JP2001229971A - Nonaqueous electrolyte secondary battery - Google Patents
Nonaqueous electrolyte secondary batteryInfo
- Publication number
- JP2001229971A JP2001229971A JP2000035136A JP2000035136A JP2001229971A JP 2001229971 A JP2001229971 A JP 2001229971A JP 2000035136 A JP2000035136 A JP 2000035136A JP 2000035136 A JP2000035136 A JP 2000035136A JP 2001229971 A JP2001229971 A JP 2001229971A
- Authority
- JP
- Japan
- Prior art keywords
- separator
- secondary battery
- electrolyte secondary
- aqueous electrolyte
- electrode body
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 51
- 238000004804 winding Methods 0.000 claims abstract description 8
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 6
- 239000000057 synthetic resin Substances 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 17
- 230000035699 permeability Effects 0.000 claims description 13
- 238000007373 indentation Methods 0.000 claims description 10
- 230000004888 barrier function Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000037303 wrinkles Effects 0.000 abstract description 8
- -1 for example Substances 0.000 description 28
- 239000000463 material Substances 0.000 description 24
- 239000000565 sealant Substances 0.000 description 21
- 239000004743 Polypropylene Substances 0.000 description 18
- 229920001155 polypropylene Polymers 0.000 description 18
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 239000004698 Polyethylene Substances 0.000 description 13
- 229920000573 polyethylene Polymers 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 239000012982 microporous membrane Substances 0.000 description 11
- 239000011149 active material Substances 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000007789 sealing Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- 229910000838 Al alloy Inorganic materials 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011245 gel electrolyte Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910019043 CoSn Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 102100031083 Uteroglobin Human genes 0.000 description 1
- 108090000203 Uteroglobin Proteins 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000002650 laminated plastic Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical class [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011331 needle coke Substances 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000006253 pitch coke Substances 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、非水電解液二次電
池に関し、特に薄型の非水電解液二次電池に係わる。The present invention relates to a non-aqueous electrolyte secondary battery, and more particularly to a thin non-aqueous electrolyte secondary battery.
【０００２】[0002]
【従来の技術】携帯電話やパーソナルコンピュータなど
電子機器の進歩に伴い、これら機器に使用される電池
は、小型化、軽量化、大容量化、高性能化、コストダウ
ンが絶えず求められてきた。このため、電池において
は、正極活物質や負極活物質など電極材料をよりエネル
ギー密度の高いものに変えたり、セパレータをより薄く
したり、電池の外装缶を鉄缶からアルミニウム缶に代え
たり、さらに外装缶内における電極体の占有率を高める
などの改善が図られてきた。2. Description of the Related Art With the progress of electronic devices such as mobile phones and personal computers, there has been a constant demand for batteries used in these devices to be smaller, lighter, larger in capacity, higher in performance and lower in cost. For this reason, in the battery, the electrode material such as the positive electrode active material and the negative electrode active material is changed to a material having a higher energy density, the separator is made thinner, the outer can of the battery is changed from an iron can to an aluminum can, and Improvements have been made such as increasing the occupancy of the electrode body in the outer can.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、前述し
た外装缶における電極体の占有率を高めると円筒形、菱
形または扁平形等の巻芯を用いて正極、セパレータおよ
び負極を渦巻状に捲回する際、正極、セパレータおよび
負極に歪が発生する。この歪は、前記巻芯を前記電極体
から抜き取った時に開放される。前記歪が開放される
と、前記電極体が撚れ、厚さが厚くなる。前記電極体の
中で、とりわけセパレータに歪が残りやすいために、こ
れが電極体に撚れが発生する原因になる。このようなこ
とから、捲回後の電極体を熱間または冷間でプレス成形
して厚さを薄くすることにより所定寸法の円筒形または
角型の電極体にすることが行われている。しかしなが
ら、このような電極体を外装缶または外装フィルムのよ
うな外装部材に収納した後の電解液の含浸や充放電にお
いて前記電極体は残留した歪を開放して元の形状に戻ろ
うとするため、厚さが厚くなって電子機器側から決定さ
れる厚さを満足することが困難になる。特に、軽量化の
ために外装部材としてアルミニウム缶や、中間にアルミ
ニウム箔のようなガスバリアフィルムを介在させたプラ
スチックのラミネートからなる外装フィルムを用いて前
記電極体を封止した場合には、電極体の変形に伴って前
記低弾性の外装部材が押し広がり易くなって厚さが厚く
なる恐れがある。本発明は、電極体の捲回時に皺が発生
し難いセパレータを用いることによって、外形厚さを薄
くすることが可能な非水電解液二次電池を提供しようと
するものである。However, when the occupation ratio of the electrode body in the above-mentioned outer can is increased, the positive electrode, the separator and the negative electrode are spirally wound using a cylindrical, rhombic or flat core. At this time, distortion occurs in the positive electrode, the separator, and the negative electrode. This distortion is released when the core is removed from the electrode body. When the strain is released, the electrode body is twisted and the thickness increases. Among the above-mentioned electrode bodies, distortion tends to remain particularly in the separator, which causes twisting of the electrode body. For this reason, the wound electrode body is press-formed hot or cold to reduce the thickness, thereby forming a cylindrical or square electrode body having a predetermined size. However, in the impregnation or charging / discharging of the electrolytic solution after such an electrode body is housed in an exterior member such as an exterior can or an exterior film, the electrode body attempts to release the remaining strain and return to the original shape. However, it becomes difficult to satisfy the thickness determined from the electronic device side. In particular, when the electrode body is sealed using an aluminum can or an exterior film made of a plastic laminate with a gas barrier film such as an aluminum foil interposed therebetween in order to reduce the weight, the electrode body is With the deformation, the low-elasticity exterior member may be easily pushed and spread, and the thickness may be increased. An object of the present invention is to provide a non-aqueous electrolyte secondary battery capable of reducing the outer thickness by using a separator that does not easily wrinkle when the electrode body is wound.
【０００４】[0004]
【課題を解決するための手段】本発明に係る非水電解液
二次電池は、帯状の正極と帯状の負極との間に合成樹脂
製の微多孔性膜からなる帯状のセパレータを介して渦巻
状に捲回してなる電極体を備え、前記セパレータは、長
さ方向の引張弾性率（Ｅl）に対する幅方向の引張弾性
率（Ｅw）の比（Ｅw／Ｅl）が０．８≦Ｅw／Ｅl≦５．
０であることを特徴とするものである。A non-aqueous electrolyte secondary battery according to the present invention is a spirally wound battery provided between a strip-shaped positive electrode and a strip-shaped negative electrode via a strip-shaped separator made of a synthetic resin microporous film. The separator has a ratio (E w / E l ) of the tensile modulus in the width direction (E w ) to the tensile modulus in the length direction (E l ) of 0.8. ≦ E w / E l ≦ 5.
It is characterized by being 0.
【０００５】本発明に係る非水電解液二次電池におい
て、前記セパレータは５〜３０μｍ、より好ましくは１
０〜２０μｍの厚さを有することが望ましい。本発明に
係る非水電解液二次電池において、前記セパレータは３
０〜６０％の気孔率を有することが好ましい。 本発明に係る非水電解液二次電池において、前記セパレ
ータは１００ｓｅｃ／１００ｃｃ〜６００ｓｅｃ／１０
０ｃｃの透気度を有することが好ましい。 本発明に係る非水電解液二次電池において、前記セパレ
ータは超微小押し込み試験機を用いて荷重５０ｍｇｆを
加えたときのヤング率（Ｙ）と硬さ（Ｈ）の比（Ｙ／
Ｈ）が９０≦Ｙ／Ｈ≦１５０であることが好ましい。 本発明に係る非水電解液二次電池において、前記電極体
として前記帯状の正極と前記帯状の負極との間に前記帯
状のセパレータを介して扁平形の巻芯に渦巻状に捲回し
てなる扁平状のものを用いることを許容する。 本発明に係る非水電解液二次電池において、前記電極体
は加熱成形されて例えばアルミニウム缶のような外装缶
に収納されることを許容する。 本発明に係る非水電解液二次電池において、前記電極体
は中間にバリアフィルムを介在した外装フィルム内に収
納され、封止されることを許容する。In the non-aqueous electrolyte secondary battery according to the present invention, the separator is 5 to 30 μm, more preferably 1 to 30 μm.
It is desirable to have a thickness of 0 to 20 μm. In the non-aqueous electrolyte secondary battery according to the present invention, the separator may be 3
It preferably has a porosity of 0 to 60%. In the non-aqueous electrolyte secondary battery according to the present invention, the separator may be 100 sec / 100 cc to 600 sec / 10.
It preferably has an air permeability of 0 cc. In the nonaqueous electrolyte secondary battery according to the present invention, the separator has a ratio (Y / Y) of Young's modulus (Y) and hardness (H) when a load of 50 mgf is applied using an ultra-fine indentation tester.
H) preferably satisfies 90 ≦ Y / H ≦ 150. In the nonaqueous electrolyte secondary battery according to the present invention, the electrode body is spirally wound around a flat core with the band-shaped separator interposed between the band-shaped positive electrode and the band-shaped negative electrode. The use of flat ones is allowed. In the nonaqueous electrolyte secondary battery according to the present invention, the electrode body is allowed to be formed by heating and housed in an outer can such as an aluminum can. In the nonaqueous electrolyte secondary battery according to the present invention, the electrode body is accommodated in an exterior film with a barrier film interposed therebetween, and is allowed to be sealed.
【０００６】[0006]
【発明の実施の形態】以下、本発明に係わる非水電解液
二次電池を外装部材として中間にガスバリアフィルムを
介在した外装フィルムを用いた薄型非水電解液二次電池
に適用した例を図１、図２を参照して詳細に説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an example in which a nonaqueous electrolyte secondary battery according to the present invention is applied to a thin nonaqueous electrolyte secondary battery using an exterior film with a gas barrier film interposed as an exterior member. 1, will be described in detail with reference to FIG.
【０００７】図１は、薄型非水電解液二次電池を示す斜
視図、図２は図１のII−II線に沿う断面図である。FIG. 1 is a perspective view showing a thin non-aqueous electrolyte secondary battery, and FIG. 2 is a sectional view taken along the line II-II in FIG.
【０００８】電極体１は、図１,図２に示すように例え
ば活物質および結着剤を含む正極活物質層２が集電体３
の両面に担持された正極４とセパレータ５と活物質およ
び結着剤を含む負極活物質層６が集電体７の両面に担持
された負極８とセパレータ５とを渦巻状に捲回し、さら
に成形した扁平で矩形状をなす。前記正負極４，８に接
続された外部リード端子９，１０は、それぞれ前記電極
体１の同一側面から外部に延出されている。As shown in FIGS. 1 and 2, the electrode body 1 is composed of a positive electrode active material layer 2 containing, for example, an active material and a binder.
The positive electrode 4 and the separator 5 supported on both sides of the current collector 7 and the negative electrode 8 supported on both sides of the current collector 7 and the negative electrode 8 and the separator 5 containing the active material and the binder are spirally wound. It is shaped flat and rectangular. External lead terminals 9 and 10 connected to the positive and negative electrodes 4 and 8, respectively, extend outside from the same side surface of the electrode body 1.
