CN103214768B - Polymeric film and preparation method thereof, has ionogen and the battery of polymeric film - Google Patents
Polymeric film and preparation method thereof, has ionogen and the battery of polymeric film Download PDFInfo
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- CN103214768B CN103214768B CN201110414845.1A CN201110414845A CN103214768B CN 103214768 B CN103214768 B CN 103214768B CN 201110414845 A CN201110414845 A CN 201110414845A CN 103214768 B CN103214768 B CN 103214768B
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- polymeric film
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- ionogen
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- 238000002360 preparation method Methods 0.000 title claims description 20
- 239000002904 solvent Substances 0.000 claims abstract description 57
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 39
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 28
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims description 40
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 36
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 25
- 239000007774 positive electrode material Substances 0.000 claims description 25
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 21
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims description 17
- 238000005266 casting Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 13
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical group COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000010907 mechanical stirring Methods 0.000 claims description 9
- 229920000128 polypyrrole Polymers 0.000 claims description 9
- 239000006230 acetylene black Substances 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 claims description 5
- 239000003760 tallow Substances 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 239000002048 multi walled nanotube Substances 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000013557 residual solvent Substances 0.000 claims description 3
- 239000002109 single walled nanotube Substances 0.000 claims description 3
- 238000000935 solvent evaporation Methods 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 10
- 230000007704 transition Effects 0.000 abstract description 5
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 42
- 239000007787 solid Substances 0.000 description 27
- 239000000243 solution Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- 229910052744 lithium Inorganic materials 0.000 description 21
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 19
- 239000012071 phase Substances 0.000 description 16
- 239000011777 magnesium Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 11
- 239000011244 liquid electrolyte Substances 0.000 description 11
- 210000004027 cell Anatomy 0.000 description 10
- 238000005034 decoration Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 229910000733 Li alloy Inorganic materials 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- 229920006254 polymer film Polymers 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- -1 silicon-aluminum (magnesium) Chemical compound 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910012424 LiSO 3 Inorganic materials 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 2
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 2
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 230000021615 conjugation Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910012305 LiPON Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical class [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- PYLLWONICXJARP-UHFFFAOYSA-N manganese silicon Chemical compound [Si].[Mn] PYLLWONICXJARP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910021483 silicon-carbon alloy Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of polymeric film, comprise the multipolymer of polyvinylidene difluoride (PVDF) and R 1216, described polymeric film also comprises the silicate with laminate structure.Compared with prior art, the present invention passes through phase transition method, solvent/non-solvent legal system is utilized to obtain a kind of polymeric film with vesicular structure, polymeric film has stronger mechanical property, to thermostability and at room temperature have very high ionic conductivity, can provide the stabilized voltage window up to 5V simultaneously.The application of polymeric film disclosed by the invention on business-like polymer Li-ion battery has considerable prospect.
Description
Technical field
The present invention relates to a kind of polymeric film.
The invention still further relates to a kind of preparation method of polymeric film.
The invention still further relates to a kind of ionogen with polymeric film.
The invention still further relates to a kind of electrolytical battery with polymeric film.
Background technology
Lithium cell is as a kind of high energy density cells of the prior art, and by industry, personnel conduct extensive research, and wherein polymer Li-ion battery is due to can arbitrary shape and obtain the extensive concern of people especially without leakage danger.The critical material of polymer Li-ion battery is ionogen, and commercial polymerization thing lithium ion battery ionogen is based on a kind of colloidal state organic micro film, wherein organic membrane is support frame, electrolytic solution is then stored in micropore, the conduction of lithium ion is realized by the sub-chain motion of polymer molecule or the migration that is stored in the electrolytic solution in micropore, and whole polymer dielectric is semi-solid structure.
Excellent polymer dielectric should possess that physical strength is large, stable electrochemical property, electronic isolation, and ionic conductivity is high, be easy to preparation and have the conditions such as wide stabilized voltage window.People were devoted to find the gel polymer and solid electrolyte that satisfy condition always in recent years.Research mainly concentrates on polyacrylonitrile (PAN), polymethylmethacrylate (PMMA) and polyethylene oxide (PEO) etc. are the polymer dielectric of matrix, but because these electrolytical conductivity at room temperature are on the low side, the verify battery performance of preparation of ionogen bad mechanical strength or polymer-based carbon has impact etc., and commercial applications is restricted.
Bellcore company of the U.S. made a breakthrough in prepared by polymer Li-ion battery in 1994, and successfully realize commercialization, they obtain the polymeric film of microvoid structure by plasticising/extraction process with polyvinylidene difluoride (PVDF)-R 1216 (PVDF-HFP), add the pick up of polymer dielectric, and therefore improve the high-rate discharge ability of electrolytical ionic conductivity and battery.The weak point of the method to adopt extraction steps to extract softening agent, thus improves battery production cost, and the safety problem bringing a large amount of organic plasticizers of process thus and occur.
Therefore, prior art is real is necessary further raising.
Summary of the invention
The invention provides a kind of can be used as electrolytic solution propping material there is high ionic conductivity, the polymeric film of very wide electrochemical stability window.
The invention provides a kind of polymeric film, comprise the multipolymer of polyvinylidene difluoride (PVDF) and R 1216, described polymeric film also comprises the silicate with laminate structure.
Preferably, described silicate comprises at least one in na-montmorillonite, organic decoration montmorillonite.
Preferably, described organic decoration montmorillonite comprises the montmorillonite that organic quaternary ammonium salt is modified.
Preferably, described organic quaternary ammonium salt comprises at least one in two-hydroxyethyl tallow methyl ammonium chloride, dimethyl diallyl ammonium chloride, octadecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide.
Preferably, described polymeric film is the vesicular structure with micron or submicron or nano level hole.
Preferably, the porosity ranges of described polymeric film is 25-75%.
