TW595035B - Separator for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery - Google Patents
Separator for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery Download PDFInfo
- Publication number
- TW595035B TW595035B TW090120999A TW90120999A TW595035B TW 595035 B TW595035 B TW 595035B TW 090120999 A TW090120999 A TW 090120999A TW 90120999 A TW90120999 A TW 90120999A TW 595035 B TW595035 B TW 595035B
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- Prior art keywords
- separator
- secondary battery
- aqueous electrolytic
- heat
- spacer
- Prior art date
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title abstract description 6
- 125000006850 spacer group Chemical group 0.000 claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 23
- 239000000835 fiber Substances 0.000 claims abstract description 7
- -1 polyethylene terephthalate Polymers 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- 150000002484 inorganic compounds Chemical class 0.000 claims description 10
- 229910010272 inorganic material Inorganic materials 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 229920006015 heat resistant resin Polymers 0.000 claims description 7
- 229920000098 polyolefin Polymers 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229920000620 organic polymer Polymers 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 230000003068 static effect Effects 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 3
- 229920002313 fluoropolymer Polymers 0.000 claims description 3
- 239000004811 fluoropolymer Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 239000011324 bead Substances 0.000 claims 1
- 239000001913 cellulose Substances 0.000 claims 1
- 238000006056 electrooxidation reaction Methods 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 61
- 239000000243 solution Substances 0.000 description 22
- 239000010408 film Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 239000000463 material Substances 0.000 description 16
- 238000011049 filling Methods 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000002131 composite material Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000002079 cooperative effect Effects 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910021383 artificial graphite Inorganic materials 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920000768 polyamine Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- 239000004760 aramid Substances 0.000 description 4
