KR20000051779A - Lithium Secondary Battery Employing Plastic Housing - Google Patents
Lithium Secondary Battery Employing Plastic Housing Download PDFInfo
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- KR20000051779A KR20000051779A KR1019990002399A KR19990002399A KR20000051779A KR 20000051779 A KR20000051779 A KR 20000051779A KR 1019990002399 A KR1019990002399 A KR 1019990002399A KR 19990002399 A KR19990002399 A KR 19990002399A KR 20000051779 A KR20000051779 A KR 20000051779A
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- South Korea
- Prior art keywords
- lithium secondary
- secondary battery
- case
- case body
- electrode
- Prior art date
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 53
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000004033 plastic Substances 0.000 title claims description 3
- 229920003023 plastic Polymers 0.000 title claims description 3
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 4
- 239000011347 resin Substances 0.000 claims abstract description 4
- 239000003063 flame retardant Substances 0.000 claims description 11
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 10
- 239000002952 polymeric resin Substances 0.000 claims description 10
- 229920003002 synthetic resin Polymers 0.000 claims description 10
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims 2
- 239000005022 packaging material Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 description 18
- 230000008569 process Effects 0.000 description 17
- 239000007789 gas Substances 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 4
- 238000009958 sewing Methods 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- YATIGPZCMOYEGE-UHFFFAOYSA-N 1,3,5-tribromo-2-[2-(2,4,6-tribromophenoxy)ethoxy]benzene Chemical compound BrC1=CC(Br)=CC(Br)=C1OCCOC1=C(Br)C=C(Br)C=C1Br YATIGPZCMOYEGE-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- BGGGMYCMZTXZBY-UHFFFAOYSA-N (3-hydroxyphenyl) phosphono hydrogen phosphate Chemical compound OC1=CC=CC(OP(O)(=O)OP(O)(O)=O)=C1 BGGGMYCMZTXZBY-UHFFFAOYSA-N 0.000 description 1
- GRPTWLLWXYXFLX-UHFFFAOYSA-N 1,1,2,2,3,3-hexabromocyclodecane Chemical compound BrC1(Br)CCCCCCCC(Br)(Br)C1(Br)Br GRPTWLLWXYXFLX-UHFFFAOYSA-N 0.000 description 1
- NDRKXFLZSRHAJE-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3,4-tribromophenyl)benzene Chemical group BrC1=C(Br)C(Br)=CC=C1C1=C(Br)C(Br)=C(Br)C(Br)=C1Br NDRKXFLZSRHAJE-UHFFFAOYSA-N 0.000 description 1
- DGZQEAKNZXNTNL-UHFFFAOYSA-N 1-bromo-4-butan-2-ylbenzene Polymers CCC(C)C1=CC=C(Br)C=C1 DGZQEAKNZXNTNL-UHFFFAOYSA-N 0.000 description 1
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
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- 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
- H01M50/121—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- H01M50/103—Primary casings; Jackets or wrappings characterised by their shape or physical structure prismatic or rectangular
-
- 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
- H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
-
- 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
- H01M50/147—Lids or covers
- H01M50/148—Lids or covers characterised by their shape
- H01M50/15—Lids or covers characterised by their shape for prismatic or rectangular cells
-
- 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
- H01M50/147—Lids or covers
- H01M50/155—Lids or covers characterised by the material
- H01M50/16—Organic material
-
- 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
- H01M50/172—Arrangements of electric connectors penetrating the casing
- H01M50/174—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells
- H01M50/176—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells for prismatic or rectangular cells
-
- 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
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/531—Electrode connections inside a battery casing
-
- 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
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/543—Terminals
- H01M50/552—Terminals characterised by their shape
- H01M50/553—Terminals adapted for prismatic, pouch or rectangular cells
- H01M50/557—Plate-shaped terminals
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Secondary Cells (AREA)
Abstract
Description
본 발명은 리튬 2차전지에 관한 것으로서, 보다 상세하게는 고분자 수지로부터 성형된 케이스를 구비하며 전지의 안정성 및 에너지 밀도가 개선된 리튬 2차전지에 관한 것이다.The present invention relates to a lithium secondary battery, and more particularly, to a lithium secondary battery having a case molded from a polymer resin and having improved battery stability and energy density.
