CN103050707B - 可再充电锂电池 - Google Patents
可再充电锂电池 Download PDFInfo
- Publication number
- CN103050707B CN103050707B CN201210279223.7A CN201210279223A CN103050707B CN 103050707 B CN103050707 B CN 103050707B CN 201210279223 A CN201210279223 A CN 201210279223A CN 103050707 B CN103050707 B CN 103050707B
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- CN
- China
- Prior art keywords
- lithium rechargeable
- rechargeable battery
- electrolyte
- polymeric layer
- lithium
- Prior art date
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 65
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229920000642 polymer Polymers 0.000 claims abstract description 48
- -1 alkyl propionate Chemical compound 0.000 claims abstract description 46
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 31
- 239000002033 PVDF binder Substances 0.000 claims abstract description 27
- 239000003792 electrolyte Substances 0.000 claims abstract description 26
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 21
- 239000000919 ceramic Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 9
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 8
- 159000000002 lithium salts Chemical class 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 229940017219 methyl propionate Drugs 0.000 claims description 4
- 239000003660 carbonate based solvent Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000013047 polymeric layer Substances 0.000 claims 8
- 239000000428 dust Substances 0.000 claims 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 230000001186 cumulative effect Effects 0.000 claims 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims 1
- 239000000347 magnesium hydroxide Substances 0.000 claims 1
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 claims 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims 1
- 235000019260 propionic acid Nutrition 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 239000008151 electrolyte solution Substances 0.000 description 18