- 229920003235 aromatic polyamide Polymers 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 239000011280 coal tar Substances 0.000 description 3
- 239000011162 core material Substances 0.000 description 3
- 150000005676 cyclic carbonates Chemical class 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910021382 natural graphite Inorganic materials 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- DZUDZSQDKOESQQ-UHFFFAOYSA-N cobalt hydrogen peroxide Chemical compound [Co].OO DZUDZSQDKOESQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920006284 nylon film Polymers 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- ZYAMKYAPIQPWQR-UHFFFAOYSA-N 1,1,1,2,2-pentafluoro-3-methoxypropane Chemical compound COCC(F)(F)C(F)(F)F ZYAMKYAPIQPWQR-UHFFFAOYSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- OQMIRQSWHKCKNJ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical group FC(F)=C.FC(F)=C(F)C(F)(F)F OQMIRQSWHKCKNJ-UHFFFAOYSA-N 0.000 description 1
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- UUAMLBIYJDPGFU-UHFFFAOYSA-N 1,3-dimethoxypropane Chemical compound COCCCOC UUAMLBIYJDPGFU-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- NFIKMTWAFREAPY-UHFFFAOYSA-N 2,2,3,3,4-pentamethylfuran Chemical compound CC=1C(C(OC=1)(C)C)(C)C NFIKMTWAFREAPY-UHFFFAOYSA-N 0.000 description 1
- OMFSJRHPFYVJSP-UHFFFAOYSA-N 2,3,4,5-tetramethylfuran Chemical compound CC=1OC(C)=C(C)C=1C OMFSJRHPFYVJSP-UHFFFAOYSA-N 0.000 description 1
- NAQNEMNLLODUCG-UHFFFAOYSA-N 2,3-dichloroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Cl)=C1Cl NAQNEMNLLODUCG-UHFFFAOYSA-N 0.000 description 1
- VWIIJDNADIEEDB-UHFFFAOYSA-N 3-methyl-1,3-oxazolidin-2-one Chemical compound CN1CCOC1=O VWIIJDNADIEEDB-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013462 LiC104 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- FHHDOYWGNLOMMA-UHFFFAOYSA-N [4-(aminomethyl)-4-phenylcyclohexa-1,5-dien-1-yl]methanamine Chemical compound C1(=CC=CC=C1)C1(CC=C(C=C1)CN)CN FHHDOYWGNLOMMA-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229920003064 carboxyethyl cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- XVVLAOSRANDVDB-UHFFFAOYSA-N formic acid Chemical class OC=O.OC=O XVVLAOSRANDVDB-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 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