일반적으로 비디오 카메라, 휴대용 전화, 휴대용 PC 등의 휴대용 무선 기기의 경량화 및 고기능화가 진행됨에 따라, 그 구동용 전원으로 사용되는 2차전지에 대해서 많은 연구가 이루어지고 있다. 이러한 2차전지는 예를 들어, 니켈 카드뮴 전지, 니켈 수소 전지, 니켈 아연 전지, 리튬 2차전지 등이 있다. 이중에서 리튬 2차전지는 수명이 길고 용량이 크다는 장점을 가지고 있다.In general, as the light weight and high performance of portable wireless devices such as a video camera, a portable telephone, a portable PC, and the like become advanced, many studies have been conducted on secondary batteries used as driving power sources. Such secondary batteries include, for example, nickel cadmium batteries, nickel hydrogen batteries, nickel zinc batteries, and lithium secondary batteries. Among them, lithium secondary battery has the advantage of long life and large capacity.
리튬 2차전지는 전해질 종류에 따라 액체 전해질을 사용하는 리튬 금속전지와 리튬 이온전지 및 고분자 고체 전해질을 사용하는 리튬 폴리머전지로 구분할 수 있다. 그리고, 리튬 폴리머전지는 고분자 고체 전해질의 종류에 따라 유기전해액이 전혀 함유되어 있지 않은 완전고체형 리튬 폴리머전지, 유기전해액을 함유하고 있는 겔형 고분자 전해질을 사용하는 리튬 이온 폴리머전지로 나눌 수 있다.The lithium secondary battery may be classified into a lithium metal battery using a liquid electrolyte and a lithium polymer battery using a lithium ion battery and a polymer solid electrolyte according to the type of electrolyte. Lithium polymer batteries can be classified into fully solid lithium polymer batteries containing no organic electrolyte solution and lithium ion polymer batteries using gel polymer electrolyte containing organic electrolyte solution, depending on the type of polymer solid electrolyte.
도 1은 통상적인 리튬 2차전지를 전극조립체와 케이스로 분리하여 도시한 사시도이다.1 is a perspective view illustrating a conventional lithium secondary battery separated into an electrode assembly and a case.
도 1을 참조하면, 리튬 2차전지는 양극판, 음극판 및 세퍼레이터(separator)를 구비하는 전극조립체(18)와 이 전극조립체(18)를 감싸서 밀봉하는 케이스(10)를 구비하여 이루어진다. 여기서, 상기 전극조립체(18)와 외부의 전기적 통로 역할을 하는 전극탭(17)은 케이스(10) 밖으로 소정 길이 노출되도록 설치된다. 또한, 상기 케이스(10)는 상면이 개방되어 있고 전극조립체(18)가 삽입되는 수납부(12)와 이 수납부(12)의 입구로부터 바깥쪽으로 소정길이 연장된 제1접합부(13)를 포함하는 케이스 본체(14), 및 제1접합부(13)에 접합되는 제2접합부(15)가 가장자리를 따라 마련되며 개방되어 있는 수납부의 상면을 밀폐하도록 상기 케이스 본체(14)와 일체형으로 형성된 판상의 덮개부(16)을 포함하여 이루어진다.Referring to FIG. 1, a lithium secondary battery includes an electrode assembly 18 including a positive electrode plate, a negative electrode plate, and a separator, and a case 10 enclosing and sealing the electrode assembly 18. In this case, the electrode assembly 18 and the electrode tab 17 serving as an external electrical passage are installed to expose a predetermined length out of the case 10. In addition, the case 10 includes an accommodating part 12 in which an upper surface is opened and an electrode assembly 18 is inserted, and a first joint part 13 extending a predetermined length outward from an inlet of the accommodating part 12. The case body 14 and the second bonding portion 15 joined to the first bonding portion 13 are provided along the edge and formed integrally with the case body 14 so as to seal the upper surface of the open receiving portion. The cover portion 16 is made of.
통상의 리튬 2차전지는 상기 전극조립체(18)를 수납부(12)에 수납한 다음, a-a'선을 따라 접어서 제1접합부(13)와 제2접합부(15)가 마주닿도록한 다음, 열융착함으로써 형성된다.In the conventional lithium secondary battery, the electrode assembly 18 is accommodated in the accommodating part 12 and then folded along the line a-a 'so that the first junction part 13 and the second junction part 15 face each other. It is formed by thermal fusion.
도 2는 이렇게 형성된 리튬 2차전지의 측면도이다.2 is a side view of the lithium secondary battery thus formed.
이와 같은 리튬 2차전지에 있어서 케이스의 소재로서 가공성이 용이하여 여러 가지 형태로 제작이 가능한 알루미늄이 널리 사용된다.In such a lithium secondary battery, aluminum is widely used as a material of the case, which can be manufactured in various forms.
