One]This application claims the benefit of priority under Korean Patent Application No. 2016-0178728, dated December 26, 2016, the entire contents of which are incorporated herein by reference.[2]The present invention relates to a cylindrical battery cell having a heat-shrinkable tube containing an ultraviolet absorber.Background technology[3]In recent years, the demand for environmentally friendly alternative energy sources has become an indispensable factor for the future, as the increase in the price of energy sources due to depletion of fossil fuels and the interest in environmental pollution are amplified. Various researches on power generation technologies such as nuclear power, solar power, wind power, and tidal power have been continuing, and electric power storage devices for more efficient use of such generated energy have also been attracting much attention.
[4]Particularly, as technology development and demand for mobile devices increase, the demand for batteries as energy sources is rapidly increasing. Recently, the use of secondary batteries as a power source for electric vehicles (EV) and hybrid electric vehicles (HEV) In addition, the use area has been expanded for use as a power auxiliary power source through a grid, and accordingly, a lot of researches on a battery that can meet various demands have been conducted.[5]In general, the secondary battery 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 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 a battery case with an anode, a cathode, and a separator between the anode and cathode. The long sheet-like shape of the active material is applied to the jelly-roll type and is classified into a number of positive and negative electrodes.
[6]
Figure 1 shows a vertical cross-sectional perspective view of a conventional cylindrical battery.
[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) (for example, of the example, is produced by combining the cap assembly 14 with the positive electrode terminal).[8]The cylindrical secondary battery, which is made of a tube, is made of a film of plastic material that is electrically insulated from the outer surface of the battery case.
[9]However, the cylindrical secondary battery shell tube of the prior art, which has been a problem for a long period of time when exposed to ultraviolet (UV), the film loses the original function and appearance of the insulation protection, etc. from being damaged or discolored by generating a crack.
[10]
The addition of a tube to the outer surface of a cylindrical rechargeable battery has caused a problem with the external shock.
[11]
Thus, the situation with high necessity for technology can 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]
In this paper, we focus on the development of a nano-based or nano-based resin, which is absorbed by the ultraviolet rays irradiated to the heat-shrinkable tube as described if the ultraviolet absorbent (UV absorber) to prevent to react to oxygen, causing the decomposition reaction, leading to the confirmation that the desired effect, and completed the present invention.
Problem solving means
[14]
A cylindrical battery cell according to the present invention for achieving these objects,
[15]
The outer surface of the cylindrical casing contains the heat-shrinkable tubing surrounding the heat-shrinkable tube,
[16]
With a heat-shrinkable polyester-based resin of the substrate tube;
[17]
A pigment which imparts color to the heat-shrinkable tube;
[18]
Tensile strength and reinforcing the nylon-based resin to increase the temperature of the heat-shrinkable tube; And
[19]
An ultraviolet absorber (UV absorber) to prevent the polymer chains of the nylon-based resin or a polyester resin reacts with oxygen to cause a decomposition reaction;
[20]
It contains characterized in that.
[21]
Thus, by using a cylindrical battery cell according to the present invention absorbs the ultraviolet ray irradiated to the heat-shrinkable tube released to the heat, to prevent the polymer chains of the nylon-based resin or a polyester resin reacts with oxygen to cause a decomposition reaction by including the ultraviolet absorber, a heat-shrinkable tube is not the film when exposed to ultraviolet rays for a long time not to damage or discoloration 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 may contain more than 70% by weight of the polyester resin, more specifically, the polyester resin may contain less than 70% by weight, exert the function of proper heat to shrinkage which requires a heat shrinkable tube, which is not less than 90% by weight when exposed to high temperatures tend to be 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 from 1 ㎛ to 100 ㎛.
[27]
In one specific example, the ultraviolet absorber may be a benzophenone-based compound, and the benzophenone-based compounds may be hydroxy-benzophenones (hydroxybenzophenone).
[28]
In addition, the ultraviolet absorber is a heat-shrinkable and the total weight of the tube can be included as 0.1% to 5% by weight, based on, or more specifically, may contain 0.5% to 5% where the UV absorber is contained in an amount of less than 0.1% by weight, it is difficult to react with a nylon-based resin or a polymer chain of the ultraviolet absorber. to avoid cracking of the UV irradiation, Conversely if it exceeds 5% by weight, there is a problem in increasing the cost of ultraviolet absorbent is excessively added to 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 10 4 kg / cm 2 , and the flexural modulus was 3.0 ㅧ 10 4 kg / cm 2 a. Compared to other nylon 6, nylon 6-10 and nylon 6-12.
[30]
