CN1684298A - Design and production of colloidal polymer lithium ion cell - Google Patents
Design and production of colloidal polymer lithium ion cell Download PDFInfo
- Publication number
- CN1684298A CN1684298A CNA2004100268149A CN200410026814A CN1684298A CN 1684298 A CN1684298 A CN 1684298A CN A2004100268149 A CNA2004100268149 A CN A2004100268149A CN 200410026814 A CN200410026814 A CN 200410026814A CN 1684298 A CN1684298 A CN 1684298A
- Authority
- CN
- China
- Prior art keywords
- battery
- electrolyte
- polymer
- lithium
- film
- 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.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 80
- 238000013461 design Methods 0.000 title claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 65
- 238000004519 manufacturing process Methods 0.000 title claims description 31
- 239000003792 electrolyte Substances 0.000 claims abstract description 55
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000012719 thermal polymerization Methods 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 43
- 230000004888 barrier function Effects 0.000 claims description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 35
- 239000012528 membrane Substances 0.000 claims description 32
- 239000002131 composite material Substances 0.000 claims description 27
- 239000004743 Polypropylene Substances 0.000 claims description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 22
- 229910052744 lithium Inorganic materials 0.000 claims description 22
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 18
- -1 polyethylene Polymers 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 11
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000005030 aluminium foil Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 8
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 239000011149 active material Substances 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 239000011889 copper foil Substances 0.000 claims description 5
- 238000012856 packing Methods 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 claims description 4
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 3
- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical compound [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-UHFFFAOYSA-N 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 238000001879 gelation Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- PBVZTJDHQVIHFR-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene Chemical compound FC(F)=C(F)C(F)(F)F.FC(F)=C(F)C(F)(F)F PBVZTJDHQVIHFR-UHFFFAOYSA-N 0.000 claims description 2
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 claims description 2
- VXEXDVFIZKWHIB-UHFFFAOYSA-N 2-ethenylpyridine Chemical compound C=CC1=CC=CC=N1.C=CC1=CC=CC=N1 VXEXDVFIZKWHIB-UHFFFAOYSA-N 0.000 claims description 2
- LNGIIXGLYTUUHJ-UHFFFAOYSA-N 2-methylbut-2-enoic acid methyl 2-methylprop-2-enoate Chemical compound COC(=O)C(C)=C.CC=C(C)C(O)=O LNGIIXGLYTUUHJ-UHFFFAOYSA-N 0.000 claims description 2
- RGHFMKJXRATUNR-UHFFFAOYSA-N C(=C)N1C(CCC1)=O.N1=CC=CC2=CC=CC=C12.C(=C)C=1NC=CC1 Chemical compound C(=C)N1C(CCC1)=O.N1=CC=CC2=CC=CC=C12.C(=C)C=1NC=CC1 RGHFMKJXRATUNR-UHFFFAOYSA-N 0.000 claims description 2
- UOIBFTLLLBZSQP-UHFFFAOYSA-N C(C1=CC=CC=C1)C=C(C(=O)OC)C.C1=CC=CC=C1.C(C(=C)C)(=O)O Chemical compound C(C1=CC=CC=C1)C=C(C(=O)OC)C.C1=CC=CC=C1.C(C(=C)C)(=O)O UOIBFTLLLBZSQP-UHFFFAOYSA-N 0.000 claims description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 2
- 229910012815 LiCoNiO Inorganic materials 0.000 claims description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 2
- 229910015645 LiMn Inorganic materials 0.000 claims description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 claims description 2
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 claims description 2
- FDOWWCFFWMGFGQ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C.OC(=O)CC=C FDOWWCFFWMGFGQ-UHFFFAOYSA-N 0.000 claims description 2
- MIOPWDLAZRCMGE-UHFFFAOYSA-N butyl 2-methylprop-2-enoate 2-methylhept-2-enoic acid Chemical compound CCCCOC(=O)C(C)=C.CCCCC=C(C)C(O)=O MIOPWDLAZRCMGE-UHFFFAOYSA-N 0.000 claims description 2
- VENJJOGQEGHFPI-UHFFFAOYSA-N butyl prop-2-enoate;2-methylidenehexanoic acid Chemical compound CCCCOC(=O)C=C.CCCCC(=C)C(O)=O VENJJOGQEGHFPI-UHFFFAOYSA-N 0.000 claims description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 2
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 239000006104 solid solution Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims 2
- 229910052749 magnesium Inorganic materials 0.000 claims 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims 1
- 229910000838 Al alloy Inorganic materials 0.000 claims 1
- 229920000049 Carbon (fiber) Polymers 0.000 claims 1
- 229910013188 LiBOB Inorganic materials 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims 1
- PMEWPXXBCPBCHB-UHFFFAOYSA-N [Li].[B].C(C(=O)O)(=O)O Chemical compound [Li].[B].C(C(=O)O)(=O)O PMEWPXXBCPBCHB-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910021383 artificial graphite Inorganic materials 0.000 claims 1
- 239000004917 carbon fiber Substances 0.000 claims 1
- 239000003575 carbonaceous material Substances 0.000 claims 1
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- 230000002687 intercalation Effects 0.000 claims 1
- 238000009830 intercalation Methods 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 229910001092 metal group alloy Inorganic materials 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 229910021382 natural graphite Inorganic materials 0.000 claims 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 claims 1
- 229920002401 polyacrylamide Polymers 0.000 claims 1
- 229920000058 polyacrylate Polymers 0.000 claims 1
- 229920002239 polyacrylonitrile Polymers 0.000 claims 1
- 229920000728 polyester Polymers 0.000 claims 1
- 229920000306 polymethylpentene Polymers 0.000 claims 1
- 239000011116 polymethylpentene Substances 0.000 claims 1
- 229920000098 polyolefin Polymers 0.000 claims 1
- 229920002635 polyurethane Polymers 0.000 claims 1
- 239000004814 polyurethane Substances 0.000 claims 1
- 229920002689 polyvinyl acetate Polymers 0.000 claims 1
- 239000011118 polyvinyl acetate Substances 0.000 claims 1
- 229920000915 polyvinyl chloride Polymers 0.000 claims 1
- 239000004800 polyvinyl chloride Substances 0.000 claims 1
- 229920001290 polyvinyl ester Polymers 0.000 claims 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims 1
- 229910001887 tin oxide Inorganic materials 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
- 239000008151 electrolyte solution Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 239000000084 colloidal system Substances 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 abstract 2
- 239000007788 liquid Substances 0.000 description 26
- 238000005516 engineering process Methods 0.000 description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 13
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000011244 liquid electrolyte Substances 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 239000007767 bonding agent Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000007872 degassing Methods 0.000 description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 6
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical class FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000004513 sizing Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 239000012943 hotmelt Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910013872 LiPF Inorganic materials 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IZJSTXINDUKPRP-UHFFFAOYSA-N aluminum lead Chemical compound [Al].[Pb] IZJSTXINDUKPRP-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000009459 flexible packaging Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010416 ion conductor Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 229910018095 Ni-MH Inorganic materials 0.000 description 2
- 229910018477 Ni—MH Inorganic materials 0.000 description 2
- 241000282376 Panthera tigris Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000010010 raising Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Images
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
Landscapes
- Secondary Cells (AREA)
Abstract
This invention provides a structure design and its preparation method for a colloid electrolyte polymer Li ionic battery, which utilizes field thermal polymerization chemical reaction and adds a certain proportion of monomers and initiators to comprise a mixed electrolyte solution to be evocated to the battery core. The monomers and the initiators generate thermal polymerization reaction to generate 2D and 3D polymer net work and generate chemical reaction with the electrolyte solution under a certain condition of temperature, pressure and time to form colloidal polymer electrolyte having strong binding effect, which binds the positive/diaphragm/negative closely together to enable the core to form a solid and independent bulk without expansion, loose or deformation.