【０００９】前記電極体１は、図１に示すように例えば
２つ折りのカップ型外装フィルム１１のカップ１２内に
その折曲げ部が前記電極体１の前記外部リード端子９，
１０が延出された側面と反対側の側面側に位置するよう
に包み込まれている。この外装フィルム１１は、図２に
示すように内面側に位置するシーラントフィルム１３、
アルミニウムまたはアルミニウム合金の箔１４および剛
性を有する有機樹脂フィルム１５をこの順序で積層した
構造を有する。前記外装フィルム１１における前記折り
曲げ部を除く前記電極体１の２つの長側面および１つの
短側面に対応する３つの側部は、前記シーラントフィル
ム１３同士を熱シールして水平方向に延出したシール部
１６ａ,１６ｂ,１６ｃが形成され、これらのシール部１
６ａ,１６ｂ,１６ｃにより前記電極体１を封口してい
る。前記電極体１の正負極４，８に接続された外部端子
９，１０は、前記折り曲げ部と反対側のシール部１６ｂ
を通して外部に延出されている。前記電極体１内部およ
び前記シール部１６ａ,１６ｂ,１６ｃで封口された前記
外装フィルム１１内には、非水電解液が含浸・収容され
ている。As shown in FIG. 1, the electrode body 1 has, for example, a bent portion formed in a cup 12 of a two-fold cup-shaped exterior film 11 with the external lead terminals 9 of the electrode body 1.
10 is wrapped so as to be located on the side surface opposite to the extended side surface. As shown in FIG. 2, the exterior film 11 includes a sealant film 13 located on the inner side,
It has a structure in which an aluminum or aluminum alloy foil 14 and a rigid organic resin film 15 are laminated in this order. Three side portions corresponding to two long side surfaces and one short side surface of the electrode body 1 excluding the bent portion in the exterior film 11 are seals extending in the horizontal direction by heat sealing the sealant films 13 to each other. Parts 16a, 16b, 16c are formed, and these seal parts 1
The electrode body 1 is sealed by 6a, 16b and 16c. The external terminals 9 and 10 connected to the positive and negative electrodes 4 and 8 of the electrode body 1 are connected to a sealing portion 16b opposite to the bent portion.
Through to the outside. A non-aqueous electrolyte is impregnated and contained in the electrode body 1 and the exterior film 11 sealed by the seal portions 16a, 16b, 16c.
【００１０】次に、前記正極４、セパレータ５、負極
８、非水電解液、外部リード端子９，１０および外装フ
ィルム１１を説明する。Next, the positive electrode 4, the separator 5, the negative electrode 8, the non-aqueous electrolyte, the external lead terminals 9, 10 and the exterior film 11 will be described.
【００１１】前記正極４は、例えば集電体３の両面に活
物質および結着剤を含む正極活物質層２を担持した構造
を有する。なお、正極は集電体の片面に正極活物質層を
担持させた構造であってもよい。The positive electrode 4 has a structure in which, for example, a positive electrode active material layer 2 containing an active material and a binder is supported on both surfaces of a current collector 3. Note that the positive electrode may have a structure in which a positive electrode active material layer is supported on one surface of a current collector.
【００１２】前記集電体としては、例えばアルミニウ
ム、ニッケルまたはステンレスの板、アルミニウム、ニ
ッケルまたはステンレスのメッシュ等を挙げることがで
きる。Examples of the current collector include a plate made of aluminum, nickel, or stainless steel, and a mesh made of aluminum, nickel, or stainless steel.
【００１３】前記活物質としては、エネルギー密度の高
いリチウム複合酸化物が好ましい。具体的には、ＬｉＣ
ｏＯ2、ＬｉＮｉＯ2、ＬｉｘＮｉｙＣｏ1-yＯ2（ただ
し、ｘ、ｙは、電池の充電状態で異なり、通常は０＜ｘ
＜１、０．７＜ｙ＜１．０である。）、ＬｉxＣｏyＳｎ
zＯ2（ただし、ｘ、ｙ、ｚは各々０．０５≦ｘ≦１．１
０、０．８５≦ｙ≦１．００、０．００１≦ｚ≦０．１
０の数を表す。）が挙げられる。リチウム複合酸化物
は、リチウムの炭酸塩、硝酸塩、酸化物あるいは水酸化
物と、コバルト、マンガンあるいはニッケル等の炭酸
塩、硝酸塩、酸化物あるいは水酸化物とを所定の組成で
混合粉砕し、酸素雰囲気下で６００〜１０００℃の温度
で焼成することにより得ることができる。中でも、Ｌｉ
xＣｏyＳｎzＯ2（ただし、ｘ、ｙ、ｚは各々０．０５≦
ｘ≦１．１０、０．８５≦ｙ≦１．００、０．００１≦
ｚ≦０．１０の数を表す。）は、少量のＳｎの添加によ
りリチウム含有化合物の粒径が小さくて均一になるの
で、サイクル特性の優れた電池が得られる。０．００１
≦ｚ≦０．１０としたのは、ｚを０．００１未満にする
と、粒径を十分に制御することが困難になる。一方、ｚ
が０．１を超えると、容量が小さくなるためである。The active material is preferably a lithium composite oxide having a high energy density. Specifically, LiC
oO 2 , LiNiO 2 , Li x Ni y Co 1 -y O 2 (where x and y vary depending on the state of charge of the battery, and usually 0 <x
<1, 0.7 <y <1.0. ), Li x Co y Sn
z O 2 (where x, y and z are each 0.05 ≦ x ≦ 1.1
0, 0.85 ≦ y ≦ 1.00, 0.001 ≦ z ≦ 0.1
Represents the number 0. ). Lithium composite oxide is obtained by mixing and grinding lithium carbonate, nitrate, oxide or hydroxide and carbonate, nitrate, oxide or hydroxide such as cobalt, manganese or nickel with a predetermined composition, It can be obtained by firing at a temperature of 600 to 1000 ° C. in an atmosphere. Among them, Li
x Co y Sn z O 2 (provided that, x, y, z are each 0.05 ≦
x ≦ 1.10, 0.85 ≦ y ≦ 1.00, 0.001 ≦
represents the number z ≦ 0.10. In the case of ()), the addition of a small amount of Sn makes the particle size of the lithium-containing compound small and uniform, so that a battery having excellent cycle characteristics can be obtained. 0.001
The reason why ≦ z ≦ 0.10 is that when z is less than 0.001, it is difficult to sufficiently control the particle size. On the other hand, z
Is more than 0.1, the capacity is reduced.
【００１４】前記結着剤としては、例えばポリテトラフ
ルオロエチレン（ＰＴＦＥ）、ポリフッ化ビニリデン
（ＰＶＤＦ）、エチレン−プロピレン−ジエン共重合体
（ＥＰＤＭ）、スチレン−ブタジエンゴム（ＳＢＲ）等
を用いることができる。As the binder, for example, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), ethylene-propylene-diene copolymer (EPDM), styrene-butadiene rubber (SBR) and the like are used. it can.
【００１５】前記正極活物質層には、例えばアセチレン
ブラック、カーボンブラック、黒鉛等の導電剤を含有す
ることを許容する。The positive electrode active material layer is allowed to contain a conductive agent such as acetylene black, carbon black, and graphite.
【００１６】前記セパレータ５は、例えばポリエチレ
ン、ポリプロピレン、エチレン−プロピレン共重合体、
エチレン-ブテン共重合体からなる微多孔性膜より作ら
れ、長さ方向の引張弾性率（Ｅl）に対する幅方向の引
張弾性率（Ｅw）の比（Ｅw／Ｅl）が０．８≦Ｅw／Ｅl
≦５．０である。ここで、引張弾性率とは前記セパレー
タから荷重−変位曲線を描き、この曲線における比較的
直線性が認められる２％のひずみに対応する荷重をセパ
レータの断面積で割った値（Ｐａ）を意味する。The separator 5 is made of, for example, polyethylene, polypropylene, ethylene-propylene copolymer,
Ethylene - made from butene copolymer comprising a polymer microporous membrane, the ratio of the tensile modulus in the longitudinal direction the width direction of the tensile modulus for the (E l) (E w) (E w / E l) is 0. 8 ≦ E w / E l
≦ 5.0. Here, the tensile elastic modulus means a value (Pa) obtained by drawing a load-displacement curve from the separator and dividing a load corresponding to a strain of 2% in which relatively linearity is recognized by the cross-sectional area of the separator. I do.
【００１７】このような特性のセパレータを用いること
により、正極、セパレータ、負極を巻芯に張力を加えて
一体的に捲回する際に、セパレータが幅方向に縮むのを
防ぐことができる。また、巻芯から電極体を抜いた際
に、セパレータが長さ方向に縮むことが少なくなり、セ
パレータに残留する歪が小さくなる。このため、巻き上
がった電極体の厚さが厚くなるのを防ぐことができる。
さらに、前記電極体を収納した非水電解液二次電池にお
いて充電・放電に伴って活物質が膨脹・収縮することに
より、捲回時に残留したセパレータの歪が開放されても
厚さが厚くなるのを抑制することができる。By using a separator having such characteristics, it is possible to prevent the separator from shrinking in the width direction when the positive electrode, the separator, and the negative electrode are wound integrally by applying tension to the core. Further, when the electrode body is removed from the core, the separator is less likely to shrink in the length direction, and the distortion remaining in the separator is reduced. For this reason, it is possible to prevent the thickness of the wound electrode body from increasing.
Further, in the non-aqueous electrolyte secondary battery containing the electrode body, the active material expands and contracts with charging and discharging, so that the thickness increases even if the distortion of the separator remaining during winding is released. Can be suppressed.
【００１８】前記セパレータは、厚さが薄い方が電池の
厚さを薄くできる。このため、セパレータは３０μｍ以
下、より好ましくは２０μｍ以下にすることが望まし
い。しかし、セパレータの厚さを薄くしすぎると正負極
間の短絡が発生するため、その厚さを５μｍ以上、より
好ましくは１０μｍ以上にすることが望ましい。 前記セパレータは、電解液の含浸性、保持性を良好に
し、電極体内に適切な量のリチウムイオンを供給できる
電解液を確保する観点から、その気孔率を３０〜６０
％、透気度（ＡＳＴＭＤ７２６に準じて求めた透気度）
を１００ｓｅｃ／１００ｃｃ〜６００ｓｅｃ／１００ｃ
ｃにすることが好ましい。セパレータの気孔率を３０％
未満、透気度を１００ｓｅｃ／１００ｃｃ未満にする
と、電解液の含浸性・保持性が低下して、二次電池の容
量が低くなったり、サイクル性が低下するおそれがあ
る。一方、セパレータの気孔率が６０％を超えたり、透
気度が６００ｓｅｃ／１００ｃｃを超えると、正負極間
の短絡が発生し易くなるおそれがある。 前記セパレータは超微小押し込み試験機(株式会社エリ
オニクス社製商品名；ＥＮＴ−１００)を用いて荷重を
加えたときのヤング率（Ｙ）と硬さ（Ｈ）の比（Ｙ／
Ｈ）が９０≦Ｙ／Ｈ≦１５０であることが好ましい。こ
こで、測定に使用した圧子は三角錐(稜間隔１１５°)、
試験荷重５０ｍｇｆ、２５０ステップに分割し、１ステ
ップ当たり４０ｍｓｅｃ、試験保持時間１ｓｅｃで試験
を行った。ヤング率（Ｙ）と硬さ（Ｈ）は図３に模式的
に示す変位−荷重曲線の傾きから求める。The thinner the separator, the thinner the battery can be. For this reason, it is desirable that the separator has a thickness of 30 μm or less, more preferably 20 μm or less. However, if the thickness of the separator is too small, a short circuit occurs between the positive electrode and the negative electrode. Therefore, it is desirable that the thickness be 5 μm or more, more preferably 10 μm or more. The separator has a porosity of 30 to 60 from the viewpoint of improving the impregnation property and the retention property of the electrolytic solution and securing an electrolytic solution capable of supplying an appropriate amount of lithium ions into the electrode body.