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- MRHPUNCYMXRSMA-UHFFFAOYSA-N nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Ni++] MRHPUNCYMXRSMA-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 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
- 150000003839 salts Chemical class 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
- H01M50/406—Moulding; Embossing; Cutting
-
- 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
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the 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
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—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
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- 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
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Description
595035 A7 B7 五、發明說明Q [發明背景] [發明領域] 本發明係有關於非水性電解二次電池用之隔片,以及 非水性電解二次電池。 [先行技術] 近年來,行動資訊設備諸如個人電腦,行動電話及資 訊終端機已廣為使用。由於此等設備具有各種多媒體功 能’故作為此類電源供應的二次電池係以極小極輕而容量 大’亦即两冑b量後度為隹。至此,水溶液型二次電池,諸 如以往之錯蓄電池及鎳鎘蓄電池,已不敷所需。可達較高 能量密度之鐘二次電池已在蓬勃開發中,尤以使用複合鋰 氧化物’諸如鋰化二氧化鈷、鋰化二氧化鎳、及尖晶石氧 化錳鋰作為陰極活性物質,並使用可摻雜/去掺雜鋰離子之 碳質材料作為陽極活性物質者。 由於此等鋰二次電池本質上能量大,必須要有改良之 安全性以防,諸如内部短路及外部短路時之異常放熱。例 如,當包括聚烯烴微孔層之隔片有熱產生時,於約8〇〇c至 180°C時使該聚烯烴層之多孔性下降形成鋰離子無法通過 之構造,停止電池之電流,因而提升安全性。(此「諸如聚 烯烴層之微孔層於熱產生時形成多孔性下降之構造並停止 電池之電流」可稱之為「具有關閉功能」)。然而,當熱產 生仍大時,隔片本身有變形之問題。 隔片之製備,已有結合主要係包括聚烯烴的微孔膜物 質作為關閉層與耐熱多孔材料之探討。例如,日本專利 M氏張尺度適用中國國家標準(CNS)A4規格(210 X 297公髮) ------------ (請先閱讀背面之注意事項再填寫本頁) 訂---------線隊 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 595035 A7 -------~^~____ 五、發明說明G ) JP-A 11 _ 144697 揭示一種隔 η > ± 裡h片’包括聚烯烴多孔膜及聚醯 亞胺多孔膜。但於非水性雷舷-4恭ι 电解一人電池中充/放電過程中會 發生耐熱多孔材料的電化學氧化之問題。 本發明之目的係在提供一種非水性電解二次電池用隔 片’該隔片含一具有關閉功能和極佳之抗電化學氧化性之 耐熱微孔層’以及含該隔片之非水性電解二次電池。 [發明概要] 一再探討之結果,本發明人等發現,可藉使用含有具 關閉功能之層及耐熱微孔層之隔片,且該隔片具有位於耐 熱微孔層表面上之間隔物來達成上述目的,而完成本發 明。 亦即’本發明係有關於非水性電解二次電池用之隔 片,其中該隔片包括一關閉層,一耐熱微孔層,及該耐熱 微孔層表面上之間隔物,而該間隔物具顆粒,纖維,網或 夕孔膜之形狀。該間隔物係設置在該耐熱微孔層設置有關 閉層之另一表面上。(此起,該表面可稱作外表面。) 並且’本發明係有關於包含上述隔片之非水性電解二 次電池。 [發明之詳細說明] 本發明之非水性電解二次電池用隔片,其特徵為:含 一關閉層及一耐熱多孔層,其中該隔片具有形狀為顆粒、 纖維、網或多孔膜之間隔。在本發明之隔片中,該耐熱多 孔層係由合適之耐熱樹脂構成,並宜與該關閉層相鄰接。 本發明之關閉層無特殊限制,僅須具有關閉功能gp . --------^--------- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐) 2 312957 595035 A7
請 先 閱 讀 背 面 之 注 意 事 項 再 填 寫 本 頁 595035 A7