Description
A large amount of rechargeable batteries that use in modern mobile electronic equipment and the communication equipment (storage battery or be called secondary cell) have experienced the evolution of four generations: first on behalf of nickel-cadmium cell (gravimetric specific energy density 50Wh/kg), second on behalf of Ni-MH battery (gravimetric specific energy density 80Wh/kg), the third generation is liquid lithium ionic cell (gravimetric specific energy density 130Wh/kg), and the 4th on behalf of polymer Li-ion battery (gravimetric specific energy density 150Wh/kg).
The liquid lithium ionic cell that uses metal shell from nineteen ninety come out and large-scale production in 1993 since, with other battery (NI-G and Ni-MH battery) incomparable excellent performance captured many market segments rapidly, obtained swift and violent development.Liquid lithium ionic cell has been widely used in mobile phone, notebook computer, laptop computer, PDA(Personal Digital Assistant), Digital Video, digital camera, portable DVD player/VCD/CD and MP3 player etc. as high-tech new forms of energy product, become various modern mobile communication equipments and the indispensable parts of electronic equipment, in moving, be engaged in for example office of various commercial activitys, management enterprise and in moving amusement many convenience are provided.But along with the renewal and the development of technology, have higher requirement to the mobile device power supply in market, for example thinner, lighter, arbitrary shape, more high-energy-density, safer and low price more.Liquid lithium ionic cell not only all can not meet the demands aspect thin, light, arbitrary shape and the energy density.And, because use inflammable in the liquid lithium ionic cell and corrosive liquids as electrolyte, its security performance makes production firm and user worry always.Battery leakage causes the accident of electronic device corrosion and damage also to happen occasionally.In addition, the manufacturing process complexity of liquid lithium ionic cell, cost height, price are expensive, for example, need to use expensive laser-beam welding machine sealing-in battery case.Under the promotion of the market demand, the 4th generation polymer Li-ion battery arise at the historic moment.
Rose since 1994, the Battery Company of industrial flourishing states such as the U.S., Japan and Korea S begins to research and develop polymer Li-ion battery, and formation in 2000 is produced in batches.In the various technology of polymer Li-ion battery, the Bellcore technology of the wealthy company of U.S. young tiger (Bell Communication Research Inc. abbreviates Bellcore as) is typical case's representative.Different with the production technology of liquid lithium ionic cell, the Bellcore technology adopts wire netting to make the substrate of electrode, the electrode film of coated and molded is compressed on the wire netting, the copolymer porous membrane that uses Kynoar-hexafluoropropylene (PVDF-HFP) is as battery diaphragm, electrolyte is attracted in the hole of PVDF-HFP copolymer barrier film, stacked battery core has replaced the coiled battery core, and the compound soft wrapping of aluminium pool/plastics has replaced metal (aluminium or stainless steel) shell.The advantage of this type of polymer Li-ion battery is that the overall dimensions variation is easy and easy, can order according to user's degree of requirement body and make battery, and is more favourable for the super book type battery below the 3mm.
But there is following shortcoming in this type of liquid electrolyte polymer Li-ion battery in producing and using:
(1) the wealthy company of U.S. young tiger (Bellcore) is admitted in its patent of invention, and the electrolyte in this type of polymer Li-ion battery is the solid-liquid two-phase coexisting body of PVDF-HFP copolymer and electrolyte, and is not the single-phase polymer colloid; Do not have chemistry and electrochemical action between electrolyte and the polymer, just physical absorption is in the hole of membrane for polymer.From technical process, there are not thermal polymerization and photopolymerization chemical reaction process in the production process of battery.When making diaphragm, PVDF-HFP copolymer and pore creating material (for example dibutyl phthalate) are coated on the polyester film in 7: 3 ratios (this moment, pore creating material was to exist among the membrane for polymer parent phase with sub form mutually) in the polymer solution, make diaphragm after drying.This diaphragm is placed between the both positive and negative polarity, after 120 ℃ of hot pressing, dissolves pore creating material in the methyl alcohol equal solvent, pore creating material is come together from barrier film again under 50-85 ℃ of temperature and through vacuum operation in 40 minutes.Pore creating material come together after, in the membrane for polymer parent, stay about 30% micropore.These micropores suck electrolyte in following one activation procedure.Therefore, electrolyte is that the solid-liquid two-phase coexisting state with polymer-electrolyte is present in the battery, does not have chemical bonding between polymer and the electrolyte, has only physical absorption.If the soft wrapping shell is sealed with defective, electrolyte still can flow out outside the shell.This type of polymer Li-ion battery leakage and corrosion phenomenon in use still exists.
(2) this type of liquid electrolyte polymer Li-ion battery technological process of production complexity, the operating time is very long, the immature and difficult quality control of technology.For example, contain pore creating material in the PVDF-HFP copolymer barrier film, the collection of this pore-creating solvent goes out, and only one procedure just needs tens of minutes.Therefore, its production cost is very high, and rate of finished products is very low, and its technology is difficult to be applied in low cost, the large-scale production.
(3) because the Bellcore technology is that electrode film/barrier film/negative electrode plate/barrier film/electrode film is made bi-cell, be that elementary cell repeatedly superposes and makes battery with each bi-cell, and do not have bondingly between the bi-cell, separate easily and come off.Therefore, battery is loose, do not have self intensity and rigidity, and shell is a flexible packaging made from plastic.The gas that produces in charge and discharge process causes problems such as the expansion of battery and distortion easily.
(4) thickness of this type of polymer electrolyte diaphragm is about the 50-200 micron, considerably beyond the thickness (20 microns) of liquid lithium battery septation.The spacing of positive, negative electrode plate is strengthened, cause the internal resistance of cell to increase.Its consequence be battery the charge-discharge performance under the big current condition of room temperature reduce and cryogenic conditions under discharge capability well below the liquid lithium battery.
(5) this type of polymer electrolyte diaphragm does not have the hot melt protection mechanism that polyethylene/the propylene composite diaphragm is had used in the liquid lithium battery.The liquid lithium battery overcharge, cross put with condition such as overheated under, polyethylene/propylene composite diaphragm can melt to melting temperature (130 ℃) because of electric core generates heat, all micro channels in the barrier film all are closed, thereby intercepted the circulation of electrolyte, promptly form infinitely great internal resistance and open circuit, cell safety is cooled down, and hydrojet do not take place, catch fire or phenomenon such as blast.Yet, because polymer electrolyte diaphragm does not have the hot melt protective effect, to compare with liquid lithium ion battery, its fail safe reduces on the contrary.
The objective of the invention is to: provide a kind of novel battery design and manufacturing technique method to prepare the colloidal electrolytic polymer lithium ion battery.The characteristics of this new design are: super, safety and at a low price.The characteristics of new process are that technological process and production equipment are simple, the per pass working procedure duration is short, running cost is low, productivity ratio is high, process is controlled easily, the rate of finished products height.The colloidal electrolytic polymer lithium ion battery that adopts process of the present invention to produce is compared with liquid lithium ion battery with the liquid electrolyte polymer Li-ion battery that prior art is produced, and has superenergy density, better security performance and lower production cost.
Technology path provided by the present invention is to add a certain proportion of monomer and initator composition mixed electrolyte solutions in electrolyte, is introduced in positive electrode/barrier film/negative electrode battery.Under certain temperature and time condition, monomer and initator generation thermal polymerization chemical reaction grow the two and three dimensions polymer network, and produce chemical action with electrolyte, form the colloidal polymer electrolyte.This colloidal polymer electrolyte addition polymerization second-complex of propylene mode separation strapping not only plays the effect of electrolyte (electronic isolation and ion conductor), and the strong binding effect is arranged.Particularly, be with the colloidal state polymer electrolyte as binding agent, with positive electrode/barrier film/negative electrode three tight bond together, make battery (takeup type or stacked) form one solid and independently whole.The aluminum composite membrane soft wrapping of battery is a medium that battery and external environment condition are isolated, rather than a stiff case, and not needing provides any rigidity and intensity support for battery.When battery in charging and discharging process, battery itself can not expand, loose and distortion, remains intensity and the rigidity of self.
