CN103214768A - Polymer membrane, preparation method of the polymer membrane, and electrolyte and cell containing the polymer membrane - Google Patents
Polymer membrane, preparation method of the polymer membrane, and electrolyte and cell containing the polymer membrane Download PDFInfo
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- CN103214768A CN103214768A CN2011104148451A CN201110414845A CN103214768A CN 103214768 A CN103214768 A CN 103214768A CN 2011104148451 A CN2011104148451 A CN 2011104148451A CN 201110414845 A CN201110414845 A CN 201110414845A CN 103214768 A CN103214768 A CN 103214768A
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- polymeric film
- solvent
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- preparation
- polymer membrane
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003792 electrolyte Substances 0.000 title abstract description 5
- 229920005597 polymer membrane Polymers 0.000 title abstract 10
- 239000002904 solvent Substances 0.000 claims abstract description 59
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 38
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920001577 copolymer Polymers 0.000 claims abstract description 10
- 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
- 238000000034 method Methods 0.000 claims description 29
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 28
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 24
- 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 23
- 239000007774 positive electrode material Substances 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 238000005266 casting Methods 0.000 claims description 19
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- 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
- 238000005034 decoration Methods 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- 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
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 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
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 150000002500 ions Chemical class 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
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000013557 residual solvent Substances 0.000 claims description 4
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 239000002109 single walled nanotube Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 34
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000002033 PVDF binder Substances 0.000 abstract 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 abstract 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 42
- 239000007787 solid Substances 0.000 description 27
- 239000000243 solution Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- 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 14
- 239000011777 magnesium Substances 0.000 description 13
- 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
- 229910013870 LiPF 6 Inorganic materials 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-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
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- -1 silicon-aluminum (magnesium) Chemical compound 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910000733 Li alloy Inorganic materials 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000001989 lithium alloy Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229920006254 polymer film Polymers 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 230000007704 transition Effects 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
- 239000006182 cathode active material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 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
- 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
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 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
- 229920006370 Kynar Polymers 0.000 description 2
- 229910012424 LiSO 3 Inorganic materials 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- 239000004902 Softening Agent Substances 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
- 239000002131 composite material Substances 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 230000005484 gravity Effects 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
- 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
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene 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
- 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
- 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
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 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
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 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
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 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
- 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
- 239000003989 dielectric material 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
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 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
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 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
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
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- 239000005518 polymer electrolyte Substances 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
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- 239000000047 product Substances 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 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
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- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Secondary Cells (AREA)
Abstract
The invention discloses a polymer membrane, a preparation method of the polymer membrane, and an electrolyte and a cell containing the polymer membrane. The polymer membrane comprises a copolymer of polyvinylidene fluoride and hexafluoropropylene and also comprises silicate having a layered structure. Compared with the prior art, the preparation method realizes preparation of the polymer membrane having a porous structure by a phase inversion technology through a solvent/non-solvent technology. The polymer membrane has strong mechanical properties, heat stability and high ionic conductivity at a room temperature and can provide a stable voltage window of 5V. The polymer membrane has a good application prospect in a commercial polymer lithium ion cell.
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 has been carried out extensive studies as a kind of high energy density cells of the prior art by the industry personnel, but wherein polymer Li-ion battery because arbitrary shapeization and no leakage danger have obtained people's extensive concern especially.The critical material of polymer Li-ion battery is an ionogen, and the commercialization polymer Li-ion battery is based on a kind of colloidal state organic micro film with ionogen, wherein organic membrane is a support frame, electrolytic solution then is stored in the micropore, the conduction of lithium ion by polymer molecule sub-chain motion or the migration that is stored in the electrolytic solution in the micropore realize that whole polymer dielectric is semi-solid structure.
Good polymer dielectric should possess big, the stable electrochemical property of physical strength, and electronic isolation, is easy to preparation and has condition such as wide stabilized voltage window the ionic conductivity height.People were devoted to seek gel polymer and the solid electrolyte that satisfies 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 the battery performance of preparation is influential etc. because on the low side, ionogen bad mechanical strength of these electrolytical conductivity at room temperature or polymer-based carbon are verified, and commercial applications is restricted.