經濟部智慧財產局員工消費合作社印製 係以具顆粒形狀之間隔物為較佳。 特別是,在塗覆含有機微粒之懸浮液的過程中,顆粒 會在财熱多孔層之表面上形成至少一層。假設直徑3微米 之顆粒排列成一層,該間隔物之厚度即為3微米。顆粒無 須完全塗覆於耐熱多孔層的整個表面,也無須互相緊密相 鄰接。 顆粒直徑宜在3微米或以下。若該直徑超過3微米, 則間隔物之厚度將超過3微米,有時電池之電容或負荷特 性會惡化。亦可使用二種或以上不同直徑之顆粒。為防顆 粒凝集,係以混合二種或以上不同直徑之顆粒為佳。 一般在非水性電解二次電池中,陰極片及陽極片係在 其間插入一隔片而積層並捲繞成螺旋狀,形成螺狀電極。 捲繞過程中,先將部份隔片環繞蕊材,再以陰極片及陽極 片間夾以隔片捲繞。如此,所生產之捲繞電極須從蕊材拉 出’如果與蕊材接觸之隔片的表面滑性不足則須額外施力 於捲繞電極,此將導致該電極無法對齊而不勻稱,甚至有 時會造成電極之斷裂。 爲材通常係用不銹鋼,隔片與不銹鋼之摩擦係數宜 低。設置有間隔物之隔片與表面以1〇〇〇號砂紙打磨之不銹 鋼的靜摩擦係數,係依JIS K7125測定。較佳者為0.5或 以下,更佳者為0.3或以下。 形成具有顆粒、纖維、網或多孔膜形狀之間隔物時, 間隔物無須完全塗覆於耐熱多孔層之表面。並且具有顆 粒、纖維、網或多孔膜形狀之間隔物其開放度宜大,以獲 * ¥ 裝--------訂--------- (請先閱讀背面之注意事項再填寫本頁) 本纸張尺度適用中國國家標準(CNS)A4規格(210 x 297公釐) 6 312957 595035 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明(7 致優異之電池負荷特性。 於耐熱多孔層之外表面上形成具有顆粒、纖維、網或 多孔膜形狀之間隔物的過程之例包含··將非織物、織物或 夕孔膜之積層於耐熱多孔層之外表面上;以直接溶吹法等 於耐熱多孔層之外表面上形成非織物,·塗覆可形成多孔膜 之聚合物溶液,等等。 關閉層或耐熱多孔層之孔隙率係如下測定。 將耐熱多孔層裁切成10公分見方,測其重量(Wg)及 厚度(Dcm)。計算出樣本中材料之重量,各材料之重量(Wi) 除以其真比重依下式求出各材料之體積、孔隙率(體積%)。 孔隙率(體積°/〇) =[1 - {( W1/真比重 1 )+(W2/真比重 2)+ · · · +(Wn/ 真比重 n)}/(100 X D)] X 100 用於本發明之間隔物的電化學安定物質之例包含,成 形為多孔膜並用作鋰離子電池之隔片的物質,而其在長時 間維持施加4.2至4.5伏特之電壓後不劣化。 其中合適的有機聚合物之例有,選自以下所構成之群 級者:聚烯烴諸如聚乙烯及聚丙烯;烯烴共聚物;含氟聚 合物諸如四氟乙烯一六氟丙烯共聚物及聚四氟乙烯;聚碳 酸酯;芳族聚酯;聚對酞酸乙二酯;及纖維素諸如羧基甲 基纖維素及羧基乙基纖維素;或含電化學安定無機化合物 之該等有機聚合物。 諸如四氟乙稀一六氟丙烯共聚物及聚四氟乙烯之含氟 聚合物,及諸如羧基甲基纖維素之纖維素係為較佳。含電 * X 裝--------訂---------^9—. (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 7 312957 595035 經濟部智慧財產局員工消費合作社印製 A7 B7 i、發明說明(8 ) 化學安定無機化合物之該等有機聚合物,因其無機化合物 可用以承受有機物所無法承受之電壓,故亦為較佳。 間隔物係以於耐熱多孔層之外表面塗覆含電化學安定 物之塗覆液所形成之隔片,從工業上之觀點來說係為合 適,因為該間隔物易於形成。尤以於耐熱多孔層之外表面 上提供具有顆粒形狀之間隔物時,該塗覆液係以懸浮液為 隹,因為間隔物之厚度可予壓低。懸浮液之例可為含有機 聚合物顆粒之懸浮液。 本發明中,耐熱多孔層即關閉層,及間隔物可含無機 化合物。含於間隔物之無機化合物可僅係一具抗電化學氧 化性之高級金屬氧化物,並對電解質不具反應性。實例雖 有氧化鋁、碳酸鈣、氧化矽等,但本發明不限於此。 本發明之非水性電解二次電池用之隔片中,各層可係 僅只互相堆疊,但為顧及操作性質係以加以接合為佳。接 合各層之方法有例如,於關閉層與耐熱多孔層,及耐熱多 孔層與間隔物間之以黏著劑接合之方法,以熱黏合接合之 方法等。 本發明之隔片,以下係例示於耐熱多孔層之外表面上 塗覆含電化學安定物的塗覆液,並形成間隔物之過程,但 本發明不限於此。 例如,間隔物可藉含以下步驟(a)至(C)之方法形成於财 熱多孔層之外表面上。 (a)製備包括電化學安定物之懸浮液。使用無機化合物 時,製備無機化合物微粉之漿液,並與該懸浮液混合。 ----------------------------- (請先閱讀背面之注音?事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 8 312957 595035 經濟部智慧財產局員工消費合作社印製 312957 A7 B7 五、發明說明(9 ) (b)將該懸浮液塗覆於耐熱多孔層,形成塗層。 (C)將該塗膜乾燥。 又,堆疊關閉層及耐熱多孔層之合適方法,係以諸如 耐熱多孔層或關閉層之多孔膜的微孔層作為基材,於該基 材上塗覆另一溶液狀態層而形成液體層並移除溶劑。 利用塗覆耐熱樹脂溶液於關閉層上並形成此一耐熱多 孔層之方法的製造方法之例呈示如下,但本發明不限於此 等。 例如,耐熱多孔層可藉包含以下(A)至(E)之步驟的方 法形成於關閉層上。 (A) 製備包括耐熱樹脂及有機溶劑之溶液。