According to the production operation that battery design provided by the present invention and technology condition carry out, soluble problem and the target division that reaches are as follows:
(1) security performance of raising polymer Li-ion battery
In the existing manufacturing technique design, liquid electrolyte polymer Li-ion battery majority is to use the PVDF-HFP copolymer as barrier film, and its mechanical strength is bad, and temperature coefficient is very big.At room temperature, PVDF-HFP copolymer barrier film still can play the effect of electronic body, and the positive and negative electrode in the electric core is separated.But, when temperature raises or battery is when being subjected to certain external pressure, this type of PVDF-HFP copolymer barrier film will soften rapidly, its mechanical performance variation so that can't keep original barrier film shape and thickness, promptly can't continue the positive and negative electrode in the electric core is separated.Therefore, the positive and negative electrode at some position can be in contact with one another the formation short circuit in the electric core, causes the battery local overheating.The local cell core is overheated, can cause more large-area PVDF-HFP copolymer barrier film softening transform, melt contraction, causes more large-area positive and negative electrode short circuit, and battery temperature can rise quickly.At last, this quasi-linkage roll response will cause the burning of catching fire of battery hydrojet.
Structural design provided by the present invention will overcome the problems referred to above effectively.In colloidal electrolytic polymer lithium ion battery of the present invention, colloidal state polymer electrolyte and the coexistence of compound PE-PP membrane, compound PE-PP membrane is a skeleton wherein, the colloidal state polymer electrolyte is to be present among the surface and micropore of compound PE-PP membrane with continuous state, and contacts with the positive and negative electrode surface.Under technology condition provided by the present invention, the colloidal state polymer electrolyte has only a kind of function as electrolyte: lithium ion conductor.The function of barrier film (electronic body) is brought by compound poly-second-propylene film and is finished.Because compound poly-second-propylene film band has the good high-temperature mechanical property, the probability that above-mentioned partial short-circuit phenomenon takes place reduces greatly.The more important thing is, the melt temperature of compound poly-second-propylene film band is between 120-150 ℃, microcellular structure in this temperature lower diaphragm plate band can be close by envelope because of fusion, causes being included in colloidal electrolyte in the micropore and sealed close and keep apart, and promptly lithium ion conductor lost efficacy.The barrier film thermal resistance effect (hot melt protective effect, thermal switch effect) often said of industry technology term just.Under this feelings row, battery becomes an insulator, no matter external condition (overcharge, cross put, overheated, overbump) how to change, polymer Li-ion battery of the present invention does not have any reaction.Therefore, polymer Li-ion battery structural design of the present invention is safest design.
(2) strengthen battery self overall mechanical strength, avoid battery to expand and be out of shape
In liquid lithium ionic cell, battery (no matter being takeup type or stacked) is loose and soft, does not have mechanical strength and the rigidity of self.In order to guarantee the normal stable charge and discharge cycles operating state of battery and the consistency of battery performance, it is minimum and invariable that the distance between positive and negative electrode must keep.Therefore, must keep the intensity that battery needs by means of rigid metal (aluminium or steel) shell.
In existing liquid electrolyte polymer Li-ion battery technology, PVDF-HFP copolymer barrier film is porousness and is bean curd-like, the mechanical strength of himself is very little, and the caking property between positive, negative electrode plate and the PVDF-HFP copolymer barrier film is very poor.Therefore, the battery that this type of polymer dielectric is formed, its mechanical strength can not got well naturally.Add the flexible plastics external packing, do not have the rigid metal shell to support, under external force or the crystal structure in the electrode material charge and discharge process when collapsing, battery can be out of shape gradually and be lost efficacy.Fill soon under the condition in room temperature, this type of polymer Li-ion battery product to fill the rate of rising very high.Under the quiescence in high temperature condition, the volume bulging rate of this type of liquid electrolyte polymer Li-ion battery can substantially exceed the scope that the user allows.
The present invention has thought better of the self structure Intensity Design of polymer Li-ion battery core, and does not rely on the strength support of outer rigid housing.On technology, adopted the structural framework of composite material as battery.The composition of this composite material is: the compound poly-second-propylene film band that (a) has knitmesh shape fibre structure; (b) be deposited on the colloidal electrolytic polymer of compound poly-second-propylene film belt surface, as powerful bonding agent.Fiber reinforcement in the colloidal electrolytic polymer core of lithium ion cell of the present invention (compound poly-second-propylene film band) adds the formed composite material of bonding agent and fiberglass (glass fibre adds epoxy resin) composite material is similar, the characteristics that all have polymer composites, promptly lightweight, high-strength, toughness and rigidity have both at the same time.The basic cell structure of battery is: composite diaphragm/positive pole/composite diaphragm/negative pole.This elementary cell repeatedly repeats to be built into the integral battery door core after the stack.Because self structure intensity height, the good rigidly of battery, the high temperature expansion rate of polymer Li-ion battery of the present invention is low, and morphotropism is little, and cycle characteristics is stable.
(3) simplify technological process, shorten activity time, reduce production costs
In order to make polymer dielectric that higher conductance be arranged, most existing liquid electrolyte polymer Li-ion battery technologies have been used pore creating material (or being called plasticizer, dibutyl phthalate).That is to say, when the preparation membrane for polymer, use two phase detachment techniques: parent phase is that the polymer of poly-difluoroethylene and so on is diaphragm main body, and son is dibutyl phthalate mutually.Son is dispersed among the parent phase with liquid microballon form.After tens of minutes, son is deviate from evaporation from parent phase, and stays many micropores in parent phase in oven dry under the 50-85 ℃ of temperature.When being immersed in barrier film in the electrolyte, liquid electrolyte is adsorbed and wraps in the micropore that is dissolved in membrane for polymer, the whole two-phase electrolyte that forms, and its lithium ion conducting rate is higher, can reach 10
-3S/cm.Yet the collection of diaphragm forming, pore creating material goes out, the suction of lamination hot pressing and electrolyte needs tens of minutes to 1 hour time to finish.Operating process complexity, activity time are oversize, cause productivity ratio to reduce, and cost rises.
Technology provided by the present invention has been cast aside polymer film forming of the prior art fully, pore creating material comes together with electrolyte and sucks such three time-consuming, loaded down with trivial details technical processs, and wards off the small stream footpath in addition.Only activity time just shortens to a few minutes from original a few hours.Adopt technology provided by the present invention to produce polymer Li-ion battery, not only technological process simplification, equipment needed thereby reduce, activity time shortens, production efficiency improves, product cost reduces, and, all benefit at aspects such as control of product quality, consistency of performance and rate of finished products raisings.
Polymer Li-ion battery production Technology provided by the present invention comprises:
(1) preparation of negative electrode:
(1.1) slurrying: the composition of negative electrode slurry (wt%) is: dedicated solvent 20-70, bonding agent (vinylidene fluoride etc.) 2-20, negative electrode active material (graphite-like, coke class, pyrobitumen, carbon fiber class, etc.) 10-50.Dedicated solvent and bonding agent are mixed with pulverous negative electrode active material respectively, through high-speed stirred evenly, vacuum or leave standstill degasification after make the cathode size of pulpous state.
(1.2) film: the slurry made according to the battery product designing requirement, is coated in positive and negative two surfaces of copper metal forming equably, and cathode pole piece is made in oven dry.
(1.3) roll-in: cathode pole piece is pressed onto the thickness of appointment at the certain pressure lower roll, improves the pole piece film density and reduce the porosity of pole piece film.