U.S. Bellcore company made a breakthrough aspect preparing at polymer Li-ion battery in 1994, and successfully realize commercialization, they make the polymeric film of microvoid structure by plasticising/extraction process with polyvinylidene difluoride (PVDF)-R 1216 (PVDF-HFP), increase the pick up of polymer dielectric, and therefore improved the high-rate discharge ability of electrolytical ionic conductivity and battery.The weak point of this method is to adopt extraction steps to extract softening agent, thereby has improved the battery production cost, and has brought the safety problem of handling a large amount of organic softening agent and occurring thus.
Therefore, prior art is necessary further raising in fact.
Summary of the invention
The invention provides a kind of high ionic conductivity of having of electrolytic solution propping material, polymeric film of very wide electrochemical stability window of can be used as.
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 a in na-montmorillonite, the 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 a in two-hydroxyethyl tallow ylmethyl ammonium chloride, dimethyl diallyl ammonium chloride, octadecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethylammonium bromide, the octadecyl trimethylammonium 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 and the nano layered silicate with polyvinylidene difluoride (PVDF) and R 1216 is dissolved in the solvent, carries out supersound process after the mechanical stirring, forms the homogeneous film-casting liquid under the room temperature;
2) add non-solvent in film-casting liquid, mechanical stirring is cast to homogeneous phase solution on the vessel until obtaining homogeneous phase solution, treat the evaporation of solvent and non-solvent after, obtain polymeric film;
3) polymeric film is placed vacuum drying oven carry out drying treatment, to remove residual solvent and non-solvent.
Preferably, described solvent is an acetone.
Preferably, described non-solvent is a t-butyl methyl ether.
Preferably, the multipolymer and the nano layered silicate of polyvinylidene difluoride (PVDF) and R 1216 is dissolved in the solvent, churned mechanically time range is 8-24h.
Preferably, described vacuum-drying temperature range is 50-80 ℃, and time of drying, scope was 12-24h.
The present invention also provides a kind of ionogen, and described ionogen comprises lithium salts, organic solvent and aforesaid polymeric film.
The present invention also provides a kind of battery, comprise positive pole, negative pole and be located at positive pole and negative pole between ionogen, described ionogen comprises aforesaid polymeric film.
Preferably, described positive pole comprises positive electrode active materials at least, described positive electrode active materials can be reversible-deviate from embedded ion.
Preferably, described positive pole comprises positive electrode active materials at least, and described positive electrode active materials comprises the sulfenyl material, and described sulfenyl material is selected from elementary sulfur, Li
2S
n, organic sulfide and carbon sulphur polymkeric substance (C
2S
v)
mIn at least a, wherein, n 〉=1,2.5≤v≤50, m 〉=2.
Preferably, described positive pole comprises positive electrode active materials at least, and described positive electrode active materials comprises AB at least
xC
yD
z, wherein A is selected from least a in polypyrrole, polyacrylonitrile, the polyacrylonitrile multipolymer; 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 multipolymer is selected from polyacrylonitrile-methylmethacrylate copolymer, at least a in polyacrylonitrile-polypyrrole multipolymer.
Preferably, described carbon-based material is selected from least a in section's qin carbon black, acetylene black, activated carbon, Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, the 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 a; 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, utilize the solvent/non-solvent method to obtain a kind of polymeric film of vesicular structure, polymeric film has stronger mechanical property, to thermostability and at room temperature have a very high ionic conductivity, the polymeric film that has absorbed liquid electrolyte simultaneously can provide the stabilized voltage window up to 5V, meets the application requiring of commercial polymer lithium ion battery fully.
Description of drawings
The invention will be further described below in conjunction with drawings and embodiments.