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 17
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011572 manganese Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 10
- 239000004020 conductor Substances 0.000 description 10
- 239000007774 positive electrode material Substances 0.000 description 10
- 239000007773 negative electrode material Substances 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229910052720 vanadium Inorganic materials 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
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- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000005676 cyclic carbonates Chemical class 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910021382 natural graphite Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910019440 Mg(OH) Inorganic materials 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229920005993 acrylate styrene-butadiene rubber polymer Polymers 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- QKBJDEGZZJWPJA-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound [CH2]COC(=O)OCCC QKBJDEGZZJWPJA-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920002620 polyvinyl fluoride Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- JYVXNLLUYHCIIH-UHFFFAOYSA-N (+/-)-mevalonolactone Natural products CC1(O)CCOC(=O)C1 JYVXNLLUYHCIIH-UHFFFAOYSA-N 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- 229910010093 LiAlO Inorganic materials 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910013372 LiC 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015118 LiMO Inorganic materials 0.000 description 1
- 229910013417 LiN(SO3C2F5)2 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- JYVXNLLUYHCIIH-ZCFIWIBFSA-N R-mevalonolactone, (-)- Chemical compound C[C@@]1(O)CCOC(=O)C1 JYVXNLLUYHCIIH-ZCFIWIBFSA-N 0.000 description 1
- 229910008326 Si-Y Inorganic materials 0.000 description 1
- 229910006773 Si—Y Inorganic materials 0.000 description 1