(1.4) cut: cathode pole piece is cut into the size that battery product designs, make negative pole band (sheet), and negative wire is welded.
(2) preparation of positive electrode:
(2.1) slurrying: the composition of positive electrode slurry (wt%) is: dedicated solvent 20-60, bonding agent (vinylidene fluoride etc.) 2-12, electric conducting material (carbon black, graphite etc.) are made additive 1-8, pulverous positive active material (lithium and cobalt oxides LiCoO
2, lithium nickel oxide LiNiO
2, lithium-cobalt-nickel oxide LiCoNiO
2, lithium manganese oxide LiMn
2O
4, or their solid solution Li
αNi
βCo
γMn
δO
2Or lithium iron phosphate LiFePO
4Deng) 30-50.Dedicated solvent, bonding agent and conductive additive are mixed with pulverous positive active material respectively, through high-speed stirred evenly, vacuum or leave standstill degasification after make the anode sizing agent of pulpous state.
(2.2) film: the slurry made according to the battery product designing requirement, is coated in positive and negative two surfaces of aluminum metallic foil equably, and anode pole piece is made in oven dry.
(2.3) roll-in: anode pole piece is pressed onto the thickness of appointment at the certain pressure lower roll, improves the pole piece film density and reduce the porosity of pole piece film.
(2.4) cut: anode pole piece is cut into the size that battery product designs, make anodal band (sheet), and negative wire is welded.
(3) barrier film: compound PE-PP membrane paper is cut into the size that battery product designs, make mode separation strapping (sheet).
(4) coiled battery core: above-mentioned ribbon element is put well by the top-down order of negative pole/barrier film/positive pole/barrier film, made Battery Pole Core through coiling.
(5) stacked battery core: above-mentioned chip component is put well by positive pole/barrier film/negative pole/barrier film/anodal top-down order, made Battery Pole Core through lamination.
(6) assembling: in the flexible package shell of compression molding in advance, place battery, on positive and negative lead wires, prepare leakproof film.Meet sb. at the airport with heat-sealing three edges of flexible package shell are sealed.
(7) monomer, initator and electrolyte mixed liquor: monomer can be at vinylidene (Vinylidene fluoride), methyl methacrylate (Methyl methacrylate), acrylonitrile (Acrylonitrile), butyl acrylate (Butyl acrylate), methyl acrylate (Methylacrylate), butyl methacrylate (Butyl methacrylate), methacrylic acid benzene methyl (benzyl methacrylate), acenaphthene (acenaphthylene), vinylpyridine (vinyl pyridine), acrylamide (acrylamide), methyl vinyl ether (methyl vinyl ether), vinylacetate (vinyl acetate), select one or more for use in hexafluoropropylene (hexafluoropropylene) and the vinyl pyrrole quinoline (vinyl pyrrolidone); Initator can select for use benzoyl peroxide (2,2-Azobis-isobutyronitrile), azodiisobutyronitrile (Diisopropyl peroxydi) etc.Join in the electrolyte behind monomer and the initator mixture by a certain percentage, through the mixing that stirs.The proportioning of monomer and initator is 1000: 1～100: 2.Electrolyte is made up of electrolytic salt and organic solvent.Electrolytic salt can be selected lithium hexafluoro phosphate LiPF for use
6With LiBF4 LiBF
4Deng.Organic solvent can be selected ethylene carbonate EC, propene carbonate PC, dimethyl carbonate DMC, methyl ethyl carbonate fat EMC and carbonic acid diethyl ester DEC etc. for use.The composition of organic solvent can be binary, ternary or even polynary.The concentration of electrolytic salt in organic solvent is every liter 0.8～1.5 gram molecule.
(8) fluid injection:, introduce in the battery the monomer for preparing in advance, initator and electrolyte mixed liquor quantity by the battery product design.Then, with sealing to meet sb. at the airport the 4th edge of Soft Roll shell is sealed.
(9) thermal polymerization chemical reaction: under 65～120 ℃ of heating and pressurized conditions, through 60～2500 seconds, polymerization and gelation reaction can take place in the monomer, initator and the electrolyte mixed liquor that are injected in the battery, be transformed into normal colloidal state polymer electrolyte, positive and negative electrode and barrier film are closely bonded together, make battery form a integral body with self bulk strength and rigidity.
(10) change into and place: with special-purpose battery charging and discharging equipment the finished product battery being charged at a slow speed changes into; form diaphragm at negative electrode surface. after placing several weeks then, remake discharge test, each battery is all detected; filter out qualified finished product battery, wait to dispatch from the factory.
Producing next life fully according to product design provided by the present invention and technology, polymer Li-ion battery will reach following technique effect:
(1) the product safety performance improves
(1.1) compare with liquid lithium ion battery: the organic electrolyte that uses in lithium ion battery is inflammable thing, and high volatility, flash point are low.Its flash point temperature is between 90-160 ℃.At over-charging of battery, cross put in producing hot or outside thermal source when making battery temperature rise in the above-mentioned temperature range, violent chemical reaction will take place with positive and negative electrode in organic electrolyte, ignites or detonates battery.Electrolyte in the polymer Li-ion battery provided by the present invention is to be gel state, and volatility is low, flash point is high, and battery ignites or detonates and must just might take place under higher temperature.Therefore, security of products can obviously improve.For example, under the condition of overcharging, for the identical electric current that overcharges, by the polymer Li-ion battery that the technology of the present invention is produced, its permission overcharged voltage will be than the high 10-50% of liquid lithium ion battery.
(1.2) compare with existing polymer Li-ion battery design: used compound PE-PP membrane band in the polymer Li-ion battery of the present invention with thermal resistance effect, its porosity is 30-50%, and colloidal electrolyte is present in these and curves complications but among the micropore that front and back connect.Under the normal temperature lithium ion can be in these micropores normally; When battery temperature rises to the fusing point of diaphragm material, wherein crooked and hole that connect can be closed because of fusion in the extremely short time.The internal resistance meeting of battery raises therefore and rapidly, even becomes open-circuit condition, and promptly interior electric current goes to zero.What this moment was extraneous overcharges or crosses to put all this battery is not had effect.In like manner, when external overheated and overbump, the barrier film with hot melt switching effect also can be protected battery effectively.Identical overcharging under the current condition, it allows overcharged voltage will exceed 10-30%.
(2) battery leakage causes the probability of corrosion to reduce
Colloidal state polymer lithium ion battery of the present invention produces chemical reaction because extraneous heating and pressure condition make between polymer and the electrolyte in process of production, really forms colloidal electrolyte, no working fluid.Therefore, the probability of battery leakage and corrosion harmfulness is tending towards 0.
(3) internal resistance of cell is low good with low temperature performance
Because used compound PE-PP membrane band in the colloidal state polymer lithium ion battery of the present invention, its thickness has only 9～20 microns, the spacing between the positive and negative electrode sheet is little, and the electrolytical lithium ion conducting rate of colloidal state polymer can reach 10
-3More than the S/cm, therefore, the internal resistance of cell is low, and discharging efficiency is able to obvious improvement under large current density performance under the normal temperature and the cryogenic conditions thereby make.
(4) energy content of battery specific density improves
Colloidal state polymer lithium ion battery by the present invention's production, the core strueture compactness, its positive and negative lead wires respectively has only one, and energy density per unit volume metric density and gravimetric specific energy density are than liquid lithium ion battery height～30%, than liquid polymer lithium ion battery height～10% of prior art production.
(5) the properties of product consistency increases
Adopted new technologies such as thermal polymerization and electrolyte polymerization-gelation in production technology of the present invention, bonding is solid and reliable between positive and negative electrode sheet and the diaphragm, and therefore, the phenomenon that electrode slice separates from diaphragm reduces and avoids, and the battery performance consistency increases.