Fig. 1 is polymeric film and pure na-montmorillonite in embodiment 1-2 provided by the invention and the Comparative Examples 1, the X-ray diffractogram of organic decoration montmorillonite (OMMT 30B);
Fig. 2 is that polymeric film passes through the observed photo of SEM in embodiment 1-2 provided by the invention and the Comparative Examples 1;
Fig. 3 is polymeric film and the electrolytical thermogravimetric curve figure of semi-solid state among embodiment 1-4 provided by the invention, the Comparative Examples 1-3;
Fig. 4 is the electrolytical ac impedance spectroscopy of semi-solid state in embodiment 3-4 provided by the invention and the Comparative Examples 3;
Fig. 5 is electrolytical cyclic voltammetry curve figure among the embodiment 4 provided by the invention;
The voltage curve that Fig. 6 discharges and recharges for 5 times for battery among the embodiment 6 provided by the invention is initial;
The enclosed pasture efficiency diagram of the battery charging and discharging that provides in embodiment 5-6 and the Comparative Examples 4 is provided Fig. 7;
The cycle performance figure of the battery charging and discharging that provides in embodiment 5-6 and the Comparative Examples 4 is provided Fig. 8.
Embodiment
A kind of polymeric film can be applied to electrochemical appliance.Electrochemical appliance includes but are not limited to battery.Use the battery of this polymeric film, can be applied to such as fields such as portable electron device, power tool, electromobiles.
A kind of polymeric film comprises the multipolymer (PVDF-HFP) of polyvinylidene difluoride (PVDF) (PVDF) and R 1216 (HFP), and further, polymer dielectric also comprises the silicate (Nano-layered Silicate) 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, the PVDF stable chemical performance, the corrosion and the swelling of energy antioxidant, acid, alkali, salt, halogen, aromatic hydrocarbons, fat and chlorinated solvent have excellent uvioresistant and ageing-resistant performance concurrently.The multipolymer (PVDF-HFP) that PVDF and HFP form combines this two kinds of polymer properties, the crystalline structure that is PVDF makes multipolymer have excellent more chemical stability, unbodied HFP can improve the plasticity of multipolymer, and this character is directly connected to the ionic conductivity of multipolymer, so PVDF-HFP at room temperature has higher ionic conductivity.
Silicate comprises the smectites material, and montmorillonite is natural ultra-high molecular weight inorganic silicon-aluminum (magnesium) silicate polymer that a class has the 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, also be that the easiest nano level that reaches is peeled off the dispersive mineral, with high polymer very strong avidity is arranged.
Concrete, the smectites material comprises na-montmorillonite (Na-MMT), at least a in the organic decoration montmorillonite (OMMT).In preferred embodiment, the smectites material comprises Na-MMT.
The organic decoration montmorillonite comprises the montmorillonite that organic quaternary ammonium salt is modified, and organic quaternary ammonium salt comprises at least a in two-hydroxyethyl tallow ylmethyl ammonium chloride, dimethyl diallyl ammonium chloride, octadecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethylammonium bromide, the octadecyl trimethylammonium bromide.In preferred embodiment, the organic decoration montmorillonite is the montmorillonite (OMMT 30B) that two-hydroxyethyl tallow ylmethyl ammonium chloride is modified.
Preferably, the smectites material need carry out pre-treatment before use, and specific in this preferred implementation, pretreated process is that the smectites material is carried out drying treatment.
In the specific embodiment of the present invention, disclosed a kind of preparation method of polymeric film, polymeric film comprises polyvinylidene difluoride (PVDF) (PVDF) and the copolymer p VDF-HFP of R 1216 (HFP) and the silicate with laminate structure at least.Concrete, the preparation method adopts phase transition method to prepare polymeric film.Phase transition method is to utilize film-casting liquid and surrounding environment to carry out solvent, the exchange of non-solvent mass transfer, makes the solution of script stable state become unstable state and produce liquid-liquid phase separation, and final curing forms membrane structure.The performance of polymeric film is mainly determined by the solidification process of transformation mutually of liquid-formed structural form of liquid phase process and polymkeric substance.