- 229910020997 Sn-Y Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910008859 Sn—Y Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- RLTFLELMPUMVEH-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[V+5] Chemical compound [Li+].[O--].[O--].[O--].[V+5] RLTFLELMPUMVEH-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910021475 bohrium Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- ZFTFAPZRGNKQPU-UHFFFAOYSA-L carboxylato carbonate Chemical compound [O-]C(=O)OC([O-])=O ZFTFAPZRGNKQPU-UHFFFAOYSA-L 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 229920005994 diacetyl cellulose Polymers 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- PHAFDKCRJVKSSR-UHFFFAOYSA-N ethene hydrofluoride Chemical group F.C=C PHAFDKCRJVKSSR-UHFFFAOYSA-N 0.000 description 1
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- 229910052730 francium Inorganic materials 0.000 description 1
- IFYYFLINQYPWGJ-UHFFFAOYSA-N gamma-decalactone Chemical compound CCCCCCC1CCC(=O)O1 IFYYFLINQYPWGJ-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
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- 229910021473 hassium Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
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- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 229910052699 polonium Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910021481 rutherfordium Inorganic materials 0.000 description 1
- 229910021477 seaborgium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- RBYFNZOIUUXJQD-UHFFFAOYSA-J tetralithium oxalate Chemical compound [Li+].[Li+].[Li+].[Li+].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O RBYFNZOIUUXJQD-UHFFFAOYSA-J 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000002733 tin-carbon composite material Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
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Abstract
一种可再充电锂电池包括正电极,负电极,所述正电极和所述负电极之间的隔板,所述隔板上的聚合物层以及包括丙酸烷基酯的电解液,所述聚合物层包括聚偏二氟乙烯类聚合物。
Description
技术领域