The invention provides a kind of preparation method of polymeric film, described preparation method comprises the steps:
1) multipolymer of polyvinylidene difluoride (PVDF) and R 1216 and nano layered silicate are dissolved in a solvent, carry out supersound process after mechanical stirring, under room temperature, form the film-casting liquid of homogeneous phase;
2) in film-casting liquid, add non-solvent, homogeneous phase solution, until obtain homogeneous phase solution, is cast on vessel by mechanical stirring, after solvent and non-solvent evaporation, obtains polymeric film;
3) polymeric film is placed in vacuum drying oven and carries out drying treatment, to remove residual solvent and non-solvent.
Preferably, described solvent is acetone.
Preferably, described non-solvent is t-butyl methyl ether.
Preferably, the multipolymer of polyvinylidene difluoride (PVDF) and R 1216 and nano layered silicate are dissolved in a solvent, churned mechanically time range is 8-24h.
Preferably, described vacuum-drying temperature range is 50-80 DEG C, and time of drying, scope was 12-24h.
Present invention also offers a kind of ionogen, described ionogen comprises lithium salts, organic solvent and polymeric film as above.
The present invention also provides a kind of battery, the ionogen comprising positive pole, negative pole and be located between positive pole and negative pole, and described ionogen comprises polymeric film as above.
Preferably, described positive pole at least comprises positive electrode active materials, described positive electrode active materials can reversible-deviate from embedded ion.
Preferably, described positive pole at least comprises positive electrode active materials, and described positive electrode active materials comprises sulfenyl material, and described sulfenyl material is selected from elementary sulfur, Li
2s
n, organic sulfide and carbon-sulfur polymer (C
2s
v)
min at least one, wherein, n>=1,2.5≤v≤50, m>=2.
Preferably, described positive pole at least comprises positive electrode active materials, and described positive electrode active materials at least comprises AB
xc
yd
z, wherein A is selected from least one in polypyrrole, polyacrylonitrile, polyacrylonitrile copolymer; B is selected from elemental sulfur; C is selected from carbon-based material; D is selected from metal oxide; Wherein, 1≤x≤20,0≤y < 1,0 < z < 1.
Preferably, described polyacrylonitrile copolymer is selected from polyacrylonitrile-methylmethacrylate copolymer, at least one in polyacrylonitrile-polypyrrole multipolymer.
Preferably, described carbon-based material is selected from least one in section's qin carbon black, acetylene black, activated carbon, Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, Graphene.
Preferably, described metal oxide is selected from Mg
ani
bo, MgO, NiO, V
2o
5, CuO, Mg
ccu
do, La
2o
3, Zr
2o
3, Ce
2o
3and Mn
2o
fin at least one; Wherein, 0 < a < 1,0 < b < 1, a+b=1; 0 < c < 1,0 < d < 1, c+d=1; The value of f is 2 or 3 or 4 or 7.
Compared with prior art, the present invention passes through phase transition method, solvent/non-solvent method is utilized to obtain a kind of polymeric film of vesicular structure, polymeric film has stronger mechanical property, to thermostability and at room temperature have very high ionic conductivity, the polymeric film of simultaneously stability liquid electrolyte can provide the stabilized voltage window up to 5V, meets the application requiring of commercial polymer lithium ion battery completely.
Accompanying drawing explanation
Below in conjunction with drawings and embodiments, the invention will be further described.
Fig. 1 is the X-ray diffractogram of polymeric film and pure na-montmorillonite in embodiment 1-2 provided by the invention and comparative example 1, organic decoration montmorillonite (OMMT30B);
Fig. 2 is the photo that in embodiment 1-2 provided by the invention and comparative example 1, polymeric film is observed by SEM;
Fig. 3 is polymeric film and the electrolytical thermogravimetric curve figure of semi-solid state in embodiment 1-4 provided by the invention, comparative example 1-3;
Fig. 4 is the electrolytical ac impedance spectroscopy of semi-solid state in embodiment 3-4 provided by the invention and comparative example 3;
Fig. 5 is electrolytical cyclic voltammetry curve figure in embodiment 4 provided by the invention;
Fig. 6 is the voltage curve of initial 5 discharge and recharges of battery in embodiment 6 provided by the invention;
The coulombic efficiency figure of battery charging and discharging of Fig. 7 for providing in embodiment 5-6 and comparative example 4;
The cycle performance figure of battery charging and discharging of Fig. 8 for providing in embodiment 5-6 and comparative example 4.
Embodiment
A kind of polymeric film, can be applied to electrochemical appliance.Electrochemical appliance includes but are not limited to battery.Apply the battery of this polymeric film, the fields such as such as portable electron device, power tool, electromobile can be applied to.
A kind of polymeric film, comprise the multipolymer (PVDF-HFP) of polyvinylidene difluoride (PVDF) (PVDF) and R 1216 (HFP), further, polymer dielectric also comprises the silicate (Nano-layeredSilicate) with laminate structure.
PVDF is a kind of functional fluoropolymer material of partial crystallization, has higher physical strength, good thermotolerance, mechanical property, resistance to chemical attack and uvioresistant, ageing-resistant performance.In addition, PVDF stable chemical performance, can antioxidant, acid, alkali, salt, halogen, aromatic hydrocarbons, the corrosion of fat and chlorinated solvent and swelling, have the uvioresistant of excellence and ageing-resistant performance concurrently.The multipolymer (PVDF-HFP) that PVDF and HFP is formed combines the performance of these two kinds of polymkeric substance, namely the crystalline structure of PVDF makes multipolymer have more excellent chemical stability, unbodied HFP can improve the plasticity of multipolymer, and this character is directly connected to the ionic conductivity of multipolymer, therefore PVDF-HFP at room temperature has higher ionic conductivity.
Silicate comprises smectites material, and montmorillonite is natural ultra-high molecular weight inorganic silicon-aluminum (magnesium) silicate polymer that a class has nanostructure characteristic, and it is that a class is by 1 × 10
4-10
6individual molecular weight is about 720, area is 4.65nm
2the ultra-high molecular weight inorganic polymer of sial (magnesium) hydrochlorate structure cell set, be also the most easily reach the mineral that nano level peels off dispersion, have very strong avidity with high polymer.
Concrete, smectites material comprises na-montmorillonite (Na-MMT), at least one in organic decoration montmorillonite (OMMT).In a preferred embodiment, smectites material comprises Na-MMT.
