[1]This application claims the benefit of priority based on the Korea Patent Application No. 2016-0178714 dated 26 December 2016, and all information disclosed in the literature of the Korea patent application are included as part of the specification.[2]The present invention relates to a cylindrical battery cell having a heat-shrinkable tube comprising a UV stabilizer.BACKGROUND[3]Recently, the prices of energy resources due to the depletion of fossil fuels, are amplified interest in environmental pollution, the demand for eco-friendly alternative sources of energy has become an indispensable factor for the future life. In nuclear power, solar power, and is continuing research for a variety of power generation technologies, such as wind power, tidal power, the power storage device to use the thus producing energy in a more efficient and also it leads a great interest.
[4]
In particular, the demand of serving as an energy source cell and rapidly increases as the development of technology and the demand for mobile devices increases, in recent years, the use of the secondary battery realization as a power source such as an electric vehicle (EV), hybrid electric vehicle (HEV) and, and the grid's (grid) is enlarged in applications such as power supply through the secondary screen is also used area, a lot of research has been conducted on the battery that can meet the various needs accordingly.[5]In general, secondary batteries according to the shape of the battery case, the electrode assembly is a cylindrical battery and a prismatic battery that is embedded in a metallic can of cylindrical shape or square shape, the electrode assembly is a pouch-shaped battery that is embedded in a pouch-shaped case of the aluminum laminate sheet It is classified. The electrode assembly is built into the battery case through an anode, a cathode, and a separator between a power generation device that can be charged and discharged consist of a membrane structure disposed between the anode and the cathode, an anode and a cathode of a long sheet-like with the active material is applied winding the jelly-roll type and is classified a number of positive and negative electrodes of a predetermined size in a stacked sequentially stacked in a state of interposing the separator.[6]Figure 1 shows a vertical cross-sectional perspective view of a conventional cylindrical battery is shown in Fig.[7]1, a cylindrical secondary battery 10 is a jelly-After receiving the rolled (wound type) electrode assembly 12, the cylindrical case 13, injecting an electrolyte into the cylindrical case 13, the case (13 ) at the open top of the electrode terminal (for example, of example, is produced by combining the cap assembly (14, with the positive electrode terminal) is formed).[8]The cylindrical secondary battery, by using a tube (tube) made of a film of plastic material of the electrically insulating to perform the insulation function and the appearance and protection of the external conductive material is coated with the outer surface of the battery case.
[9]
However, the conventional tube for the outer covering of the cylindrical secondary battery technologies, there is a problem that is inherent in the isolation and exterior protection is lost such that a long period of time when exposed to ultraviolet (UV), the film is damaged or discolored.
[10]
In addition, or exposed to high temperature after adding a tube outer surface on the battery case of the cylindrical rechargeable battery, there were problems due to the external shock that the tube is a defect occurs easily deformed is generated.
[11]
Thus, the situation with high necessity for technology that can effectively solve the problems of the prior art described above.
Detailed Description of the Invention
SUMMARY
[12]
An object of the present invention is to solve the technical problem, which has been requested from the problems, and of the prior art.
[13]
The inventors of the present application are at the end of extensive research and various experiments in depth, as will be described later, the polymer chains of the nylon-based resin or a polyester resin with an ultraviolet irradiated to the heat-shrinkable tube is cut in the generated free radicals when comprise a UV stabilizer (UV stabilizer) for inhibiting a chain reaction, it confirmed that this provides effects desired, and completed the present invention.Problem solving means[14]A ylindrical battery cell according to the present invention for achieving these objects,[15]The outer surface of the cylindrical casing than the electrode terminal portion as the cylindrical battery cells in which the heat-shrinkable tubing surrounding,[16]The heat-shrinkable tube,[17]With a heat-shrinkable polyester-based resin of the substrate tube;[18]Reinforcing agent of the nylon-based resin to increase the tensile strength and the temperature of the heat-shrinkable tube; And
[19]
By ultraviolet rays irradiated to the heat-shrinkable tube UV stabilizer for suppressing the chain reaction of free radicals with the nylon-based resin or a polymer chain of the polyester resin is cut produced (UV Stabilizer);
[20]
It containing characterized in that.