本申请涉及可再充电锂电池。
背景技术
近来锂可再充电电池作为用于小的便携式电子设备的电源已引起关注。锂可再充电电池使用有机电解液从而具有两倍于使用碱性水溶液的传统电池的放电电压。因此,锂可再充电电池具有相对高的能量密度。
可再充电锂电池包括含正电极,面向正电极的负电极,正电极和负电极之间的隔板,以及浸泡该正电极、负电极和隔板的电解液的电极组件。
电解液主要包括锂盐和非水有机溶剂的混合物。该非水有机溶剂主要包括直链碳酸酯和环状碳酸酯的混合物。
然而,通常由上述制造的可再充电锂电池的循环寿命的改善有限。
发明内容
本发明实施方式的方面涉及一种具有良好循环寿命和改善的在过充电时的安全性的可再充电锂电池。
在本发明的一个实施方式中,可再充电锂电池包括正电极;负电极;所述正电极和所述负电极之间的隔板;所述隔板上的聚合物层,所述聚合物层包括聚偏二氟乙烯类聚合物;以及浸泡所述隔板的电解液,所述电解液包括丙酸烷基酯。
所述聚合物层可在所述隔板和所述正电极之间和/或在所述隔板和所述负电极之间。
所述聚偏二氟乙烯类聚合物可包括选自聚偏二氟乙烯、聚偏二乙烯-六氟丙烯共聚物、或它们的组合的聚合物。
所述聚偏二氟乙烯类聚合物可以0.5至3.0g/m2的负载量加载。所述聚偏二氟乙烯类聚合物可以1.5至2.5g/m2的负载量加载。
所述聚合物层可进一步包括选自有机粉末、陶瓷粉末、或它们的组合的填料。所述聚合物层可包括含聚甲基丙烯酸甲酯(PMMA)的有机粉末。所述聚合物层可包括选自Al2O3、Mg(OH)2、或它们的组合的陶瓷粉末。
基于所述聚合物层的总重量,所述陶瓷粉末的含量可为0.1至98wt%。基于所述聚合物层的总重量,所述陶瓷粉末的含量可为3至20wt%。
所述丙酸烷基酯可包括丙酸C1-10烷基酯。所述丙酸烷基酯可包括选自丙酸甲酯、丙酸乙酯、或它们的组合的化合物。基于所述电解液的总体积,所述丙酸烷基酯的含量可为10至70体积%。基于所述电解液的总体积,所述丙酸烷基酯的含量可为20至70体积%。基于所述电解液的总体积,所述丙酸烷基酯的含量可为50至60体积%。
所述电解液可进一步包括锂盐和非水有机溶剂。
所述电解液可进一步包括碳酸酯类溶剂,且所述碳酸酯类溶剂和所述丙酸烷基酯的体积比可为4:6至5:5。
所述电解液可为液体。
附图说明
通过以下详细描述结合附图将使本发明实施方式的特征和方面更加明显。
图1为根据一个实施方式的可再充电锂电池的示意图。
图2至图9为示出了根据实施例1至6和对比例1至2在过充电时可再充电锂电池状态的图。
标号的说明
100:可再充电锂电池
10:电极组件
20:袋状壳体
13:电极片
具体实施方式
将在下文详细描述本公开示例性的实施方式。然而,这些实施方式仅是示例性的,本公开并不限于此。
图1中说明了根据一个实施方式的可再充电锂电池。图1为根据一个实施方式的可再充电锂电池的示意图。
参见图1,根据一个实施方式的可再充电锂电池100包括电极组件10,容纳该电极组件的袋状壳体20,以及将由电极组件产生的电流向外电导的电极片13。通过交叠其彼此相对的两面将袋状壳体20密封。
电极组件10包括正电极,面向正电极的负电极,插在正电极和负电极间的隔板,以及浸泡正电极、负电极和隔板的电解液。
根据一个实施方式,可再充电锂电池可为圆柱形电池、棱柱形电池、硬币电池、袋状电池等。在一些实施方式中,可再充电锂电池可为如图1所示的袋状电池。
隔板可为单层或多层,且由例如玻璃纤维、聚酯、特氟隆、聚乙烯、聚丙烯、聚四氟乙烯、或它们的组合制成。
隔板可在表面上包括聚合物层。具体地,聚合物层可被置于隔板的表面上,(1)在隔板的表面和正电极的表面之间和/或(2)在隔板的表面和负电极的表面之间中任一个。
聚合物层可包括聚偏二氟乙烯类聚合物。聚偏二氟乙烯类聚合物可包括选自聚偏二氟乙烯、聚偏二乙烯-六氟丙烯共聚物、或它们的组合的聚合物。
当在隔板的表面上形成包括聚偏二氟乙烯类聚合物的聚合物层时,隔板可被电解液更充分地浸泡,从而改善可再充电锂电池的循环寿命特性和改善在过充电时的安全性。它也可将隔板更加牢固地粘附到基板(例如电极)上,从而增加可再充电锂电池的强度并减少可再充电锂电池的厚度。
聚偏二氟乙烯类聚合物可以0.5至3.0g/m2范围且特别是1.5至2.5g/m2范围内的负载量加载(即在一些实施方式中,负载量可为1.6g/m2,而在其它的实施方式中,负载量可为2.0g/m2)。负载量表示每单位面积的隔板表面上聚合物重量。在一个实施方式中,以上述范围内的负载量加载聚偏二氟乙烯类聚合物,隔板被电解液更加充分地浸泡,从而改善可再充电锂电池的电导率,且更加牢固地将隔板粘附至基板(例如电极)的粘合剂上,从而制造出具有改善的强度的可再充电锂电池。
