by adding 500 ppm of peroxy carbonate (4-t-butylcyclohexyl) peroxydicarbonate and 250 ppm of butyric acid as polymerization initiators. d) Battery assembly A battery was fabricated in the same manner as in Example 2. (Example 17) The battery of Example 17 was produced by the following procedure. -37- 200409394 a) Production of negative electrode The same operation as in Example 3 was repeated to produce a negative electrode. b) Production of positive electrode The same operation as in Example 1 was repeated to produce a positive electrode. c) Preparation of gel electrolyte precursor solution at EC + y-BL + MEC (volume ratio 25:55:20), LiBF4 was dissolved to a concentration of 1.8 mol / 1, and VC 3 wt% was added to prepare Electrolyte for lithium secondary batteries. In the aforementioned electrolytic solution, 96 wt%, TA 3 wt% having an average molecular weight of 7,500 to 9,000, and GX 1.0 wt% having an average molecular weight of 200 to 300 were mixed. Next, 500 ppm of m-toluene-benzene peroxide and 250 ppm of butyric acid as diethylpyrene peroxide as a polymerization initiator were added to obtain a precursor solution. d) Battery assembly A battery was fabricated in the same manner as in Example 2. (Example 18) The battery of Example 18 was produced by the following procedure. a) Production of negative electrode A negative electrode was produced in the same manner as in Example 1 except that the negative electrode active material was changed to artificial graphite (KS-25) and the composition of the negative electrode was changed to 100 parts by weight of a carbon element material and 9 parts by weight of PVdF9. b) Production of positive electrode The same operation as in Example 1 was repeated to produce a positive electrode. c) The precursor solution of the gel electrolyte was prepared in EC + y-BL + MEC (volume ratio 25:55:20), LiBF4 was dissolved to a concentration of 1.8 mol / 1, and VC 3 wt ° / was added to this. In order to prepare the lithium secondary battery electricity, 200409394, the solution is decomposed. In the aforementioned electrolytic solution, 97 wt%, TA 2.4 wt% with an average molecular weight of 7,500 to 9,000, and GX 0.6 wt% with an average molecular weight of 200 to 300 were mixed. Next, BPN 150 ppm, BPP 150 ppm, and butyric acid 103 ppm as polymerization initiators were added to obtain a precursor solution. d) Battery assembly A battery was fabricated in the same manner as in Example 2. (Example 19) The battery of Example 19 was produced by the following procedure. a) Production of negative electrode A negative electrode was produced in the same manner as in Example 1 except that the negative electrode active material was changed to natural graphite and the composition of the negative electrode was changed to 100 parts by weight of a carbon element material and 9 parts by weight of PVdF9. b) Production of positive electrode The same operation as in Example 1 was repeated to produce a positive electrode. c) Preparation of gel electrolyte precursor solution at EC + y-BL + DEC (volume ratio 30:50:20), LiBF4 was dissolved to a concentration of 1.8 mol / 1, and VC 3 wt% was added to prepare Electrolyte for lithium secondary batteries. In the aforementioned electrolytic solution, 97 wt%, TA 2-4 wt% with an average molecular weight of 7,500 to 9,000, and GX 0.6 wt% with an average molecular weight of 200 to 300 were mixed. Then, BPN 150 ppm, BPP 150 ppm, and butyric acid 102 ppm as polymerization initiators were added to obtain a precursor solution. d) Battery assembly A battery was fabricated in the same manner as in Example 2. (Comparative Example 1) 200409394 A battery of Comparative Example 1 was produced in the following procedure. a) Production of negative electrode The same operation as in Example 3 was repeated to make a negative electrode. b) Production of positive electrode The same operation as in Example 1 was repeated to produce a positive electrode. c) Preparation of gel electrolyte precursor solution at EC + y-BL + DEC (volume ratio 25: 55 ·· 20), LiBF4 was dissolved to a concentration of 1.8 mol / 1, and VC 2 wt% was added to this An electrolyte for a lithium secondary battery is prepared. In the foregoing electrolytic solution, 95 wt ° / 〇, 2.5 wt% of TA having an average molecular weight of 7,500 to 9,000, and 2.5 wt% of GX having an average molecular weight of 200 to 300 were mixed. Secondly, 150 ppm of BPN as a polymerization initiator can be used to obtain a precursor solution. d) Assembly of battery A battery was produced in the same manner as in Example 3. (Comparative Example 2) The battery of Comparative Example 2 was produced by the following procedure. a) Production of negative electrode The same operation as in Example 2 was repeated to make a negative electrode. b) Production of positive electrode The same operation as in Example 1 was repeated to produce a positive electrode. c) Preparation of gel electrolyte precursor solution in EC + EMC (volume ratio 30:70), LiBF4 was dissolved to a concentration of 1.8 mol / 1, and VC 3 wt% was added to prepare electrolyte for lithium secondary battery. liquid. In the aforementioned electrolytic solution, 96 wt%, TA 3.0 wt% having an average molecular weight of 7,500 to 9,000, and GX 1.0 wt% having an average molecular weight of 200 to 300 were mixed. Secondly, 150 ppm of BPN as a poly 200409394 initiator is added to obtain a precursor solution. d) Assembly of battery A battery was produced in the same manner as in Example 3. (Comparative Example 3) A battery of Comparative Example 3 was produced by the following procedure. a) Production of negative electrode The same operation as in Example 3 was repeated to make a negative electrode. b) Production of positive electrode The same operation as in Example 1 was repeated to produce a positive electrode. c) Preparation of precursor solution of gel electrolyte A precursor solution was prepared in the same manner as in Example 3 except that the amount of butyric acid added was changed to 603 ppm. d) Assembly of battery A battery was produced in the same manner as in Example 3. (Comparative Example 4) A battery of Comparative Example 4 was produced by the following procedure. a) Production of negative electrode The same operation as in Example 2 was repeated to make a negative electrode. b) Production of positive electrode The same operation as in Example 1 was repeated to produce a positive electrode. c) Preparation of the precursor solution of the gel electrolyte A precursor solution was prepared in the same manner as in Example 11 except that the addition amount of butyric acid was changed to 0 ppm. d) Battery assembly and Example 6

(4 目 目 同 地 智] I (Comparative Example 5) Also used as a battery. In the following procedure, a) Production of a negative electrode I was used as the battery of Comparative Example 5. Repeat the same operation as in the fabrication of the positive electrode of Example _ b) to make the negative electrode. Repeat the procedure with the example. C) Gel electrolysis station,-° <operation to make a positive electrode. ^^ Preparation of the precursor solution In addition to changing the amount of butyric acid, the precursor solution was prepared. Except for t4GpPm, the same procedure as in Example d was performed. d) Assembly of battery The battery was fabricated in the same manner as in Example 2. (Evaluation) 丁 Butyric acid content in the gel electrolyte From the batteries produced in Examples 1 to 19 and Comparative Examples 1 to 3, the gel was extracted with a solvent, and the content of the butyric acid in the extract was extracted. . And the body: gel electrolysis: immersed in THF, after 72 hours of ultrasonic treatment to: proceed: the extraction solution with the above _ 遽, using gas chromatography to Ding I 疋, hunting Ding from Equation 3 Acid content. The results are shown in Table ^. (2) The capacity retention rate of the battery will be based on the example! ~ 19 and the battery produced in Comparative Example 充电 were charged with a fixed current value of 0.2C so that the battery voltage reached 4 · 2 v, and after reaching 4 · 2 v, the battery was repeatedly charged with a solid battery until the total charging time reached 12 hours. . ^ "The cell voltage reaches 2.75V and is carried out at a fixed current value. To investigate the large current • 42- 200409394 discharge characteristics, that is, load characteristics, determine the capacitance retention rate at 2 ° C discharge at 20 ° C (= 2C discharge discharge Capacitance / 0.2C discharge capacitor X 100). To investigate the low temperature characteristics, after charging for 12 hours at a constant current of 0.2C and a constant voltage of 4.2 V at 20 ° C, determine the capacity retention rate at 0.2C discharge at -20 ° C ( = -20 ° C discharge capacitor / 20 ° C discharge capacitor X 100). In order to investigate the charge and discharge cycle characteristics, repeat charging at a constant current of 0.2C and a constant voltage of 4.2 V for 12 hours at 20 ° C, and at 0.2C The constant current discharge cycle was used to determine the capacitance retention rate at the 300th cycle (second discharge capacitor at the 300th cycle / discharge capacitor at the first cycle X 100). In addition, the battery evaluations were performed in a glove box under an inert gas environment. Table 1 shows the butyric acid content of the battery capacitors of Examples 1 to 10 and Comparative Examples 1 to 3, the butyric acid content of the precursor solution, the butyric acid content of the gel electrolyte, and Battery characteristics. In addition, gel electrolysis used in Comparative Examples 1 to 2. It is a gel electrolyte containing no butyric acid disclosed in the aforementioned Japanese Patent Application Laid-Open No. 2001-210380. [Table 1] Addition of butyric acid (ppm) in capacitor (Ah) precursor drop solution Butyric acid content in gel (ppm) Capacitance retention