Organic decoration montmorillonite comprises the montmorillonite that organic quaternary ammonium salt is modified, and organic quaternary ammonium salt comprises at least one in two-hydroxyethyl tallow methyl ammonium chloride, dimethyl diallyl ammonium chloride, octadecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide.In preferred embodiment, organic decoration montmorillonite is the montmorillonite (OMMT30B) that two-hydroxyethyl tallow methyl ammonium chloride is modified.
Preferably, smectites material needs to carry out pre-treatment before use, and specific in this preferred implementation, pretreated process is that smectites material is carried out drying treatment.
In the specific embodiment of the present invention, disclose a kind of preparation method of polymeric film, polymeric film at least comprises the copolymer p VDF-HFP of polyvinylidene difluoride (PVDF) (PVDF) and R 1216 (HFP) and has the silicate of laminate structure.Concrete, preparation method mainly adopts phase transition method to prepare polymeric film.Phase transition method utilizes that film-casting liquid and surrounding environment carry out solvent, non-solvent mass transfer exchanges, and make the solution of stable state originally become unstable state and produce liquid-liquid phase separation, final curing forms membrane structure.The performance of polymeric film determined primarily of the phase in version solidification process of the structural form that liquid-liquid phase process is formed and polymkeric substance.
Specific in present embodiment, preparation method comprises the steps:
The copolymer p VDF-HFP of polyvinylidene difluoride (PVDF) (PVDF) and R 1216 (HFP) and granular nanometer layered silicate are dissolved in a solvent, carries out supersound process after mechanical stirring, make it at room temperature form the film-casting liquid of homogeneous phase; Subsequently, in film-casting liquid, add non-solvent, homogeneous phase solution, until obtain homogeneous phase solution, casts on clean vessel by mechanical stirring, after solvent and non-solvent evaporation, namely obtains polymeric film; Finally, polymeric film is placed in vacuum drying oven and carries out drying treatment, to remove residual solvent and non-solvent.
Phase transition method prepares polymeric film, first need to prepare macromolecular solution, find suitable solvent to carry out dissolve polymer usually should to follow the solubility parameters of solvent and polymkeric substance close, the Lewis acid of the polarity of solvent and polymkeric substance close and solvent and polymkeric substance, alkalescence such as to match at the principle.Preferably, solvent is acetone.
Non-solvent is the poor solvent of polymkeric substance, and mainly make polymers soln produce precipitation and form film, non-solvent is selected from ether solvent, and preferably, non-solvent is t-butyl methyl ether.
In order to make copolymer p VDF-HFP and granular nanometer layered silicate dissolve uniformly in a solvent, churned mechanically time range is 8-24h.
In addition, in order to remove the solvent and non-solvent that may remain in polymeric film further, finally polymeric film is carried out drying treatment in vacuum drying oven, the temperature range in vacuum drying oven is 50-80 DEG C, and time of drying, scope was 12-24h.
In a concrete embodiment, by phase inversion process, acetone and ether is used to prepare polymeric film respectively as solvent and non-solvent.The nano layered silicate of PVDF-HFP and particulate form is dissolved in acetone (weight percent that nano layered silicate accounts for PVDF-HFP is 2.5wt%), mechanical stirring spend the night after supersound process 1h, make it at room temperature form uniform film-casting liquid (castingsolution), in film-casting liquid, the concentration of PVDF-HFP is 4wt%.Subsequently, t-butyl methyl ether (t-butyl methyl ether: acetone=1: 10, wt%) is joined in film-casting liquid, and continue to stir until solution becomes even.The homogeneous phase solution of gained is cast on a clean aluminium scale pan, after acetone and ether evaporation, obtains white, opaque film.Finally, by film dry 24h in the vacuum drying oven of 80 DEG C, remove acetone and the ether of trace further.
When ether as non-solvent adds in film-casting liquid, have Precipitation, after stirred for several hour, precipitation can be dissolved again.When the amount of non-solvent is less, polymkeric substance can dissolve completely, and film-casting liquid is homogeneous phase solution; But when the amount of non-solvent increases, polymkeric substance can be precipitated out, be difficult to be dissolved into again be integrated.The formation mechenism of film is the same with typical dry method (typicaldryphaseinversion) masking mechanism in this process.Can bring out when solvent and non-solvent volatilization and be separated, when solvent and non-solvent volatilize completely, namely obtain the polymeric film with vesicular structure.
By the structure using x-ray photoelectron spectroscopy (XRD), the polymeric film of final molding can be tested and confirm to scanning electronic microscope (SEM) and synchronous solving (DSC-TGA), configuration of surface and to thermostability.The polymeric film that the preparation method disclosed by the present invention is obtained is the vesicular structure with micron order or submicron order or nano level hole, and the porosity ranges of polymeric film is 25-75%, and has good connectedness between Kong Yukong.In addition, the polymeric film that with the addition of the silicates material of laminate structure has excellent thermostability, dimensional stability, workability and physical strength.
In the specific embodiment of the present invention, further disclose a kind of ionogen, ionogen comprises lithium salts, organic solvent and polymeric film.Polymeric film at least comprises the multipolymer of polyvinylidene difluoride (PVDF) (PVDF) and R 1216 (HFP) and has the silicate of laminate structure.
Lithium salts include but are not limited in following material one or more: LiSCN, LiBr, LiI, LiClO
4, LiAsF
6, LiSO
3cF
3, LiSO
3cH
3, LiBF
4, LiB (Ph)
4, LiC (SO
2cF
3)
3, LiPF
6with LiN (SO
2cF
3)
2.In organic solvent, the concentration range of adoptable lithium salts is 0.2-2.0M.Preferably, lithium salt is 0.5-1.5M.
Organic solvent can be the solvent of one-component or the mixed organic solvents of at least two kinds of components.Organic solvent include but are not limited in following material one or more: dme (DME), methylcarbonate (DMC), ethylene carbonate (EC), carbonic acid diethyl ester (DEC), methyl ethyl carbonate alkene ester (EMC), propene carbonate (PC), methyl propyl carbonate (MPC), 1,3-dioxolane (DIOX), ether, glyme, lactone, sulfone, tetramethylene sulfone.