(6) production cost decline, rate of finished products improve
Because a series of novel techniques of the present invention have reduced the time of several critical processes, reduced consumption, the kind (for example not needing to use pore creating material) of chemical raw material and reduced requirement to material (for example do not require use expensive wire netting and with the current collection substrate of metal forming) as positive and negative electrode, do not need to use expensive and complicated production equipment, improved the properties of product consistency, thereby reduced cost, increased rate of finished products.
By structure and each element of reference accompanying drawing and detailed description colloidal state polymer lithium ion battery of the present invention, above-mentioned purpose of the present invention and advantage will be apparent, wherein:
Fig. 1 is the generalized section of colloidal state polymer lithium ion battery of the present invention, and battery wherein has self mechanical strength and rigidity for multiple layer takeup type, uses flexible packaging as shell.The coiling number of turns of battery will be determined according to design parameters such as battery capacities.
Fig. 2 is partial cross section's details enlarged drawing of colloidal state polymer lithium ion battery of the present invention.
Fig. 3 is the generalized section of colloidal state polymer lithium ion battery of the present invention, and battery wherein has self mechanical strength and rigidity for multiple stacked chip, uses flexible packaging as shell.The lamination number of plies of battery will be determined according to design parameters such as battery capacities.
Fig. 4 is charging and the discharge curve by a colloidal state polymer lithium ion battery of the inventive method design and preparation.
Fig. 5 is the cycle life test curve by a colloidal state polymer lithium ion battery of the inventive method design and preparation.
Explain most preferred embodiment of the present invention with reference to the accompanying drawings.
Referring to Fig. 1, it shows the internal structure of colloidal state polymer lithium ion battery 10 of the present invention, and multiple layer coiled battery core 12 is wherein arranged; Comprise negative electrode 16 and positive electrode 18 in the battery, and colloidal state polymer electrolyte/PE-PP membrane complex 20 that positive and negative electrode is separated (amplify see Fig. 2 about partial cross section's 22 details of positive, negative electrode plate and colloidal state polymer electrolyte/PE-PP membrane complex) is soft wrapping shell 26 at last.Particularly, colloidal state polymer lithium ion battery of the present invention is to be made of four elements, and each element all is complex (composite material).Their structure is similar: the mixture that the positive and negative electrode complex is made up of active material+conductive agent+binding agent is coated on two surfaces of metal forming, the mixture that the barrier film complex is made up of the colloidal state polymer electrolyte is deposited on two surfaces of PE-PP membrane band, and the external packing complex is that polyethylene film+polypropylene screen is attached on two surfaces of aluminium foil.
Fig. 2 shows partial cross section's 22 details of amplification, and colloidal electrolyte 28 is wherein arranged, polymer network 30 and PE-PP membrane 32.The colloidal state polymer electrolyte is present in PE-PP membrane two surfaces and the micropore.The colloidal state polymer electrolyte acts on the surface of positive, negative electrode plate and PE-PP membrane sheet, and the three is bonded together securely, forms a rigid unitary, and this is that colloidal state polymer lithium ion battery of the present invention is better than one of distinguishing feature of other technology.
Fig. 3 shows the another kind of battery structure 40 of the embodiment of the invention, and wherein battery 42 has adopted laminated structure.Comprise negative electrode 44 and positive electrode 46 in the battery, and colloidal state polymer electrolyte/PE-PP membrane complex 48 that positive and negative electrode is separated; Be soft wrapping shell 50 at last.Identical with embodiment shown in Figure 1, this colloidal state polymer lithium ion battery embodiment is made of four elements, and each element all is complex (composite material).Their structure is similar: the mixture that the positive and negative electrode complex is made up of active material+conductive agent+binding agent is coated on two surfaces of metal forming, the mixture that the barrier film complex is made up of the colloidal state polymer electrolyte is deposited on two surfaces of PE-PP membrane band, and the external packing complex is that polyethylene film+polypropylene screen is attached on two surfaces of aluminium foil.Yet the battery of laminated structure can have two kinds of various combinations:
(1) by the positive electrode of two single face films outermost layer (as shown in Figure 3) as battery.Positive, negative electrode plate therebetween all is a double-side membrane.
(2) by the negative electrode of two single face films outermost layer (not providing accompanying drawing) as battery.Positive, negative electrode plate therebetween all is a double-side membrane.Compare with embodiment shown in Figure 1, the advantage of this colloidal state polymer lithium ion battery embodiment is that internal resistance is low, and high rate during charging-discharging is good under room temperature and the low temperature, is specially adapted to equipment high-power, that charge and discharge soon, as electric power bicycle and Electric power car.Shortcoming is that the production operation of lamination and lead-in wire is comparatively complicated, may reduce productive rate and increase cost.
Fig. 4 shows the colloidal state polymer lithium ion battery electrochemical properties of the embodiment of the invention.The charging and the discharging efficiency of this battery sample reach 99.9%.
Fig. 5 shows the colloidal state polymer lithium ion battery of the embodiment of the invention in 0.8 ℃ of charging and 1C discharge cycles life-span.This battery sample through 430 times the charging and discharge cycles after, the socking out capacity still reaches 82% of initial discharge capacity.
By describing following two preferred embodiments in detail, will understand superiority of the present invention better.
Example one:
Produce takeup type colloidal state polymer lithium ion battery with following method.
The manufacture method of negative electrode band:
The poly-inclined to one side vinylidene fluoride of 10 grams is dissolved in dimethyl formamide, and it is black to add 2.5 gram acetone then, adds 115 gram graphite powders at last.Through high-speed stirred evenly, vacuum or leave standstill degasification after make the cathode size of pulpous state.Cathode size is coated on two surfaces of Copper Foil of 20 micron thickness.At 100 ℃ of dry down dimethyl formamides that desolvate that remove, the THICKNESS CONTROL of electrode band is at 300 ± 10 microns.The THICKNESS CONTROL of electrode band after roll-in is at 120 ± 5 microns.Negative electrode band cutting is become 30 * 340mm
2Size.Nickel down-lead of spot welding on the initial copper-clad surface of not filming then.
The manufacture method of positive electrode band:
The poly-inclined to one side vinylidene fluoride of 16 grams is dissolved in dimethyl formamide, and it is black to add 11 gram acetone then, adds 200 gram lithium and cobalt oxides at last.Through high-speed stirred evenly, vacuum or leave standstill degasification after make the anode sizing agent of pulpous state.Anode sizing agent is coated on two surfaces of aluminium foil of 25 micron thickness.At 100 ℃ of dry down dimethyl formamides that desolvate that remove, the THICKNESS CONTROL of electrode band is at 350 ± 10 microns.The THICKNESS CONTROL of electrode band after roll-in is at 140 ± 5 microns.Positive electrode band cutting is become 27 * 310mm
2Size.Aluminum lead of spot welding on the initial aluminium foil surface of not filming then.
The manufacture method of coiled battery core:
Positive and negative electrode band and PE-PP membrane band are sequenced in proper order by positive electrode/barrier film/negative electrode/barrier film, be placed on the up-coiler, be wound into 3.2 * 30 * 50mm
3Battery.Total positive, negative electrode plate 10 circles of battery.The positive and negative electrode lead-in wire grows battery 15mm, parallel interval 10mm.Battery is packed in the foil laminated film outer packaging bag, use hot press to seal and edge sealing, stay a mouth to be used for fluid injection.
The preparation of monomer, initator and electrolyte mixed liquor:
Electrolytic salt is selected lithium hexafluoro phosphate LiPF for use
6Organic solvent is that ethylene carbonate EC, dimethyl carbonate DMC and carbonic acid diethyl ester DEC ternary are formed (1: 1: 1).1.2 gram molecule electrolytic salt lithium hexafluoro phosphate LiPF
6Be dissolved in this organic solvent and be prepared into electrolyte.Monomer is two kinds of methyl methacrylate and methyl acrylates; Initator is selected benzoyl peroxide for use.Monomer and initator join in the electrolyte in 1000: 1 ratio, and the concentration of monomer in electrolyte is 6%, and is standby after evenly mixing.