Also, the nylon-based resin may contain 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 Celsius in 50-degree atmosphere, the conditions of light intensity is 61.5 W / m according to the present invention 2 and crack even when the wavelength of the light exposure 1,000 hours in the 300 nm to 400 nm ultraviolet (crack) is It can not occur.
[34]
In one specific example, the heat-shrinkable tubes are irradiated with ultraviolet (UV) stabilizers for suppressing the free radicals generated in the polymer chains of the nylon-based resin or a polyester resin is cut For example, the UV stabilizer may be a benzoate-based compound, a benzoate-based compound, for example butyl-4-hydroxybenzoate (butyl-4-hydroxybenzoate).
[35]
Thus, the heat-shrinkable tube according to the present invention, as well as a crack in the film caused by the ultraviolet absorber, by the irradiated UV rays are polymer chains of the nylon- further comprising a UV stabilizer for suppressing the chain reaction of free radicals, it is possible to prevent the deterioration of the tube according to the ultraviolet rays for a longer period of time.
[36]
In one specific example, the cylindrical battery may be a secondary battery, the secondary battery is a lithium secondary battery, 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 a positive electrode material, a positive electrode material, a positive electrode material, and a positive electrode material. necessary, in the positive electrode material mixture.
[40]
The cathode current collector is generally made of a thickness of 3 ~ 201 ㎛, if it has suitable conductivity, and the fabricated battery is not limited to for example, stainless steel, aluminum, nickel, titanium, and may be one It can be used as an aluminum bead or as an aluminum bead. 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.
[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 7 Vanadium 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 to 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 to 0.1 Im) or Li 2 Mn 3MO 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 LiMn 2 O 4 ; Disulfide compounds; Fe 2 (MoO 4 ) 3 may be a like, and is not limited to these.
[42]
Based on the total weight of the mixture, including the cathode active material, the conductive material is typically added at 0.1 to 30% by weight. This conductive material is so long as it has suitable conductivity for causing chemical changes in the fabricated battery. 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 positive electrode is a positive electrode. The positive electrode has a total weight of 0.1 to 30, which is the total active compound. % 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 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.
[45]
The anode current collector is generally fabricated to a thickness of 3 to 500 micrometers. The anode current collector is made of copper, stainless steel, aluminum, nickel, titanium, sintered carbon, copper or stainless steel. surface-treated with carbon, nickel, titanium or silver, and aluminum-cadmium alloys. Also, the cathode current collector can form fine irregularities on the surface and enhance the bonding strength between the negative electrode active materials, films, sheets, foils, nets, porous structures, foams and non-woven fabrics or the like can be used in various forms.
[46]
The cathodic active material is, for example, I carbon as graphitized carbon, graphite-based carbon; Li x Fe 2 O 3 (0≤x≤1), Li x WO 2 (0≤x≤1), Sn x Me 1-x Me ' y O z (Me: Mn, Fe, Pb, Ge; Me' : Al, B, P, Si, Group 1 of the Periodic Table, Group 2, Group 3 element, a halogen, a metal composite oxide, such as 1? 0 & lt; x & lt; 1? Y? 3; Lithium metal; Lithium alloy; Silicon-based alloys; Tin-based alloys; SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2O 4 , Sb 2 O 5 , GeO 2 , GeO 2 , Bi 2 O 3 , Bi 2 O 4 , and Bi 2 O 5 metal oxide and the like; Conductive polymers such as polyacetylene; And Li-Co-Ni-based material may be used.
[47]
The separator is interposed between the positive electrode and the negative electrode, an insulating thin film having high ion permeability and mechanical strength is used. Pore ​​size of the membrane is generally 0.01 to 10 μm, and the thickness is generally from 5 to 300 μm. As the separator, for example, olefin polymers such as chemically resistant and hydrophobic polypropylene; A sheet or non-woven fabrics made of glass fiber or polyethylene, etc. are used. When a solid electrolyte such as a polymer is employed, the solid electrolyte may also serve as the separator.
[48]
Non-aqueous liquid electrolyte containing the lithium salt, the non-aqueous electrolyte and a lithium salt consisting of a. The non-aqueous electrolyte is used as a non-aqueous liquid such as an organic solvent, an organic solid electrolyte, an inorganic solid electrolyte, but is not limited to these.
Brief Description of the Drawings
[49]
1 is a perspective view showing a vertical cross section of a conventional cylindrical battery technology;
[50]
Figure 2 is a picture showing the experimental procedure of Experiment 1 of the present invention;
[51]
Figure 3 is a schematic diagram for explaining the mechanism of a UV absorber that contains a heat-shrinkable tube of the present invention.
[52]
Figure 4 is a photograph showing the results of Example 1 in Experimental Example 2.
[53]
Figure 5 Example 2 in Experimental Example 2
[54]
6 shows a stress-strain curve (SS Curve) of Example 1 in Experiment 3.
[55]
7 shows a stress-strain curve (SS Curve) of Comparative Example 3 in Experimental Example 3.
Mode for the Invention
[56]
The present invention is not limited to the description of the invention, which is limited to it.
[57]
[58]