In a preferred embodiment, by 1.0MLiPF
6be dissolved in organic solvent NSC 11801 (EC), diethyl carbonate (DEC) (EC: DEC=1: 1v/v) as liquid electrolyte.Polymeric film is immersed in liquid electrolyte and obtains semi-solid gel electrolyte.Finally, by filter paper, drying treatment is carried out to polymer film surface, thus obtained semi-solid polymer dielectric.
The polymeric film with vesicular structure is a kind of organic micro film based on colloidal state, mainly as support frame, liquid electrolyte is stored in micropore, electrolytical ionic conducting property realizes mainly through the sub-chain motion of polymer molecule or the migration that is stored in the ion in micropore, and whole ionogen is semi-solid structure.The hole of polymeric film enriches, and absorb liquid electrolyte ability strong, the surface of film and the back side are all microvoid structure, thus makes ion transport can run through whole polymeric film to make polymer dielectric at room temperature have very high ionic conductivity.Simultaneously known by cyclic voltammetry, the polymer dielectric that the present invention discloses has the electrochemical stability window up to 5V, by the polymer dielectric in the present invention with there is high-tension electrode materials be combined the battery that not only can form and there is high-energy-density, but also solve a large technical barrier of field of batteries, namely there is high-tension electrode materials but to can not find collocation with it there is the ionogen of high stable voltage window, therefore, the polymer dielectric that discloses of the present invention has considerable prospect building in the battery applications with high-energy-density.
In the specific embodiment of the present invention, further disclose a kind of battery, the ionogen comprising positive pole, negative pole and be located between positive pole and negative pole, ionogen comprises polymeric film.
Positive pole comprises positive electrode active materials, positive electrode active materials can reversible-deviate from embedded ion.Preferably, positive electrode active materials comprises sulfenyl material, and sulfenyl material accounts for the 70-90% of positive electrode active materials gross weight.In a preferred embodiment, the weight proportion of the sulfenyl material in positive electrode active materials is 80%.
Sulfenyl material is selected from elementary sulfur, Li
2s
n, organic sulfide and carbon-sulfur polymer (C
2s
v)
min at least one, wherein, n>=1,2.5≤v≤50, m>=2.
In a preferred embodiment, sulfenyl material contains AB
xc
yd
z, wherein, A is selected from polypyrrole, polyacrylonitrile (PAN), at least one in polyacrylonitrile copolymer; B is selected from elemental sulfur (S); C is selected from carbon-based material; D is selected from metal oxide; Wherein, 1≤x≤20,0≤y < 1,0 < z < 1.
Polyacrylonitrile copolymer is selected from PAN-methylmethacrylate copolymer, at least one in PAN-PPy.PPy is a kind of high conductive polymkeric substance, is widely used in electrode face finish and electrode materials; PAN issues raw pyrolytic reaction at 200-300 DEG C and contains the cyclisation of cyano group, dehydrogenation, conjugation, the process such as crosslinked, generate the conjugation coalescence pyrroles with conductivity, the low temperature pyrogenation performance of PAN is prepare sulfenyl material to provide good carrier, and PAN-methylmethacrylate copolymer is because possessing the structural unit of PAN in its structure, therefore the double properties that PAN-PPy combines PAN and PPy especially all can be used as the carrier of sulfenyl material.Meanwhile, the mass content of A in sulfenyl material is no more than 20%.As preferred embodiment, A is selected from PAN.
Carbon-based material is selected from section's qin carbon black (KB), acetylene black (AB), gac (AC), Single Walled Carbon Nanotube, multi-walled carbon nano-tubes (MWCNT), at least one in Graphene.Carbon-based material general characteristic is that specific surface is very large, has stronger adsorption function, also has excellent electroconductibility simultaneously, be suitable as conduction adding material.As preferred embodiment, C is selected from KB, and the particle size of KB is about 30nm, and specific surface area but reaches 1400m
2/ g, there is superpower adsorptive power simultaneously, it not only can improve the electroconductibility of material, and in the process preparing matrix material, the specific surface area larger because of it and strong adsorptive power, effectively can suppress the agglomerating phenomenon of the gathering of material, makes the particle size of sulfenyl material less and be more evenly distributed, decrease the evolving path of lithium ion, improve the ionic conductivity of material.In addition, the price of KB is also relatively cheap, and the cost of the sulfenyl material containing KB is also lower, has practicality.
Metal oxide is selected from Mg
ani
bo, MgO, NiO, V
2o
5, CuO, Mg
ccu
do, La
2o
3, Zr
2o
3, Ce
2o
3and Mn
2o
fin at least one, wherein, 0 < a < 1,0 < b < 1, a+b=1; 0 < c < 1,0 < d < 1, c+d=1; The value of f is 2 or 3 or 4 or 7.
As preferred embodiment, D is selected from Mg
0.6ni
0.4o, Mg
0.6ni
0.4o can improve the electroconductibility of sulfenyl material further, and the cycle performance of battery is improved.
In more preferably embodiment, sulfenyl material is S/PAN/Mg
0.6ni
0.4o trielement composite material.
Although elemental sulfur has considerable theoretical specific capacity, under room temperature, elemental sulfur is the isolator of electronics and ion, and the lithium-sulfur cell of the elemental sulfur positive pole composition of sulphur content 100% is at room temperature impossible carry out discharge and recharge.Therefore, positive electrode active materials also comprises conductive agent and binding agent.
Conductive agent, in order to accelerate the transmission of electronics, effectively improves the rate of migration of lithium ion in positive electrode active materials simultaneously.Concrete, conductive agent be selected from conductive polymers, activated carbon, Graphene, carbon black, carbon fiber, steel fiber, metal-powder and sheet metal one or more.The weight proportion scope of conductive agent in positive electrode active materials is 5-15%.In a preferred embodiment, conductive agent comprises acetylene black (AB).