In present embodiment, the preparation method comprises the steps:
The copolymer p VDF-HFP and the granular nanometer layered silicate of polyvinylidene difluoride (PVDF) (PVDF) and R 1216 (HFP) are dissolved in the solvent, carry out supersound process after the mechanical stirring, make it at room temperature form the homogeneous film-casting liquid; Subsequently, add non-solvent in film-casting liquid, mechanical stirring casts in homogeneous phase solution on the vessel of cleaning until obtaining homogeneous phase solution, treat the evaporation of solvent and non-solvent after, promptly obtain polymeric film; At last, place vacuum drying oven to carry out drying treatment polymeric film, to remove residual solvent and non-solvent.
Phase transition method prepares polymeric film, at first need to prepare macromolecular solution, seeking suitable solvent, to come dissolve polymer should follow the solubility parameters of solvent and polymkeric substance usually close, the polarity of solvent and polymkeric substance Lewis acid, alkalescence close and solvent and polymkeric substance principle such as match.Preferably, solvent is an acetone.
Non-solvent is the poor solvent of polymkeric substance, mainly is to make polymers soln produce precipitation and formation film, and non-solvent is selected from ether solvent, and preferred, non-solvent is a t-butyl methyl ether.
For copolymer p VDF-HFP and granular nanometer layered silicate are dissolved in the solvent uniformly, churned mechanically time range is 8-24h.
In addition, in order further to remove residual solvent and the non-solvent of possibility in the polymeric film, at last polymeric film is carried out drying treatment in vacuum drying oven, the temperature range in the vacuum drying oven is 50-80 ℃, and time of drying, scope was 12-24h.
In a concrete embodiment,, use acetone and ether to prepare polymeric film as solvent and non-solvent respectively by phase inversion process.The nano layered silicate of PVDF-HFP and particulate form is dissolved in (weight percent that nano layered silicate accounts for PVDF-HFP is 2.5wt%) in the acetone, supersound process 1h after mechanical stirring is spent the night, make it at room temperature form uniform film-casting liquid (casting solution), the concentration of PVDF-HFP is 4wt% in the film-casting liquid.Subsequently, (t-butyl methyl ether: acetone=1: 10 wt%) join in the film-casting liquid, and the continuation stirring gets evenly up to solution becomes with t-butyl methyl ether.The homogeneous phase solution of gained is cast on the clean aluminium scale pan, treat acetone and ether the evaporation after, obtain white, opaque film.At last, with film dry 24h in 80 ℃ vacuum drying oven, further remove the acetone and the ether of trace.
When adding in the film-casting liquid as the ether of non-solvent, have precipitation and separate out, after stirred for several hour, precipitation is dissolving again.When the amount of non-solvent hour, polymkeric substance can dissolve fully, film-casting liquid is a homogeneous phase solution; But when the amount of non-solvent increased, polymkeric substance can be precipitated out, and being difficult to again, dissolving becomes one.The formation mechanism of film is the same with typical dry method (typical dry phase inversion) film-making machine reason in this process.Can bring out being separated during the volatilization of solvent and non-solvent, when solvent and non-solvent volatilize fully, promptly make polymeric film with vesicular structure.
Can test and confirm the structure of the polymeric film of final molding, configuration of surface and to thermostability by using x-ray photoelectron spectroscopy (XRD), scanning electronic microscope (SEM) and simultaneous thermal analysis instrument (DSC-TGA).The polymeric film that the preparation method who discloses by the present invention obtains 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 good connectedness is arranged between the Kong Yukong.In addition, the polymeric film that has added the silicates material of laminate structure has excellent thermostability, dimensional stability, workability and physical strength.
In the specific embodiment of the present invention, also disclosed a kind of ionogen, ionogen comprises lithium salts, organic solvent and polymeric film.Polymeric film comprises polyvinylidene difluoride (PVDF) (PVDF) and the multipolymer of R 1216 (HFP) and the silicate with laminate structure at least.