使用無機化 合物時,製備包括以100公克之耐熱樹脂計,1至200重 量份的無機化合物微粉之漿液。 (B) 塗覆該懸浮液或漿液於關閉層上形成塗膜。 (C) 沈積塗臈中之耐熱樹脂。 (D) 從該塗膜移除有機溶劑。 (E) 將該塗膜乾燥。 在此’有機溶劑通常係用極性有機溶劑。極性有機 溶劑之例有N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮(此後稱Nmp)、四甲基尿素等。 本發明之非水性電解二次電池,其特徵為:含上述之 隔片。 在本發明之非水性電解二次電池中,以間隔物配置成 與陰極相鄰接之隔片為佳,此時鄰接於間隔物之耐熱多孔 &氏張尺度翻_家標準(CNS)A4 “(21G χ 297公[) ---------------------訂---------線赢 (請先閱讀背面之注咅?事項再填寫本頁) 595035 A7 ~ ______B7__ 五、發明說明(10 ) 層不易起電化學氧化。 以下說明非水性電解二次電池之隔片以外的其它部 分’但非以此為限。 用作本發明之非水性電解二次電池的非水性電解質溶 液,可用例如將鋰鹽溶於有機溶劑之非水性電解質溶液。 至於鋰鹽之例有 LiC1〇 4、LiPF 6、UAsF 6、USbF 6、ubf 4、LiCF 3S0 3、LiN(CF 3S0 2)2、LiC(CF 3S0 2)3、Li 2b i〇C1 u、低碳脂族羧酸鋰鹽、LiAlCl4等,可單獨或結合二種以 上使用。其中,較佳係使用選自以下所構成之群組的至少 一種含氟鹽:LiPF 6、LiAsF 6、LiSbF 6、LiBF 4、LiCF 3S0 3、LiN(CF 3S0 2)2、及 LiC(CF 3S0 2)3。 用作本發明之非水性電解二次電池的有機溶劑,可用 例如碳酸酯類諸如碳酸丙烯酯、碳酸乙烯酯、碳酸二甲醋、 碳酸二乙酯、碳酸甲乙酯、4-三氟甲基·1,3-二噚烷-2-酮及 1,2-二(甲氧基幾基氧)乙烧;醚類諸如1,2_二甲氧基乙 烷、1,3-二甲氧基丙烷、五氟丙基甲基醚、2, 3, 3·四氟 丙基二氟甲基_、四氳咲喃及2 -甲基四氳咲喃;酯類諸如 甲酸甲酯、醋酸甲酯及7-丁内酮;腈類諸如乙腈及丁腈; 醯胺類諸如Ν,Ν-二甲基甲醯胺及Ν,Ν-二甲基乙醯胺;胺 甲酸酯類諸如3-甲基-2_噁唑啶酮;含硫化合物諸如環丁 楓、二甲亞碾及1,3-丙烷磺内酯;及導入氟取代基之上述 溶劑。經常,以上有機溶劑可混合二種以上使用。 其中以含碳酸酯之混合溶劑為合適,更合適者包括環 狀碳酸酯與非環狀碳酸酯或環狀碳酸酯與醚之混合溶劑。 (請先閱讀背面之注意事項再填寫本頁) -裝--------訂---- 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 10 312957 ^5035 A7
595035 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明(U ) 乙烯共聚物、亞乙烯氟化物—六氟丙烯_四氟乙烯共聚 物、熱塑性聚醯亞胺、羧基甲基纖維素、聚乙烯、聚丙烯 等。 作為導電物質之碳質材料之例有,天然石墨、人工石 墨、焦炭、碳黑等。導電物質可單獨使用,亦可用複合導 電物質,諸如人工石墨與碳黑之混合物。 本發明之陽極片可用例如,摻雜/去摻雜鋰離子、鋰金 屬或鋰合金之材料。摻雜/去摻雜鋰離子的材料之例有,碳 質材料諸如天然石墨、人工石墨、焦炭、碳黑、熱解碳、 碳纖及有機聚合物之加熱物;氧族化合物諸如氧化物或硫 化物,其在低於陰極之電位進行鋰離子之摻雜/去摻雜。碳 質材料係以包括諸如天然石墨及人工石墨之石墨材料為主 要成刀之碳質材料為合適,此時與陰極結合可得高能量密 度,因其電位平坦性高,平均放電電位低。 作為本發明非水性電解二次電池之陽極集電器,可用 Cu、Ni、不錄鋼等。特別是在鋰二次電池,係以α為佳, 因其不易與鐘形成合金且易於加工成薄膜。將含陽極活性 物質之組成物支撐於陽極集電器的過程之例有:進行壓塑 之方法;及包括以溶劑製成糊劑、塗覆於集電器上、乾燥、 及壓合之步驟的方法。 本發明之鐘二次電池不限於特定形&,可係任何形 狀’諸如紙片狀、硬幣狀、圓筒狀及矩形長方體狀。 [實施例] 以下,本發明_以實施例進一步詳細說明,但本發明 12 312957 --------^--------- (請先閱讀背面之注意事項再填寫本頁) 595035 A7
經濟部智慧財產局員工消費合作社印製 五、發明說明(13 ) 絕非僅限於此等實施例。 (1) 固有黏度 以毛細管黏度計於301:對96至98 %馀缺 /❾硫酸,及於100 毫升之96至98 %硫酸溶解0.5公克之對婪始絲 凡<對方族醯胺聚合物 的溶液測定流動時間。從所得之流動時間比依據下气叶算 固有黏度: ° 固有黏度=ln(T/T0)/C [單位:公合/公克] 其中T及T。各指對芳族聚釀胺硫酸溶液及硫酸之流 動時間,C代表對芳族聚醯胺硫酸溶液中對芳族聚醯胺之 濃度(公克/公合)。 (2) 透氣度 透氣度係依HS P 8117測定。 (3) 膜厚 膜厚係依JIS K 7130測定。 (4) 靜摩擦係數 膜對表面經1〇〇〇號砂紙打磨之不銹鋼的靜摩擦係數 係依JIS K7125測定。 (5) 電池之負荷特性 為評估使用該隔片之電池的功能,如下述製備盤狀電 池,測定電池之負荷特性。 於NMP中溶解3重量份之聚亞乙烯氟化物,分散作 為導電物質之9重量份之人工石墨粉及1重量份之乙炔 黑’及87重量份作為陰極活性物質之鋰化二氧化鈷粉並捏 合成陰極組成物糊劑。將此一糊劑塗覆於厚20微米之鋁猪 &張尺度適用中_標$__4規格⑽χ 297公餐)— 13 312957 (請先閱讀背面之注意事項再填寫本頁)