可通过混合聚偏二氟乙烯类聚合物和填料形成聚合物层。填料可包括选自有机粉末、陶瓷粉末、或它们的组合中的一种。
有机粉末可包括聚甲基丙烯酸甲酯(PMMA)。陶瓷粉末可包括选自Al2O3、Mg(OH)2、或它们的组合中的一种。
基于聚合物层的总重量,陶瓷粉末的含量可为0.1至98wt%。在一些实施方式中,基于聚合物层的总重量,陶瓷粉末的含量可为3至20wt%。在一个实施方式中,当陶瓷粉末的含量在上述范围内时,减弱了静电并减少了摩擦,从而改善了制造锂电池的工艺。
电解液可包括丙酸烷基酯。当电解液中包括丙酸烷基酯时,形成隔板表面上的聚合物层的聚偏二氟乙烯类聚合物和丙酸烷基酯可具有良好的相容性,因此有助于隔板和正电极以及负电极中电解液的浸泡。因此,本发明可提供具有良好循环寿命特性和改善的过充电时安全性的可再充电锂电池。
丙酸烷基酯可包括C1至C10烷基。在一些实施方式中,丙酸烷基酯可包括选自丙酸甲酯、丙酸乙酯、或它们的组合中的一种。这些材料具有低粘度和与聚偏二氟乙烯类聚合物的良好相容性,从而能够制造具有改善的循环寿命特性和改善的过充电时安全性的可再充电锂电池。
基于电解液的总体积,丙酸烷基酯的含量可为10至70体积%。在一些实施方式中,基于电解液的总体积,丙酸烷基酯的含量可为20至70体积%,而在其它实施方式中,基于电解液的总体积,丙酸烷基酯的含量可为30至70体积%。在其它的实施方式中,基于电解液的总体积,丙酸烷基酯的含量可为40至70体积%,而在其它实施方式中,基于电解液的总体积,丙酸烷基酯的含量可为50至60体积%。在一个实施方式中,当电解液内的丙酸烷基酯的含量在上述范围内时,丙酸烷基酯与形成隔板表面上的聚合物层的聚偏二氟乙烯具有更好的相容性,电解液更好地浸泡隔板与正电极和负电极。因此,本发明的实施方式可提供具有良好循环寿命特性和改善的过充电时的安全性的可再充电锂电池。
电解液除了丙酸烷基酯以外可包括锂盐和非水有机溶剂。
溶解在非水有机溶剂内的锂盐提供在电池内的锂离子并改善正电极和负电极之间的锂离子传输。
锂盐可包括选自LiPF6、LiBF4、LiSbF6、LiAsF6、LiN(SO3C2F5)2、LiC4F9SO3、LiClO4、LiAlO2、LiAlCl4、LiN(CxF2x+1SO2)(CyF2y+1SO2)(其中x和y为自然数)、LiCl、LiI、LiB(C2O4)2(二(草酸)硼酸锂;LiBOB)、或它们的组合中的一种。
锂盐可以约0.1M至约2.0M的范围内的浓度使用。在一个实施方式中,当锂盐的含量在以上范围内时,由于电解液具有选定的电导率和粘度,电解液具有良好的性能和锂离子迁移率。
非水有机溶剂用作传送参与电池电化学反应的离子的介质。非水有机溶剂可包括选自碳酸酯类溶剂、酯类溶剂、酮类溶剂、醇类溶剂、非质子溶剂、或它们的组合中的一种。
碳酸酯类溶剂可包括,例如碳酸二甲酯(DMC)、碳酸二乙酯(DEC)、碳酸二丙酯(DPC)、碳酸甲丙酯(MPC)、碳酸乙丙酯(EPC)、碳酸甲乙酯(MEC)、碳酸乙基甲酯(EMC)、碳酸乙二酯(EC)、碳酸丙二酯(PC)、碳酸丁二酯(BC)等。
当通过混合环状碳酸酯和直链碳酸酯制备碳酸酯类溶剂时,该溶剂可具有低粘度并具有增加的介电常数。在一个实施方式中,环状碳酸酯和直链碳酸酯以约1:1至1:9的体积比混合在一起。
酯类溶剂可包括,例如乙酸甲酯、乙酸乙酯、乙酸正丙酯、丙酸甲酯、丙酸乙酯、γ-丁内酯、癸内酯、戊内酯、甲瓦龙酸内酯、己内酯等。
醚类溶剂可包括,例如二丁醚、四乙二醇二甲醚、二乙二醇二甲醚、二甲氧基乙烷、2-甲基四氢呋喃、四氢呋喃等。
酮类溶剂可包括环己酮等。
醇类溶剂可包括乙醇、异丙醇等。
非水有机溶剂可单独或在混合物中使用。当在混合物中使用有机溶剂时,可根据所需的电池性能控制混合物的比例。
非水电解液可进一步包括过充保护添加剂如碳酸乙二酯、焦碳酸酯等。
正电极可包括集流体和位于集流体上的正极活性物质层。正极活性物质层可包括正极活性物质、粘合剂和可选的导电材料。
集流体可为Al(铝),但不限于此。
正极活性物质包括可逆地嵌入和脱嵌锂离子的锂插层化合物。正极活性物质可包括含钴、锰、镍或它们的组合中的至少一种以及锂的复合氧化物。例如,可使用以下化合物:
LiaA1-bHbD2(其中0.90≤a≤1.8和0≤b≤0.5);LiaE1-bHbO2-cDc(其中0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05);LiE2-bHbO4-cDc(其中0≤b≤0.5和0≤c≤0.05);LiaNi1-b-cCobHcDα(其中0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05和0<α≤2);LiaNi1-b-cCobHcO2-αLα(其中0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05和0<α<2);LiaNi1-b-cCobHcO2-αL2(其中0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05和0<α<2);LiaNi1-b-cMnbHcDα(其中0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05和0<α≤2);LiaNi1-b-cMnbHcO2-αLα(其中0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05和0<α<2);LiaNi1-b-cMnbHcO2-αL2(其中0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05和0<α<2);LiaNibEcGdO2(其中0.90≤a≤1.8,0≤b≤0.9,0≤c≤0.5和0.001≤d≤0.1);LiaNibCocMndGeO2(其中0.90≤a≤1.8,0≤b≤0.9,0≤c≤0.5,0≤d≤0.5和0.001≤e≤0.1);LiaNiGbO2(其中0.90≤a≤1.8和0.001≤b≤0.1);LiaCoGbO2(其中0.90≤a≤1.8和0.001≤b≤0.1);LiaMnGbO2(其中0.90≤a≤1.8和0.001≤b≤0.1);LiaMn2GbO4(其中0.90≤a≤1.8和0.001≤b≤0.1);QO2;QS2;LiQS2;V2O5;LiV2O5;LiMO2;LiNiVO4;Li(3-f)J2(PO4)3(0≤f≤2);Li(3-f)Fe2(PO4)3(0≤f≤2)或LiFePO4。
在以上化学式中,A为Ni、Co、Mn或它们的组合;H为Al、Ni、Co、Mn、Cr、Fe、Mg、Sr、V、稀土元素或它们的组合;D为O、F、S、P或它们的组合,E为Co、Mn或它们的组合;L为F、S、P或它们的组合;G为Al、Cr、Mn、Fe、Mg、La、Ce、Sr、V或它们的组合;Q为Ti、Mo、Mn或它们的组合;M为Cr、V、Fe、Sc、Y或它们的组合;和J为V、Cr、Mn、Co、Ni、Cu或它们的组合。
锂插层化合物可在其表面上具有涂层,或者可与另外一种具有涂层的化合物混合。涂层可包括选自涂覆元素的氧化物、涂覆元素的氢氧化物、涂覆元素的羟基氧化物、涂覆元素的碳酸氧化物或涂覆元素的羟基碳酸盐的至少一种涂覆元素化合物。涂层的涂覆元素化合物可为无定形的或结晶的。包括在涂层内的涂覆元素可包括Mg、Al、Co、K、Na、Ca、Si、Ti、V、Sn、Ge、Ga、B、As、Zr或它们的混合物。在化合物中使用这些元素,可通过对正极活性物质的性质无不利影响(或基本没有不利影响)的方法放置涂层。例如,可通过如喷涂、浸渍等的方法放置涂层。然而,不会更详细地说明这些方法因为它们对在相关领域工作的人是已知的。
粘合剂改善了正极活性物质彼此之间和对集流体的粘合性能。粘合剂的实例包括聚乙烯醇、羧甲基纤维素、羟丙基纤维素、二乙酰基纤维素、聚氯乙烯、羧基聚氯乙烯、聚氟乙烯、含环氧乙烷的聚合物、聚乙烯吡咯烷酮、聚氨酯、聚四氟乙烯、聚偏二氟乙烯、聚乙烯、聚丙烯、苯乙烯-丁二烯橡胶、丙烯酸酯化的苯乙烯-丁二烯橡胶、环氧树脂、尼龙等,但粘合剂不限于此。
通过包括导电材料以改善电极电导率。只要它不会引起电池内的化学变化,任何传导电的材料都可用作导电材料。导电材料的实例包括如天然石墨、人造石墨、碳黑、乙炔黑、科琴黑、碳纤维等的碳类材料;包括含铜、镍、铝或银中一种或更多种的金属粉末或金属纤维的金属类材料;如聚亚苯基衍生物的导电聚合物;或它们的混合物。
负电极包括负极集流体和置于其上的负极活性物质层。
负极集流体可为铜箔。
负极活性物质层可包括负极活性物质、粘合剂和可选的导电材料。
负极活性物质包括能可逆地嵌入/脱嵌锂离子的材料、锂金属、锂金属合金、能掺杂/去掺杂锂的材料、或过渡金属氧化物。
能可逆地嵌入/脱嵌锂离子的材料包括碳材料。碳材料可为任何在锂离子可再充电电池内常用的碳类负极活性物质。碳材料的实例包括结晶碳、无定形碳或它们的混合物。结晶碳可为未成形的或薄板形、薄片形、球形或纤维形天然石墨或人造石墨。无定形碳可为软碳、硬碳、中间相沥青的碳化产物、焦炭等。
锂金属合金的实例包括锂和选自Na、K、Rb、Cs、Fr、Be、Mg、Ca、Sr、Si、Sb、Pb、In、Zn、Ba、Ra、Ge、Al或Sn的金属。