[21]
Thus, by the cylindrical battery cell according to the invention, comprises a UV stabilizer for suppressing the nylon-based resin or a polyester resin of the chain reaction of free radical polymer chain is cut produced by the ultraviolet ray irradiation on the heat-shrinkable tube, the heat-shrinkable tube film do not become damaged or discolored when exposed to ultraviolet rays for a long time can well maintain the original appearance of the insulation and protection.
[22]
Furthermore, a cylindrical battery cell according to the present invention, by using the reinforcing agent in the nylon-based resin to increase the tensile strength and the temperature of the heat-shrinkable tube in a heat-shrinkable tube or tube is exposed to high temperatures, due to an external impact that the tube is easily deformed It can be prevented.
[23]
The heat-shrinkable tube may be displayed to distinguish the differences in the capacity of the bar, the battery cell can further include a pigment for imparting color to color, there are advantages that can easily classify and differentiate.
[24]
In one specific example, the polyester resin may be, for example, polyethylene terephthalate (polyethylene terephthalate) resin.
[25]
Specifically, the polyester resin is the case may be contained by 70% by weight to 90% by weight based on the total weight of the tube, more specifically, the polyester resin contain less than 70% by weight, the the invention is difficult to exert the function of properly difficult to obtain adequate heat shrinkage which needs a heat shrinkable tube, on the contrary it is not less than 90% by weight when exposed to high temperatures tend to be easily caused excessive deformation of the tube to deterioration problem.[26]In one specific example, the thickness of the cylindrical secondary battery, the heat-shrinkable tube may be a 1 ㎛ to 100 ㎛.
[27]
In one specific example, the UV stabilizer may be a benzoate-based compound, and may be specific, the benzoate-based compound is butyl-4-hydroxybenzoate (butyl-4-hydroxybenzoate).
[28]
In addition, the above UV stabilizer is heat-shrinkable may be included as 0.1% to 5% by weight, based on the total weight of the tube, or more specifically, may contain from 0.5% to 5% by weight, and more particularly, the UV stabilizer If contain less than 0.1% by weight, when the suppression of a chain reaction of free radicals generated in the UV stabilizers are not be exhibited to the tube generally, it is difficult to prevent cracks due to ultraviolet light irradiation, whereas more than 5% by weight, high of the UV stabilizer is excessively added, there is a problem increasing excessively the UV stabilizing efficacy compared to the manufacturing cost.
[29]
In one specific example, the nylon-based resin, nylon may be 66 days, the Nylon 66 is the thermal deformation temperature is high and 70 degrees relative Celsius, heat-resistant temperature is Celsius 105 degrees, a tensile elastic modulus of 2.9 ㅧ 104 kg / cm2, flexural modulus is 3.0 ㅧ 104 kg / cm2. Compared to other nylon 6, nylon 6-10 and nylon 6-12 is high in heat resistance is high mechanical strength.
[30]
Also, the nylon-based resin may comprise from about 3% to about 10% by weight based on the total weight of the heat-shrinkable tube.
[31]
Also, the nylon-based resin may contain a blend state to the polyester-based resin.
[32]
In one specific example, the pigment may be included in the 10% to 20% by weight based on the total weight of the heat-shrinkable tube.
[33]
In one specific example, the heat-shrinkable tube according to the present invention, the optical intensity of the ultraviolet 61.5 W / m 2 and not a crack even if the wavelength of the light exposure in the 300 nm to 400 nm condition 1000 hours (crack) to occur can.
[34]
In one specific example, the heat-shrinkable tube had a UV absorber which emits a thermal energy absorbing an irradiated ultraviolet ray can be further included, in particular, the UV absorber may be a benzophenone-based compound, a benzophenone-based compounds can be, for example, hydroxy-benzophenone (hydroxy benzophenone).