集電器上,乾燥並以輥壓成陰極片電極。 隹疊該陰極片及鋰金屬陽極以使塗覆間隔物之隔片置 酴接該陰極片處。盤狀電池係以添加Lij>F6 3〇體積%碳 :乙自旨、碳酸甲乙醋、35體積%碳酸二f醋之混 合溶劑中形成1M的電解質而生產。 ^對所得之盤狀電池作固定電流/固定電壓之充電及固 定電流放電,用以下條件評估該電池之負荷特性。 負何特性係以其定義為「(充電/放電X之放電容 量)/(充電/放電Y之放電容量)」之值表示。 以上之充電/放電X條件係: 最大充電電壓:4.3伏特 充電時間·· 8小時 充電電流:0·5毫安培/平方公分 最小放電電壓:3.0伏特,及 放電電流·· 0.5毫安培/平方公分。 充電/放電Υ條件係: 最大充電電壓:4.3伏特 充電時間:8小時 充電電流:0.5毫安培/平方公分 最小放電電壓:3.0伏特,及 放電電流:10毫安培/平方公分。 (6)抗電化學氧化性之評估 (請先閱讀背面之注意事項再填寫本頁)
--------訂---------線I 經濟部智慧財產局員工消費合作社印製 如同電池之負荷特性之評估,製備盤狀電池,以下條 件之固定電流及固定電壓充電。
14 312957 595035 經濟部智慧財產局員工消費合作社印製 A7 發明說明(15 j 最大充電電壓:4.5伏特 充電時間:24小時,及 充電電流·· 0.5毫安培/平方公分 充電後,拆解電池,取出隔片加以觀察。 ίίΜΜΛ. 1.耐熱多孔層之施用,及隔片之生產 (1) 對芳族聚醯胺之合成 於5又有攪拌器、溫度計、氮氣吹入管及粉末入口之5 A升的分離式燒瓶合成聚(對苯基對苯二甲醯胺)(以下稱 作PPTA) °於充分乾燥之燒瓶中加200°c乾燥二小時之 272.65公克之氯化鈣至42〇〇公克之NMp。將該燒瓶加熱 至100 C °氣化鈣完全溶解後將該燒瓶冷卻至室溫,加入 132.91公克之對亞苯基二胺(以下稱作ppD)並使其完全溶 解。維持該溶液於20 土 2。(;,以十等分於5分鐘之間隔加 入243· 32公克之二氯化對苯二甲酸(以下稱作Tpc)。保持 該溶液於20 士 2°C —小時,在減壓下攪拌3〇分鐘去除氣 /包。所得聚合物溶液呈光學各向異性。從該聚合物溶液取 樣’於水中沈澱使該聚合物由取樣之聚合物溶液分出。如 此測得之PPTA的固有黏度為ι·97公合/公克。 於設有攪拌器、溫度計、氮氣吹入管及粉末入口之5〇〇 毫升的分離式燒瓶加入1〇〇公克之聚合物溶液並緩慢加入 NMP溶液。製成ρρτΑ濃度為2· 0重量%之溶液,稱作「p 溶液」。 (2) 對芳族聚醯胺溶液之運用及隔片之生產 表纸張尺度適用中國國家標準(CNS)A4規格(210 x297公釐) (請先閱讀背面之注意事項再填寫本頁)
595035 A7 B7 五、發明說明(16 ) (請先閱讀背面之注意事項再填寫本頁) 用聚乙烯(膜厚25微米,透氣度700秒/100立方公分, 平均空孔半徑〇·〇4微米(水銀孔隙計))之多孔膜作為關閉 層。以棒塗機(間隙200微米:Tester Sangyo Co·,Ltd.生 產)塗覆耐熱樹脂溶液「P溶液」於放置在玻璃板上之多孔 臈上成為膜狀材料。於實驗室中就此靜置3分鐘後,PPTA 沈澱可得膜狀材料。將該膜狀材料浸泡於離子交換水。5 分鐘後,從玻璃板剝除膜狀材料。以離子交換水充分清洗 後’抹除自由水。將膜狀材料夾於尼龍片間,再夾於芳族 聚醯胺氈之間。膜狀材料夾於尼龍片間,再夾於芳族聚醯 胺氈之間的狀態下,其上置一鋁板,其上蓋上尼龍膜,以 膠密封尼龍膜及鋁板,附加一降壓管。整體置於烤箱中, 將膜狀材料於減壓下在60°C乾燥,得到包括聚乙烯之多孔 膜及芳族聚醯胺多孔層(厚度5微米)之複合膜。 2.關閉功能之評估 經濟部智慧財產局員工消費合作社印製 將製得之複合膜裁成40毫米見方,夾於不錄鋼製且各 為18毫米φ及90毫米見方之電極間。於3〇體積%碳酸乙 酿、35體積%碳酸甲乙酯、35體積%碳酸二甲醋之混合溶 劑中溶有1M之LiPF 6的電解質以生產測試電池。施加i 千赫之1伏特電壓於電極間,測定測試電池之電阻。將該 測試電池置入電烤箱,以2°C/分鐘之升溫率從25°C升溫至 200 C,測定電阻。此一過程中,見電阻增加之溫度即關閉 啟動溫度。 在25t之電阻係2〇歐姆。當該電池升溫時,在約14〇 C電阻驟升至10千歐姆。確認該樣本之關閉功能已 本紙張尺度適用中國國豕標準(CNS)A4規格(210 X 297公爱) 16 312957 A7
595035 五、發明說明(Π ) 動0 3 ·間隔物之運用 將實施例1之1中生產的複合膜置於玻璃板上,以添 加離子交換水調整固體濃度為2〇 %之聚丙烯懸浮液[三 井化學公司產品,Chemipearl WP100,粒徑1微米(以煤焦 油計數器方法測定)]以棒塗機(間隙1〇微米:Tester Sangyo Co·,Ltd·生產)塗覆於芳族聚醯胺多孔層側之表 面,於空氣中乾燥。間隔物之厚度為1微米。 該隔片之評估結果示於表1。 f施例2 將實施例1之1中生產的複合膜置於玻璃板上,以添 加離子交換水調整固體濃度為20 %之聚乙烯懸浮液[三 井化學公司產品,Chemipearl W950,粒徑〇· 6微米(以煤 焦油計數器方法測定)]以棒塗機(間隙1〇微米:Tester Sangyo Co·,Ltd·生產)塗覆於芳族聚醯胺多孔層侧之表 面,於空氣中乾燥。間隔物之厚度為i微米。 該隔片之評估結果示於表1。 