The thermal polymerization method of the drying of battery and colloidal electrolyte:
Battery after 90 ℃ of following vacuumize a few hours, cool to room temperature.Inject 1.9 milliliters of monomers that prepare in advance, initator and electrolyte mixed liquors, close liquid injection port is sealed in hot pressing.85 ℃ of heating down, methyl methacrylate and methyl acrylate respectively with initator benzoyl peroxide generation chemical reaction, heat polymerization finishes after 10 minutes, and monomers methyl methacrylate and methyl acrylate generate polymethyl methacrylate co-methyl acrylate.The mechanism of thermal polymerization chemical reaction is summarized as follows:
Monomers methyl methacrylate and methyl acrylate all have the two key machine groups of carbon, and under the double action of initator benzoyl peroxide and temperature, the two keys in the two key machine of the free carbon group are opened the formation free radical.Under the free radical guiding, crosslinked and copolymerization takes place in methyl methacrylate and methyl acrylate.Along with continuing of thermal polymerization chemical time, free radical grafting between methyl methacrylate and the methyl acrylate repeats to take place, the carbochain of copolymer constantly prolongs, molecular weight constantly increases, copolymer is constructed the two and three dimensions polymer network gradually, and contain with organic compound ethylene carbonate, dimethyl carbonate and carbonic acid diethyl ester in the electrolyte, reaction such as hydrogen bond, make liquid monomer, initator and electrolyte mixed liquor change gel state or solid electrolyte gradually into.
Changing into and exhaust mouth-sealing method again of battery:
Use special-purpose battery charging and discharging equipment that battery is carried out 4.2V/0.2C (CC+CV) and charge at a slow speed and change into, at negative electrode surface formation diaphragm.Be emitted on a small amount of gas that produces in the formation process then, seal at last and finish whole preparation technology's operations.
Example two:
Produce stacked polymer Li-ion battery with following method.
The manufacture method of negative electrode plate:
The poly-inclined to one side vinylidene fluoride of 10 grams is dissolved in dimethyl formamide, and it is black to add 3 gram acetone then, adds 115 gram graphite powders at last.Through high-speed stirred evenly, vacuum or leave standstill degasification after make the cathode size of pulpous state.Cathode size is coated on two surfaces of Copper Foil of 20 micron thickness.At 100 ℃ of dry down dimethyl formamides that desolvate that remove, the THICKNESS CONTROL of electrode band is at 300 ± 10 microns.The THICKNESS CONTROL of electrode band after roll-in is at 130 ± 5 microns.Negative electrode band cutting is become kitchen knife shape: the operator area is 30 * 50mm
2Size, hilt area are 5 * 7mm
2Size, hilt partly are the Copper Foils of not filming, and its surface will be at the subsequent handling mid point nickel down-lead of burn-oning.
The manufacture method of electrode film:
The poly-inclined to one side vinylidene fluoride of 19 grams is dissolved in dimethyl formamide, and it is black to add 12 gram acetone then, adds 200 gram lithium cobalt nickel oxygen at last.Through high-speed stirred evenly, vacuum or leave standstill degasification after make the anode sizing agent of pulpous state.80% anode sizing agent is coated on two surfaces of aluminium foil of 25 micron thickness, the slurry of residue 20% is coated on the aluminium foil list surface of 25 micron thickness.At 100 ℃ of dry down dimethyl formamides that desolvate that remove, the THICKNESS CONTROL of the two-sided electrode band of filming is at 350 ± 10 microns.The THICKNESS CONTROL of electrode slice after roll-in is at 160 ± 5 microns.The THICKNESS CONTROL of single face electrodeposited coating film pole piece is at 200 ± 7 microns.The THICKNESS CONTROL of electrode slice after roll-in is at 90 ± 3 microns.The electrode film cutting is become kitchen knife shape: the operator area is 27 * 47mm
2Size, hilt area are 5 * 7mm
2Size, hilt partly are the aluminium foils of not filming, and its surface will be at the subsequent handling mid point aluminum lead of burn-oning.
The manufacture method of stacked battery core:
With positive, negative electrode plate and PE-PP membrane sheet press positive electrode/barrier film/negative electrode/barrier film/... the order of/electrode film sequences, and has 11 negative electrode plates, 10 double-side membrane electrode films and 2 single face film electrode films.Constitute 3 * 30 * 50mm
3Battery.The hilt Copper Foil of 11 negative electrode plates pools together and is welded on the nickel down-lead.10 double-side membrane electrode films and 2 single face film electrode film hilt aluminium foils pool together and are welded on the aluminum lead.The positive and negative electrode lead-in wire grows battery 15mm, parallel interval 10mm.
The preparation of monomer, initator and electrolyte mixed liquor:
Electrolytic salt is selected lithium hexafluoro phosphate LiPF for use
6Organic solvent is that ethylene carbonate EC, dimethyl carbonate DMC and methyl ethyl carbonate fat EMC ternary are formed (2: 1: 1).1.2 gram molecule electrolytic salt lithium hexafluoro phosphate LiPF
6Be dissolved in this organic solvent and be prepared into electrolyte.Monomer is two kinds of vinylidene and hexafluoropropylenes; Initator is selected benzoyl peroxide for use.Monomer and initator join in the electrolyte in 1000: 1 ratio, and the concentration of monomer in electrolyte is 8%, and is standby after evenly mixing.
The thermal polymerization method of the drying of battery and colloidal electrolyte:
Battery after 90 ℃ of following vacuumize a few hours, cool to room temperature.Inject 1.9 milliliters of monomers that prepare in advance, initator and electrolyte mixed liquors, close liquid injection port is sealed in hot pressing.85 ℃ of down heating, vinylidene and hexafluoropropylene respectively with initator benzoyl peroxide generation chemical reaction, heat polymerization finishes after 10 minutes, monomer vinylidene and hexafluoropropylene generate Kynoar-hexafluoropropylene copolymer.The mechanism of thermal polymerization chemical reaction is summarized as follows:
Monomer vinylidene and hexafluoropropylene all have the two key machine groups of carbon, and under the double action of initator benzoyl peroxide and temperature, the two keys in the two key machine of the free carbon group are opened the formation free radical.Under the free radical guiding, crosslinked and copolymerization takes place in vinylidene and hexafluoropropylene.Along with continuing of thermal polymerization chemical time, free radical grafting between vinylidene and the hexafluoropropylene repeats to take place, the carbochain of copolymer constantly prolongs, molecular weight constantly increases, copolymer is constructed the two and three dimensions polymer network gradually, and contain with organic compound ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate fat in the electrolyte, reaction such as hydrogen bond, make liquid monomer, initator and electrolyte mixed liquor change gel state or solid electrolyte gradually into.The positive electrode/barrier film/negative electrode/barrier film of stacked battery core/... each of/electrode film is in the pole piece, because the powerful cementation of gel state electrolyte, all positive, negative electrode plates and PE-PP membrane sheet are bonded together firmly, form a rigid unitary.
Changing into and exhaust mouth-sealing method again of battery:
Use special-purpose battery charging and discharging equipment that battery is carried out 4.2V/0.2C (CC+CV) and charge at a slow speed and change into, at negative electrode surface formation diaphragm.Be emitted on a small amount of gas that produces in the formation process then, seal at last and finish whole preparation technology's operations.