[35]
Thus, the heat-shrinkable tube according to the present invention, as well as to prevent a crack in the film to a UV stabilizer, by further comprising an ultraviolet absorber which emits a thermal energy absorbing an irradiated ultraviolet ray, the material of the tube oxygen and oxidation bar may help prevent the cause (decomposition) reaction, it is possible to prevent the deterioration of the tube according to the more UV light for a long time.
[36]
In one specific example, the cylindrical battery cell may be a secondary battery, the secondary battery is that its type is not particularly limited, as a specific example, lithium has the advantage such as high energy density, discharge voltage, output stability It may be a lithium secondary battery, such as ion batteries, lithium ion polymer batteries.
[37]
In general, the lithium secondary battery consists of a cathode, an anode, a separator, and a lithium salt-containing non-aqueous electrolyte.
[38]
Hereinafter, a description will be given of the other components of the lithium secondary battery.
[39]
Specifically, the positive electrode is, for example, and the positive electrode active material, a conductive material and a binder consisting of a positive electrode active material particles in the positive electrode current collector can be produced by coating a mixed positive electrode material mixture, if necessary, in the positive electrode material mixture It may be added fillers.
[40]
The cathode current collector is generally made of a thickness of 3 ~ 201 ㎛, if it has suitable conductivity without causing chemical changes in the fabricated battery is not particularly limited, for example, stainless steel, aluminum, nickel, titanium , and may be one selected from among those treated with aluminum, carbon, nickel, titanium or silver on the surface of the stainless steel surface, specifically, there is an aluminum can be used. Current collector may increase the adhesive strength of the positive electrode active material to form fine irregularities on the surface thereof, films, sheets, foils, nets, porous structures, foams and non-woven fabrics and so on can take various forms.
[41]
The positive electrode active material is, for example, in addition to the above-described positive electrode active material particles, lithium nickel oxide (LiNiO 2 ) layered compounds or one or more transition compounds substituted with a metal such as; Formula Li 1 + x Mn 2-x O 4 (where, x is from 0 to 0.33), LiMnO 3 , LiMn 2 O 3 , LiMnO 2 Li-Mn oxide and the like; Lithium copper oxide (Li 2 CuO 2 ); LiV 3 O 8 , LiV 3 O 4 , V 2 O 5 , Cu 2 V 2 O 7Vanadium oxide and the like; Formula LiNi 1-x M x O 2 (where, the M = Co, Mn, Al, Cu, Fe, Mg, B or Ga, x = 0.01 ~ 0.3 Im) Ni site type lithium nickel oxide which is represented by; Formula LiMn 2-x M x O 2 (where, M = Co, Ni, Fe , Cr, and Zn, or Ta, x = 0.01 ~ 0.1 Im) or Li 2 Mn 3 MO 8 (where, M = Fe, Co, lithium manganese composite oxide represented by Ni, Cu or Zn); A portion of Li is substituted with alkaline earth metal ions formula LiMn 2 O 4 ; Disulfide compounds; Fe 2 (MoO 4 ) 3 may be of a like, and is not limited to these.
[42]
Based on the total weight of the mixture including the cathode active material with the conductive material it is typically added at 0.1 to 30% by weight. This conductive material so long as it has suitable conductivity without causing chemical changes in the fabricated battery is not particularly limited, for example, graphite such as natural graphite or artificial graphite; Carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, carbon black and thermal black; Conductive fibers such as carbon fibers and metallic fibers; Metal such as carbon fluoride, aluminum, nickel powder, powder; Conductive whiskers such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Poly is a conductive material such as phenylene derivative may be used.
[43]
The binder contained in the positive electrode is a component assisting in binding to the total binding and the home, such as the active material and the conductive material, it is commonly added to the mixture total weight of the positive electrode active material containing 0.1 to 30% by weight, based on. Examples of the binder include polyvinylidene fluoride, polyvinyl alcohol, carboxymethylcellulose by Woods (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinyl pyrrolidone, ethylene, polyethylene tetrafluoroethylene , polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluoro rubber and various copolymers and the like.
[44]
The anode is fabricated by applying and drying a negative active material on a negative electrode current collector, and, if desired, may optionally contain further ingredients as contained in the above-described positive electrode.
[45]
The anode current collector is generally fabricated to have a thickness of 3 to 500 micrometers. The anode current collector on if not particularly limited, for example, the surface of example, copper, stainless steel, aluminum, nickel, titanium, sintered carbon, copper or stainless steel has suitable conductivity without causing chemical changes in the fabricated battery. surface-treated with carbon, nickel, titanium or silver, and aluminum-cadmium alloys. Also Similar to the cathode current collector, to form fine irregularities on the surface may enhance the bonding strength between the negative electrode active material, films, sheets, foils, nets, porous structures, foams and non-woven fabrics or the like can be used in various forms.
[46]
The cathode active material is, for example, I carbon such as graphitized carbon, graphite-based carbon; Li x Fe 2 O 3 (0≤x≤1), Li x WO2 (0≤x≤1), Sn x Me 1-x Me ' y O z (Me: Mn, Fe, Pb, Ge; Me': metal composite oxides such as 1≤z≤8); Al, B, P, Si, Group 1 of the Periodic Table, Group 2, Group 3 element, a halogen; 0
[59]
Polyethylene terephthalate based on the total weight of the composition (polyethylene terephthalate) resin, 80 g, of UV stabilizer-butyl-4-hydroxybenzoate (butyl-4-hydroxybenzoate) 2 g, the pigment (pigment) 8 g and 10 g of nylon 66 a rear melt blended to prepare a resin composition mixed with, and rapidly cooled to cure the resin composition prepared in the cooling apparatus to prepare a cylindrical heat-shrinkable tube with a top and bottom opening.
[60]
[61]

[62]
The resin composition was prepared in the manufacture of a UV stabilizer-butyl-4-hydroxybenzoate (butyl-4-hydroxybenzoate), and and are in the same manner as in Example 1 except that the prepared without the use of heat-shrinkable nylon 66 tube.
[63]
[64]

[65]
Was identical to prepare a heat-shrinkable tube as in Example 1 except that the resin composition prepared without the use of UV stabilizer in the manufacture of butyl-4-hydroxybenzoate (butyl-4-hydroxybenzoate).
[66]
[67]

[68]
The resin composition was prepared and is a heat-shrinkable tube in the same manner as in Example 1 except that made without the manufacturing nylon 66.
[69]
[70]

[71]
Of the present invention 2, there are pictures showing the experimental procedure of Experiment 1 is disclosed. As with the 2, Example 1 and Comparative Examples 1 to 3 disposed so as to be spaced apart lamp with 3cm of the heat-shrinkable tube 110, the UV irradiator 200 is prepared in the intensity of light is 61.5 W / m 2 and the light of a wavelength of 300 nm to 400 nm, it was confirmed whether or not the cracks occur in the back, the surface of the tube 1000 hours exposure at ambient conditions of 50 ° C.
[72]
[73]
TABLE 1
Cracks occurred or not (○, X)
Example 1 X
Comparative Example 1 ○
Comparative Example 2 X
Comparative Example 3 X
[74]
Referring to Table 1, in the case of Comparative Examples did not use all of the nylon and UV stabilizer 1, but the crack is generated in Example 1, Comparative Example 2 and that of Comparative Example 3, cracks occur even after 1000 hours UV irradiation Did not do it. That is, when Comparative Example 2 The tube base material of nylon-based resin to the polyester resin added as shown, it is possible to prevent a crack generated in the heat-shrinkable tube by the elasticity of the nylon unique properties. In Comparative Example, such as 3 if it contains a UV stabilizer to the tube base material of polyester resin, suppress the chain reaction of free radicals with the UV stabilizer is a polymer chain of the nylon-based resin and polyester-based resin is cut produce by the crack it can be prevented from occurring.
[75]
In addition, when containing a nylon-based resin and a UV stabilizer in the tube base material of a polyester resin as in Example 1, the effect is further increased by the synergistic effect thereof occurs to prevent the generation of cracks.
[76]
On the other hand, Figure 3 is a schematic diagram for explaining the mechanism of a UV stabilizer, which contains a heat-shrinkable tube of the present invention. 3, the ultraviolet irradiator 200 from the heat-shrinkable tube 110, the free radical (120) and UV stabilizer (130 by the irradiated UV nylon-based resin or a polymer chain of the polyester resin is cut produced in ) it can be reacted by suppressing the chain reaction of free radical (120).
[77]

[78]
Preparing a heat-shrinkable tube and the heat-shrinkable tube produced in Comparative Example 2 prepared in Example 1 was printed with black print on the tube surface. The heat-shrinkable tube of the optical intensity is 61.5 W / m 2 , and then the wavelength of the light 500 hours of exposure to ultraviolet irradiation from 300 nm to 400 nm, it was confirmed the color change of the black text, 4 and the results are It is shown in Fig.[79][80]Figure 4 shows a change in color of the heat-shrinkable tube according to the first embodiment, Figure 5 shows a change in color of the heat-shrinkable tube of the Comparative Example 2.
[81]
Figures 4 and 5, the first embodiment of the case, the ultraviolet ray irradiation state before and but without UV is little change in color of the letters in the state after the irradiation appear in Comparative Example 2, discoloration to gray in color of the letters on black For It is can be seen that very blurred. Thus, if it contains an ultraviolet absorbent and it can be seen that the case which does not include does not affect the color change of the tube, the color change is remarkably appears.
[82]
[83]

[84]
Using the above-described embodiment to a method and one of three heat-shrinkable tube produced in accordance with one produced by the process according to Comparative Example 3 A heat-shrinkable tube 3, a universal material testing machine (Universal Test In order to measure their tensile strength and elongation was used to Machine).
[85]
After placing the said insulating casing specimen in the tester was while stretched at a constant rate measuring the stress-strain curve (SS Curve), Example 1 shows the results in Figure 6 of, was the result of Comparative Example 3 shown in Figure 7, the specific value is shown in Table 2 below.
[86]
[87]
TABLE 2
Example 1 Comparative Example 3
Tensile strength (Kgf / cm 2 ) 636 (average) 569 (average)
Elongation (%) 750 (average) 683 (average)
[88]
When the table 2 and 6 and 7, exemplary tensile strength and elongation of the heat-shrinkable tube of example 1 shows significantly improved values ​​as compared with the heat-shrinkable tubes of Comparative Example 3. Thus, the heat-shrinkable tube comprising a UV stabilizer, or nylon may be seen that the mechanical stiffness is improved heat-shrinkable tubes that do not contain nylon. This high tensile strength is likely due to the inclusion in the elasticity of nylon.
[89]
As noted in the heat-shrinkable tube of the present invention is a heat-shrinkable tube comprising any one of the bar, the nylon-based resin or a UV stabilizer comprising a nylon-based resin and a UV stabilizer in the tube base material is that cracks It is suppressed. In addition, the nylon-based resin comprises a case which does not include a UV light stabilizer include, but to obtain the effects of increased tensile strength and elongation, it was confirmed that the color change for the ultraviolet irradiation significantly appear.
[90]
That is, the present invention can to prevent a crack in the bar and tube to create synergies that can be obtained by including all of the nylon-based resin and an ultraviolet absorber effect, it is possible to prevent the discoloration of the ultraviolet rays.
[91]
[92]
Above has been described with reference to embodiments of the invention, those skilled in the art that the invention would be possible that various and modifications within the scope of the invention as disclosed in the accompanying claims.