Binding agent is selected from polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyimide, polyester, polyethers, fluorinated polymer, poly-divinyl polyoxyethylene glycol, polyethyleneglycol diacrylate, the one in glycol dimethacrylates, or the mixture of above-mentioned polymkeric substance and derivative.The weight proportion scope of binding agent in positive electrode active materials is 5-15%.In preferably embodiment, binding agent comprises tetrafluoroethylene (PTFE).
Specific in present embodiment, positive pole also comprises plus plate current-collecting body, and plus plate current-collecting body is selected from but is not limited only to Copper Foil, copper mesh, aluminium foil, the one in nickel foam or stainless (steel) wire.In a preferred embodiment, plus plate current-collecting body is nickel foam.
Negative pole comprises negative pole currect collecting and negative electrode active material, and negative electrode active material is selected from metallic lithium, lithium alloy, the negative active core-shell material of lithium carbon or silica-base material.Lithium alloy comprises lithium-aluminium alloy, lithium-magnesium alloy or lithium-tin alloy; The selection of the carbon-based material in lithium carbon is unrestricted, comprises crystalline carbon, decolorizing carbon, or its mixture.Silica-base material is selected from elemental silicon, silicon alloy, the silicon of metallic cover, at least one in metal-doped silicon.Silicon alloy comprises silicon-carbon alloys, silicon-lithium alloy and silicon-manganese alloy.In order to improve the specific conductivity of material silicon, generally the Surface coating of silicon or in silicon doping metals, metal is selected from but is not limited only to have the copper of good electronic conduction ability, tin, silver etc.
Negative current collector is selected from but is not limited only to Copper Foil, copper mesh, aluminium foil, and the one in nickel foam or stainless (steel) wire, when negative active core-shell material is metallic lithium, metallic lithium itself also can be used as negative current collector.
In order to ensure in charge and discharge process, between the positive pole of battery and negative pole, there is the lithium ion of deviating from-embedding, when the sulfenyl material of selection and silica-base material be not simultaneously containing lithium, to positive pole and/or the pre-embedding lithium process of negative pole.Concrete pre-embedding lithium mode is not limit, and comprises the embedding lithium of chemical reaction or the embedding lithium of electrochemical reaction.
In a particular embodiment, anode adopts S/PAN/Mg
0.6ni
0.4the trielement composite material of O, ionogen is PVDF-HFP/OMMT, and negative pole is metallic lithium, because sulphur has very high theoretical specific capacity, further by PAN and Mg on the basis of sulphur
0.6ni
0.4o optimizes the conductivity of positive electrode active materials, polymer dielectric effectively can not only suppress the loss of many lithium sulfides intermediate product in charge and discharge process, and there is higher ionic conductivity, the battery be assembled into not only all is improved a lot in cell container or on cycle performance.
As well known to those skilled in the art; in order to avoid metallic lithium as negative pole time; negative terminal surface produces dendrite because depositing inequality; usual meeting forms layer protecting film in negative terminal surface; protective membrane can be the LiPON compound interface film formed at metallic lithium surface, also can be the interfacial film that lithium alloy is formed.Therefore, the scope of the invention is included in the negative pole that negative active core-shell material surface forms protective membrane equally.
The battery of the employing polymer dielectric that the present invention discloses, because polymer dielectric has excellent mechanical property, to leading ionic nature and the voltage stability window up to 5V under thermostability, room temperature fast, battery in the present invention tool in capacity and cycle performance is improved a lot, simultaneously, polymer dielectric is semi-solid, make battery can use barrier film in formation, decrease the real cost of battery.
Unit in percent weight in volume in the present invention is well-known to those skilled in the art, such as, refer to the weight of solute in the solution of 100 milliliters.Unless otherwise defined, all specialties used in literary composition and scientific words and one skilled in the art the same meaning be familiar with.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The use that better implementation method described in literary composition and material only present a demonstration.
Below in conjunction with embodiment, further illustrate content of the present invention.Should be appreciated that enforcement of the present invention is not limited to the following examples, any pro forma accommodation make the present invention and/or change all will fall into scope.In the present invention, if not refer in particular to, all parts, per-cent are weight unit, and all equipment and raw material etc. all can be buied from market or the industry is conventional.
Embodiment 1
Polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer (PVDF-HFP, KynarFlex2801,12wt%HFP) directly uses after buying.The montmorillonite (OMMT, 30B) of montmorillonite sodium (Na-MMT) and organic decoration is bought from SouthernClayproducts (SCP, USA), the first using in the baking oven of 473K dry one week.Acetone can directly use as solvent and not need to be further purified.T-butyl methyl ether, as non-solvent, is buied from Acrosorganics.Acetone and t-butyl methyl ether are respectively as solvent and non-solvent.
PVDF-HFP and granular montmorillonite sodium (Na-MMT) (2.5wt%) are dissolved in acetone, mechanical stirring spend the night after supersound process 1 hour, form uniform film-casting liquid (castingsolution) under room temperature, the concentration of PVDF-HFP is 4wt%.T-butyl methyl ether (t-butyl methyl ether: acetone=1: 10, wt%) is joined in film-casting liquid, and continues to stir until solution becomes even.The homogeneous phase solution of gained is cast on a clean aluminium scale pan, after acetone and ether evaporation, obtains white, opaque porous-film.Finally, by film dry 24h in the vacuum drying oven of 80 DEG C, remove acetone and the ether of trace further, i.e. the obtained PVDF-HFP/Na-MMT film with vesicular structure.
Embodiment 2
In embodiment 2, smectites material is the montmorillonite (OMMT of organic decoration, 30B), that is to say the montmorillonite that two-hydroxyethyl tallow methyl ammonium chloride is modified, all the other materials and preparation method the same manner as in Example 1, the obtained PVDF-HFP/OMMT film with vesicular structure.
Comparative example 1
The PVDF-HFP bought is dissolved in acetone, mechanical stirring spend the night after supersound process one hour, form uniform film-casting liquid (castingsolution) under room temperature, the concentration of PVDF-HFP is 4wt%.T-butyl methyl ether (t-butyl methyl ether: acetone=1: 10, wt%) is joined in film-casting liquid, and continues to stir until solution becomes even.The homogeneous phase solution of gained is cast on a clean aluminium scale pan, after acetone and ether evaporation, obtains white, opaque porous-film.Subsequently, by film dry 24h in the vacuum drying oven of 80 DEG C, remove acetone and the ether of trace further, i.e. the obtained PVDF-HFP film with vesicular structure.