Claims (9)
1. the structural design of a colloidal electrolytic polymer lithium ion battery mainly is made of four kinds of composite components:
1a. the mixture that the negative electrode composite component is made up of active material+conductive agent+binding agent is coated on the metal copper foil surface;
1b. the mixture that the positive electrode composite component is made up of active material+conductive agent+binding agent is coated on the metal aluminum foil surface;
1c. the barrier film composite component is to add the mixture that the colloidal state polymer electrolyte is formed with PE-PP membrane band skeleton;
1d. being multilayer polyethylene film+polypropylene screen, the external packing composite component is attached on the surface of aluminium foil.
2. according to claim 1a, the active material in the negative electrode composite component is the combination of one or more carbonaceous materials, for example natural or synthetic graphite, oil reef, activated carbon, carbon fiber etc.Active material also can be metal alloy or metal oxide, for example lithium-aluminium alloy and tin-oxide etc.The shape of material can be fine powder or fiber.The specific area of conductive agent is between the 20-100 meters squared per gram.Binding agent can be polymer (for example Kynoar) or rubber polymer.
3. according to claim 1b, the active material in the positive electrode composite component is the combination of one or more lithium intercalation oxides, for example lithium and cobalt oxides LiCoO
2, lithium nickel oxide LiNiO
2, lithium-cobalt-nickel oxide LiCoNiO
2, lithium manganese oxide LiMn
2O
4, or their solid solution Li
αNi
βCo
γM
δO
2(M=Mn, Ti, Mg, Al and Cr), and lithium iron phosphate LiFePO
4Deng.The conductive agent specific area is between the 40-220 meters squared per gram.Binding agent is polymer (a for example Kynoar).
4. according to claim 1c, the mode separation strapping in the barrier film composite component (sheet) can be multiple layer or the poly-second-propylene film of individual layer, polyolefin film, polyethylene film, polypropylene screen and polymethylpentene film etc.Thickness is between 5 to 50 microns, and the pore size of film is between 0.1 to 2 micron, and the microporosity of film is between 25% to 65%.Polymer in the colloidal electrolyte is the product that forms through on-the-spot thermal polymerization chemical reaction, and they are in polymethyl methacrylate, polybutyl methacrylate, polyvinyl ester, polyvinyl chloride, polyacrylate, polyacrylamide, polymethylacrylic acid benzene methyl, polymethyl acrylate, polyacrylonitrile, Kynoar, polyethylene, polyvinyl acetate, polyvinylpyrrolidone, poly(ethylene oxide) and the polyurethanes one or more.Electrolytic salt in the colloidal electrolyte is lithium hexafluoro phosphate LiPF
6, LiBF4 LiBF
4With among the six oxalic acid boron lithium LiBOB one or more.Organic solvent in the colloidal electrolyte is ethylene carbonate EC, propene carbonate PC, dimethyl carbonate DMC, methyl ethyl carbonate fat EMC and carbonic acid diethyl ester DEC etc.The composition of organic solvent can be binary, ternary or even polynary.The concentration of electrolytic salt in organic solvent is every liter 0.8～1.5 gram molecule.
5. according to claim 1d, the moistureproof composite membrane of the plastic/metal paper tinsel in the external packing composite component can be the composite multilayer membrane of polyethylene, polypropylene, polyester, the third cyclic group formic acid and metal forming materials such as (for example aluminium, magnesium or titaniums).Plastic/metal paper tinsel composite membrane gross thickness is the 80-250 micron.
6. the manufacture method of a colloidal electrolytic polymer lithium ion battery, its battery can have two kinds of manufacture methods: takeup type and stacked.Takeup type is the multi-turn battery core body that three kinds of composite component 1a, 1b of claim 1 and 1c are formed through coiling; Stacked is through the overlapping multi-layer cell core body that forms with three kinds of composite component 1a, 1b of claim 1 and 1c.
7. the colloidal state polymer electrolyte in the battery is the product that is formed through on-the-spot thermal polymerization chemical reaction by monomer, initator and electrolyte mixed solution.Monomer can be at vinylidene (Vinylidene fluoride), methyl methacrylate (Methyl methacrylate), acrylonitrile (Acrylonitrile), butyl acrylate (Butyl acrylate), methyl acrylate (Methylacrylate), butyl methacrylate (Butyl methacrylate), methacrylic acid benzene methyl (benzyl methacrylate), acenaphthene (acenaphthylene), vinylpyridine (vinyl pyridine), acrylamide (acrylamide), methyl vinyl ether (methyl vinyl ether), vinylacetate (vinyl acetate), select one or more for use in hexafluoropropylene (hexafluoropropylene) and the vinyl pyrrole quinoline (vinyl pyrrolidone); Initator can select for use benzoyl peroxide (2,2-Azobis-isobutyronitrile), azodiisobutyronitrile (Diisopropyl peroxydi) etc.Monomer and initator join in the electrolyte after by 1000: 1～100: 2 mixed, through the mixing that stirs.The concentration of monomer in electrolyte is 1～20%.
8. the condition of thermal polymerization chemical reaction is 65～120 ℃ of heating-up temperatures and moulding pressure 0～5 kg/cm, and the time of thermal polymerization chemical reaction is 10～2500 seconds.Under these conditions, be injected into monomer, initator and generation polymerization of electrolyte mixed liquor and gelation reaction in the battery, be transformed into normal colloidal state polymer electrolyte, positive and negative electrode and barrier film are closely bonded together, make battery form a integral body with self bulk strength and rigidity.
9. be the battery that three kinds of composite component 1a, 1b and 1c bonded together, had self mechanical strength and rigidity securely through the battery of claim 6,7 and 8 processes preparation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100268149A CN100444454C (en) | 2004-04-12 | 2004-04-12 | Design and production of colloidal polymer lithium ion cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100268149A CN100444454C (en) | 2004-04-12 | 2004-04-12 | Design and production of colloidal polymer lithium ion cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1684298A true CN1684298A (en) | 2005-10-19 |
| CN100444454C CN100444454C (en) | 2008-12-17 |
Family
ID=35263500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100268149A Expired - Fee Related CN100444454C (en) | 2004-04-12 | 2004-04-12 | Design and production of colloidal polymer lithium ion cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100444454C (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008144968A1 (en) * | 2007-05-28 | 2008-12-04 | Dongguan Amperex Electronics Technology Co. , Ltd, | Method of laminated lithium ion battery |
| CN101677140A (en) * | 2008-09-17 | 2010-03-24 | 江苏海四达电源股份有限公司 | Manufacturing method of two-step polymerized electrolyte matrix and polymer lithium-ion battery |
| CN101990719A (en) * | 2008-02-28 | 2011-03-23 | 魁北克水电公司 | Composite electrode material |
| CN101685876B (en) * | 2008-09-27 | 2013-06-26 | 深圳市比克电池有限公司 | Preparation method of polymer battery |
| CN103296245A (en) * | 2013-05-02 | 2013-09-11 | 浙江努奥罗新能源科技有限公司 | Cylinder lithium battery |
| CN103346348A (en) * | 2013-06-25 | 2013-10-09 | 南开大学 | Polymer electrolyte for organic lithium secondary battery and preparation method of polymer electrolyte |
| CN103489644A (en) * | 2013-09-13 | 2014-01-01 | 北京航空航天大学 | Polymer iodide gel electrolyte and preparation method thereof |
| CN105826578A (en) * | 2016-03-25 | 2016-08-03 | 广州鹏辉能源科技股份有限公司 | Primary lithium battery and inflaming retarding electrolyte solution thereof |