그러나, 알루미늄 소재로 된 리튬 2차전지용 케이스는 다음과 같은 몇가지 치명적인 문제점을 내포하고 있다:However, the case for a lithium secondary battery made of aluminum presents several fatal problems:
첫째, 알루미늄은 강도가 매우 약하므로 외부의 충격에 의해 쉽게 변형되어 전극조립체들이 손상될 가능성이 많다는 것이다. 또한, 고율충전 및 고온방치시에는 매우 약한 외압에도 전지의 단락 등이 발생하여 발화가 일어날 수 있는데, 이때 알루미늄이 함께 발화됨으로써 화재로 이어질 수 있는 위험성이 있다.First, since aluminum is very weak in strength, it is easily deformed by external impacts, and thus the electrode assemblies are likely to be damaged. In addition, when high-rate charging and high temperature stand-by may cause a short circuit of the battery even in a very weak external pressure, ignition may occur, and there is a risk that aluminum may be ignited together to lead to a fire.
둘째, 알루미늄 소재로 된 리튬 2차전지용 케이스는 케이스의 상단 플랜지부에 전극이 존재하지 않는 데드 볼륨 (dead volume)이 존재함으로써 단위 부피당 에너지 밀도를 감소시킨다.Second, the lithium secondary battery case made of aluminum material has a dead volume in which no electrode exists in the upper flange of the case, thereby reducing energy density per unit volume.
즉, 통상의 리튬 2차전지를 나타낸 도 2를 참조하여 보면 열융착된 부분을 따라 넓은 플랜지부(19)가 형성되어 있는 것을 알 수 있다. 이러한 플랜지부중 좌우에 위치한 부분은 b-b' 및 c-c'선을 따라 접어넣을 수 있지만 탭이 위치하는 부분인 윗부분은 접어넣을 수 없기 때문에 전극 부피만 차지하고 전극 용량에는 기여하지 못하는 소위 데드 볼륨(D1×D2)이 존재하는데, 이로 인해 전지용량 감소 및 단위 부피당 에너지 밀도의 감소가 초래된다.That is, referring to FIG. 2 illustrating a conventional lithium secondary battery, it can be seen that a wide flange portion 19 is formed along the heat-sealed portion. The left and right parts of these flanges can be folded along the bb 'and c-c' lines, but the upper part, where the tab is located, can't be folded, so it is a so-called dead volume that occupies only the electrode volume and does not contribute to the electrode capacity. D 1 × D 2 ), which leads to a reduction in battery capacity and a reduction in energy density per unit volume.
셋째, 전지 제조 공정이 증가한다. 전술한 바와 같이 알루미늄은 강도가 약하기 때문에 화성공정 (formation)시 발생하는 가스에 의해 케이스가 부풀어 올라 전지의 외관을 불량하게 하고 전지 부피도 증가시킨다. 이를 방지하기 위하여 전지조립체와 나란하게 가스실 (gas room)을 설치하고 진공펌프를 이용하여 화성공정시 발생하는 가스를 가스실로 뽑아내는 가스제거공정 (degassing)을 실시한 다음, 가스실을 절단, 제거하고 전지조립체가 있는 공간만을 다시 봉합하여야 한다. 즉, 가스제거공정과 재봉합공정등 후속 공정이 필수적으로 수반되어야 하므로 전지 제조 공정이 증가하게 된다.Third, battery manufacturing processes increase. As described above, aluminum has a weak strength, causing the case to swell due to the gas generated during the formation process, thereby deteriorating the appearance of the battery and increasing the battery volume. To prevent this, a gas chamber is installed in parallel with the battery assembly, and a gas chamber is degassed to extract gas generated during the chemical conversion process into a gas chamber using a vacuum pump, and then the gas chamber is cut and removed. Only the space containing the assembly should be resealed. That is, the battery manufacturing process is increased because a subsequent process such as a gas removal process and a sewing process must be necessarily accompanied.
넷째, 탭의 위치가 전지 케이스 상에 수직하게 돌출되어 있어서 미관상 바람직하지 않을 뿐 아니라 화성공정시 탭을 일일이 잭에 물려야 하므로 작업상 번거롭기도 하려니와 작업이 불연속적으로 이루어지기 때문에 시간이 많이 걸리고 결과적으로 생산성이 저하된다.Fourth, because the position of the tab protrudes vertically on the battery case, it is not only aesthetically desirable, but it is also cumbersome in operation because the tab has to be bited into the jack one by one during the chemical conversion process, and it takes a lot of time because the work is made discontinuously. As a result, productivity decreases.