%, Air permeability (air permeability determined according to ASTM D726)
100 sec / 100 cc to 600 sec / 100 c
It is preferably set to c. 30% porosity of the separator
If the air permeability is less than 100 sec / 100 cc, the impregnation and retention of the electrolyte may be reduced, and the capacity of the secondary battery may be reduced, or the cycleability may be reduced. On the other hand, if the porosity of the separator exceeds 60% or the air permeability exceeds 600 sec / 100 cc, a short circuit between the positive and negative electrodes may easily occur. The separator has a ratio of Young's modulus (Y) to hardness (H) (Y /
H) preferably satisfies 90 ≦ Y / H ≦ 150. Here, the indenter used for the measurement is a triangular pyramid (edge interval 115 °),
The test load was 50 mgf, the test was divided into 250 steps, and the test was performed with a test holding time of 1 msec per step of 40 msec. The Young's modulus (Y) and hardness (H) are determined from the slope of the displacement-load curve schematically shown in FIG.
【００１９】硬さＨは、圧子をセパレータに押込んだと
きのめり込み難さを表わす指標で、高いほど、めり込み
難いことを意味する。また、ヤング率（Ｙ）はめり込ん
だ後の戻り易さを表わす指標であり、高いほど戻り易い
ことを意味する。The hardness H is an index indicating the degree of indentation when the indenter is pushed into the separator. The higher the hardness, the more difficult it is to indent. Further, the Young's modulus (Y) is an index indicating the ease of return after the indentation, and the higher the value, the easier the return.
【００２０】前記セパレータのヤング率（Ｙ）と硬さ
（Ｈ）の比（Ｙ／Ｈ）を９０未満にすると、セパレータ
が捲回時に正極や負極と馴染みにくく、突っ張るために
歪が残留し易くなるおそれがある。一方、Ｙ／Ｈが１５
０を超えると捲回時にセパレータが伸び過ぎたり、押さ
れて孔が塞がり、伝導性が低下するおそれがある。When the ratio (Y / H) of the Young's modulus (Y) to the hardness (H) of the separator is less than 90, the separator is hardly adapted to the positive electrode and the negative electrode at the time of winding, and the strain tends to remain because it is stretched. Could be. On the other hand, when Y / H is 15
If it exceeds 0, the separator may be excessively stretched during winding or may be pushed to close the hole, resulting in a decrease in conductivity.
【００２１】前記微多孔性膜の作り方は、湿式法と乾式
法とに大別される。The method of forming the microporous membrane is roughly classified into a wet method and a dry method.
【００２２】前記乾式法は、ポリエチレン（ＰＥ）また
はポリプロピレン（ＰＰ）の樹脂を融解しフィルム状に
押出し、このフィルムをアニーリングにより結晶部と非
晶部が混在した状態にした後、延伸して多数の微細孔を
開ける方法である。In the dry method, a resin of polyethylene (PE) or polypropylene (PP) is melted and extruded into a film, and this film is annealed so that a crystalline portion and an amorphous portion are mixed, and then stretched to form a film. This is a method of forming micro holes.
【００２３】前記湿式法は、ポリエチレン（ＰＥ）また
はポリプロピレン（ＰＰ）の樹脂を炭化水素溶媒および
フィラーと混合し、加熱溶融し、シート状に加工した
後、溶媒およびフィラーを揮発性溶媒で抽出し、延伸を
行うか、または前記シートを延伸した後、溶媒およびフ
ィラーを揮発性溶媒で抽出するか、いずれかにより微多
孔性膜を得る方法である。In the wet method, a resin of polyethylene (PE) or polypropylene (PP) is mixed with a hydrocarbon solvent and a filler, heated and melted, processed into a sheet, and the solvent and the filler are extracted with a volatile solvent. Or stretching the sheet, or extracting the solvent and filler with a volatile solvent after stretching the sheet, to obtain a microporous membrane.
【００２４】前記乾式法で採用される押出し法として
は、Ｔ−ダイフィルム成形法やインフレーション成形法
が適用できる。前者は一軸配向であるため、成形後の後
処理でフィルムを面配向させなければならないが、後者
は膨比を適当に選ぶことによりフィルムを面配向させる
ことができる。As the extrusion method employed in the dry method, a T-die film molding method and an inflation molding method can be applied. Since the former is uniaxially oriented, the film must be plane-oriented by post-processing after molding, but the latter can be plane-oriented by appropriately selecting the expansion ratio.
【００２５】前記湿式法で採用される延伸法としては、
幅方向の収縮を最小限に抑えた一軸延伸、テンタークリ
ップで幅方向の収縮を抑えた一軸延伸や、テンタークリ
ップ方式による逐次もしくは同時二軸延伸、または一段
目を一対のロールで延伸し、つづいてテンタークリップ
で幅方向に延伸する連続逐次二軸延伸、あるいは連続テ
ンタークリップ方式の連続同時二軸延伸が適用できる。The stretching method used in the wet method includes:
Uniaxial stretching to minimize shrinkage in the width direction, uniaxial stretching to suppress shrinkage in the width direction with a tenter clip, sequential or simultaneous biaxial stretching by a tenter clip method, or stretching the first stage with a pair of rolls and continuing Continuous biaxial stretching in which the film is stretched in the width direction with a tenter clip, or continuous simultaneous biaxial stretching using a continuous tenter clip method.
【００２６】なお、延伸後の微多孔性膜はその皺の除
去、熱収縮の低減化などのために、微多孔性膜の直交す
る方向に固定した状態でヒートセットを行ってもよい。The stretched microporous membrane may be heat-set while being fixed in a direction orthogonal to the microporous membrane in order to remove wrinkles and reduce thermal shrinkage.
【００２７】前述した原材料、押出し成形法、延伸法な
どの原料・製造条件を適切に組み合せることにより、膜
厚、気孔率、透気度、突刺強度、引張り強さ、引張り弾
性率、伸び、熱収縮率、閉塞温度、融点、極大細孔径、
融点など、最適な特性を有するセパレータを得ることが
可能になる。By properly combining the raw materials and the production conditions such as the extrusion molding method and the stretching method described above, the film thickness, porosity, air permeability, piercing strength, tensile strength, tensile elastic modulus, elongation, Heat shrinkage, closing temperature, melting point, maximum pore size,
It is possible to obtain a separator having optimum characteristics such as a melting point.
【００２８】前記負極８は、集電体７の両面に活物質お
よび結着剤を含む負極活物質層６を担持した構造を有す
る。なお、負極は集電体の片面に負極活物質層を担持さ
せた構造であってもよい。The negative electrode 8 has a structure in which a negative electrode active material layer 6 containing an active material and a binder is supported on both surfaces of a current collector 7. Note that the negative electrode may have a structure in which a negative electrode active material layer is supported on one surface of a current collector.
【００２９】前記集電体としては、例えば銅、ニッケル
の板またはメッシュ等を挙げることができる。Examples of the current collector include a copper or nickel plate or mesh.
【００３０】前記活物質は、リチウムをドープ・脱ドー
プできるものであればよく、例えばグラファイト類、コ
ークス類（石油コークス、ピッチコークス、ニードルコ
ークス等）、熱分解炭素類、有機高分子化合物の焼成体
（フェノール樹脂等を適切な温度で焼成し、炭化したも
の）あるいは金属リチウム、ポリアセチレン、ポリピロ
ール等があげられる。The active material may be any material capable of doping and undoping lithium, such as graphites, cokes (petroleum coke, pitch coke, needle coke, etc.), pyrolytic carbons, and calcination of organic polymer compounds. (A phenol resin or the like fired at an appropriate temperature and carbonized) or lithium metal, polyacetylene, polypyrrole, or the like.
【００３１】前記結着剤としては、例えばポリテトラフ
ルオロエチレン、ポリビニリデンフルオロライド、エチ
レン−プロピレン−ジエン共重合体、スチレン−ブタジ
エンゴム、カルボキシメチルセルロース等の結着剤を含
有することが好ましい。The binder preferably contains, for example, a binder such as polytetrafluoroethylene, polyvinylidene fluoride, ethylene-propylene-diene copolymer, styrene-butadiene rubber, and carboxymethyl cellulose.
【００３２】前記非水電解液は、電解質を非水溶媒で溶
解した組成を有する。The non-aqueous electrolyte has a composition in which an electrolyte is dissolved in a non-aqueous solvent.
【００３３】電解質としては、例えば過塩素酸リチウム
（ＬｉＣｌＯ4）、四フッ化硼酸リチウム（ＬｉＢ
Ｆ4）、六フッ化燐酸リチウム（ＬｉＰＦ6）、六フッ化
砒素酸リチウム（ＬｉＡｓＦ6）、トリフルオロメタン
スルホン酸リチウム（ＬｉＣＦ3ＳＯ3）、ＬｉＮ（ＣＦ
3ＳＯ2）2、リチウムビス［５−フルオロ−２オラト−
１−ベンゼン−スルホナト（２−）］ボレート等を用い
ることができる。As the electrolyte, for example, lithium perchlorate (LiClO 4 ), lithium tetrafluoroborate (LiB
F 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), LiN (CF
3 SO 2 ) 2 , lithium bis [5-fluoro-2-orato-
1-benzene-sulfonato (2-)] borate and the like can be used.
【００３４】非水溶媒としては、例えばγ−ブチロラク
トン、エチレンカーボネート、プロピレンカーボネー
ト、ジエチルカーボネート、メチルエチルカーボネー
ト、１，２−ジメトキシエタン、１，２−ジエトキシエ
タン、テトラヒドロフラン、１，３−ジオキソラン、メ
チルスルホラン、アセトニトリル、プロピルニトリル、
アニソール、酢酸エステル、プロピオン酸エステル等を
用いることができ、２種類以上混合して使用してもよ
い。Examples of the non-aqueous solvent include γ-butyrolactone, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl ethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 1,3-dioxolan, Methylsulfolane, acetonitrile, propylnitrile,
Anisole, acetate, propionate and the like can be used, and two or more kinds may be used in combination.
【００３５】前記非水溶媒中の前記電解質の濃度は、
０．５モル／Ｌ以上にすることが好ましい。The concentration of the electrolyte in the non-aqueous solvent is as follows:
It is preferable to set it to 0.5 mol / L or more.