Comparative example 2
By polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer of directly buying as a comparison case (PVDF-HFP, KynarFlex2801,12wt%HFP).
The X-ray diffracting spectrum that the polymeric film that Fig. 1 is na-montmorillonite Na-MMT, provide in organic decoration montmorillonite OMMT30B, embodiment 1-2, comparative example 1 is obtained by X-ray diffractometer (XRD, D8Discover, Bruker).Can find out from collection of illustrative plates: OMMT30B and Na-MMT in diffraction angle 2 θ=5 ° and 8 ° there is obvious diffraction peak respectively.But in the XRD figure spectrum of PVDF-HFP/Na-MMT polymeric film and PVDF-HFP/OMMT polymeric film, but the characteristic diffraction peak of montmorillonite is not observed, illustrate that the montmorillonite in these two kinds of polymeric films exists with limellar stripping state, this is because the molecular chain of PVDF-HFP enters the sheet interlayer of montmorillonite, thus make the lamella of polynite softened so that peel off.
The polymeric film obtained in embodiment 1-2 and comparative example 1 is carried out the structure in the configuration of surface of Study Polymer Melts film, pore size distribution and hole by high resolving power field emission scanning electron microscope (Zeiss, LEO1515).
Fig. 2 is followed successively by the form of PVDF-HFP polymeric film, PVDF-HFP/Na-MMT polymeric film and the PVDF-HFP/OMMT polymeric film observed under identical multiplying power by SEM from left to right.As can be seen from the figure, the polymeric film containing layered nano-structure montmorillonite is relative to PVDF-HFP polymeric film, and aperture obviously diminishes, and the connectedness in the quantity in hole, hole and homogeneity substantially increase.Hole appropriate in polymeric film can support sufficient liquid electrolyte and connection between Kong Yukong can ensure that ion moves fast in film, thus polymeric film is at room temperature had lead ionic nature fast.
Embodiment 3
By 1.0MLiPF
6be dissolved in organic solvent ethyl-carbonate (EC), diethyl carbonate (DEC) (EC: DEC=1: 1v/v).The obtained PVDF-HFP/Na-MMT polymeric film with vesicular structure is flooded the semi-solid state ionogen that 6h in the solution obtains porous.Then, blot the solution remaining in film surface with filter paper, the final PVDF-HFP/Na-MMT semi-solid state ionogen obtaining porous.
Embodiment 4
By 1.0MLiPF
6be dissolved in organic solvent ethyl-carbonate (EC), diethyl carbonate (DEC) (EC: DEC=1: 1v/v).The obtained PVDF-HFP/OMMT polymeric film with vesicular structure is flooded the semi-solid state ionogen that 6h in the solution obtains porous.Then, blot the solution remaining in film surface with filter paper, the final PVDF-HFP/OMMT semi-solid state ionogen obtaining porous.
Comparative example 3
By 1.0MLiPF
6be dissolved in organic solvent ethyl-carbonate (EC), diethyl carbonate (DEC) (EC: DEC=1: 1v/v).The obtained PVDF-HFP polymeric film with vesicular structure is flooded the semi-solid state ionogen that wherein 6h obtains porous.Then, blot the solution remaining in film surface with filter paper, the final PVDF-HFP semi-solid state ionogen obtaining porous.
By synchronous thermogravimetric analyzer DSC-TGA (DSC: dsc; TGA: thermogravimetric analyzer) (TAinstruments, Q-600) analyze semi-solid state ionogen in the polymeric film in embodiment 1-2, comparative example 1, the multipolymer in comparative example 2 and embodiment 3-4, comparative example 3 to thermal stability.Experiment condition: temperature rise rate 10 DEG C/min, sweep limit: room temperature-500 DEG C.
Fig. 3 is thermal gravimetric analysis results curve.The melt temperature of pure PVDF-HFP is 159 DEG C, but as can be seen from the figure: the thermostability of the multipolymer in the polymeric film provided in embodiment 1-2, comparative example 1 and comparative example 2 is up to 400 DEG C.Meanwhile, the initial degradation temperature of polymeric film that with the addition of the silicate of nanometer laminated structure declines to some extent, and about has the weight loss of 5%, and this phenomenon can be decomposed owing to the organic group between the silicate layer of nanometer laminated structure.Semi-solid state ionogen loses from 90 DEG C of weight, shows that the polymeric film absorbing liquid electrolyte is all stable at 0-90 DEG C.In addition, between temperature range 100-200 DEG C, there is obvious weight loss in the polymeric film absorbing liquid electrolyte, the decomposition of the liquid electrolyte in polymeric film pore texture is described.Another phenomenon: all semi-solid state ionogen are between 100-200 DEG C, and weight loss is all about 50%, shows that apertured polymeric film can absorb the liquid electrolyte of high level.
The electrolytical ionic conductivity of semi-solid state in research performation example 3-4 and comparative example 3 is carried out by electrochemical impedance (EIS).The calculation formula of electrolyte ion specific conductivity (σ): σ=d/R
bs, wherein d is the thickness of polymeric film, and S is the area of film, R
bfor passing through to test to the alternating-current impedance of stainless steel/semi-solid state ionogen/stainless steel battery the solution bulk impedance recorded.Alternating-current impedance experiment is all carried out on CHI660 electrochemical workstation.AC amplitude is 10mV, and range of frequency is 0.1Hz to 100kHz.