본 발명이 이루고자 하는 기술적 과제는 전지의 안정성과 에너지 밀도가 개선되면서 제조공정은 간소화된 리튬 2차전지를 제공하기 위한 것이다.The technical problem to be achieved by the present invention is to provide a simplified lithium secondary battery manufacturing process while improving the stability and energy density of the battery.
도 1은 알루미늄 외장재를 채용하는 통상의 리튬 2차전지의 각 부분을 분리하여 도시한 사시도이다.1 is a perspective view showing each part of a typical lithium secondary battery that employs an aluminum exterior material separately.
도 2는 도 1에 개시된 통상의 리튬 2차전지의 측면도이다.FIG. 2 is a side view of the conventional lithium secondary battery disclosed in FIG. 1.
도 3은 본 발명에 따른 리튬 2차전지의 각 부분을 분리하여 도시한 사시도이다.3 is a perspective view separately showing each part of the lithium secondary battery according to the present invention.
도 4a는 본 발명에 따른 리튬 2차전지의 측면도이다.4A is a side view of a lithium secondary battery according to the present invention.
및 4b는 본 발명에 따른 리튬 2차전지중 A 부분의 확대도이다.And 4b is an enlarged view of a portion A of the lithium secondary battery according to the present invention.
*도면의 주요부분에 대한 부호의 설명** Description of the symbols for the main parts of the drawings *
30... 케이스 31... 케이스 본체30 ... case 31 ... case body
32... 수납부 33... 인입부32. Storage 33. Entry
34... 전극조립체 35... 커버부재34. Electrode assembly 35 ... Cover member
36... 전극탭36 ... electrode tab
본 발명의 기술적 과제는 전극 탭이 돌출되어 있는 전극조립체 및 상기 전극조립체를 밀봉하는 케이스를 포함하는 리튬 2차전지에 있어서, 상기 케이스가 상면이 개방되어 있으며 상기 전극조립체를 수납하기 위한 수납부를 포함하는 케이스 본체 및 상기 케이스 본체의 상면을 폐쇄하도록 형성된 커버부재를 구비하며, 상기 케이스 본체와 커버부재가 고분자 수지를 포함하는 케이스 형성용 조성물로부터 각각 별도로 성형가공된 것을 특징으로 하는 리튬 2차전지에 의하여 이루어질 수 있다.SUMMARY OF THE INVENTION The present invention provides a lithium secondary battery including an electrode assembly protruding from an electrode tab and a case sealing the electrode assembly, wherein the case has an open upper surface and includes an accommodating part for accommodating the electrode assembly. To a lithium secondary battery comprising a case body and a cover member formed to close the upper surface of the case body, wherein the case body and the cover member is molded separately from the case-forming composition comprising a polymer resin It can be done by.
본 발명에 따른 리튬 2차전지에 있어서, 상기 케이스 본체의 측면에는 전극조립체로부터 돌출되어 있는 탭이 절곡되어 인입될 수 있도록 인입부가 형성될 수 있다.In the lithium secondary battery according to the present invention, an inlet portion may be formed on a side surface of the case body so that a tab protruding from the electrode assembly is bent and drawn in.
또한, 상기 케이스 형성용 조성물에 있어서, 고분자 수지로는 내충격성 및 성형성이 우수하고 전해액과의 반응성이 없으며 소정의 난연성을 갖는 것이면 특별하게 제한되지 않고 사용될 수 있는데, 바람직하기로는 ABS (아크릴로니트릴-부타디엔-스티렌) 수지, 폴리스티렌, 폴리카보네이트, 폴리에틸렌테레프탈레이트와 폴리부틸렌테프탈레이트를 비롯한 폴리에스테르, 폴리비닐클로라이드 등을 예로 들 수 있다.Further, in the case forming composition, the polymer resin may be used without particular limitation as long as the polymer resin is excellent in impact resistance and moldability, has no reactivity with the electrolyte, and has a predetermined flame retardancy. Nitrile-butadiene-styrene) resins, polystyrenes, polycarbonates, polyesters including polyethylene terephthalate and polybutylenetephthalate, polyvinyl chloride and the like.
또한, 상기 케이스 형성용 조성물은 난연제를 더 포함할 수 있는데, 난연제로는 본 발명의 기술분야에서 통상적으로 사용될 수 있는 것이면 제한없이 사용될 수 있으며 주성분인 고분자 수지의 종류에 따라 적합한 것을 선택하여 사용할 수 있다. 사용될 수 있는 난연제의 구체적인 예로는 브롬, 헥사브로모싸이클로데칸, 데카브롬 (데카브로모디페닐 옥사이드), 비스(트리브로모페녹시)에탄, 옥타브로모디페닐 디옥사이드, 테트라브로모비스페놀 A, 블롬화 폴리스티렌, 브롬화 아크릴산, 브롬화 에폭시, 브롬화인산염 (Bromonated phosphate), 브롬화 폴리카보네이트 등과 같은 할로겐 화합물; 알킬화 포스페이트 에테르, 레소르시놀 디포스페이트, 트리페놀 포스페이트 등과 같은 인 화합물; 및 산화 안티몬, 수산화마그네슘 등과 같은 금속의 산화물 또는 수산화물 등을 들 수 있다.In addition, the case-forming composition may further include a flame retardant, any flame retardant can be used without limitation as long as it can be commonly used in the art of the present invention can be used by selecting a suitable one according to the type of the polymer resin as the main component have. Specific examples of flame retardants that can be used include bromine, hexabromocyclodecane, decabrom (decabromodiphenyl oxide), bis (tribromophenoxy) ethane, octabromodiphenyl dioxide, tetrabromobisphenol A, brominated Halogen compounds such as polystyrene, brominated acrylic acid, brominated epoxy, bromonated phosphate, brominated polycarbonate, and the like; Phosphorus compounds such as alkylated phosphate ethers, resorcinol diphosphate, triphenol phosphate and the like; And oxides or hydroxides of metals such as antimony oxide, magnesium hydroxide, and the like.
이러한 난연제는 케이스 형성용 조성물 제조시 고분자 수지와 함께 첨가될 수 있거나 케이스 성형후 케이스 표면에 직접 도포할 수도 있으나, 전자의 경우가 바람직하다.Such a flame retardant may be added together with the polymer resin in preparing the case-forming composition, or may be directly applied to the case surface after the case molding, the former case is preferred.
상기 난연제는 발포성난염제로서 작용하여 발화를 억제하거나 발화시간을 줄이는 역할을 한다. 특히 금속의 산화물 또는 수산화물이 난연제로서 사용되는 경우에는 열이 발생하면 H2O를 형성함으로써 발화를 억제하는 메카니즘을 갖는다.The flame retardant acts as an effervescent flame retardant and serves to suppress ignition or reduce ignition time. In particular, when an oxide or a hydroxide of a metal is used as a flame retardant, it has a mechanism of suppressing ignition by forming H 2 O when heat is generated.
한편, 커버부재는 바람직하게는 초음파 융착에 의해 케이스 본체에 결합된다.On the other hand, the cover member is preferably coupled to the case body by ultrasonic welding.
도 3은 본 발명에 따른 리튬 2차전지의 각 부분을 분리하여 나타낸 사시도이다.3 is a perspective view separately showing each part of the lithium secondary battery according to the present invention.
도면을 참조하여 보면, 본 발명에 따른 리튬 2차 전지는 양극, 음극 및 세퍼레이터를 포함하며 전극 탭(36)이 돌출되어 있는 전극조립체(34)와 이 전극조립체(34)를 수납할 수 있는 케이스(30)을 포함하는데, 상기 케이스(30)는 상면이 개방되어 있고 상기 전극조립체(34)를 수납할 수 있는 수납부(32)를 구비하는 케이스 본체(31) 및 개방된 상면에 도입되어 케이스 본체(31)을 밀폐할 수 있는 커버부재(35)를 포함한다. 여기서, 상기 케이스 본체(31)와 커버부재(35)는 고분자 수지, 및 필요에 따라서는 난연제를 포함하는 조성물로부터 각각 별도로 성형가공된다.Referring to the drawings, a lithium secondary battery according to the present invention includes a positive electrode, a negative electrode, and a separator, and an electrode assembly 34 having a protruding electrode tab 36 and a case for accommodating the electrode assembly 34. 30, wherein the case 30 has an upper surface open and a case body 31 having an accommodating portion 32 capable of accommodating the electrode assembly 34 and an open upper surface of the case 30. It includes a cover member 35 that can seal the main body 31. Here, the case body 31 and the cover member 35 are molded separately from the composition containing a polymer resin and, if necessary, a flame retardant.