【００３６】前記電解液の他に、電解液を含浸させた高
分子ゲル電解質、または溶媒を含まない全固体型高分子
固体電解質でもよい。In addition to the above-mentioned electrolyte, a polymer gel electrolyte impregnated with the electrolyte or an all-solid polymer solid electrolyte containing no solvent may be used.
【００３７】前記高分子ゲル電解質として用いる高分子
としては特に限定するものではないが、ポリアクリルニ
トリル系樹脂、ポリエチレンオキサイド系樹脂、ポリエ
ーテル系樹脂、ポリエステル系樹脂、ポリアクリレート
系樹脂、フッ素系樹脂等があげられる。The polymer used as the polymer gel electrolyte is not particularly limited, but includes polyacrylonitrile resin, polyethylene oxide resin, polyether resin, polyester resin, polyacrylate resin, and fluorine resin. And the like.
【００３８】前記外部リード端子の材料は、正極がアル
ミニウム、負極がニッケル、銅などが挙げられる。The material of the external lead terminals includes aluminum for the positive electrode, nickel and copper for the negative electrode.
【００３９】前記外装フィルム１１のシーラントフィル
ムは、シーラントフィルム同士や、シーラントフィルム
と外部リード端子間、シーラントフィルムと後述する接
着性絶縁フィルムとを熱圧着することにより電極体を封
止するものである。このシーラントフィルムは、電解液
に溶解したり、膨潤したりしない無延伸のフィルムが好
ましい。例えば、延伸していないポリプロピレン（Ｐ
Ｐ）等のポリオレフィン系ポリマー、エチレン・酢酸ビ
ニル（ＥＶＡ）共重合体、アイオノマー（ＩＯ）、ポリ
アミド（ＰＡ）、ナイロン（Ｎｙ）、ポリエチレンテレ
フタレート（ＰＥＴ）、ポリブチレンテレフタレート
（ＰＢＴ）、ポリ塩化ビニル（ＰＶＣ）、ポリ塩化ビニ
リデン（ＰＶＤＣ）、ポリビニルアルコール（ＰＶ
Ａ）、エチレン・ビニルアルコール（ＥＶＯＨ）、ポリ
カーボネート（ＰＣ）、ポリスチレン（ＰＳ）、ポリア
クリロニトリル（ＰＡＮ）、エチレン・アクリル酸共重
合体（ＥＡＡ）、エチレン・メタクリル酸共重合体（Ｅ
ＭＭＡ）、エチレン・メチルアクリレート共重合体（Ｅ
ＭＡ）、エチレン・メチルメタクリレート共重合体（Ｅ
ＭＭＡ）、エチレン・エチルアクリレート共重合体（Ｅ
ＥＡ）、ポリメチルペンテン（ＰＭＰ）等からなる樹脂
フィルムを用いることができる。特に、金属との接着性
を増すために、これら樹脂をベースポリマーにして、例
えば無水マレイン酸等酸無水物をグラフト重合させたも
のが好ましい。The sealant film of the exterior film 11 seals the electrode body by thermocompression bonding between sealant films, between sealant films and external lead terminals, and between a sealant film and an adhesive insulating film described later. . The sealant film is preferably a non-stretched film that does not dissolve or swell in the electrolytic solution. For example, unstretched polypropylene (P
P) and other polyolefin-based polymers, ethylene / vinyl acetate (EVA) copolymer, ionomer (IO), polyamide (PA), nylon (Ny), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinyl alcohol (PV
A), ethylene-vinyl alcohol (EVOH), polycarbonate (PC), polystyrene (PS), polyacrylonitrile (PAN), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (E
MMA), ethylene / methyl acrylate copolymer (E
MA), ethylene / methyl methacrylate copolymer (E
MMA), ethylene / ethyl acrylate copolymer (E
EA), a resin film made of polymethylpentene (PMP) or the like can be used. In particular, in order to increase the adhesiveness to a metal, it is preferable to use one of these resins as a base polymer and graft-polymerize an acid anhydride such as maleic anhydride.
【００４０】前記シーラントフィルムは、電池を小型、
軽量化する観点から、できるだけ厚さを薄くすることが
望ましいが、正負極の外部リード端子回りに十分シーラ
ント樹脂を回り込ませるために、十分な厚さを確保する
必要がある。このため、シーラントフィルムの厚さは、
後述する接着性絶縁フィルムを使用しない場合は、正負
極の外部リード端子の厚さをＤとすると、Ｄ／２〜Ｄに
することが好ましい。また、後述する接着性絶縁フィル
ムを用いる場合、シーラントフィルムの厚さは、正負極
の外部リード端子の厚さをＤとすると、Ｄ／７〜Ｄにす
ることが好ましい。The above-mentioned sealant film makes the battery small,
From the viewpoint of weight reduction, it is desirable to reduce the thickness as much as possible. However, it is necessary to secure a sufficient thickness so that the sealant resin can sufficiently flow around the external lead terminals of the positive and negative electrodes. For this reason, the thickness of the sealant film is
When the adhesive insulating film described below is not used, it is preferable that the thickness of the external lead terminals of the positive and negative electrodes be D / 2 to D / 2. When an adhesive insulating film described later is used, the thickness of the sealant film is preferably D / 7 to D, where D is the thickness of the external lead terminals of the positive and negative electrodes.
【００４１】前記アルミニウムまたはアルミニウム合金
の箔は、電解液やガスの透過を防ぐバリアとして作用を
なす。The aluminum or aluminum alloy foil functions as a barrier for preventing the permeation of the electrolyte or gas.
【００４２】前記外装フィルムの剛性を有する有機樹脂
フィルムは、前記アルミニウムまたはアルミニウム合金
の箔を保護し、かつ電池の機械的構造特性を維持する機
能を持つ。この有機樹脂フィルムとしては、例えばポリ
マーを配向させるために二軸延伸したポリエチレン（Ｐ
Ｅ）やポリプロピレン（ＰＰ）等のポリオレフィン系ポ
リマー、ポリエチレンテレフタレート（ＰＥＴ）、ポリ
アミド（ＰＡ）、およびこれらのポリ塩化ビニリデン
（ＰＶＤＣ）コートフィルムが使用できる。The organic resin film having the rigidity of the exterior film has a function of protecting the aluminum or aluminum alloy foil and maintaining the mechanical structural characteristics of the battery. As this organic resin film, for example, biaxially stretched polyethylene (P
E), polyolefin polymers such as polypropylene (PP), polyethylene terephthalate (PET), polyamide (PA), and polyvinylidene chloride (PVDC) coated films thereof.
【００４３】本発明に係る電池において、図４に示すよ
うに前記正負極の外部リード端子９，１０と前記外装フ
ィルム１１のシーラントフィルム１３との間に接着性絶
縁フィルム１７を介在させることを許容する。In the battery according to the present invention, as shown in FIG. 4, an adhesive insulating film 17 is allowed to be interposed between the positive and negative external lead terminals 9 and 10 and the sealant film 13 of the exterior film 11. I do.
【００４４】前記接着性絶縁フィルムとしては、シーラ
ントと同等の特性、成形性を備えつつ、外部リード端子
の金属と外装フィルムのシーラントフィルムとの接着性
が良好な融点が１１５〜１７５℃の有機ポリマーを用い
ればよい。具体的には、ポリエチレンやポリプロピレン
等のポリオレフィン樹脂に酸無水物を数％付加したもの
が好ましく、特にポリプロピレンに無水マレイン酸を数
％グラフト化することによって得られるフィルム（以下
マレイン化ＰＰフィルムという）が好ましい。As the adhesive insulating film, an organic polymer having a melting point of 115 to 175 ° C., which has good adhesiveness between the metal of the external lead terminal and the sealant film of the exterior film while having the same properties and moldability as the sealant. May be used. Specifically, a resin obtained by adding a few percent of an acid anhydride to a polyolefin resin such as polyethylene or polypropylene is preferable. In particular, a film obtained by grafting a few percent of maleic anhydride to polypropylene (hereinafter referred to as a maleated PP film) Is preferred.
【００４５】前記接着性絶縁フィルムとシーラントフィ
ルムは、異なっていてもよいが、同一系統のもの、さら
には全く同一材料のものを用いると、正負極の外部リー
ド端子回りが均質で信頼性の高い封止構造を実現でき
る。The adhesive insulating film and the sealant film may be different from each other. However, if the same type or the same material is used, the periphery of the external lead terminals of the positive and negative electrodes is uniform and highly reliable. A sealing structure can be realized.
【００４６】次に、前述した薄型非水電解液二次電池の
製造方法を説明する。Next, a method of manufacturing the above-mentioned thin non-aqueous electrolyte secondary battery will be described.
【００４７】まず、活物質および結着剤を含む正極活物
質層が例えば集電体両面に担持された正極、セパレー
タ、活物質および結着剤を含む負極活物質層が例えば集
電体両面に担持された負極およびセパレータを渦巻状に
捲回してほぼ円筒状の電極体を作製する。なお、この捲
回時に正負極に外部リード端子を例えば溶接により接続
する。First, a positive electrode in which a positive electrode active material layer containing an active material and a binder is carried on, for example, both surfaces of a current collector, and a negative electrode active material layer containing an active material and a binder are provided on, for example, both surfaces of the current collector. The supported negative electrode and separator are spirally wound to produce a substantially cylindrical electrode body. At the time of this winding, external lead terminals are connected to the positive and negative electrodes by, for example, welding.
【００４８】次いで、得られた円筒状の電極体を成形し
て扁平状にする。つづいて、前記電極体の長辺より僅か
に長く、かつその短辺の例えば２倍の長さの寸法を有す
る二つ折りのカップ型外装フィルム素材を用意し、図５
に示すようにこの外装フィルム素材１８のカップ１２内
に前記扁平状の電極体１をその外部リード端子９，１０
と反対側の側面が前記素材の折り曲げ部に位置するよう
に収納する。この時、必要に応じて前記外装フィルム素
材と前記外部リード端子との接触部分に接着性絶縁フィ
ルムとを介在させてもよい。ひきつづき、前記電極体１
の長辺に対応する前記素材１８の左端部および前記外部
リード端子９，１０の延出側に対応する前記素材１８の
端部を熱シールしてシール部を形成する。その後、非水
電解液を前記外装フィルム素材の未シール部を通して注
液し、未シール部を熱シールし、余分な外装フィルム素
材を裁断除去することにより前述した図１に示す薄型非
水電解液二次電池を製造する。Next, the obtained cylindrical electrode body is formed into a flat shape. Subsequently, a two-fold cup-shaped exterior film material having a dimension slightly longer than the long side of the electrode body and twice as long as the short side is prepared, and FIG.
As shown in FIG. 3, the flat electrode body 1 is placed in the cup 12 of the exterior film material 18 by the external lead terminals 9 and 10.
The material is stored such that the side opposite to the above is located at the bent portion of the material. At this time, if necessary, an adhesive insulating film may be interposed at a contact portion between the exterior film material and the external lead terminal. The electrode body 1 is continued.
The left end of the material 18 corresponding to the long side and the end of the material 18 corresponding to the extension side of the external lead terminals 9 and 10 are heat-sealed to form a seal portion. Thereafter, a non-aqueous electrolyte is injected through the unsealed portion of the exterior film material, the unsealed portion is heat-sealed, and the excess exterior film material is cut and removed. Manufacture secondary batteries.