rate during discharge at 2C (%) -20 ° C Capacitance retention rate during discharge (%) Capacitance retention rate at 300th cycle (%) Example 1 0.79 15 12 80 80 75 Example 2 0.80 51 48 84 83 79 Example 3 0.81 102 97 86 86 82 Example 4 0.81 254 247 86 87 83 Example 5 0.80 452 445 84 83 81 Example 6 0.81 503 496 81 80 77 Example 7 0.77 9 5 76 69 68 Example 8 0.79 13 9 80 78 72 Example 9 0.80 511 506 81 78 75 -43-200409394 Example 10 Comparative Example 1 Comparative Example 2 Comparative Example 3 550 544 80 77 ~~ ^ 72 0 0 68 66 1 "~~ ~~- ——_ 62 0 0 71 62 ~~~ 63 -_〇79 '------- ^ 610 603 ^^ 70 65 &quot; I know that the content of cyanine acid is 10 ~ 50 One of the degraded examples, K6, A Langdi, 廿 〇6 芡, human fast pool, meet the capacitor retention rate at 2C discharge, the capacitor retention rate at 80C above 80%, the 300th cycle of strict capacitor retention rate 70% Significant effect on the properties. The secondary batteries of Examples 7 to 10 in this example are also better than those in Comparative Example j = 2 without butyric acid. The content of butyric acid in Examples 7 and 8 was less than 10%, because the precursor cold liquid did not fill the compartment and the electrode penetrated evenly. After the bridging, good ion conductivity could not be ensured in the gel electrolysis, so It is estimated that the characteristics as in Examples 1 to 6 cannot be obtained. Furthermore, it is considered that the effect of increasing the affinity between the electrode active material and the gel electrolyte is insufficient. / On the other hand, the content of butyric acid in Examples 9 and 10 is more than 5000 ppm. Although it is better than Comparative Examples 1 and 2, the content of butyric acid is more than 600 as in Comparative Example 3. At ppm, the effect of the addition cannot be seen. Although the precursor solution penetrated into the interlayer and the electrode had no problem, it is presumed that the excess butyric acid had a side reaction during the charge-discharge reaction, which was reflected in the decrease in charge-discharge efficiency, and caused the cycle characteristics and low cattle [Comparative Example 3 It is more significant, even if it contains butyric acid, the effect is seen by the gray method. "" Secondly, in order to review the composition of the macromonomers ，, ^ Xishe, η τ, ..., κ, the battery capacitors, precursors 浼, ι of Example 11 and 12 and Comparative Examples 4 and 5 are combined. The bismuth bismuth content, the butyl fe content in the gel electrolyte, and battery characteristics are shown in Table 2. -44-200409394 [Table 2] Capacitance (Ah) Addition amount of D-precursor solution (PPm) Butyric acid content in gel j (ppm) _ Capacitance retention rate during 2C discharge (%) -20 Capacitance during discharge Maintenance rate (%) Capacitance retention rate at 300th cycle (0 / Λ Example 11 0.80 100 93 72 64 \ / 0) Example 12 0.79 101 94 ~~ 73 68 OH- Comparative Example 4 0.80 0 0 58 54 UVJ 4 Comparative Example 5 0.80 0 0 61 56 45 ^ n 1 ㈢ 夂 Yan 0 Ί 卞 is the early body (performed in Example 1 and an example using trifunctional and difunctional acrylic esters as macromonomers) 12bis. She is also inferior to Example M, which uses trifunctional acrylic acid and monofunctional acrylic acid as the macromonomer, but only uses the example of page energy acrylate as the macromonomer. Comparative Example 4 And Example η using trifunctional acrylates and difunctional acrylates as macromonomers. When comparing with the secondary battery of Comparative Example 5, the gel electrolyte contains butyric acid &lt; It is learned that regardless of the composition of the macromonomer, the battery characteristics can be improved. "For example, in the trifunctional acrylate only of Example 11 or Comparative Example 4, the Insufficient softness, &amp; due to skin expansion or contraction caused by expansion and contraction of the bridge, or gel electrolysis temporarily due to insufficient flexibility near the electrode due to charge and discharge reactions (Destruction. Therefore, the battery characteristics are poor. For example, even if a difunctional acrylate is added in Example 12 or Comparative Example 5, the same reason is considered. Therefore, the composition of the macromonomer is also an important factor for achieving the present invention Next, in order to review the non-aqueous solvents, the butyric acid content of the battery driver solutions of Examples 13 to 15, the butyric acid content of the gel electrolyte, and -45-200409394 battery characteristics are shown in Table 3. [Table 3] Capacitance (Ah) Addition of butyric acid (ppm) from the precursor drop solution Butyric acid content (ppm) in the gel Capacitance retention rate (%) during 2C discharge -20 ° C Capacitance retention rate during discharge ( %) Capacitance retention rate at the 300th cycle (%) Example 13 0.80 500 492 75 72 57 Example 14 0.80 500 493 69 52 74 Example 15 0.79 500 491 73 68 66 It can