본 발명에 따른 리튬 2차전지에 있어서, 상기 케이스 본체와 커버부재는 통상의 리튬 2차전지와는 달리 접합부를 포함하지 않으며, 바람직하게는 초음파 융착에 의해 결합된다.In the lithium secondary battery according to the present invention, the case body and the cover member, unlike a conventional lithium secondary battery, do not include a junction, and are preferably bonded by ultrasonic welding.
이렇게 형성된 본 발명의 리튬 2차전지가 도 4a에 도시되어 있다.The lithium secondary battery of the present invention thus formed is shown in FIG. 4A.
도 4a로부터 알 수 있듯이, 본 발명에 따른 리튬 2차전지에는 플랜지부가 형성되지 않다. 따라서, 데드 볼륨이 발생하지 않게 되므로 전지 용량 및 전지의 단위 부피당 에너지 밀도가 증가된다.As can be seen from Figure 4a, the flange portion is not formed in the lithium secondary battery according to the present invention. Therefore, no dead volume is generated, thereby increasing the battery capacity and the energy density per unit volume of the battery.
또한, 본 발명에 따른 리튬 2차 전지는 케이스 본체 외부로 돌출되어 있는 전극 탭(26)이 90°절곡되어 인입될 수 있도록 케이스 본체의 측면에 전극 탭용 인입부(23)를 구비할 수 있다.In addition, the lithium secondary battery according to the present invention may include an electrode tab inlet 23 on the side of the case body so that the electrode tab 26 protruding outside the case body may be bent by 90 °.
도 4b는 본 발명에 따른 리튬 2차전지중 A 부분, 즉 전지탭 인입부를 확대하여 나타낸 도면이다. 도 4b로부터 알 수 있듯이, 전극 탭(36)이 90°로 절곡, 인입되도록 케이스 본체(31)의 측면에 전극 탭 인입부(33)를 형성하여 전극 탭을 인입, 고정시킨다. 따라서, 본 발명에 따른 리튬 2차전지는 탭이 전지 케이스와 수직하게 외부로 돌출되어 있지 않아 외관상 보기 좋을 뿐 아니라 화성공정시 전극 탭을 일일이 잭에 물려주어야 하는 번거로움이 없이 연속적으로 공정을 수행할 수 있어 생산효율도 향상될 수 있다.4B is an enlarged view of a portion A of the lithium secondary battery according to the present invention, that is, a battery tab inlet portion. As can be seen from FIG. 4B, the electrode tab inlet portion 33 is formed on the side surface of the case main body 31 so that the electrode tab 36 is bent and drawn at 90 ° to insert and fix the electrode tab. Therefore, the lithium secondary battery according to the present invention does not protrude outwardly perpendicularly to the battery case, which is not only good in appearance but also continuously performs the process without the hassle of having to pass the electrode tab to the jack during the chemical conversion process. The production efficiency can also be improved.
본 발명에 따른 리튬 2차전지에 있어서 케이스의 소재로 사용되는 고분자 수지는 성형성이 우수하여 목적하는 임의의 형태로의 성형이 가능하고 충격강도가 우수하여 외부의 충격으로부터 전지내부를 보호함으로써 전지의 단락으로 인한 발화나 폭발등을 예방할 수 있으며 화성 공정시 발생하는 가스에 의해 전지 표면이 부풀어오르는 현상이 없으므로 후속의 탈기 공정 및 재봉합 공정등을 실시할 필요가 없어 결과적으로 공정을 단축시킬 수 있다.In the lithium secondary battery according to the present invention, the polymer resin, which is used as the material of the case, has excellent moldability and can be molded into any desired shape and has excellent impact strength to protect the battery from external shocks. It is possible to prevent ignition or explosion due to short circuit, and there is no phenomenon that the surface of the battery is swelled by the gas generated during the chemical conversion process, so there is no need to perform the subsequent degassing and sewing process. have.
이하, 실시예를 들어 본 발명을 보다 상세하게 설명할 것이나, 본 발명이 이에 한정되지는 않는다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.
한편, 실시예에 의해 얻어지는 전지용 케이스의 난연성을 평가하기 위하여 다음과 같은 UL-94 테스트를 실시한다.On the other hand, in order to evaluate the flame retardancy of the battery case obtained by the embodiment, the following UL-94 test is carried out.
UL-94 테스트UL-94 test
먼저, 분젠버너를 이용하여 케이스 본체 또는 커버부재를 가열하여 발화가 지속되는 시간을 측정한다. 이어서, 케이스 본체의 아래에 12인치의 면섬유를 놓은 다음, 케이스 본체 또는 커버부재를 분젠버너로 가열하여 불이 붙어 떨어지는 케이스 본체 또는 커버부재들에 의해 면섬유가 발화하는지 여부를 관찰한다.First, by using a Bunsen burner to heat the case body or the cover member to measure the duration of the ignition. Subsequently, a 12-inch cotton fiber is placed under the case body, and then the case body or cover member is heated with a Bunsen burner to observe whether or not the cotton fiber is ignited by the case body or cover members which fall on fire.
상기 두가지 방법에 의해 테스트된 결과를 다음과 같은 등급에 따라 분류한다.The results tested by the two methods are classified according to the following grades.
<실시예><Example>
ABS 수지를 아세톤에 용해시키고, 여기에 비스-(트리브로모페녹시)에탄과 산화안티몬을 용해시켜 제조한 난연제 용액을 첨가하여 리튬 2차전지 케이스 형성용 조성물을 제조하였다.The ABS resin was dissolved in acetone, and a flame retardant solution prepared by dissolving bis- (tribromophenoxy) ethane and antimony oxide was added thereto to prepare a composition for forming a lithium secondary battery case.
이어서, 이 조성물을 통상의 방법에 따라서 성형한 다음 열처리하여 상면이 개방되어 있고 전극조립체를 수납할 수 있는 수납부가 구비된 케이스 본체 및 상기 케이스 본체의 상면을 덮어 케이스 본체를 밀폐하는 커버부재를 제조하였다.Subsequently, the composition is molded according to a conventional method, and then heat-treated to manufacture a case body having an upper surface open and an accommodating portion for accommodating the electrode assembly, and a cover member covering the upper surface of the case body to seal the case body. It was.
제조된 케이스 본체 또는 커버부재에 대하여 UL-94 테스트를 실시한 결과, UL-94-V0 등급인 것으로 판정되었다.A UL-94 test was conducted on the manufactured case body or cover member, and it was determined to be UL-94-V0 rating.
케이스 본체의 수납부에 양극, 음극 및 세퍼레이터가 적층, 조립되어 있으며 전극 탭이 외부로 돌출되어 있는 전극조립체를 넣은 다음, 커버부재를 덮고 초음파 융착등의 결합 수단에 의해 케이스 본체와 커버부재를 결합시킴으로써 리튬 2차전지를 제조하였다.A positive electrode, a negative electrode, and a separator are stacked and assembled in the housing of the case main body, and the electrode assembly with the electrode tab protruding is inserted into the housing. Then, the cover body is covered and the case main body and the cover member are joined by a coupling means such as ultrasonic welding. The lithium secondary battery was manufactured by doing this.
이렇게 제조된 리튬 2차전지는 에너지 밀도를 측정한 결과, 통상의 리튬 2차전지에 비하여 높은 에너지 밀도를 나타낸다. 보다 구체적으로 언급하자면, 알루미늄 외장재를 갖는 종래의 리튬 2차전지의 부피당 에너지 밀도가 약 282Wh/ℓ인데 반하여, 본 발명에 따른 플라스틱 외장재를 갖는 리튬 2차전지의 에너지 밀도는 최소한 300Wh/ℓ로 나타났다.As a result of measuring the energy density of the lithium secondary battery thus prepared, the lithium secondary battery exhibits a higher energy density than that of a conventional lithium secondary battery. More specifically, the energy density per volume of the conventional lithium secondary battery having an aluminum enclosure is about 282 Wh / L, whereas the energy density of the lithium secondary battery having a plastic enclosure according to the present invention was at least 300 Wh / L. .
본 발명에 따른 리튬 2차전지에 의하여 얻어질 수 있는 효과는 다음과 같다.Effects obtained by the lithium secondary battery according to the present invention are as follows.
첫째, 내충격성이 강하여 외부의 충격에 의한 전지의 단락등이 발생하지 않아 전지 안정성이 강화된다.First, since the impact resistance is strong, battery short circuit due to external impact does not occur, thereby enhancing battery stability.
둘째, 난연성이 우수하여 전지 내부에서 발화가 발생하더라도 케이스는 발화되지 않으므로 화재의 위험성이 없다.Second, even if ignition occurs inside the battery due to excellent flame retardancy, there is no risk of fire because the case does not ignite.
셋째, 데드볼륨을 없앰으로써 전지의 용량이 증가되며 전지의 단위 부피당 에너지 밀도 역시 현저하게 증가된다.Third, the capacity of the battery is increased by eliminating dead volumes, and the energy density per unit volume of the battery is also significantly increased.