[59]
Polyethylene terephthalate based on total composition of polyethylene terephthalate resin, 80 g, a UV absorber is hydroxyl benzophenone (hydroxy benzophenone) 2 g, the pigment 8 g and nylon 66 10 ga rear melt blended miscible with the to prepare a resin composition, followed by rapid cooling 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]
Advantageously same manner as in Example 1 except that the UV absorber prepared in-hydroxy benzophenone (hydroxy benzophenone), and the resin composition without the use of nylon 66 was prepared in a heat-shrinkable tube.
[63]
[64]

[65]
Except for the use of the ultraviolet absorber-hydroxy benzophenone (hydroxy benzophenone) to produce the resin composition in the same manner as in Example 1 to prepare a heat-shrinkable tube.
[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 nylon 66.
[69]
[70]

[71]
Of the present invention 2, there are pictures showing the experimental procedure of Experiment 1 is disclosed. Example 1 and comparative lamp and 3 cm in Example 1 to compare the heat-shrinkable tube 110, the ultraviolet to the respective emitter (200) prepared in Example 3 Figure 2, the intensity of light 61.5 W / m 2 and is the wavelength of light from 300 nm to 400 nm, it was found whether or not the cracks occur in the back,
[72]
[73]
TABLE 1
Cracks occurred or not (O, 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, it was found that all of the nylon and the ultraviolet absorber 1, but cracks occurred in Example 1, not do it. That is, when comparative Example 2 The tube base material of the nylon-based resin is added as shown, it is possible to prevent a crack generated in the heat-shrinkable tube by the nylon unique properties. Further, if it contains an ultraviolet absorber in the tube base material of the polyester-based resin as in Comparative Example 3, the ultraviolet absorber is caused by a polymer chain in the nylon-based resin and polyester-based resin is decomposed can do.
[75]
Example 1, the effect is further increased by the synergistic effect, which results in the generation of cracks in the nylon-based resin and a UV absorber in the tube base material.
[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 nylon-based resin or a polymer chain by suppressing the chain reaction of free radicals (120).
[77]