be clearly seen from Table 3 that the volume of EC Compared with Comparative Examples 1 and 2, Example 13 in which the proportion is less than 10% In addition to poor characteristics, other battery characteristics are improved. Because it is difficult to cover the surface of graphite particles with a dense protective film when there are few ECs, graphite particles react with γ-BL. Therefore, it is considered that even if the gel electrolyte contains butyric acid It also has no effect and causes a reduction in cycle characteristics. Compared with Comparative Examples 1 and 2, Example 14 in which the volume ratio of EC was more than 50% had improved load characteristics and low-temperature characteristics, but improved cycle characteristics. This is because the viscosity of the precursor solution increases when there are many ECs. Therefore, even if it contains butyric acid, the difficulty of permeating the separator and the electrode cannot be eliminated. After the bridge is bridged, since the gel electrolyte cannot be formed in the separator and the electrode, good battery characteristics cannot be obtained. In addition, when the volume ratio of γ-BL is 29%, it is also considered to be less when it is used to improve low temperature characteristics. Compared with Comparative Examples 1 and 2, Example 15 in which the third solvent was not used was slightly improved as a whole. However, since the viscosity of the precursor solution becomes high when the third solvent is not used, it is difficult to permeate the barrier layer and the electrode as in Example 14, and sufficient gel electrolyte cannot be formed in the barrier layer and the electrode after bridging. Examples 1 to 6 have good battery characteristics. Therefore, the composition of the non-aqueous solution is also an important factor in realizing the present invention. Next, in order to review the polymerization initiator, Table 4 shows the battery capacitors of Examples 16 and 17, the butyric acid content of the precursor solution, the butyric acid content of the gel electrolyte, and battery characteristics. [Table 4] Capacitor (Ah) Butyric acid addition amount (ppm) of the precursor solution, butyric acid content (ppm) in the gel Capacitance retention rate (%) at 2C discharge -20 ° C Capacitance retention rate (%) at discharge ) Capacitance retention rate at the 300th cycle (%) Example 16 0.80 250 241 72 68 66 Example 17 0.80 250 242 74 70 64 It can be clearly seen from Table 4 that the use of the second percarbonate (4-t- Example 16 using butylcyclohexyl) peroxydicarbonate as a polymerization initiator and Example 17 using m-toluene-benzene-peroxybenzene as a polymerization initiator of diethylperoxide Although the secondary batteries of Examples 1 to 10 in which the peroxy esters were used as polymerization initiators had poor battery characteristics as a whole, they were improved over Comparative Examples 1 and 2. It is not related to about the same 10-hour half-life temperature, and those who show the difference in battery characteristics think that the difference in reactivity between the negative electrode and the polymerization initiator is one reason. As for why, it was shown that the initial charge and discharge efficiency of the secondary batteries of Examples 1 to 6 was about 10% higher than that of the secondary batteries of Examples 16 and 17, and the good efficiency was. Therefore, the selection of the polymerization initiator is also an important factor for realizing the present invention. Second, in order to review the carbon element material of the negative electrode, Examples 18 and 19 in which carbon element material of amorphous carbon was not adhered to the surface of graphite particles, the butyric acid content of the battery-47- 200409394 capacitor, precursor solution, The butyric acid content in the gel electrolyte and battery characteristics are shown in Table 5. [Table 5] Capacitor (Ah) Addition of butyric acid in the precursor solution (ppm) Butyric acid content in the gel (ppm) Capacitance retention rate (%) during discharge at -20 ° C Capacitance retention rate during discharge at -20 ° C (%) Capacitance retention rate at the 300th cycle (%) Example 18 0.80 103 92 74 69 67 Example 19 0.80 102 91 71 67 64 It is clear from Table 5 that compared to the use of surface amorphous graphite as the carbon element Examples of materials: For the secondary battery of Example 10, although the battery characteristics of Examples 18 and 19 as a whole are poor, they are improved compared to Comparative Examples 1 and 2. This is because the γ-BL contained in the gel electrolyte is more likely to react with the solvent during charging, i.e., under electrochemical reduction, and causes side reactions with the crystalline graphite material, which lowers battery characteristics. Therefore, by using surface amorphous graphite, it is thought that the cycle deterioration can be prevented. From the above, it is known that the