【００４９】前記外装フィルム素材の熱シールは、１８
０℃〜２４０℃で行うことにより、外装フィルム素材の
ナイロンのような外側フィルムが熱シール時に用いるプ
レスヘッドに溶着することなく、外部リード端子とシー
ラントフィルムおよびシーラントフィルム同士の接着を
完全に行え、電解液の染み出しのない十分な封止ができ
る。熱シール温度を１８０℃未満にすると、シーラント
フィルムや接着性絶縁フィルムが十分溶融せず、十分な
熱シールを行なうことが困難になる。一方、熱シール温
度が２４０℃を超えるとシーラントフィルムや接着性絶
縁フィルムの流れが大きくなりすぎ、外装フィルムがプ
レスヘッドに溶着したり、また外装フィルムの樹脂系フ
ィルムの溶融が生じる恐れがある。The heat sealing of the exterior film material is 18
By performing at 0 ° C. to 240 ° C., the outer lead terminal and the sealant film and the sealant film can be completely adhered to each other without the outer film such as nylon of the exterior film material being welded to the press head used at the time of heat sealing. Sufficient sealing without exudation of the electrolyte can be achieved. When the heat sealing temperature is lower than 180 ° C., the sealant film and the adhesive insulating film are not sufficiently melted, and it is difficult to perform sufficient heat sealing. On the other hand, when the heat sealing temperature exceeds 240 ° C., the flow of the sealant film or the adhesive insulating film becomes too large, and the exterior film may be welded to the press head or the resin film of the exterior film may be melted.
【００５０】なお、前述した図１および図２に示す薄型
非水電解液二次電池は正極、セパレータおよび負極を捲
回し、成形により扁平状にした電極体を用いたが、正
極、セパレータおよび負極を積層した構造の電極体を用
いてもよい。The thin non-aqueous electrolyte secondary battery shown in FIGS. 1 and 2 uses a positive electrode, a separator and a negative electrode which are wound and formed into a flat electrode body. May be used.
【００５１】また、前記外装フィルムは、カップ型に限
らず、パウチ、ピロー構造のものを用いてもよい。The exterior film is not limited to the cup type, but may be a pouch or pillow structure.
【００５２】次に、本発明に係わる非水電解液二次電池
を外装部材として角型外装缶を用いた角型非水電解液二
次電池に適用した例を図６を参照して詳細に説明する。
ここで、角型とは外装缶を発電要素を含む面で切断した
ときの形状が長方形であることを意味するが、コーナ部
においてアールが付けられることを許容するものであ
る。Next, an example in which the nonaqueous electrolyte secondary battery according to the present invention is applied to a square nonaqueous electrolyte secondary battery using a square outer can as an outer member will be described in detail with reference to FIG. explain.
Here, the square shape means that the shape when the outer can is cut at the surface including the power generation element is a rectangle, but allows the corner to be rounded.
【００５３】図６は、角型非水電解液二次電池を示す斜
視図である。FIG. 6 is a perspective view showing a prismatic nonaqueous electrolyte secondary battery.
【００５４】角型の電池ケース２１は、例えばアルミニ
ウム系金属からなる有底矩形筒状をなす外装缶２２の開
口部にアルミニウム系金属からなる蓋体２３を例えばレ
ーザ溶接により気密に接合した構造を有する。前記外装
缶２２は、例えば正極端子を兼ね、底部内面に絶縁フィ
ルム２４が配置されている。The rectangular battery case 21 has a structure in which a lid 23 made of an aluminum-based metal is air-tightly joined to an opening of an outer can 22 having a bottomed rectangular cylindrical shape made of, for example, an aluminum-based metal by, for example, laser welding. Have. The outer can 22 also serves as a positive electrode terminal, for example, and has an insulating film 24 disposed on the inner surface of the bottom.
【００５５】電極体２５は、前記電池ケース２１の外装
缶２２内に収納されている。前記電極体２５は、例えば
負極２６とセパレータ２７と正極２８とを前記正極２８
が最外周に位置するように渦巻状に捲回した後、扁平状
にプレス成形することにより作製される。中心付近にリ
ード取出穴を有する例えば合成樹脂からなるスペーサ２
９は、前記外装缶２２内の前記電極体２５上に配置され
ている。The electrode body 25 is housed in the outer case 22 of the battery case 21. The electrode body 25 includes, for example, a negative electrode 26, a separator 27, and a positive electrode 28.
Is spirally wound so as to be located at the outermost periphery, and then press-formed into a flat shape. Spacer 2 made of, for example, synthetic resin having a lead extraction hole near the center
9 is arranged on the electrode body 25 in the outer can 22.
【００５６】前記蓋体２３の中心付近には、負極端子の
取出し穴３０が開口されている。注入孔３１は、前記取
出し穴３０から離れた前記蓋体２３の箇所に開口されて
いる。電解液は、前記注入孔３１を通して前記外装缶２
２内に注入されている。負極端子３２は、前記蓋体２３
の穴３０にガラス製または樹脂製の絶縁材３３を介して
ハーメティクシールされている。前記負極端子３２の下
端面には、リード３４が接続され、かつこのリード３４
の他端は前記電極体２５の負極２６に接続されている。In the vicinity of the center of the lid 23, an extraction hole 30 for a negative electrode terminal is opened. The injection hole 31 is opened at a position of the lid 23 away from the extraction hole 30. The electrolytic solution is supplied to the outer can 2 through the injection hole 31.
2 has been injected. The negative electrode terminal 32 is connected to the lid 23.
Is hermetically sealed via an insulating material 33 made of glass or resin. A lead 34 is connected to the lower end surface of the negative electrode terminal 32, and the lead 34
Is connected to the negative electrode 26 of the electrode body 25.
【００５７】上部側絶縁紙３７は、前記蓋体２３の外表
面全体に被覆されている。スリット３８を有する下部側
絶縁紙３９は、前記外装缶２２の底面に配置されてい
る。二つ折りされたＰＴＣ（Positive Thermal Coeff
icient）素子４０は、一方の面が前記外装缶２２の底面
と前記下部側絶縁紙３９の間に介装され、かつ他方の面
が前記スリット３８を通して前記絶縁紙３９の外側に延
出されている。外装チューブ４１は、前記外装缶２２側
面から上下面の絶縁紙３７、３９の周辺まで延出するよ
うに配置され、前記上部側絶縁紙３７および下部側絶縁
紙３９を前記外装缶２に固定している。このような外装
チューブ２１の配置により、外部に延出された前記ＰＴ
Ｃ素子４０の他方の面が前記下部側絶縁紙３９の底面に
向けて折り曲げられる。The upper insulating paper 37 covers the entire outer surface of the lid 23. The lower insulating paper 39 having the slit 38 is disposed on the bottom surface of the outer can 22. PTC (Positive Thermal Coeff)
The element 40 has one surface interposed between the bottom surface of the outer can 22 and the lower insulating paper 39, and the other surface extending outside the insulating paper 39 through the slit 38. I have. The outer tube 41 is disposed so as to extend from the side of the outer can 22 to the periphery of the insulating papers 37 and 39 on the upper and lower surfaces, and fixes the upper insulating paper 37 and the lower insulating paper 39 to the outer can 2. ing. Due to such an arrangement of the outer tube 21, the PT extended to the outside is used.
The other surface of the C element 40 is bent toward the bottom surface of the lower insulating paper 39.
【００５８】前記電池ケースの材質であるアルミニウム
系金属としては、例えば純アルミニウム、０．０５重量
％以下のＭｇおよび０．２重量％以下のＣｕを含むアル
ミニウム合金等を挙げることができる。このようなアル
ミニウム系金属としては、例えばＪＩＳの合金番号でＡ
１０５０、Ａ１１００、Ａ１２００、Ａ３００３等を挙
げることができる。ただし、電池ケースはアルミニウム
系金属の他にステンレスまたは鉄を用いることを許容す
る。Examples of the aluminum-based metal as the material of the battery case include pure aluminum and an aluminum alloy containing 0.05% by weight or less of Mg and 0.2% by weight or less of Cu. As such an aluminum-based metal, for example, A
1050, A1100, A1200, A3003 and the like. However, the battery case allows the use of stainless steel or iron in addition to the aluminum-based metal.
【００５９】前記電池ケースをアルミニウム系金属によ
り作った場合には、その厚さを０．５ｍｍ以上、より好
ましくは１ｍｍ以上にすることが望ましい。電池ケース
の厚さを０．５ｍｍ未満にすると、強度が低下して外装
缶に収納された発電要素を十分に保護することが困難に
なる。When the battery case is made of an aluminum-based metal, it is desirable that its thickness is 0.5 mm or more, more preferably 1 mm or more. When the thickness of the battery case is less than 0.5 mm, the strength is reduced, and it becomes difficult to sufficiently protect the power generation element housed in the outer can.
【００６０】前記電池ケースを鉄またはステンレスによ
り作った場合には、その厚さを０．２ｍｍ以上、より好
ましくは１ｍｍ以上にすることが望ましい。電池ケース
の厚さを０．２ｍｍ未満にすると、強度が低下して外装
缶に収納された発電要素を十分に保護することが困難に
なる。When the battery case is made of iron or stainless steel, it is desirable that its thickness be 0.2 mm or more, more preferably 1 mm or more. When the thickness of the battery case is less than 0.2 mm, the strength is reduced, and it becomes difficult to sufficiently protect the power generation element housed in the outer can.
【００６１】前記電池ケースを構成する外装缶と蓋体
は、レーザ溶接により接合する場合に限らず、カシメに
より接合してもよい。The outer can and the lid constituting the battery case are not limited to being joined by laser welding, but may be joined by caulking.