Lithium salts includes but are not limited to one or more in the following material: LiSCN, LiBr, LiI, LiClO
4, LiAsF
6, LiSO
3CF
3, LiSO
3CH
3, LiBF
4, LiB (Ph)
4, LiC (SO
2CF
3)
3, LiPF
6And LiN (SO
2CF
3)
2The concentration range of adoptable lithium salts is 0.2-2.0M in the organic solvent.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 includes but are not limited to one or more in the following material: dme (DME), methylcarbonate (DMC), ethylene carbonate (EC), carbonic acid diethyl ester (DEC), methyl ethyl carbonate alkene ester (EMC), propene carbonate (PC), carbonic acid first propyl ester (MPC), 1,3-dioxolane (DIOX), ether, glyme, lactone, sulfone, tetramethylene sulfone.
In preferred embodiment, with 1.0M LiPF
6Be dissolved in organic solvent NSC 11801 (EC), diethyl carbonate (DEC) (EC: DEC=1: 1v/v) as liquid electrolyte.Polymeric film is immersed in obtains semi-solid gel electrolyte in the liquid electrolyte.At last, polymer film surface is carried out drying treatment, thereby make semi-solid polymer dielectric by filter paper.
Polymeric film with vesicular structure is a kind of based on the colloidal organic micro film, mainly as support frame, liquid electrolyte is stored in the micropore, electrolytical ionic conducting property is the sub-chain motion by polymer molecule or be stored in ionic in the micropore and move and realize that whole ionogen is semi-solid structure mainly.The hole of polymeric film is abundant, and it is strong to absorb the liquid electrolyte ability, and the surface of film and the back side are microvoid structure all, make polymer dielectric at room temperature have very high ionic conductivity thereby make ion transport can run through whole polymeric film.Simultaneously as can be known by the cyclic voltammetric test, the polymer dielectric that the present invention discloses has the electrochemical stability window up to 5V, with the polymer dielectric among the present invention with have high-tension electrode materials and combine not only and can form battery with high-energy-density, but also solved a big technical barrier of field of batteries, promptly exist high-tension electrode materials but to can not find the ionogen that collocation with it has the high stable voltage window, therefore, the polymer dielectric that discloses of the present invention has at structure on the battery applications of high-energy-density and has considerable prospect.
In the specific embodiment of the present invention, also disclosed a kind of battery, comprise positive pole, negative pole and be located at positive pole and negative pole between ionogen, ionogen comprises polymeric film.
Positive pole comprises positive electrode active materials, positive electrode active materials can be reversible-deviate from embedded ion.Preferably, positive electrode active materials comprises the sulfenyl material, and the sulfenyl material accounts for the 70-90% of positive electrode active materials gross weight.In preferred embodiment, the weight proportion of the sulfenyl material in the positive electrode active materials is 80%.
The sulfenyl material is selected from elementary sulfur, Li
2S
n, organic sulfide and carbon sulphur polymkeric substance (C
2S
v)
mIn at least a, wherein, n 〉=1,2.5≤v≤50, m 〉=2.
In preferred embodiment, the sulfenyl material contains AB
xC
yD
z, wherein, A is selected from polypyrrole, polyacrylonitrile (PAN), at least a in the polyacrylonitrile multipolymer; 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.