能掺杂/去掺杂锂的材料可包括Si、SiOx(0<x<2)、Si-C复合材料、Si-Y合金(其中Y不为Si且选自碱金属、碱土金属、13族至16族元素、过渡元素、稀土元素或它们的组合)、Sn、SnO2、Sn-C复合材料、Sn-Y合金(其中Y不为Si且选自碱金属、碱土金属、13族至16族元素、过渡元素、稀土元素或它们的组合)等。这些材料中的至少一种可和SiO2混合。元素Y可选自Mg、Ca、Sr、Ba、Ra、Sc、Y、Ti、Zr、Hf、Rf、V、Nb、Ta、Db、Cr、Mo、W、Sg、Tc、Re、Bh、Fe、Pb、Ru、Os、Hs、Rh、Ir、Pd、Pt、Cu、Ag、Au、Zn、Cd、B、Al、Ga、Sn、In、Ti、Ge、P、As、Sb、Bi、S、Se、Te、Po或它们的组合。
过渡金属氧化物可包括氧化钒、锂钒氧化物等。
粘合剂改善了负极活性物质颗粒彼此之间以及与集流体之间的粘合性。粘合剂的实例包括聚乙烯醇、羧甲基纤维素、羟丙基纤维素、聚氯乙烯、羧基聚氯乙烯、聚氟乙烯、含环氧乙烷的聚合物、聚乙烯吡咯烷酮、聚氨酯、聚四氟乙烯、聚偏二氟乙烯、聚乙烯、聚丙烯、苯乙烯-丁二烯橡胶、丙烯酸酯化的苯乙烯-丁二烯橡胶、环氧树脂、尼龙等,但粘合剂不限于此。
通过包括导电材料以改善电极电导率。任何传导电的材料都可用作导电材料,只要它不会引起电池内的化学变化。导电材料的实例包括如天然石墨、人造石墨、碳黑、乙炔黑、科琴黑、碳纤维等的碳类材料;包括含铜、镍、铝或银中一种或更多种的金属粉末或金属纤维的金属类材料;如聚亚苯基衍生物的导电聚合物;或它们的混合物。
可通过将活性物质、导电材料和粘合剂混合至活性物质组合物并在集流体上涂覆该组合物分别制造负电极和正电极。
电极的制造方法是已知的,因此在本说明书中不再详细描述。可将溶剂如N-甲基吡咯烷酮用于活性材料组合物中,但溶剂不限于此。
以下,将参照实施例更详细地说明这些实施方式。然而,以下是示例性的实施方式并非限制。
此外,该说明书中没有描述的且本领域技术人员充分理解的内容不会在此描述或说明。
(可再充电锂电池单元的制造)
实施例1
通过以92:4:4的重量比混合LiCoO2(正极活性物质)、聚偏二氟乙烯(PVdF)(粘合剂)和碳(导电材料),并将该混合物分散在N-甲基-2-吡咯烷酮(溶剂)中来制备正极活性物质层组合物。将正极活性物质层组合物涂覆在12μm厚的铝箔集流体上并压缩,从而制造正电极。
通过以98:1:1的重量比混合石墨(负极活性物质)、苯乙烯-丁二烯橡胶(SBR)(粘合剂)和羧甲基纤维素(CMC)(增稠剂/粘合剂),并将该混合物分散在水中来制备负极活性物质层组合物。将负极活性物质层组合物涂覆在8μm厚的铜箔(集流体)上、干燥并压缩,从而制造负电极。
然后,通过以3:1:6的体积比混合碳酸乙二酯(EC)、碳酸丙二酯(PC)和丙酸乙酯(EP),并溶解1.3M LiPF6和0.2重量份的LiBF4(基于100重量份的混合溶液)来制备电解液。
将正电极和负电极以及电解液与聚乙烯隔板一起使用来制造在1C时具有1400mAh/g容量的层压型电池单元。以2.3g/m2的负载量将聚偏二氟乙烯涂覆在聚乙烯隔板(在两面上)上。
实施例2
根据与实施例1相同的方法制造半电池,除了混合电解液包括体积比为3:1:6的碳酸乙二酯(EC)、碳酸乙基甲酯(EMC)和丙酸乙酯(EP)。
实施例3
根据与实施例1相同的方法制造半电池,除了混合电解液包括体积比为3:1:6的碳酸乙二酯(EC)、碳酸二乙酯(DEC)和丙酸乙酯(EP)。
实施例4
根据与实施例1相同的方法制造半电池,除了混合电解液包括体积比为3:1:1:5的碳酸乙二酯(EC)、碳酸丙二酯(PC)、碳酸乙基甲酯(EMC)和丙酸乙酯(EP)。
实施例5
根据与实施例1相同的方法制造半电池,除了混合电解液包括体积比为3:1:1:5的碳酸乙二酯(EC)、碳酸乙基甲酯(EMC)、碳酸二乙酯(DEC)和丙酸乙酯(EP)。
实施例6
根据与实施例1相同的方法制造半电池,除了混合电解液包括体积比为3:1:1:5的碳酸乙二酯(EC)、碳酸丙二酯(PC)、碳酸二乙酯(DEC)和丙酸乙酯(EP)。
对比例1
根据与实施例1相同的方法制造半电池,除了混合电解液包括体积比为3:5:2的碳酸乙二酯(EC)、碳酸乙基甲酯(EMC)和碳酸二乙酯(DEC),LiPF6为1.15M,且基于100重量份的混合溶液LiBF4的含量为0.2重量份。
对比例2
根据与实施例1相同的方法制造半电池,除了聚乙烯隔板未涂覆聚偏二氟乙烯。
评价1:在过充电时的可再充电锂电池单元
将根据实施例1至6以及对比例1和2的每个可再充电锂电池单元过充电并测量电压和温度。结果如图2至9所示。
以2A、5.25V和950mAh对根据实施例1至6以及对比例1和2的每个可再充电锂电池单元充电。
图2至图9为分别示出了根据实施例1至6以及对比例1和2的可再充电锂电池单元在过充电时状态的图。
参见图2至9,根据实施例1至6的使用在其表面上涂覆有包括聚偏二氟乙烯类聚合物的聚合物层的隔板以及包括丙酸烷基酯的电解液的可再充电锂电池单元在过充电时比对比例1中的使用无丙酸烷基酯的电解液的可再充电锂电池单元以及对比例2中的使用在其表面上未涂覆包括聚偏二氟乙烯类聚合物的聚合物层的隔板的可再充电锂电池单元更安全。
评价2:在过充电时可再充电锂电池单元的安全性
以700mA和5.25V对根据实施例1至6的充电的(即充分充电的)可再充电锂电池单元过充电10小时,以2A和5.25V对根据对比例1和2的充电的(即充分充电的)可再充电锂电池单元过充电230分钟。检查它们以评价在过充电时的安全性。结果如下表1中所示。
根据以下标准评价在过充电时的安全性:L1:引燃,L5:破裂,L10:良好。
表1
参见表1,根据实施例1至6的使用在其表面上涂覆有包括聚偏二氟乙烯类聚合物的聚合物层的隔板以及包括丙酸烷基酯的电解液的可再充电锂电池单元在过充电时比对比例1中的使用无丙酸烷基酯的电解液的可再充电锂电池单元以及对比例2中的使用在其表面上未涂覆包括聚偏二氟乙烯类聚合物的聚合物层的隔板的可再充电锂电池单元更安全。
尽管已结合目前认为是实际的示例性实施方式描述本公开,应理解的是本发明不限于所公开的实施方式,相反的,旨在覆盖包括在所附权利要求的精神和范围内的各种修改和等价排列,以及它们的等价方案。
Claims (16)
1.一种可再充电锂电池,包括:
正电极;
负电极;
所述正电极和所述负电极之间的隔板;
所述隔板上的聚合物层,所述聚合物层包括聚偏二氟乙烯类聚合物;和
浸泡所述隔板的电解液,所述电解液包含丙酸烷基酯,
其中所述聚偏二氟乙烯类聚合物以0.5至3.0g/m2的负载量加载,且其中基于所述电解液的总体积,所述丙酸烷基酯的含量为50至60体积%。
2.如权利要求1所述的可再充电锂电池,其中所述聚合物层在所述隔板和所述正电极之间和/或所述隔板和所述负电极之间。
3.如权利要求1所述的可再充电锂电池,其中所述聚偏二氟乙烯类聚合物包括选自由聚偏二氟乙烯、聚偏二氟乙烯-六氟丙烯共聚物和它们的组合组成的组中的聚合物。
4.如权利要求1所述的可再充电锂电池,其中所述聚偏二氟乙烯类聚合物以1.5至2.5g/m2的负载量加载。
5.如权利要求1所述的可再充电锂电池,其中所述聚合物层进一步包括选自由有机粉末、陶瓷粉末和它们的组合组成的组中的填料。
6.如权利要求5所述的可再充电锂电池,其中所述聚合物层包括所述有机粉末。
7.如权利要求6所述的可再充电锂电池,其中所述有机粉末包括聚甲基丙烯酸甲酯。
8.如权利要求5所述的可再充电锂电池,其中所述聚合物层包括所述陶瓷粉末。
9.如权利要求8所述的可再充电锂电池,其中所述陶瓷粉末选自由Al2O3、Mg(OH)2和它们的组合组成的组中。
10.如权利要求8所述的可再充电锂电池,其中基于所述聚合物层的总重量,所述陶瓷粉末的含量为0.1至98wt%。
11.如权利要求10所述的可再充电锂电池,其中基于所述聚合物层的总重量,所述陶瓷粉末的含量为3至20wt%。
12.如权利要求1所述的可再充电锂电池,其中所述丙酸烷基酯包括丙酸C1-10烷基酯。
13.如权利要求12所述的可再充电锂电池,其中所述丙酸烷基酯包括选自由丙酸甲酯、丙酸乙酯和它们的组合组成的组中的化合物。
14.如权利要求1所述的可再充电锂电池,其中所述电解液进一步包括锂盐和非水有机溶剂。
15.如权利要求1所述的可再充电锂电池,其中所述电解液进一步包括碳酸酯类溶剂,且所述碳酸酯类溶剂和所述丙酸烷基酯的体积比为4:6至5:5。
16.如权利要求1所述的可再充电锂电池,其中所述电解液为液体。
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US10461358B2 (en) | 2019-10-29 |
CN103050707A (zh) | 2013-04-17 |
US20130089794A1 (en) | 2013-04-11 |
JP6071389B2 (ja) | 2017-02-01 |
JP2013084598A (ja) | 2013-05-09 |
EP2581977B1 (en) | 2015-03-18 |
EP2581977A1 (en) | 2013-04-17 |
KR101744088B1 (ko) | 2017-06-07 |
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