【００６２】前記正極２６、セパレータ２７、負極２８
および非水電解液は、前記薄型非水電解液二次電池で説
明したのと同様な材料、構造のものを用いることができ
る。以上説明したように、本発明の非水電解液二次電池
は帯状の正極と帯状の負極との間に合成樹脂製の微多孔
性膜からなる帯状のセパレータを介して渦巻状に捲回し
てなる電極体を備え、前記セパレータは長さ方向の引張
弾性率（Ｅl）に対する幅方向の引張弾性率（Ｅw）の比
（Ｅw／Ｅl）が０．８≦Ｅw／Ｅl≦５．０である構成を
有する。 このような構成によれば、正極、セパレータ、負極を張
力を加えて一緒に捲回して電極体にする際に、セパレー
タが幅方向に縮みにくく、セパレータに皺が発生し難く
なる。その結果、正負極間に皺の発生に起因して電極体
内に隙間が形成されるのを抑制ないし防止できるため、
電極体の厚さが厚くなるのを回避できる。なお、前記皺
は熱と圧力を加えれば、一旦は潰すことができるが、後
工程で電解液を含浸したり、充放電を加えることにより
歪が開放されて元に戻り、結局厚さが厚くなる。本発明
のように正極、セパレータ、負極を捲回した電極体の状
態で前記セパレータへの皺の発生を防止することによっ
て、後工程で電解液を含浸、充放電の後においても電極
体の厚さが厚くなるのを回避できる。 したがって、本発明の非水電解液二次電池は厚さが薄
く、かつ厚さのばらつきが少ない特徴を有し、円筒形、
角形いずれにも好適であるが、中でも薄い二次電池に多
用される角形、特に外装部材としてアルミニウム缶や外
装フィルムを用いて封止する形態に最適である。The positive electrode 26, the separator 27, and the negative electrode 28
As the non-aqueous electrolyte, those having the same material and structure as described in the thin non-aqueous electrolyte secondary battery can be used. As described above, the nonaqueous electrolyte secondary battery of the present invention is spirally wound via a band-shaped separator made of a synthetic resin microporous film between a band-shaped positive electrode and a band-shaped negative electrode. The separator has a ratio (E w / E l ) of the tensile modulus in the width direction (E w ) to the tensile modulus in the length direction (E l ) of 0.8 ≦ E w / E l. ≦ 5.0. According to such a configuration, when the positive electrode, the separator, and the negative electrode are wound together by applying tension to form an electrode body, the separator does not easily shrink in the width direction, and the separator does not easily wrinkle. As a result, it is possible to suppress or prevent a gap from being formed in the electrode body due to the occurrence of wrinkles between the positive and negative electrodes,
An increase in the thickness of the electrode body can be avoided. Note that the wrinkles can be once crushed by applying heat and pressure, but the electrolyte is impregnated in a later step, or the strain is released by charging and discharging, and the strain returns to its original state, and eventually the thickness is increased. Become. As in the present invention, by preventing the occurrence of wrinkles on the separator in the state of the electrode body in which the positive electrode, the separator, and the negative electrode are wound, impregnation with an electrolytic solution in a later step, and the thickness of the electrode body even after charging and discharging. The thickness can be prevented from becoming thick. Therefore, the non-aqueous electrolyte secondary battery of the present invention is characterized in that it has a small thickness and a small variation in thickness.
Although it is suitable for any square shape, it is particularly suitable for a square shape often used for a thin secondary battery, and particularly for a form sealed with an aluminum can or an outer film as an outer member.
【００６３】[0063]
【実施例】以下、本発明に係る実施例を前述した図面を
参照して詳細に説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments according to the present invention will be described below in detail with reference to the drawings.
【００６４】（実施例１） ＜正極の作製＞正極活物質として平均粒径３μｍのＬｉ
ＣｏＳｎ0.02Ｏ2８９重量部、導電フィラーとしてグラ
ファイト（ロンザ社製ＫＳ６）６重量部、結着剤として
ポリフッ化ビニリデン（呉羽化学社製商品名；＃１１０
０）３重量部を溶剤であるＮ−メチルピロリドン２５重
量部に加え、均一せん断攪拌した後、ビーズミルを用い
て分散して正極スラリーを調製した。このスラリーの見
掛けの粘度は、７５００ｍＰａ・ｓであった。つづい
て、この正極スラリーを集電体である厚さ２０μｍの帯
状アルミニウム箔の両面に均一に塗付し、溶剤を乾燥さ
せ、さらにロールプレス機で加圧成形した。得られた正
極原反を所定の大きさに切断することで、帯状の正極を
作製した。この正極の集電体の一端に正極側のアルミニ
ウム製外部リード端子を溶接により取り付けた。Example 1 <Preparation of Positive Electrode> Li having an average particle diameter of 3 μm was used as a positive electrode active material.
89 parts by weight of CoSn 0.02 O 2, 6 parts by weight of graphite (KS6 manufactured by Lonza) as a conductive filler, and polyvinylidene fluoride (brand name; # 110 manufactured by Kureha Chemical Co., Ltd.) as a binder
0) 3 parts by weight was added to 25 parts by weight of N-methylpyrrolidone as a solvent, and after uniform shear stirring, dispersed using a bead mill to prepare a positive electrode slurry. The apparent viscosity of this slurry was 7,500 mPa · s. Subsequently, the positive electrode slurry was uniformly applied to both surfaces of a 20 μm-thick strip-shaped aluminum foil as a current collector, the solvent was dried, and the mixture was pressure-formed by a roll press. The obtained positive electrode raw material was cut into a predetermined size to produce a belt-shaped positive electrode. An aluminum external lead terminal on the positive electrode side was attached to one end of the positive electrode current collector by welding.
【００６５】＜負極の作製＞カルボキシメチルセルロー
ス１．５重量部に鱗片状黒鉛５０重量部を分散し、カー
ボンのマスターバッチ塗料を作製した。この分散液に繊
維状炭素材を５０重量部添加し同様にせん断分散し、更
にスチレンブタジエンゴムラテックス２．４重量部を添
加し均一混合攪拌し、負極スラリーを調製した。このス
ラリーの見掛けの粘度は、４５００ｍＰａ・ｓであっ
た。つづいて、この負極スラリーを集電体である厚さ１
０μｍの帯状の銅箔の両面に均一に塗布し、溶剤を乾燥
させ、さらにロールプレス機で加圧成形した。得られた
負極原反を、所定の大きさに切断することで帯状の負極
８を作製した。この負極の集電体の一端に厚さ０．１ｍ
ｍ、幅５ｍｍ、長さ５０ｍｍのニッケル製外部リード端
子を溶接により取り付けた。<Preparation of Negative Electrode> 50 parts by weight of flaky graphite was dispersed in 1.5 parts by weight of carboxymethylcellulose to prepare a carbon master batch paint. To this dispersion, 50 parts by weight of a fibrous carbon material was added, similarly shear-dispersed, 2.4 parts by weight of styrene-butadiene rubber latex was further added, and the mixture was uniformly mixed and stirred to prepare a negative electrode slurry. The apparent viscosity of this slurry was 4500 mPa · s. Subsequently, this negative electrode slurry was applied to a thickness of 1 as a current collector.
It was uniformly applied to both sides of a 0 μm strip-shaped copper foil, the solvent was dried, and then pressure-molded with a roll press. The obtained negative electrode raw material was cut into a predetermined size to produce a strip-shaped negative electrode 8. One end of the current collector of the negative electrode has a thickness of 0.1 m.
A nickel external lead terminal having a length of m, a width of 5 mm and a length of 50 mm was attached by welding.
【００６６】次いで、前記帯状の正極と帯状の負極をポ
リエチレン製微多孔性膜からなるセパレータを介して、
正極／セパレータ／負極／セパレータの順序に積層し、
断面が扁平状の巻芯で渦巻状に捲回し、さらに油圧式プ
レスで圧縮し、成形して扁平状の電極体を作製した。な
お、前記ポリエチレン製微多孔性膜は長さ方向の引張弾
性率（Ｅl）に対する幅方向の引張弾性率（Ｅw）の比
（Ｅw／Ｅl）が１．３６で、厚さが１２μｍ、透気度が
２００ｓｅｃ／１００ｃｃ、気孔率が４２％、超微小押
し込み試験機(株式会社エリオニクス社製商品名；ＥＮ
Ｔ−１００)を用いて前述した測定条件の試験によるヤ
ング率（Ｙ）と硬さ（Ｈ）の比（Ｙ／Ｈ）が１０８．２
の性状を有する。 次いで、厚さ２５μｍの延伸ナイロンフィルムと厚さ４
０μｍのアルミニウム箔（ＪＩＳ Ｈ ４１６０の８０
７９材）と厚さ７０μｍのマレイン化ＰＰフィルム（シ
ーラントフィルム）とをこの順序でウレタン系接着剤を
介して積層・接着した外装フィルム素材に前記マレイン
化ＰＰフィルム側から成形パンチおよび成形ダイを用い
て加熱押圧して、カップを形成した。なお、前記マレイ
ン化ＰＰフィルムの融点は１３８℃である。つづいて、
これを短冊状に切断し、マレイン化ＰＰフィルム面が内
側で対向するように、外装フィルム素材のカップの短辺
側成形機で、１８０゜折り曲げた。前述した図５に示す
ように外装フィルム素材１８のカップ１２内に前記方法
で作製し、６０℃で予め真空加熱乾燥し、水分を３００
ｐｐｍ以下になるよう除去した扁平状の電極体１を正負
極の外部リード端子９，１０が外装フィルム素材１８の
外部へ突き出すように収納した。この状態で２１０℃に
加熱したプレスヘッド（図示せず）により、４秒間加圧
し正負極の外部リード端子９．１０とマレイン化ＰＰフ
ィルム、およびマレイン化ＰＰフィルム同士を接着させ
てシール部１６ｂを形成した。正負極の外部リード端子
９，１０が存在しない外装フィルム素材１８の長辺側の
部分も２１０℃に加熱したプレスヘッド（図示せず）に
より、４秒間加圧し、マレイン化ＰＰフィルム同士を接
着してシール部１６ａを形成した。これらの熱シール順
序は、同時でも、どちらかを先にしても構わない。Next, the strip-shaped positive electrode and the strip-shaped negative electrode were separated via a separator made of a microporous polyethylene membrane.
Laminated in the order of positive electrode / separator / negative electrode / separator,
The flat electrode body was produced by spirally winding the core with a flat cross section, and further compressing and molding with a hydraulic press. Incidentally, the polyethylene microporous membrane tensile modulus in the longitudinal direction tensile elastic modulus in the width direction with respect to (E l) ratio (E w) (E w / E l) is 1.36, the thickness 12 μm, air permeability: 200 sec / 100 cc, porosity: 42%, ultra-fine indentation tester (trade name, manufactured by Elionix Inc .; EN
T-100), the ratio (Y / H) of the Young's modulus (Y) to the hardness (H) in the test under the measurement conditions described above was 108.2.
It has the following properties. Next, a stretched nylon film having a thickness of 25 μm and a thickness of 4
0 μm aluminum foil (80 in JIS H 4160)
79 material) and a maleated PP film (sealant film) having a thickness of 70 μm are laminated and bonded in this order via a urethane-based adhesive, using a forming punch and a forming die from the maleated PP film side. And heated and pressed to form a cup. The melting point of the maleated PP film is 138 ° C. Then,
This was cut into strips and bent 180 ° by a molding machine on the short side of the cup of the exterior film material so that the maleated PP film faces inside on the inside. As shown in FIG. 5 described above, it is produced in the cup 12 of the exterior film material 18 by the above-described method, and is previously dried by heating under vacuum at 60 ° C.
The flat electrode body 1 removed so as to be less than ppm is housed such that the external lead terminals 9 and 10 of the positive and negative electrodes protrude outside the exterior film material 18. In this state, a press head (not shown) heated to 210 ° C. applies pressure for 4 seconds to adhere the external lead terminals 9.10 of the positive and negative electrodes to the maleated PP film, and to bond the maleated PP film to each other to seal the seal portion 16b. Formed. The long side of the exterior film material 18 where the positive and negative external lead terminals 9 and 10 are not present is also pressed for 4 seconds by a press head (not shown) heated to 210 ° C. to bond the maleated PP films together. Thus, a seal portion 16a was formed. The order of these heat seals may be simultaneous or either may be first.
【００６７】外装フィルム素材１８の開放された長辺側
部分を通して、電解液を真空下で注入・含浸させた。こ
の電解液としては、ＥＣ／γ−ＢＬ＝１／３（体積比）
の溶媒に対してＬｉＢＦ4を１．５モル／Ｌとなるよう
添加したものを用いた。その後、未シール部を２１０℃
に加熱したプレスヘッド（図示せず）により、５秒間加
圧し、マレイン化ＰＰフィルム同士を接着してシール部
１６ｃを形成し、余分な外装フィルム素材部分を裁断除
去することにより前述した図１および図２に示す外寸法
で厚さ３．６ｍｍ、幅３５ｍｍ、高さ６２ｍｍで、容量
が５６０ｍＡｈ（０．２Ｃ放電）の薄型非水電解液二次
電池を製造した。The electrolyte was injected and impregnated under vacuum through the open long side portion of the exterior film material 18. As the electrolytic solution, EC / γ-BL = 1/3 (volume ratio)
To which 1.5 mol / L of LiBF 4 was added to the solvent. After that, the unsealed part is 210 ° C
Pressing for 5 seconds with a press head (not shown) heated to form a seal portion 16c by bonding the maleated PP films together, and cutting and removing the excess exterior film material portion as described in FIGS. A thin nonaqueous electrolyte secondary battery having external dimensions shown in FIG. 2 and having a thickness of 3.6 mm, a width of 35 mm, a height of 62 mm, and a capacity of 560 mAh (0.2 C discharge) was manufactured.
【００６８】（実施例２）セパレータとして長さ方向の
引張弾性率（Ｅl）に対する幅方向の引張弾性率（Ｅw）
の比（Ｅw／Ｅl）が０．９７で、厚さが１６．５μｍ、
透気度が２３０ｓｅｃ／１００ｃｃ、気孔率が５０％、
超微小押し込み試験機 (株式会社エリオニクス社製商品
名；ＥＮＴ−１００)を用いて前述した測定条件の試験
によるヤング率（Ｙ）と硬さ（Ｈ）の比（Ｙ／Ｈ）が９
４．２の性状を有するポリエチレン製微多孔性膜からな
るものを用いた以外、実施例１と同様な薄型非水電解液
二次電池を製造した。Example 2 As a separator, the tensile modulus in the width direction (E w ) with respect to the tensile modulus in the length direction (E l )
The ratio (E w / E l ) is 0.97, the thickness is 16.5 μm,
Air permeability is 230 sec / 100cc, porosity is 50%,
The ratio (Y / H) of the Young's modulus (Y) to the hardness (H) in the test under the measurement conditions described above was 9 using an ultra-small indentation tester (trade name: ENT-100, manufactured by Elionix Inc.)
A thin non-aqueous electrolyte secondary battery similar to that of Example 1 was produced except that a polyethylene microporous membrane having the properties of 4.2 was used.
【００６９】（比較例１）セパレータとして長さ方向の
引張弾性率（Ｅl）に対する幅方向の引張弾性率（Ｅw）
の比（Ｅw／Ｅl）が０．６２で、厚さが１６．０μｍ、
透気度が４５０ｓｅｃ／１００ｃｃ、気孔率が３８％、
超微小押し込み試験機 (株式会社エリオニクス社製商品
名；ＥＮＴ−１００)を用いて前述した測定条件の試験
によるヤング率（Ｙ）と硬さ（Ｈ）の比（Ｙ／Ｈ）が７
５．７の性状を有するポリエチレン製微多孔性膜からな
るものを用いた以外、実施例１と同様な薄型非水電解液
二次電池を製造した。Comparative Example 1 The tensile modulus in the width direction (E w ) with respect to the tensile modulus in the length direction (E l ) as a separator
The ratio (E w / E l ) is 0.62, the thickness is 16.0 μm,
Air permeability is 450 sec / 100cc, porosity is 38%,
The ratio (Y / H) of the Young's modulus (Y) to the hardness (H) in the test under the measurement conditions described above was 7 using an ultra-fine indentation tester (trade name, manufactured by Elionix Inc .; ENT-100).
A thin non-aqueous electrolyte secondary battery similar to that of Example 1 was manufactured except that a polyethylene microporous membrane having the properties of 5.7 was used.
【００７０】（比較例２）セパレータとして長さ方向の
引張弾性率（Ｅl）に対する幅方向の引張弾性率（Ｅw）
の比（Ｅw／Ｅl）が０．５０で、厚さが１７．５μｍ、
透気度が３７５ｓｅｃ／１００ｃｃ、気孔率が３３％、
超微小押し込み試験機 (株式会社エリオニクス社製商品
名；ＥＮＴ−１００)を用いて前述した測定条件の試験
によるヤング率（Ｙ）と硬さ（Ｈ）の比（Ｙ／Ｈ）が６
０．５の性状を有するポリエチレン製微多孔性膜からな
るものを用いた以外、実施例１と同様な薄型非水電解液
二次電池を製造した。(Comparative Example 2) As a separator, the tensile modulus in the width direction (E w ) with respect to the tensile modulus in the length direction (E l )
The ratio (E w / E l ) is 0.50, the thickness is 17.5 μm,
Air permeability is 375 sec / 100cc, porosity is 33%,
The ratio (Y / H) of the Young's modulus (Y) to the hardness (H) in the test under the measurement conditions described above was 6 using an ultra-fine indentation tester (trade name, manufactured by Elionix Inc .; ENT-100).
A thin non-aqueous electrolyte secondary battery similar to that of Example 1 was produced except that a polyethylene microporous membrane having a property of 0.5 was used.
【００７１】（比較例３）セパレータとして長さ方向の
引張弾性率（Ｅl）に対する幅方向の引張弾性率（Ｅw）
の比（Ｅw／Ｅl）が０．６２で、厚さが１５．７μｍ、
透気度が４５０ｓｅｃ／１００ｃｃ、気孔率が３８％、
超微小押し込み試験機 (株式会社エリオニクス社製商品
名；ＥＮＴ−１００)を用いて前述した測定条件の試験
によるヤング率（Ｙ）と硬さ（Ｈ）の比（Ｙ／Ｈ）が８
０．１の性状を有するポリエチレン製微多孔性膜からな
るものを用いた以外、実施例１と同様な薄型非水電解液
二次電池を製造した。(Comparative Example 3) Tensile elastic modulus in the width direction (E w ) against tensile elastic modulus in the length direction (E l ) as a separator
The ratio (E w / E l ) is 0.62, the thickness is 15.7 μm,
Air permeability is 450 sec / 100cc, porosity is 38%,
The ratio (Y / H) of the Young's modulus (Y) to the hardness (H) in the test under the above-mentioned measurement conditions was 8 using an ultra-fine indentation tester (trade name, manufactured by Elionix Inc .; ENT-100).
A thin non-aqueous electrolyte secondary battery similar to that of Example 1 was manufactured except that a polyethylene microporous membrane having a property of 0.1 was used.
【００７２】得られた実施例１，２および比較例１〜３
について、電極体そのものの厚さ、未充電時の二次電池
の厚さと標準偏差、および２０℃、０．７Ｃの充電後の
二次電池の厚さと標準偏差を測定した。なお、電極体ま
たは二次電池の厚さは次のように測定した。すなわち、
四隅に穴をあけて厚さ１０ｍｍ、幅６０ｍｍ、長さ９０
ｍｍの２枚のガラス板を用意し、垂直に配置した４本の
支持棒に前記穴を通すことにより、２枚のガラス板が平
行に移動できるようにし、この２枚のガラス板間に被測
定物としての電極体または二次電池を挟み、前記被測定
物に３００ｇの荷重を加えたときの２枚のガラス板間の
距離を厚さとして求めた。また、実施例１，２および比
較例１〜３の二次電池について、２０℃、０．７Ｃの充
電／１．０Ｃの放電条件で５００サイクルの充放電を行
った後の初期容量に対する容量維持率を測定した。これ
らの結果を下記表１に示す。なお、下記表１にはセパレ
ータの長さ方向の引張弾性率（Ｅl）、幅方向の引張弾
性率（Ｅw）、これらの比（Ｅw／Ｅl）、厚さ、透気
度、気孔率、および超微小押し込み試験機によるヤング
率（Ｙ）、硬さ（Ｈ）、これらの比（Ｙ／Ｈ）を併記し
た。The obtained Examples 1 and 2 and Comparative Examples 1 to 3
The thickness of the electrode body itself, the thickness and standard deviation of the uncharged secondary battery, and the thickness and standard deviation of the secondary battery after charging at 20 ° C. and 0.7 C were measured. In addition, the thickness of the electrode body or the secondary battery was measured as follows. That is,
Drill holes at four corners, thickness 10mm, width 60mm, length 90
2 mm glass plates were prepared, and the holes were passed through four vertically arranged support rods so that the two glass plates could move in parallel. The distance between the two glass plates when a load of 300 g was applied to the object to be measured with the electrode body or the secondary battery as the object to be measured interposed therebetween was determined as the thickness. Further, with respect to the secondary batteries of Examples 1 and 2 and Comparative Examples 1 to 3, the capacity retention with respect to the initial capacity after performing 500 cycles of charge / discharge at 20 ° C., charging at 0.7 C / discharging at 1.0 C. The rate was measured. The results are shown in Table 1 below. In Table 1 below, the tensile modulus in the length direction (E l ), the tensile modulus in the width direction (E w ), the ratio thereof (E w / E l ), the thickness, the air permeability, The porosity, Young's modulus (Y), hardness (H), and ratio (Y / H) of the test pieces using an ultra-fine indentation tester are also shown.
【表１】 [Table 1]
【００７３】前記表１から明らかなように本発明の実施
例１，２は、比較例１〜３に比べて電極体そのものの厚
さが薄く、かつその厚さのばらつきが小さいことがわか
る。また、本発明の実施例１，２の二次電池は比較例１
〜３の二次電池に比べて未充電時および初充電後の厚さ
も薄く、それら厚さの標準偏差も小さくてばらつきが少
ないことがわかる。As is clear from Table 1, in Examples 1 and 2 of the present invention, the thickness of the electrode body itself is smaller than that in Comparative Examples 1 to 3, and the variation in the thickness is small. In addition, the secondary batteries of Examples 1 and 2 of the present invention correspond to Comparative Example 1
As compared with the secondary batteries of Nos. 1 to 3, the thicknesses at the time of non-charging and after the initial charging are thinner, and the standard deviation of the thicknesses is smaller and the variation is smaller.
【００７４】このように比較例１〜３の二次電池が本発
明の実施例１，２に比べて初充電後に厚さがより厚く、
ばらつきが大きくなるのは、電極体の捲回時や成形時に
残留した歪が、充電により活物質が膨脹した際に開放さ
れて、電極体が膨らみ、外装フィルムを押し広げるため
である。As described above, the secondary batteries of Comparative Examples 1 to 3 are thicker after the first charge than those of Examples 1 and 2 of the present invention.
The reason for the large variation is that the strain remaining during winding or molding of the electrode body is released when the active material expands due to charging, so that the electrode body swells and the outer film is spread.