The polyacrylonitrile multipolymer is selected from the PAN-methylmethacrylate copolymer, at least a among the PAN-PPy.PPy is a kind of high conductive polymkeric substance, is widely used in electrode face finish and the electrode materials; Cyclisation that pyrolytic reaction comprised cyano group, dehydrogenation, conjugation, process such as crosslinked take place down at 200-300 ℃ in PAN, generation has the conjugation coalescence pyrroles of conductivity, the low temperature pyrogenation performance of PAN provides good carrier for preparation sulfenyl material, and the PAN-methylmethacrylate copolymer is because of possessing the structural unit of PAN in its structure, and therefore the double properties that PAN-PPy combines PAN and PPy especially all can be used as the carrier of sulfenyl material.Simultaneously, the mass content of A in the 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 a in the Graphene.The carbon-based material general characteristic is that specific surface is very big, has stronger adsorption function, and good electroconductibility is also arranged simultaneously, is suitable as conduction and adds material.As preferred embodiment, C is selected from KB, and the particle size of KB is about 30nm, and specific surface area has but reached 1400m
2/ g, has superpower adsorptive power simultaneously, it not only can improve the electroconductibility of material, and in the process of preparation matrix material, because of its bigger specific surface area and strong adsorptive power, can effectively suppress the agglomerating phenomenon of gathering of material, make the particle size of sulfenyl material littler and be more evenly distributed, reduce the evolving path of lithium ion, improved the ionic conductivity of material.In addition, the price of KB is also relatively cheap, and the cost of sulfenyl material that contains 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 a, 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 further improve the electroconductibility of sulfenyl material, and the cycle performance of battery is improved.
In embodiment more preferably, the sulfenyl material is S/PAN/Mg
0.6Ni
0.4The O trielement composite material.
Though elemental sulfur has considerable theoretical specific capacity, elemental sulfur is electronics and ionic isolator under the room temperature, and the anodal lithium-sulfur cell of forming of the elemental sulfur of sulphur content 100% at room temperature is impossible discharge and recharge.Therefore, positive electrode active materials also comprises conductive agent and binding agent.
Conductive agent effectively improves the rate of migration of lithium ion in positive electrode active materials simultaneously in order to the transmission of accelerated electron.Concrete, conductive agent is selected from one or more in conductive polymers, activated carbon, Graphene, carbon black, carbon fiber, steel fiber, metal-powder and the sheet metal.The weight specific gravity range of conductive agent in positive electrode active materials is 5-15%.In 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, a kind of in the polyoxyethylene glycol dimethacrylate, or above-mentioned mixture of polymers and derivative.The weight specific gravity range of binding agent in positive electrode active materials is 5-15%.In more excellent embodiment, binding agent comprises polytetrafluoroethylene (PTFE).
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, a kind of in nickel foam or the stainless (steel) wire.In preferred embodiment, plus plate current-collecting body is a 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 the 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 a in the metal-doped silicon.Silicon alloy comprises the silico-carbo alloy, silicon-lithium alloy and silicon-manganese alloy.In order to improve the specific conductivity of material silicon, generally coat on the surface 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, and aluminium foil, a kind of in nickel foam or the stainless (steel) wire, when negative active core-shell material was metallic lithium, metallic lithium itself also can be used as negative current collector.
In order to guarantee that in charge and discharge process the lithium ion that existence is deviate from-embedded between the positive pole of battery and the negative pole when sulfenyl material of selection and silica-base material do not contain lithium, is handled positive pole and/or the pre-embedding lithium of negative pole simultaneously.Concrete pre-embedding lithium mode is not limit, and comprises chemical reaction embedding lithium or electrochemical reaction embedding lithium.
In concrete embodiment, anode adopts S/PAN/Mg
0.6Ni
0.4The trielement composite material of O, ionogen are PVDF-HFP/OMMT, and negative pole is a metallic lithium because sulphur has very high theoretical specific capacity, on the basis of sulphur further by PAN and Mg
0.6Ni
0.4O optimizes the conductivity of positive electrode active materials, polymer dielectric not only can effectively suppress the loss of many lithium sulfides intermediate product in the charge and discharge process, and have higher ionic conductivity, make the battery that is assembled into not only still all improve a lot on the cycle performance on the cell container.
As well known to those skilled in the art; for fear of metallic lithium during as negative pole; negative terminal surface produces dendrite because of depositing inequality; usually can on negative terminal surface, form layer protecting film; protective membrane can be the LiPON compound interfacial film that forms on the metallic lithium surface, also can be the interfacial film that lithium alloy forms.Therefore, the scope of the invention is included in the negative pole that the negative active core-shell material surface forms protective membrane equally.