Fig. 4 under room temperature by the electrolytical ac impedance spectroscopy of semi-solid state that EIS testing example 3-4 and comparative example 3 provide.Learnt by test result: the electrolytical impedance of PVDF-HFP, PVDF-HFP/Na-MMT and PVDF-HFP/OMMT semi-solid state is respectively 4.5 Ω, 4 Ω and 5.7 Ω.The impedance of these three kinds of semi-solid state polymer dielectrics is all very low, that is to say that the polymeric film that the solvent/non-solvent method disclosed by the present invention is prepared at room temperature has very high ionic conductivity.This result just in time conforms to SEM result, the hole of the polymeric film that the present invention discloses enriches, absorb liquid electrolyte ability strong, the surface of film and the back side are all microvoid structure, thus ion transport can be run through under whole polymeric film makes polymer dielectric room temperature to have high ionic conductivity.
By assembling stainless steel/semi-solid state ionogen/lithium metal battery, adopt cyclic voltammetry to carry out PVDF-HFP/OMMT semi-solid state electrolyte electrochemical stability window in research performation example 4, stainless steel is working electrode, and lithium is supporting electrode and reference electrode.Linear time base sweep experiment is all carried out on CHI660 electrochemical workstation.
The PVDF-HFP/OMMT semi-solid state electrolyte circulation cyclic voltammetric result of 10 weeks that Fig. 5 provides for embodiment 4.As can be seen from the figure: porous polymer electrolyte first week anodic stabilization voltage window, up to 4.8V, shows that electrochemical decomposition can not occur lower than 4.8V.At second week, electrochemical stability strengthens, and dielectric film stabilized voltage arrives 5V.The electrochemical stability voltage of bibliographical information PVDF-HFP film is about 4.38V.This result clearly shows that the electrochemical stability of the apertured polymeric film that the preparation method that the present invention discloses obtains is more excellent and highly stable under the operating voltage of lithium polymer battery.In addition, less electric current remains and does not occur that when voltage is lower other assorted peak all shows that the nanometer polymer film purity that this preparation method obtains is very high.
Embodiment 5
By ternary positive electrode active material S/PAN/Mg
0.6ni
0.4o, binding agent PVDF, electrically conductive material KB mix according to the mass ratio of 8: 1: 1, add N-Methyl pyrrolidone as solvent, the slurry obtained is coated in plus plate current-collecting body nickel foam by scraper for coating technology, vacuum-drying 24h at 50 DEG C, positive plate is obtained at tabletting machine lower sheeting, take metallic lithium as negative pole, the PVDF-HFP/Na-MMT semi-solid state ionogen of porous is arranged between positive pole and cathode of lithium, instills 2 containing 1MLiPF
6eC/DEC solution after, in the glove box being full of argon gas, be assembled into CR2032 button cell.
Embodiment 6
By ternary positive electrode active material S/PAN/Mg
0.6ni
0.4o, binding agent PVDF, electrically conductive material KB mix according to the mass ratio of 8: 1: 1, add N-Methyl pyrrolidone as solvent, the slurry obtained is coated in plus plate current-collecting body nickel foam by scraper for coating technology, vacuum-drying 24h at 50 DEG C, positive plate is obtained at tabletting machine lower sheeting, take metallic lithium as negative pole, the PVDF-HFP/OMMT semi-solid state ionogen of porous is arranged between positive pole and cathode of lithium, instills 2 containing 1MLiPF
6eC/DEC solution after, in the glove box being full of argon gas, be assembled into CR2032 button cell.
The voltage pattern of battery at room temperature initial 5 discharge and recharges that Fig. 6 provides for embodiment 6, voltage range is 1.5-3V, and charge-discharge velocity is 0.2C.
Comparative example 4
By ternary positive electrode active material S/PAN/Mg
0.6ni
0.4o, binding agent PVDF, electrically conductive material KB mix according to the mass ratio of 8: 1: 1, add N-Methyl pyrrolidone as solvent, the slurry obtained is coated in plus plate current-collecting body nickel foam by scraper for coating technology, vacuum-drying 24h at 50 DEG C, positive plate is obtained at tabletting machine lower sheeting, take metallic lithium as negative pole, the PVDF-HFP semi-solid state ionogen of porous is arranged between positive pole and cathode of lithium, instills 2 containing 1MLiPF
6eC/DEC solution after, in the glove box being full of argon gas, be assembled into CR2032 button cell.
In order to detect the performance of battery, the battery in embodiment 5-6 and comparative example 4 is carried out charge-discharge test.During discharge and recharge, voltage range is 1.0-3.0V, and discharge rate is 0.2C.
Fig. 7 and Fig. 8 be respectively the circulating battery that provides in embodiment 5-6 and comparative example 4 after 250 weeks coulombic efficiency and loading capacity to the schematic diagram of cycle index.The good capability retention adopting the battery of apertured polymeric film all to embody and reversibility, at the coulombic efficiency of circulation after 250 weeks close to 100%, and the loading capacity of polymer dielectric containing nano layered silicate significantly increases.The initial discharge capacity of the battery that embodiment 5 and 6 provides is identical, but the battery in embodiment 5, namely adopts the loading capacity of the battery of PVDF-HFP/Na-MMT nanometer polymer film to there is decay, in circulation after 60 weeks, the loading capacity of battery is identical with the capacity of the battery in comparative example 4.And adopt the battery of PVDF-HFP/OMMT nanometer polymer film to show very high loading capacity in embodiment 8 and decay slowly after experienced by longer circulation, the loading capacity first of battery in the cell container of circulation after 250 weeks is still close to comparative example 4.Concrete, lithium-sulfur cell shows initial specific capacities up to 950mAh/gr (content relative to sulphur), and still remains on 650mAh/gr at circulation 250 weeks rear capacity, and the coulombic efficiency of 250 weeks is 100%.
Although contriver has done more detailed elaboration to technical scheme of the present invention and has enumerated, be to be understood that, to those skilled in the art, above-described embodiment to be modified and/or flexible or adopt equivalent replacement scheme to be obvious, all can not depart from the essence of spirit of the present invention, the term occurred in the present invention, for the elaboration of technical solution of the present invention and understanding, can not be construed as limiting the invention.
Claims (16)
1. a polymeric film, comprises the multipolymer of polyvinylidene difluoride (PVDF) and R 1216, it is characterized in that: described polymeric film also comprises the silicate with laminate structure, and described silicate is the montmorillonite that two-hydroxyethyl tallow methyl ammonium chloride is modified.