results of careful review in order to improve the electrode into a rolled secondary battery and its manufacturing method, because the precursor solution of the gel electrolyte contains butyric acid, the precursor solution can easily penetrate into the separator and the electrode. Among them, it is particularly easy to penetrate into the negative electrode, so the manufacturing process of the secondary battery can be improved. Furthermore, when butyric acid was contained in the gel electrolyte, it was also found that the load characteristics and low temperature characteristics could be improved, and the deterioration of the cycle characteristics could be prevented. According to the present invention, it is found that the manufacturing process can be improved because the precursor solution of the gel electrolyte contains D-48-200409394 acid because the precursor liquid will easily dream into the separator and the electrode. Furthermore, when butyric acid is present in the gel electrolyte, it was also found that the load characteristics and low temperature characteristics can be improved, and the deterioration of the cycle characteristics can be prevented. Therefore, the industrial significance of the present invention is extremely important. -49-

Claims (1)

200409394 Patent application scope: 1. A gel electrolyte secondary battery, comprising: a positive electrode and a negative electrode containing an active material capable of inserting / detaching clock ions; and a gel electrolyte disposed between the positive electrode and the negative electrode; The gel electrolyte contains butyric acid at a concentration of 5 to 550 ppm. 2. The gel electrolyte secondary battery according to item 1 of the patent application range, wherein the aforementioned gel electrolyte includes a polymer bridge body of surface salt, non-aqueous solvent, and butyric acid; wherein the polymer includes: at least Polymers or copolymers of PO / EOO ~ 5 trifunctional acrylates with ethylene oxide (EO) units or propylene oxide (PO) units, and PO / EO 0 with EO units or PO units ~ 5 monofunctional polymer or copolymer of propionic acid. 3. The gel electrolyte secondary battery according to item 2 of the patent application range, wherein the non-aqueous solvent system includes: ethylene carbonate, γ-butyrolactone, and selected from the group consisting of diethyl carbonate and methyl ethyl carbonate And one or more solvents of vinyl carbonate; and contains vinyl carbonate in a volume ratio of 10 to 50%. 4. The gel electrolyte secondary battery according to item 1 of the patent application range, wherein the active material of the foregoing negative electrode is graphite particles with amorphous carbon adhered to the surface. 5. The gel electrolyte secondary battery according to item 1 of the application, wherein the aforementioned butyric acid is n-butyric acid, isobutyric acid, or a mixture thereof. 6. The gel electrolyte secondary battery according to item 2 of the patent application, wherein the lithium salt in the gel electrolyte is contained in a ratio of 0.8 to 2.5 mol / 1 for the non-aqueous solvent. 7. The gel electrolyte secondary battery according to item 4 of the patent application, wherein the graphite particles having amorphous carbon adhered to the surface described above have a specific surface area of 1 to 5 m2 / g. 200409394 8. —A method for manufacturing a gel electrolyte secondary battery, the gel electrolyte secondary battery comprising: a positive electrode and a negative electrode containing an active material capable of inserting / removing lithium ions; and a coagulation disposed between the positive electrode and the negative electrode. The gel electrolyte is characterized in that the gel electrolyte is obtained by bridging the polymer of the gel electrolyte raw material in the presence of butyric acid at a concentration of 5 to 550 ppm. 9. The method for manufacturing a gel electrolyte secondary battery according to item 8 of the application, wherein the gel electrolyte is obtained by including at least an ethylene oxide (EO) unit or a propylene oxide ( PO) polymer or copolymer of PO / EO 20 to 5 trifunctional acrylate and polymer or copolymer of PO / EO 20 to 5 monofunctional acrylate with PO unit or PO unit Manufactured in the presence of a non-aqueous solvent containing a bell salt, a polymerization initiator, and butyric acid. 10. The method for manufacturing a gel electrolyte secondary battery according to item 9 of the application, wherein the aforementioned polymerization initiator is selected from t-butylperoxyneodecanoate, t-hexylpervalerate, and One or more polymerization initiators of t-butylpervalerate. 200409394 (1) Designated representative map: (1) The designated representative map in this case is: (). (II) Brief description of the representative symbols of the components in this representative diagram ... 捌, if there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention ...