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WO2018124673A2 - Élément de batterie cylindrique ayant un tube thermorétractable comprenant un absorbeur d'ultraviolets - Google Patents

Élément de batterie cylindrique ayant un tube thermorétractable comprenant un absorbeur d'ultraviolets Download PDF

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Publication number
WO2018124673A2
WO2018124673A2 PCT/KR2017/015427 KR2017015427W WO2018124673A2 WO 2018124673 A2 WO2018124673 A2 WO 2018124673A2 KR 2017015427 W KR2017015427 W KR 2017015427W WO 2018124673 A2 WO2018124673 A2 WO 2018124673A2
Authority
WO
WIPO (PCT)
Prior art keywords
heat
shrinkable tube
battery cell
cylindrical battery
nylon
Prior art date
Application number
PCT/KR2017/015427
Other languages
English (en)
Korean (ko)
Other versions
WO2018124673A3 (fr
Inventor
김준탁
이제준
황보광수
정상석
이길영
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to ES17886393T priority Critical patent/ES2995783T3/es
Priority to US16/337,572 priority patent/US11476523B2/en
Priority to JP2019515620A priority patent/JP6791372B2/ja
Priority to PL17886393.2T priority patent/PL3531465T3/pl
Priority to CN201780074859.9A priority patent/CN110073512B/zh
Priority to EP17886393.2A priority patent/EP3531465B1/fr
Priority claimed from KR1020170179154A external-priority patent/KR102178893B1/ko
Publication of WO2018124673A2 publication Critical patent/WO2018124673A2/fr
Publication of WO2018124673A3 publication Critical patent/WO2018124673A3/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/107—Primary casings; Jackets or wrappings characterised by their shape or physical structure having curved cross-section, e.g. round or elliptic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a cylindrical battery cell having a heat shrinkable tube containing an ultraviolet absorber.
  • the secondary battery is a cylindrical battery and a rectangular battery in which the electrode assembly is embedded in a cylindrical or rectangular metal can, and a pouch type battery in which the electrode assembly is embedded in a pouch type case of an aluminum laminate sheet according to the shape of the battery case.
  • the electrode assembly embedded in the battery case is a power generator capable of charging and discharging composed of a positive electrode, a negative electrode, and a separator structure interposed between the positive electrode and the negative electrode. It is roughly classified into a wound jelly-roll type and a stack type in which a plurality of positive and negative electrodes of a predetermined size are sequentially stacked in a state of being interposed in a separator.
  • FIG. 1 schematically shows a vertical cross-sectional perspective view of a conventional cylindrical battery.
  • the cylindrical secondary battery 10 accommodates a jelly-roll type (wound) electrode assembly 12 in a cylindrical case 13 and injects an electrolyte solution into the cylindrical case 13, followed by a case 13.
  • the cap assembly 14 in which the electrode terminal (for example, a positive electrode terminal) is formed in the open upper end of the) is manufactured.
  • the cylindrical secondary battery covers the outer surface of the battery case using a tube made of a film of an electrically insulating plastic material in order to perform an insulating function and an external protective function with an external conductive material.
  • the tube was added to the outer surface of the battery case of the cylindrical secondary battery, the tube was exposed to high temperature, or the tube was easily deformed due to an external impact, thereby causing problems.
  • the present invention aims to solve the problems of the prior art as described above and the technical problems that have been requested from the past.
  • the inventors of the present application absorb the ultraviolet rays irradiated to the heat-shrinkable tube and release them as thermal energy, as will be described later, so that the polymer chain of the nylon resin or the polyester resin When it contains the ultraviolet absorber (UV Absorber) which prevents the decomposition reaction by reacting with oxygen, it was confirmed that the desired effect can be exhibited, and came to complete the present invention.
  • UV Absorber ultraviolet absorber
  • a cylindrical battery cell is wrapped around the outer surface of the cylindrical case except the electrode terminal portion, the heat shrinkable tube, the heat shrinkable tube,
  • UV absorber which absorbs ultraviolet rays irradiated to the heat-shrinkable tube and releases them as thermal energy, thereby preventing polymer chains of the nylon resin or polyester resin from reacting with oxygen to cause a decomposition reaction
  • the cylindrical battery cell according to the present invention absorbs ultraviolet rays irradiated onto the heat-shrinkable tube and releases the thermal energy, thereby preventing the polymer chain of the nylon resin or the polyester resin from reacting with oxygen to cause a decomposition reaction.
  • the ultraviolet absorbent even if the heat-shrinkable tube is exposed to ultraviolet rays for a long time, the film is not damaged or discolored, so that the insulator and the appearance protection function can be maintained well.
  • the cylindrical battery cell according to the present invention by using a reinforcing agent of nylon resin to increase the tensile strength and the use temperature of the heat-shrinkable tube in the heat-shrinkable tube is exposed to high temperature, or the tube is easily deformed due to external impact Can be prevented.
  • the heat-shrinkable tube may further include a pigment for imparting color, and thus may be distinguished and displayed by different colors, such as capacity of a battery cell, and thus may be easily classified and distinguished.
  • the polyester-based resin may be, for example, polyethylene terephthalate resin.
  • the polyester-based resin may be included in 70% to 90% by weight based on the total weight of the tube, more specifically, when the polyester-based resin is included in less than 70% by weight, Difficult to obtain the proper heat shrinkage rate required by the invention is difficult to properly exhibit the function of the heat shrink tube, on the contrary, when more than 90% by weight when exposed to high temperature easily deformed or deformed of the tube easily occurs.
  • the thickness of the heat shrinkable tube for the cylindrical secondary battery may be 1 ⁇ m to 100 ⁇ m.
  • the ultraviolet absorber may be a benzophenone-based compound, specifically, the benzophenone-based compound may be hydroxy benzophenone.
  • the ultraviolet absorber may be included in 0.1% by weight to 5% by weight based on the total weight of the heat-shrinkable tube, in detail may be included in 0.5% by weight to 5% by weight, more specifically the ultraviolet absorber
  • the ultraviolet absorber When included in less than 0.1% by weight, it is difficult to exert the effect of preventing the polymer chain of the nylon-based resin or polyester-based resin of the ultraviolet absorber react with oxygen to cause a decomposition reaction, it is difficult to prevent the occurrence of cracks due to ultraviolet irradiation, On the contrary, if it exceeds 5% by weight, an expensive ultraviolet absorber is excessively added, resulting in an excessively high manufacturing cost compared to the UV stabilizing effect.
  • the nylon-based resin may be nylon 66
  • the nylon 66 has a relatively high heat deformation temperature of 70 degrees Celsius, a heat resistance temperature of 105 degrees Celsius, tensile modulus of 2.9 ⁇ 10 4 kg / cm 2
  • the flexural modulus is 3.0 ⁇ 10 4 kg / cm 2 .
  • nylon 6-10 and nylon 6-12 it has high heat resistance and high mechanical rigidity.
  • nylon-based resin may be included in 3% by weight to 10% by weight based on the total weight of the heat shrinkable tube.
  • nylon-based resin may be included in a blended state in the polyester-based resin.
  • the pigment may be included in 10% to 20% by weight based on the total weight of the heat shrinkable tube.
  • the heat-shrinkable tube according to the present invention has a crack even when exposed to ultraviolet light having a light intensity of 61.5 W / m 2 and a wavelength of light of 300 nm to 400 nm for 1,000 hours in an ambient condition of 50 degrees Celsius. May not occur.
  • the heat-shrinkable tube further includes a UV stabilizer (UV Stabilizer) for inhibiting the chain reaction of the free radicals generated by cutting the polymer chain of the nylon resin or polyester resin by the irradiated ultraviolet light
  • a UV stabilizer UV Stabilizer
  • the UV stabilizer may be a benzoate compound, and the benzoate compound may be, for example, butyl-4-hydroxybenzoate.
  • the heat-shrinkable tube according to the present invention can not only prevent cracks in the film with an ultraviolet absorber, but also be produced by cutting the polymer chain of the nylon resin or the polyester resin by the irradiated ultraviolet light.
  • an ultraviolet stabilizer that suppresses the chain reaction of free radicals, it is possible to prevent the deterioration of the tube due to ultraviolet rays for a longer time.
  • the cylindrical battery cell may be a secondary battery
  • the secondary battery is not particularly limited in its kind, but as a specific example, lithium having advantages such as high energy density, discharge voltage, output stability, etc.
  • Lithium secondary batteries such as ion batteries, lithium ion polymer batteries, and the like.
  • a lithium secondary battery is composed of a positive electrode, a negative electrode, a separator, and a lithium salt-containing nonaqueous electrolyte.
  • the positive electrode may be prepared by, for example, applying a positive electrode active material composed of positive electrode active material particles to a positive electrode current collector, and a positive electrode mixture in which a conductive material and a binder are mixed. More fillers may be added.
  • the positive electrode current collector is generally manufactured to a thickness of 3 to 201 ⁇ m, and is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • stainless steel, aluminum, nickel, titanium , And one selected from surface treated with carbon, nickel, titanium, or silver on the surface of aluminum or stainless steel may be used, and in detail, aluminum may be used.
  • the current collector may form fine irregularities on its surface to increase the adhesion of the positive electrode active material, and may be in various forms such as film, sheet, foil, net, porous body, foam, and nonwoven fabric.
  • the conductive material is typically added in an amount of 0.1 to 30% by weight based on the total weight of the mixture including the positive electrode active material.
  • a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof include graphite such as natural graphite and artificial graphite; Carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and summer black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • the binder included in the positive electrode is a component that assists in bonding the active material, the conductive material, and the like to the current collector, and is generally added in an amount of 0.1 to 30 wt% based on the total weight of the mixture including the positive electrode active material.
  • binders examples include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene , Polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers, and the like.
  • CMC carboxymethyl cellulose
  • EPDM ethylene-propylene-diene terpolymer
  • EPDM ethylene-propylene-diene terpolymer
  • EPDM ethylene-propylene-diene terpolymer
  • EPDM ethylene-propylene-diene terpolymer
  • sulfonated EPDM styrene-butadiene rubber
  • fluorine rubber various copolymers, and the like.
  • the negative electrode is manufactured by coating and drying a negative electrode active material on a negative electrode current collector, and optionally, the components included in the positive electrode described above may be further included as necessary.
  • the negative electrode current collector is generally made to a thickness of 3 to 500 micrometers.
  • the negative electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • a surface of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper, or stainless steel may be used.
  • Surface-treated with carbon, nickel, titanium, silver and the like, aluminum-cadmium alloy and the like can be used.
  • fine concavities and convexities may be formed on the surface to enhance the bonding strength of the negative electrode active material, and may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • carbon such as hardly graphitized carbon and graphite type carbon
  • the separator is interposed between the anode and the cathode, and an insulating thin film having high ion permeability and mechanical strength is used.
  • the pore diameter of the separator is generally from 0.01 to 10 ⁇ m ⁇ m, thickness is generally 5 ⁇ 300 ⁇ m.
  • a separator for example, olefin polymers such as chemical resistance and hydrophobic polypropylene; Sheets or non-woven fabrics made of glass fibers or polyethylene are used.
  • a solid electrolyte such as a polymer
  • the solid electrolyte may also serve as a separator.
  • the said lithium salt containing non-aqueous electrolyte solution consists of a nonaqueous electrolyte solution and a lithium salt.
  • nonaqueous electrolyte nonaqueous organic solvents, organic solid electrolytes, inorganic solid electrolytes, and the like are used, but not limited thereto.
  • FIG. 1 is a vertical cross-sectional perspective view of a cylindrical cell of the prior art
  • FIG. 3 is a schematic view for explaining the mechanism of the ultraviolet absorber contained in the heat-shrinkable tube of the present invention.
  • Figure 4 is a photograph showing the results of Example 1 in Experimental Example 2.
  • FIG. 6 shows a stress deformation curve (S-S Curve) of Example 1 in Experimental Example 3.
  • FIG. 6 shows a stress deformation curve (S-S Curve) of Example 1 in Experimental Example 3.
  • a heat shrinkable tube was manufactured in the same manner as in Example 1, except that the resin composition was prepared without using the ultraviolet absorbent hydroxy benzophenone and nylon 66.
  • a heat shrinkable tube was manufactured in the same manner as in Example 1 except that the resin composition was prepared without using hydroxy benzophenone, which is an ultraviolet absorber.
  • a heat shrinkable tube was prepared in the same manner as in Example 1 except that the resin composition was prepared without using nylon 66.
  • each of the heat-shrinkable tubes 110 manufactured in Example 1 and Comparative Examples 1 to 3 is disposed to be 3 cm away from the lamp of the ultraviolet irradiator 200, so that the light intensity is 61.5 W / m. 2 and the wavelength of light is 300 nm to 400 nm, after exposure for 1,000 hours in an ambient condition of 50 degrees Celsius, it was confirmed whether the crack was generated on the tube surface.
  • Figure 3 is a schematic diagram for explaining the mechanism of the ultraviolet stabilizer contained in the heat shrinkable tube of the present invention.
  • free radicals 120 and ultraviolet stabilizers 130 generated by cutting polymer chains of a nylon-based resin or a polyester-based resin by ultraviolet rays irradiated to the heat-shrinkable tube 110 from the ultraviolet irradiator 200. ) May inhibit the chain reaction of the free radicals 120.
  • the heat-shrinkable tube prepared in Example 1 and the heat-shrinkable tube prepared in Comparative Example 2 were prepared, and black letters were printed on the tube surface.
  • the heat shrinkable tubes were exposed to an ultraviolet irradiator having a light intensity of 61.5 W / m 2 and a wavelength of light of 300 nm to 400 nm for 500 hours, and then the color change of the black letters was confirmed. 5 is shown.
  • FIG. 4 shows the color change of the heat-shrinkable tube of Example 1
  • FIG. 5 shows the color change of the heat-shrinkable tube of Comparative Example 2.
  • Example 1 the color change of the letter is hardly seen in the state before and after the UV irradiation, but in Comparative Example 2, the color of the letter is changed from black to gray. You can see that it is very cloudy. Therefore, when the ultraviolet absorber is included, it does not affect the color change of the tube, but when it is not included, it can be seen that the color change is remarkable.
  • Example 1 The results of Example 1 are shown in FIG. 6, and the results of Comparative Example 3 are shown in FIG. 7. The specific values are shown in Table 2.
  • Example 1 Comparative Example 3 Tensile Strength (Kgf / cm 2 ) 636 (average) 569 (average) Elongation (%) 750 (average) 683 (average)
  • the tensile strength and elongation of the heat-shrinkable tube of Example 1 show a remarkably improved value when compared to the heat-shrinkable tube of Comparative Example 3. Therefore, it can be seen that the heat shrinkable tube including the ultraviolet absorbent and the nylon has improved mechanical rigidity than the heat shrinkable tube without the nylon. This is believed to be due to the high tensile strength and elastic nylon.
  • the heat-shrinkable tube of the present invention includes a nylon-based resin and an ultraviolet absorber in the tube base material, and the heat-shrinkable tube containing any one of the nylon-based resin or the ultraviolet absorber may cause cracks. Suppressed.
  • the nylon-based resin is included but does not contain an ultraviolet absorber, the effect of increasing the tensile strength and elongation can be obtained, but it was confirmed that the color change was remarkable for ultraviolet irradiation.
  • the present invention exhibits the synergistic effect obtained by including both the nylon-based resin and the ultraviolet absorber, so that cracks can be prevented from occurring in the tube, and discoloration against ultraviolet rays can be prevented.
  • the cylindrical battery cell according to the present invention absorbs ultraviolet rays irradiated to the heat-shrinkable tube and releases them as thermal energy, so that the polymer chains of the nylon resin or the polyester resin react with oxygen to decompose.
  • the UV absorber is included, the heat shrinkable tube is not damaged or discolored even when exposed to ultraviolet rays for a long time, thereby maintaining the natural insulation and appearance protection.
  • the cylindrical battery cell according to the present invention by using a reinforcing agent of nylon-based resin to increase the tensile strength and the use temperature of the heat shrinkable tube in the heat shrinkable tube, the tube is exposed to high temperature, or the tube is easily deformed due to external impact It is effective to prevent that.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sealing Battery Cases Or Jackets (AREA)

Abstract

La présente invention concerne une cellule de batterie cylindrique ayant un tube thermorétractable enveloppant la surface externe d'un boîtier cylindrique à l'exclusion de parties de borne d'électrode, le tube thermorétractable comprenant : une base de tube faite d'une résine à base de polyester ayant une rétractabilité à la chaleur ; un agent de renforcement fait d'une résine de nylon permettant d'augmenter la résistance à la traction et la température d'utilisation du tube thermorétractable ; et un absorbeur d'ultraviolets qui absorbe les rayons ultraviolets irradiés vers le tube thermorétractable et émet les rayons ultraviolets sous forme d'énergie thermique, empêchant ainsi que les chaînes polymères d'une résine à base de nylon ou d'une résine à base de polyester ne réagissent à l'oxygène pour provoquer une réaction de décomposition.
PCT/KR2017/015427 2016-12-26 2017-12-26 Élément de batterie cylindrique ayant un tube thermorétractable comprenant un absorbeur d'ultraviolets WO2018124673A2 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
ES17886393T ES2995783T3 (en) 2016-12-26 2017-12-26 Cylindrical battery cell having heat-shrinkable tube comprising ultraviolet absorber
US16/337,572 US11476523B2 (en) 2016-12-26 2017-12-26 Cylindrical battery cell having heat-shrinkable tube comprising ultraviolet absorber
JP2019515620A JP6791372B2 (ja) 2016-12-26 2017-12-26 紫外線吸収剤を含む熱収縮性チューブを備えた円筒型電池セル
PL17886393.2T PL3531465T3 (pl) 2016-12-26 2017-12-26 Cylindryczne ogniwo akumulatorowe mające rurkę termokurczliwą zawierającą absorber ultrafioletu
CN201780074859.9A CN110073512B (zh) 2016-12-26 2017-12-26 具有含紫外线吸收剂的热收缩管的圆柱形电池单元
EP17886393.2A EP3531465B1 (fr) 2016-12-26 2017-12-26 Élément de batterie cylindrique ayant un tube thermorétractable comprenant un absorbeur d'ultraviolets

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20160178728 2016-12-26
KR10-2016-0178728 2016-12-26
KR10-2017-0179154 2017-12-26
KR1020170179154A KR102178893B1 (ko) 2016-12-26 2017-12-26 자외선 흡수제를 포함하는 열수축성 튜브를 구비한 원통형 전지셀

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WO2018124673A2 true WO2018124673A2 (fr) 2018-07-05
WO2018124673A3 WO2018124673A3 (fr) 2018-10-11

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Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2896445B1 (fr) * 2006-01-25 2010-08-20 Arkema Film flexible a base de polymere fluore
JP2007323907A (ja) * 2006-05-31 2007-12-13 Sony Corp 電池外装材及びこれを用いた非水電解質二次電池
KR101524506B1 (ko) * 2009-12-21 2015-06-01 생-고뱅 퍼포먼스 플라스틱스 코포레이션 열전도성 폼 재료
KR101569452B1 (ko) * 2012-11-29 2015-11-16 주식회사 엘지화학 열수축성 튜브를 포함하는 이차전지
US9209443B2 (en) * 2013-01-10 2015-12-08 Sabic Global Technologies B.V. Laser-perforated porous solid-state films and applications thereof

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