2. polymeric film according to claim 1, is characterized in that: described polymeric film is the vesicular structure with micron or submicron or nano level hole.
3. polymeric film according to claim 2, is characterized in that: the porosity ranges of described polymeric film is 25-75%.
4. a preparation method for polymeric film, is characterized in that: described preparation method comprises the steps:
1) multipolymer of polyvinylidene difluoride (PVDF) and R 1216 and nano layered silicate are dissolved in a solvent, carry out supersound process after mechanical stirring, under room temperature, form the film-casting liquid of homogeneous phase;
2) in film-casting liquid, add non-solvent, homogeneous phase solution, until obtain homogeneous phase solution, is cast on vessel by mechanical stirring, after solvent and non-solvent evaporation, obtains polymeric film;
3) polymeric film is placed in vacuum drying oven and carries out drying treatment, to remove residual solvent and non-solvent.
5. the preparation method of polymeric film according to claim 4, is characterized in that: described solvent is acetone.
6. the preparation method of polymeric film according to claim 4, is characterized in that: described non-solvent is t-butyl methyl ether.
7. the preparation method of polymeric film according to claim 4, is characterized in that: the multipolymer of polyvinylidene difluoride (PVDF) and R 1216 and nano layered silicate are dissolved in a solvent, churned mechanically time range is 8-24h.
8. the preparation method of polymeric film according to claim 4, is characterized in that: described vacuum-drying temperature range is 50-80 DEG C, and time of drying, scope was 12-24h.
9. an ionogen, is characterized in that: described ionogen comprises lithium salts, organic solvent and as the polymeric film in claim 1-3 as described in any one.
10. a battery, the ionogen comprising positive pole, negative pole and be located between positive pole and negative pole, is characterized in that: described ionogen comprises as the polymeric film in claim 1-3 as described in any one.
11. batteries according to claim 10, is characterized in that: described positive pole at least comprises positive electrode active materials, described positive electrode active materials can reversible-deviate from embedded ion.
12. batteries according to claim 10, is characterized in that: described positive pole at least comprises positive electrode active materials, and described positive electrode active materials comprises sulfenyl material, and described sulfenyl material is selected from elementary sulfur, Li
2s
n, organic sulfide and carbon-sulfur polymer (C
2s
v)
min at least one, wherein, n>=1,2.5≤v≤50, m>=2.
13. batteries according to claim 10, is characterized in that: described positive pole at least comprises positive electrode active materials, and described positive electrode active materials at least comprises AB
xc
yd
z, wherein A is selected from least one in polypyrrole, polyacrylonitrile, polyacrylonitrile copolymer; B is selected from elemental sulfur; C is selected from carbon-based material; D is selected from metal oxide; Wherein, 1≤x≤20,0≤y<1,0<z<1.
14. batteries according to claim 13, is characterized in that: described polyacrylonitrile copolymer is selected from polyacrylonitrile-methylmethacrylate copolymer, at least one in polyacrylonitrile-polypyrrole multipolymer.
15. batteries according to claim 13, is characterized in that: described carbon-based material is selected from least one in section's qin carbon black, acetylene black, activated carbon, Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, Graphene.
16. batteries according to claim 13, is characterized in that: described metal oxide is selected from Mg
ani
bo, MgO, NiO, V
2o
5, CuO, Mg
ccu
do, La
2o
3, Zr
2o
3, Ce
2o
3and Mn
2o
fin at least one; Wherein, 0<a<1,0<b<1, a+b=1; 0<c<1,0<d<1, c+d=1; The value of f is 2 or 3 or 4 or 7.
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| CN104993139B (en) * | 2015-06-17 | 2018-11-09 | 北京大学深圳研究生院 | A kind of composition silicate all-solid-state battery and preparation method thereof |
| CN106532104B (en) * | 2015-09-09 | 2019-03-19 | 中国科学院大连化学物理研究所 | A kind of lithium-sulfur cell gel electrolyte porous electrode and its preparation and application |
| CN107163288B (en) * | 2017-05-10 | 2019-03-29 | 郑州大学 | Super-hydrophobic three-dimensional porous polymer matrix composite and preparation method thereof |
| CN109585917B (en) * | 2018-12-11 | 2022-02-08 | 广东永邦新能源股份有限公司 | Polymer electrolyte, preparation method thereof and battery comprising polymer electrolyte |
| CN110483924B (en) * | 2019-08-21 | 2021-06-15 | 陕西科技大学 | Super-hydrophobic self-cleaning radiation cooling film and preparation method thereof |
| CN111662479B (en) * | 2020-07-21 | 2022-04-29 | 江西省纳米技术研究院 | Gel polymer electrolyte composite membrane and preparation method and application thereof |
| CN114335705B (en) * | 2020-09-28 | 2024-05-03 | 中国科学院苏州纳米技术与纳米仿生研究所 | Integrated all-solid-state battery and preparation method thereof |
| CN112397780A (en) * | 2020-11-24 | 2021-02-23 | 贵州大学 | Polymer electrolyte film material and preparation method thereof |
| CN113851704B (en) * | 2021-09-24 | 2023-12-15 | 中化学南方建设投资有限公司 | Preparation method of polymer electrolyte membrane |
| CN113889598B (en) * | 2021-09-30 | 2022-10-14 | 四川大学 | Solid electrolyte and anode material integrated battery anode and preparation and application thereof |
| CN113932950B (en) * | 2021-10-13 | 2024-08-06 | 中国科学院苏州纳米技术与纳米仿生研究所 | Flexible pressure sensor and manufacturing method thereof |
| CN114437603B (en) * | 2022-03-10 | 2023-03-24 | 山东鑫纳超疏新材料有限公司 | Preparation method of durable super-hydrophobic micro-droplet self-cleaning coating based on conductive nanoparticles |
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| EP1202609A2 (en) * | 2000-10-23 | 2002-05-02 | Atofina Chemicals, Inc. | Polyvinylidene fluoride films |
| CN1914264A (en) * | 2004-01-30 | 2007-02-14 | 日东电工株式会社 | Porous film and method for preparation thereof |
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