實施例3 將實施例1之1中生產的複合膜置於玻璃板上,以添 加離子交換水調整固體濃度為20%,以固體比2 ·· 1混合 聚乙稀懸浮液[三井化學公司產品,Chemipearl W950,粒 徑0 · 6微米(以煤焦油计數益方法測定)]及四氟乙稀_六 氟丙稀共聚物懸浮液[大金工業股份有限公司產品;ND 一 1,粒徑〇·1至〇·25微米]之懸浮液,以棒塗機(間隙1〇 ---------------------訂---------線秦 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 17 312957 595035 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(18 ) 微米:Tester Sangyo Co·,Ltd·生產)塗覆於芳族聚醯胺多 孔層侧之表面,於空氣中乾燥。間隔物之厚度為1微米。 該隔片之評估結果示於表1。 實施例4 將實施例1中之1中生產的複合膜置於玻璃板上。溶 解魏基甲基纖維素[第一工業製藥股份有限公司產品; Cellogen 4H]於離子交換水,於其中分散氧化鋁細粉[日 本氣矽膠股份有限公司產品;Alumina C,粒徑0.013微 米]’以添加離子交換水調整固體濃度為15〇/〇。將該溶液 塗覆於芳族聚醯胺多孔層侧之表面,於空氣中乾燥。間隔 物之厚度為1微米。 該隔片之評估結果示於表1。 比較例1 實施例1之1中的複合膜不形成間隔物即加以評估。 該隔片之評估結果示於表1。 ---------------------訂--------- (請先閱讀背面之注意事項再填寫本頁) 表1 抗電化學氧化性 負荷特性 靜摩擦係數 實施例1 不變色 52% 0.40 實施例2 不變色 58% 0.41 實施例3 不變色 68% 0.19 實施例4 ^ 不變色 68% Γ 0.44 比較例1 變色 Γ 69% 0.59 ^ 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 18 312957
Claims (1)
- 595035 經濟部中央標準局員工福利委員會印製 7Ρ/ 2-- 1 Η3 第9〇12〇999號專利申請案I 说&命 申請專利範圍修正本 (92年8月21曰) 1. 一種非水性電解二次電池用之隔片,其中該隔片包括 一關閉層,一耐熱微孔層,該耐熱微孔層係選自 18.6kg/cm2負荷下依Jis K7207測定之撓曲溫度在1〇〇 °C至300°C的耐熱樹脂所構成;及一位於耐熱微孔層 上並具有顆粒、纖維、網或多孔膜形狀之間隔物,該 間隔物係由在長時間維持施加4.2至4.5V之電壓後不 劣化之電化學安定物質。 2. 如申請專利範圍第丨項之非水性電解二次電池用之隔 片’其中該電化學安定物質係一電化學安定有機聚合 物’或一含電化學安定無機化合物之電化學安定有機 聚合物。 3. 如申請專利範圍第1項之非水性電解二次電池用之隔 片’其中該間隔物具有顆粒之形狀且粒徑為3微米或 以下。 4·如申請專利範圍第1項之非水性電解二次電池用之隔 片’其中該設置有間隔物之隔片表面與一經1000號砂 紙打磨之不銹鋼表面之間的靜摩擦係數為0 5或以下。 5.如申請專利範圍第1項之非水性電解二次電池用之隔 片’其中該間隔物係於該耐熱微孔層之表面上塗覆含 有電化學安定物質之塗覆液而形成。 6·如申請專利範圍第4項之非水性電解二次電池用之隔 本紙張尺度適用中國國家標準(CNS) A4規格(210 x 297公釐) 312957 595035 片,其中該塗覆液係一懸浮液。 7. ΠΓ範圍第2項之非水性電解二次電池用之隔 片,其中該電化學安定物質係一有機聚合物, =合物係選自聚烯烴、烯烴共聚物、含氟聚合物、聚 方知聚醋、聚對酞酸乙二醋及纖維素所構成 8. -種非水性電解二次電池,包含如中請專利範圍第i 至7項中任一項之非水性電解二次電池用之隔片。 9 ·如申明專利範圍第8項之非水性電解二次電池,其中 該間隔物與一陰極相鄰接。 經濟部中央標準局員工福利委員會印製 本紙張尺度適用中國國家標準(CNS).A4規格(210 x297公釐) 2 312957
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| KR101268231B1 (ko) * | 2011-12-21 | 2013-05-31 | 삼성토탈 주식회사 | 셧다운 특성을 갖는 리튬 이차전지용 분리막 |
| EP3046163B1 (en) * | 2013-09-10 | 2020-07-22 | Toray Industries, Inc. | Separator for secondary cell, and secondary cell |
| KR102108280B1 (ko) * | 2013-11-07 | 2020-05-07 | 삼성에스디아이 주식회사 | 리튬 이차 전지 |
| CN104868155A (zh) * | 2014-02-21 | 2015-08-26 | 深圳华粤宝电池有限公司 | 一种薄层锂离子电池及制作该薄层锂离子电池的方法 |
| WO2018027652A1 (zh) * | 2016-08-10 | 2018-02-15 | 东莞新能源科技有限公司 | 隔膜、制备方法及电化储能装置 |
| CN108878746B (zh) * | 2017-05-12 | 2022-07-01 | 住友化学株式会社 | 非水电解液二次电池用绝缘性多孔层 |