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

[84]
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]
Example 3 shows the results of the stress-strain curve (SS Curve), which is measured at constant rate, the specific value is shown in Table 2.
[86]
[87]
TABLE 2
Example 1 Comparative Example 3
Tensile strength (Kgf / cm 2 ) 636 (average) 569 (average)
Elongation (%) 750 (average) 683 (average)
[88]
Example 3: Thus, the heat-shrinkable tube was made as a result of the heat-shrinkable tube a UV absorber, and 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 of the elasticity of nylon.
[89]
The present invention relates to a heat-shrinkable tube comprising at least one nylon-based resin or an ultraviolet absorber comprising a nylon-based resin and a UV absorber in the tube base material is That cracks It is suppressed. In addition, the nylon-based resin does not include any an ultraviolet absorber, but increases the tensile strength and elongation, and it was confirmed that the ultraviolet irradiation significantly appears.
[90]
The ultraviolet rays of the nylon-based resin and an ultraviolet absorber effect are prevented from the discoloration of the ultraviolet rays.
[91]
[92]
Above has been described with reference to the invention of the invention, and the skilled artisan of the invention is as possible as possible.
Industrial Applicability
[93]
The heat-shrinkable by ultraviolet radiation to the tube is released by the heat, the nylon-based resin or the polyester-based resin. The ultraviolet absorber can be used in a variety of applications, such as a vacuum cleaner, a vacuum cleaner, a vacuum cleaner, and a vacuum cleaner.
[94]
The heat-shrinkable tube is a tube-shaped tube that is exposed to high temperatures. The heat-shrinkable tubes are used to heat the tubes. due to an external impact that the tube is easily deformed.
[95]
3

WE CLAIMS

[Claim 1]
The outer surface of the cylindrical casing is a heat-shrinkable tube that surrounds the heat-shrinkable tube. Reinforcing agent of the nylon-based resin to increase the tensile strength and the temperature of the heat-shrinkable tube; An ultraviolet absorber (UV absorber) is a UV-absorbing material that absorbs the ultraviolet radiation to the heat-shrinkable tube. The nylon-based resin or polyester-based resin reacts with oxygen to cause a decomposition reaction; And a cylindrical battery cells, characterized in that 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 cell, characterized in that a polyethylene terephthalate (PET) resin.
[Claim 4]
4. The method of claim 3 wherein the polyester resin is a cylindrical battery cell, characterized in that it comprises 70 wt% to 90 wt% based on total weight of the tube.
[Claim 5]
The method of claim 1, wherein the cylindrical secondary battery has a thickness in the range of 1 to 100 μm.
[Claim 6]
The method of claim 1, wherein the ultraviolet absorber is a cylindrical battery cell, characterized in that it is a benzophenone compound.
[Claim 7]
The method of claim 6, wherein the benzophenone-based compounds are cylindrical battery cells, characterized in that the hydroxy-benzophenone (hydroxybenzophenone).
[Claim 8]
The method of claim 1, wherein the ultraviolet absorber is a cylindrical battery cell, characterized in that the range of 0.1% to 5% by weight based on the total weight of the heat-shrinkable tube.
[Claim 9]
According to claim 1, there is said nylon resin comprising a cylindrical battery cells, characterized in that nylon 66.
[Claim 10]
The method of claim 9 comprises a cylindrical battery cell, characterized in that it comprises 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 the heat-shrinkable tube comprises 10 wt% to 20 wt% of the total weight.
[Claim 12]
The method of claim 1, wherein the heat-shrinkable tube is at an ambient temperature of 61.5 W / m at ambient temperatures of 50 ° C degrees 2. The wavelength of light is from 300 nm to 400 nm. cracks (crack) does not occur.
[Claim 13]
According to claim 1, the nylon resin comprises a cylindrical battery cell, characterized in that it is provided as a blended state to the polyester-based resin.