【００７５】さらに、本発明の実施例１，２の二次電池
は比較例１〜３の二次電池に比べて容量維持率が高く、
優れたサイクル特性を有することがわかる。また、本発
明の実施例１，２の二次電池は比較例１〜３の二次電池
に比べて一般特性も優れていた。比較例１〜３は、電極
体が膨らみ、正負極間の距離が広がり、インピーダンス
が増すために特性低下が起きるものと考えられる。Further, the secondary batteries of Examples 1 and 2 of the present invention have a higher capacity retention ratio than the secondary batteries of Comparative Examples 1 to 3,
It turns out that it has excellent cycle characteristics. Further, the secondary batteries of Examples 1 and 2 of the present invention also had better general characteristics than the secondary batteries of Comparative Examples 1 to 3. In Comparative Examples 1 to 3, it is considered that the electrode body swells, the distance between the positive electrode and the negative electrode is widened, and the impedance is increased.
【００７６】なお、外装部材としてアルミニウム缶を用
いた例えば図６に示す構造の角型非水電解液二次電池に
おいても前述した実施例１,２と同様に未充電時および
初充電後の厚さも薄く、それら厚さの標準偏差も小さ
く、かつ高い容量維持率を有することが確認されたIn the case of a prismatic nonaqueous electrolyte secondary battery having a structure shown in FIG. 6, for example, using an aluminum can as an exterior member, as in the case of the first and second embodiments described above, the thickness after uncharging and after the first charging is obtained. It was confirmed that the thickness was small, the standard deviation of the thickness was small, and the capacity retention rate was high.
【００７７】[0077]
【発明の効果】以上の説明したように、本発明によれば
長さ方向の引張弾性率（Ｅl）に対する幅方向の引張弾
性率（Ｅw）の比（Ｅw／Ｅl）が０．８≦Ｅw／Ｅl≦
５．０である合成樹脂製の微多孔性膜からなるセパレー
タを用いることによって、正極,セパレータおよび負極
を前記セパレータに張力を加えて捲回する際に、幅方向
への縮みが起き難く、皺の発生が少ないため、厚さが薄
く、かつ厚さのばらつきの少ない携帯電話やパーソナル
コンピュータなど電子機器の電源として好適な小型、軽
量、大容量、高性能の非水電解液二次電池電池を提供で
きる。As described above, according to the present invention, according to the present invention the tensile modulus of the longitudinal tensile modulus in the width direction with respect to (E l) ratio (E w) (E w / E l) 0 .8 ≦ E w / E l ≦
By using a separator made of a synthetic resin microporous membrane having a thickness of 5.0, when the positive electrode, the separator and the negative electrode are wound by applying tension to the separator, shrinkage in the width direction hardly occurs, and wrinkles are prevented. Small, lightweight, large-capacity, high-performance non-aqueous electrolyte rechargeable batteries suitable for power supplies of electronic devices such as mobile phones and personal computers, which are thin and have a small thickness variation due to low occurrence of Can be provided.
【図１】本発明に係わる外装部材として外装フィルムを
用いた薄型非水電解液二次電池を示す斜視図。FIG. 1 is a perspective view showing a thin non-aqueous electrolyte secondary battery using an exterior film as an exterior member according to the present invention.
【図２】図１のII−II線に沿う断面図。FIG. 2 is a sectional view taken along the line II-II in FIG.
【図３】セパレータの変位−荷重曲線を示す特性図。FIG. 3 is a characteristic diagram showing a displacement-load curve of a separator.
【図４】本発明の薄型非水電解液二次電池の他の形態を
示す断面図。FIG. 4 is a cross-sectional view showing another embodiment of the thin non-aqueous electrolyte secondary battery of the present invention.
【図５】本発明の薄型非水電解液二次電池の製造工程を
示す斜視図。FIG. 5 is a perspective view showing a manufacturing process of the thin non-aqueous electrolyte secondary battery of the present invention.
【図６】本発明に係わる外装部材としてアルミニウム缶
を用いた角型非水電解液二次電池を示す部分切欠斜視
図。FIG. 6 is a partially cutaway perspective view showing a prismatic nonaqueous electrolyte secondary battery using an aluminum can as an exterior member according to the present invention.
１…電極体、 ４…正極、 ８…負極、 ９…正極側外部リード端子、 １０…負極側外部リード端子、 １１…外装フィルム、 １２…カップ、 １３…シーラントフィルム、 １６ａ,１６ｂ,１６ｃ…シール部、 ２１…電池ケース ２２…外装缶、 ２３…蓋体、 ２５…電極体、 ２６…正極、 ２７…セパレータ、 ２８…負極、 ４０…ＰＴＣ素子、 ４１…外装チューブ。 DESCRIPTION OF SYMBOLS 1 ... Electrode body, 4 ... Positive electrode, 8 ... Negative electrode, 9 ... Positive side external lead terminal, 10 ... Negative side external lead terminal, 11 ... Exterior film, 12 ... Cup, 13 ... Sealant film, 16a, 16b, 16c ... Seal Reference numeral 21: Battery case 22: Outer can, 23: Lid, 25: Electrode, 26: Positive electrode, 27: Separator, 28: Negative electrode, 40: PTC element, 41: Outer tube.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 5H011 AA09 CC02 CC06 CC10 DD13 5H021 AA01 BB04 BB17 BB20 CC08 EE04 HH00 HH02 HH03 HH06 5H029 AJ14 AK03 AL07 AL12 AL16 AM03 AM04 AM05 AM07 AM16 BJ02 BJ04 BJ14 CJ02 CJ03 CJ05 CJ06 CJ07 DJ02 DJ04 DJ14 EJ01 EJ12 HJ00 HJ04 HJ09 5H050 AA01 AA19 BA17 CA08 CB07 CB08 DA19 FA05 FA13 GA02 GA08 GA09 HA00 HA04 HA09 ────────────────────────────────────────────────── ─── Continued on the front page F term (reference) 5H011 AA09 CC02 CC06 CC10 DD13 5H021 AA01 BB04 BB17 BB20 CC08 EE04 HH00 HH02 HH03 HH06 5H029 AJ14 AK03 AL07 AL12 AL16 AM03 AM04 AM05 AM07 AM16 BJ02 BJ04 CJJ CJJ CJC DJ14 EJ01 EJ12 HJ00 HJ04 HJ09 5H050 AA01 AA19 BA17 CA08 CB07 CB08 DA19 FA05 FA13 GA02 GA08 GA09 HA00 HA04 HA09
Claims (10)
脂製の微多孔性膜からなる帯状のセパレータを介して渦
巻状に捲回してなる電極体を備え、 前記セパレータは、長さ方向の引張弾性率（Ｅl）に対す
る幅方向の引張弾性率（Ｅw）の比（Ｅw／Ｅl）が０．
８≦Ｅw／Ｅl≦５．０であることを特徴とする非水電解
液二次電池。An electrode body spirally wound between a strip-shaped positive electrode and a strip-shaped negative electrode via a strip-shaped separator made of a synthetic resin microporous film, wherein the separator has a length the ratio of the direction of the tensile modulus tensile modulus in the width direction with respect to (E l) (E w) (E w / E l) is 0.
A non-aqueous electrolyte secondary battery, wherein 8 ≦ E w / E l ≦ 5.0.
であることを特徴とする請求項１記載の非水電解液二次
電池。2. The method according to claim 1, wherein the separator has a thickness of 5 to 30 μm.
The non-aqueous electrolyte secondary battery according to claim 1, wherein
ｍであることを特徴とする請求項１記載の非水電解液二
次電池。3. The separator has a thickness of 10 to 20 μm.
2. The non-aqueous electrolyte secondary battery according to claim 1, wherein m is m.
％であることを特徴とする請求項１記載の非水電解液二
次電池。4. The separator has a porosity of 30 to 60.
%. The non-aqueous electrolyte secondary battery according to claim 1, wherein
ｃ／１００ｃｃ〜６００ｓｅｃ／１００ｃｃであること
を特徴とする請求項１記載の非水電解液二次電池。5. The separator has an air permeability of 100 seconds.
The non-aqueous electrolyte secondary battery according to claim 1, wherein c / 100 cc to 600 sec / 100 cc.
機を用いて荷重５０ｍｇｆを加えたときのヤング率
（Ｙ）と硬さ（Ｈ）の比（Ｙ／Ｈ）が９０≦Ｙ／Ｈ≦１
５０であることを特徴とする請求項１記載の非水電解液
二次電池。6. The separator has a Young's modulus (Y) to hardness (H) ratio (Y / H) of 90 ≦ Y / H ≦ when a load of 50 mgf is applied using an ultra-fine indentation tester. 1
The non-aqueous electrolyte secondary battery according to claim 1, wherein the number is 50.
状の負極との間に前記帯状のセパレータを介して扁平形
の巻芯に渦巻状に捲回してなる扁平状をなすことを特徴
とする請求項１記載の非水電解液二次電池。7. The electrode body has a flat shape formed by spirally winding a flat core around the strip-shaped positive electrode and the strip-shaped negative electrode via the strip-shaped separator. The non-aqueous electrolyte secondary battery according to claim 1.
収納されることを特徴とする請求項１ないし７いずれか
記載の非水電解液二次電池。8. The non-aqueous electrolyte secondary battery according to claim 1, wherein the electrode body is formed by heating and housed in an outer can.
とを特徴とする請求項８記載の非水電解液二次電池。9. The non-aqueous electrolyte secondary battery according to claim 8, wherein the outer can is an aluminum can.
を介在した外装フィルム内に収納され、封止されること
を特徴とする請求項１ないし７いずれか記載の非水電解
液二次電池。10. The non-aqueous electrolyte secondary battery according to claim 1, wherein the electrode body is housed and sealed in an exterior film with a barrier film interposed therebetween.
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| JP2000035136A JP2001229971A (en) | 2000-02-14 | 2000-02-14 | Nonaqueous electrolyte secondary battery |
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| JP2001229971A true JP2001229971A (en) | 2001-08-24 |
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| JP2002042772A (en) * | 2000-07-25 | 2002-02-08 | Mitsubishi Electric Corp | Battery |
| JP2003168411A (en) * | 2001-12-04 | 2003-06-13 | Hitachi Maxell Ltd | Nonaqueous secondary battery |
| WO2003063269A1 (en) * | 2002-01-24 | 2003-07-31 | Hitachi Maxell, Ltd. | Nonaqueous secondary cell and electronic device incorporating same |
| JP2006073243A (en) * | 2004-08-31 | 2006-03-16 | Sanyo Electric Co Ltd | Battery |
| JP2006156412A (en) * | 2002-01-24 | 2006-06-15 | Hitachi Maxell Ltd | Electronic instrument containing non-aqueous secondary battery |
| JP2008004536A (en) * | 2006-05-22 | 2008-01-10 | Matsushita Electric Ind Co Ltd | Separator, and nonaqueous electrolyte secondary battery |
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| JP2010056076A (en) * | 2008-08-01 | 2010-03-11 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
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| WO2017073781A1 (en) * | 2015-10-30 | 2017-05-04 | 宇部興産株式会社 | Porous film and electricity storage device |
| JP2017107840A (en) * | 2015-11-30 | 2017-06-15 | 住友化学株式会社 | Laminate separator for nonaqueous electrolyte secondary battery, member for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
| WO2020189795A1 (en) * | 2019-03-20 | 2020-09-24 | 帝人株式会社 | Separator for non-aqueous secondary battery and non-aqueous secondary battery |
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