| HUE063695T2 (hu) * | 2019-06-04 | 2024-01-28 | Teijin Ltd | Elválasztóelem nemvizes újratölthetõ telephez, valamint nemvizes újratölthetõ telep |
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2001
- 2001-08-27 TW TW090120999A patent/TW595035B/zh not_active IP Right Cessation
- 2001-08-28 CA CA2356033A patent/CA2356033C/en not_active Expired - Fee Related
- 2001-08-28 EP EP01119788A patent/EP1184917B1/en not_active Expired - Lifetime
- 2001-08-28 DE DE60137479T patent/DE60137479D1/de not_active Expired - Lifetime
- 2001-08-29 US US09/940,474 patent/US20020055036A1/en not_active Abandoned
- 2001-08-29 KR KR1020010052442A patent/KR100855510B1/ko not_active Expired - Lifetime
- 2001-08-30 CN CN011371501A patent/CN1217432C/zh not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI415321B (zh) * | 2006-11-20 | 2013-11-11 | Teijin Ltd | Non-aqueous battery separator, manufacturing method thereof and non-water storage battery |
| TWI422092B (zh) * | 2006-11-20 | 2014-01-01 | Teijin Ltd | Non-aqueous battery separator, nonaqueous battery separator manufacturing method, and non-aqueous battery |
| US8906538B2 (en) | 2006-11-20 | 2014-12-09 | Teijin Limited | Separator for non-aqueous secondary battery, process for producing the same, and non-aqueous secondary battery |
| US8906537B2 (en) | 2006-11-20 | 2014-12-09 | Teijin Limited | Separator for non-aqueous secondary battery, process for producing same, and non-aqueous secondary battery separator for non-aqueous secondary battery, process for producing same, and non-aqueous secondary battery |
| TWI385837B (zh) * | 2007-10-12 | 2013-02-11 | Lg Chemical Ltd | 避免膠捲式電極組變形之製備方法 |
| US8870978B2 (en) | 2007-10-12 | 2014-10-28 | Lg Chem, Ltd. | Preparation process for preventing deformation of jelly-roll type electrode assembly |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1184917A3 (en) | 2005-08-17 |
| DE60137479D1 (de) | 2009-03-12 |
| CA2356033A1 (en) | 2002-02-28 |
| CA2356033C (en) | 2011-09-13 |
| CN1217432C (zh) | 2005-08-31 |
| KR20020018104A (ko) | 2002-03-07 |
| KR100855510B1 (ko) | 2008-09-02 |
| CN1340868A (zh) | 2002-03-20 |
| EP1184917B1 (en) | 2009-01-21 |
| US20020055036A1 (en) | 2002-05-09 |
| EP1184917A2 (en) | 2002-03-06 |
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| MM4A | Annulment or lapse of patent due to non-payment of fees |