| CN105845928A (en) * | 2016-06-17 | 2016-08-10 | 天津中聚新能源科技有限公司 | Lithium-ion power battery and preparation method thereof |
| CN106058315A (en) * | 2016-08-04 | 2016-10-26 | 宁德时代新能源科技股份有限公司 | Lithium ion battery additive, battery containing additive and preparation method |
| CN106532190A (en) * | 2016-12-09 | 2017-03-22 | 厦门华戎能源科技有限公司 | Rapid heating battery |
| CN108400380A (en) * | 2018-04-24 | 2018-08-14 | 珠海光宇电池有限公司 | A kind of preparation method and lithium ion battery of composite polymer electrolyte membrane |
| CN113471401A (en) * | 2021-05-28 | 2021-10-01 | 上海空间电源研究所 | High-safety high-load lithium ion electrode piece and manufacturing method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1249838C (en) * | 2002-04-10 | 2006-04-05 | 黄穗阳 | Design for high-energy safety polymer lithium ion battery and productive process thereof |
-
2004
- 2004-04-12 CN CNB2004100268149A patent/CN100444454C/en not_active Expired - Fee Related
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008144968A1 (en) * | 2007-05-28 | 2008-12-04 | Dongguan Amperex Electronics Technology Co. , Ltd, | Method of laminated lithium ion battery |
| CN101990719A (en) * | 2008-02-28 | 2011-03-23 | 魁北克水电公司 | Composite electrode material |
| US9905839B2 (en) | 2008-02-28 | 2018-02-27 | Hydro-Quebec | Composite electrode material |
| CN101677140A (en) * | 2008-09-17 | 2010-03-24 | 江苏海四达电源股份有限公司 | Manufacturing method of two-step polymerized electrolyte matrix and polymer lithium-ion battery |
| CN101685876B (en) * | 2008-09-27 | 2013-06-26 | 深圳市比克电池有限公司 | Preparation method of polymer battery |
| CN103296245A (en) * | 2013-05-02 | 2013-09-11 | 浙江努奥罗新能源科技有限公司 | Cylinder lithium battery |
| CN103346348A (en) * | 2013-06-25 | 2013-10-09 | 南开大学 | Polymer electrolyte for organic lithium secondary battery and preparation method of polymer electrolyte |
| CN103489644B (en) * | 2013-09-13 | 2017-02-01 | 北京航空航天大学 | Polymer iodide gel electrolyte and preparation method thereof |
| CN103489644A (en) * | 2013-09-13 | 2014-01-01 | 北京航空航天大学 | Polymer iodide gel electrolyte and preparation method thereof |
| CN105826578A (en) * | 2016-03-25 | 2016-08-03 | 广州鹏辉能源科技股份有限公司 | Primary lithium battery and inflaming retarding electrolyte solution thereof |
| CN105845928A (en) * | 2016-06-17 | 2016-08-10 | 天津中聚新能源科技有限公司 | Lithium-ion power battery and preparation method thereof |
| CN105845928B (en) * | 2016-06-17 | 2019-05-31 | 天津中聚新能源科技有限公司 | A kind of lithium-ion-power cell and preparation method thereof |
| WO2018024095A1 (en) * | 2016-08-04 | 2018-02-08 | 宁德时代新能源科技股份有限公司 | Lithium-ion battery additive, battery containing additive, and preparation method |
| CN106058315A (en) * | 2016-08-04 | 2016-10-26 | 宁德时代新能源科技股份有限公司 | Lithium ion battery additive, battery containing additive and preparation method |
| CN106532190A (en) * | 2016-12-09 | 2017-03-22 | 厦门华戎能源科技有限公司 | Rapid heating battery |
| CN108400380A (en) * | 2018-04-24 | 2018-08-14 | 珠海光宇电池有限公司 | A kind of preparation method and lithium ion battery of composite polymer electrolyte membrane |
| CN108400380B (en) * | 2018-04-24 | 2021-01-29 | 珠海冠宇电池股份有限公司 | Preparation method of composite polymer electrolyte membrane and lithium ion battery |
| CN113471401A (en) * | 2021-05-28 | 2021-10-01 | 上海空间电源研究所 | High-safety high-load lithium ion electrode piece and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100444454C (en) | 2008-12-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103620850B (en) | There is the electrode assemblie of new structure and use its secondary cell | |
| KR101723994B1 (en) | Separator, method of manufacturing the same, lithium polymer secondary battery including the same, and method of manufacturing lithium polymer secondary battery using the same | |
| WO2022141473A1 (en) | Electrochemical device, electronic device, and preparation method for electrochemical device | |
| US20030194607A1 (en) | Polymer-gel lithium ion battery | |
| CN105074989B (en) | The manufacturing method of electrode-membrane compound, the electrode-membrane compound manufactured by the manufacturing method and comprising its lithium secondary battery | |
| CN113474913B (en) | Electrochemical device, electronic device, and preparation method of electrochemical device | |
| CN114175387A (en) | Isolating membrane, electrochemical device comprising same and electronic device | |
| JP2012195314A (en) | Nonaqueous electrolyte secondary battery | |
| CN103636051A (en) | Novel polymer electrolyte and lithium secondary battery including same | |
| WO2022141508A1 (en) | Electrochemical device and electronic device | |
| CN101340009A (en) | Polymer electrolyte hard packaging lithium ionic cell | |
| CN100444454C (en) | Design and production of colloidal polymer lithium ion cell | |
| US20080199764A1 (en) | Safer high energy battery | |
| CN1249838C (en) | Design for high-energy safety polymer lithium ion battery and productive process thereof | |
| KR101966181B1 (en) | Flexible battery using the flexible pouch | |
| CN1741313A (en) | High-energy and low-cost lithium polymer battery | |
| CN103370825B (en) | Integrated electrode assembly and use its secondary cell | |
| JP2001035535A (en) | Nonaqueous secondary battery and manufacture thereof | |
| CN101677140A (en) | Manufacturing method of two-step polymerized electrolyte matrix and polymer lithium-ion battery | |
| CN1929185A (en) | Colloidal electrolyte lithium ion electrokinetic cell for electric vehicle | |
| KR102024898B1 (en) | Separator and lithium battery comprising the same | |
| CN1622382A (en) | Design and production process for high security polymer lithium ion power cell | |
| JP5066804B2 (en) | Lithium ion secondary battery | |
| CN116154276A (en) | Structure battery based on solid-state battery cell, structure battery pack comprising structure battery cell and manufacturing method of structure battery pack | |
| KR102772214B1 (en) | LiMoP coated cathode active material and Lithium battery comprising thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Free format text: FORMER OWNER: HUANG YOULIN Effective date: 20121231 Owner name: SHENZHEN GENERAL ELECTRONICS BATTERY CO., LTD. Free format text: FORMER OWNER: HUANG SUIYANG Effective date: 20121231 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 510620 GUANGZHOU, GUANGDONG PROVINCE TO: 518109 SHENZHEN, GUANGDONG PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20121231 Address after: 518109 Guangdong city of Shenzhen province Longhua Dalang street Tinglu Chao Hui Lou Hua Science and Technology Industrial Park 2 6 floor Patentee after: GENERAL ELECTRONICS BATTERY CO., LTD. Address before: 1208, room 73, 510620 West Broad Road, Guangzhou, Guangdong Patentee before: Huang Suiyang Patentee before: Huang Youlin |
|
| ASS | Succession or assignment of patent right |
Owner name: VANTAGE POWER GLOBAL LIMITED Free format text: FORMER OWNER: SHENZHEN GENERAL ELECTRONICS BATTERY CO., LTD. Effective date: 20130828 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 518109 SHENZHEN, GUANGDONG PROVINCE TO: HONG KONG, CHINA |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20130828 Address after: The Hongkong Special Administrative Region China Ashley Road No. 33, Kowloon Kowloon Center 9 building 903-906A room Patentee after: Global New Energy Ltd Address before: 518109 Guangdong city of Shenzhen province Longhua Dalang street Tinglu Chao Hui Lou Hua Science and Technology Industrial Park 2 6 floor Patentee before: GENERAL ELECTRONICS BATTERY CO., LTD. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081217 Termination date: 20150412 |
|
| EXPY | Termination of patent right or utility model |