Industrial Applicability
[93]
UV stabilizer which, as inhibiting the cylindrical battery cell, nylon with an ultraviolet irradiated to the heat-shrinkable tube-based resin or a polyester resin of the chain reaction of free radical polymer chain is cut produced according to the present invention described above, when comprise, a heat-shrinkable tube, the effect of not even when exposed to ultraviolet rays for a long time the tube is not damaged or discolored well maintaining the original function and appearance of the insulation protection.
[94]
Furthermore, a cylindrical battery cell according to the present invention, by using the reinforcing agent in the nylon-based resin to increase the tensile strength and the temperature of the heat-shrinkable tube in a heat-shrinkable tube or tube is exposed to high temperatures, due to an external impact that the tube is easily deformed this has the effect of preventing.
[95]
[96]

WE CLAIMS

[Claim 1]The outer surface of the cylindrical casing than the electrode terminal portion as a heat-shrinkable tube is cylindrical battery cells that surround the heat-shrinkable tube, the tube base material of a polyester resin having a heat shrinkable; Tensile strength and reinforcing the nylon-based resin to increase the temperature of the heat-shrinkable tube; And by the ultraviolet rays irradiated to the heat-shrinkable tube UV stabilizer for suppressing the chain reaction of free radicals generated the polymer chains of the nylon-based resin or a polyester resin is cut (UV Stabilizer); And a cylindrical battery cells, characterized in that comprises a.
[Claim 2]
The method of claim 1, wherein the heat-shrinkable tube is a cylindrical battery cell according to claim 1, further comprising a pigment for imparting color.
[Claim 3]
The method of claim 1, wherein the polyester resin is a cylindrical battery cells, characterized in that a polyethylene terephthalate (polyethylene terephthalate) resin.
[Claim 4]
4. The method of claim 3 wherein the polyester resin is a cylindrical battery cells, characterized in that included as 70 wt% to 90 wt% based on the total weight of the tube.
[Claim 5]
The method of claim 1, wherein the cylindrical battery cells in the thickness of the cylindrical secondary battery, the heat-shrinkable tube is characterized in that 1 ㎛ to 100 ㎛.
[Claim 6]
The method of claim 1, wherein the UV stabilizer is a cylindrical battery cells, characterized in that the benzoate-based compound.
[Claim 7]
The method of claim 6, wherein the benzoate-based compounds are cylindrical battery cells, characterized in that butyl-4-hydroxybenzoate (butyl-4-hydroxybenzoate).
[Claim 8]
The method of claim 1, wherein the UV stabilizer is a cylindrical battery cells, characterized in that included on the total weight of the heat-shrinkable tube to be 0.1% to 5% by weight, based on.
[Claim 9]
According to claim 1, wherein said nylon resin comprises a cylindrical battery cells, characterized in that nylon 66.
[Claim 10]
The method of claim 9 wherein said nylon resin comprises a cylindrical battery cells, characterized in that, which is provided as a 3% to 10% by weight based on the total weight of the heat-shrinkable tube.
[Claim 11]
The method of claim 2 wherein the pigments are cylindrical battery cells, characterized in that included as 10 wt% to 20 wt% based on the total weight of the heat-shrinkable tube.
[Claim 12]
The method of claim 1, wherein the heat-shrinkable tube is the intensity of light is 61.5 W / m 2 cylindrical, characterized in that and that the crack (crack) be 1,000 hours of exposure in the condition the wavelength of light from 300 nm to 400 nm occurring cells.
[Claim 13]
According to claim 1, wherein said nylon resin comprises a cylindrical battery cells, characterized in that, which is provided as a blended state to the polyester-based resin.
[Claim 14]The method of claim 1, wherein the heat-shrinkable tube, the cylindrical battery cells, characterized in that the UV absorber absorbs heat energy emitted by an irradiated ultraviolet rays are further included.
[Claim 15]15. The method of claim 14 wherein the ultraviolet absorber is a cylindrical battery cells, characterized in that a benzophenone compound.