넷째, 케이스의 측면에 전극 탭용 인입부를 형성하여 이 인입부로 전극 탭을 절곡시켜 인입, 고정시킴으로써 외관상 보기 좋고 안전할 뿐 아니라 화성 공정시 전극 탭을 일일이 잭에 물리지 않고 연속적으로 공정을 진행시킬 수 있기 때문에 생산성이 향상된다.Fourth, the inlet for electrode tab is formed on the side of the case and the electrode tab is bent into the inlet and fixed to the inlet to secure the appearance and safety, and the process can be continuously performed without biting the electrode tab in the chemical conversion process. This improves productivity.
다섯째, 본 발명에 따른 리튬 2차 전지는 화성 공정시 발생하는 가스에 의해 변형되는 일이 없으므로 가스제거공정 및 재봉합공정등의 후속 공정을 필요로 하지 않으므로 공정의 단축과 함께 단가 감소 효과를 얻을 수 있다.Fifth, since the lithium secondary battery according to the present invention does not need to be deformed by the gas generated during the chemical conversion process, it does not require a subsequent process such as a gas removal process and a sewing process, thereby reducing the process and reducing the cost. Can be.
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| KR1019990002399A KR100307450B1 (en) | 1999-01-26 | 1999-01-26 | Lithium Secondary Battery Employing Plastic Housing |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011078554A2 (en) * | 2009-12-21 | 2011-06-30 | 주식회사 이아이지 | Material for covering an electrochemical device, including a fire retardant material and heat-resistant material for improved safety, and electrochemical device including the covering material |
| US20130273405A1 (en) * | 2012-04-17 | 2013-10-17 | Semiconductor Energy Laboratory Co., Ltd. | Power storage device and method for manufacturing the same |
| KR101415588B1 (en) * | 2012-04-12 | 2014-07-15 | 에스케이이노베이션 주식회사 | PLASTIC Battery |
| KR101441530B1 (en) * | 2011-06-09 | 2014-09-17 | 주식회사 엘지화학 | Battery Cell of Novel Structure And Battery Pack Employed with the Same |
| KR101471666B1 (en) * | 2008-04-24 | 2014-12-10 | 주식회사 엘지화학 | Wrapping material for Secondary Batteries and Secondary Batteries comprising the same |
| US9240578B2 (en) | 2010-03-09 | 2016-01-19 | Samsung Sdi Co., Ltd. | Secondary battery |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130047151A (en) * | 2011-10-31 | 2013-05-08 | 에스케이이노베이션 주식회사 | Battery cell, manufacturing method thereof, and secondary battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1012280A (en) * | 1996-06-20 | 1998-01-16 | Sony Corp | Secondary battery |
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1999
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101471666B1 (en) * | 2008-04-24 | 2014-12-10 | 주식회사 엘지화학 | Wrapping material for Secondary Batteries and Secondary Batteries comprising the same |
| WO2011078554A2 (en) * | 2009-12-21 | 2011-06-30 | 주식회사 이아이지 | Material for covering an electrochemical device, including a fire retardant material and heat-resistant material for improved safety, and electrochemical device including the covering material |
| WO2011078554A3 (en) * | 2009-12-21 | 2011-11-17 | 주식회사 이아이지 | Material for covering an electrochemical device, including a fire retardant material and heat-resistant material for improved safety, and electrochemical device including the covering material |
| US9240578B2 (en) | 2010-03-09 | 2016-01-19 | Samsung Sdi Co., Ltd. | Secondary battery |
| KR101441530B1 (en) * | 2011-06-09 | 2014-09-17 | 주식회사 엘지화학 | Battery Cell of Novel Structure And Battery Pack Employed with the Same |
| KR101415588B1 (en) * | 2012-04-12 | 2014-07-15 | 에스케이이노베이션 주식회사 | PLASTIC Battery |
| US20130273405A1 (en) * | 2012-04-17 | 2013-10-17 | Semiconductor Energy Laboratory Co., Ltd. | Power storage device and method for manufacturing the same |
| US9735443B2 (en) * | 2012-04-17 | 2017-08-15 | Semiconductor Energy Laboratory Co., Ltd. | Power storage device and method for manufacturing the same |
| US10665888B2 (en) | 2012-04-17 | 2020-05-26 | Semiconductor Energy Laboratory Co., Ltd. | Power storage device and method for manufacturing the same |
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| Publication number | Publication date |
|---|---|
| KR100307450B1 (en) | 2001-09-26 |
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