The battery of the employing polymer dielectric that the present invention discloses, because of polymer dielectric have excellent mechanical property, to the sub-performance of diversion fast under thermostability, the room temperature and up to the voltage stability window of 5V, make the battery among the present invention improve a lot at tool aspect capacity and the cycle performance, simultaneously, polymer dielectric is a semi-solid, make battery on constituting, can use barrier film, reduced the real cost of battery.
Unit in the percent weight in volume among the present invention is well-known to those skilled in the art, for example is meant the weight of solute in 100 milliliters solution.Unless otherwise defined, the same meaning that employed all specialties and scientific words and one skilled in the art are familiar with in the literary composition.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The usefulness that preferable implementation method described in the literary composition and material only present a demonstration.
Below in conjunction with embodiment, be described more specifically content of the present invention.Should be appreciated that enforcement of the present invention is not limited to the following examples, all will fall into protection domain of the present invention any pro forma accommodation and/or the change that the present invention made.In the present invention, if not refer in particular to, all part, per-cents are weight unit, and all equipment and raw material etc. all can be buied from market or the industry is commonly used.
Embodiment 1
(PVDF-HFP, Kynar Flex 2801 12wt%HFP) buy the back and directly use polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer.The montmorillonite of montmorillonite sodium (Na-MMT) and organic decoration (OMMT, 30B) from Southern Clay products (SCP USA) buys, before using in the baking oven of 473K a dry week.Acetone can directly use as solvent and not need to be further purified.T-butyl methyl ether is buied from Acros organics as non-solvent.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 the acetone, and supersound process was 1 hour after mechanical stirring was spent the night, and formed uniform film-casting liquid (casting solution) under the room temperature, and the concentration of PVDF-HFP is 4wt%.(t-butyl methyl ether: acetone=1: 10 wt%) join in the film-casting liquid, and the continuation stirring gets evenly up to solution becomes with t-butyl methyl ether.The homogeneous phase solution of gained is cast on the clean aluminium scale pan, treat acetone and ether the evaporation after, obtain white, opaque porous-film.At last,, further remove the acetone and the ether of trace, promptly make PVDF-HFP/Na-MMT film with vesicular structure with film dry 24h in 80 ℃ vacuum drying oven.
Embodiment 2
The smectites material is the montmorillonite (OMMT of organic decoration among the embodiment 2,30B), that is to say the montmorillonite that two-hydroxyethyl tallow ylmethyl ammonium chloride is modified, all the other materials are the same with embodiment 1 with the preparation method, make the PVDF-HFP/OMMT film with vesicular structure.
Comparative Examples 1
The PVDF-HFP that buys is dissolved in the acetone, and supersound process was one hour after mechanical stirring was spent the night, and formed uniform film-casting liquid (casting solution) under the room temperature, and the concentration of PVDF-HFP is 4wt%.(t-butyl methyl ether: acetone=1: 10 wt%) join in the film-casting liquid, and the continuation stirring gets evenly up to solution becomes with t-butyl methyl ether.The homogeneous phase solution of gained is cast on the clean aluminium scale pan, treat acetone and ether the evaporation after, obtain white, opaque porous-film.Subsequently,, further remove the acetone and the ether of trace, promptly make PVDF-HFP film with vesicular structure with film dry 24h in 80 ℃ vacuum drying oven.
Comparative Examples 2
With polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer of directly buying as a comparison case (PVDF-HFP, Kynar Flex 2801,12wt%HFP).
Fig. 1 passes through X-ray diffractometer (XRD, D8 Discover, the X-ray diffracting spectrum that Bruker) obtains for the polymeric film that provides in na-montmorillonite Na-MMT, organic decoration montmorillonite OMMT 30B, embodiment 1-2, the Comparative Examples 1.From collection of illustrative plates as can be seen: OMMT 30B and Na-MMT occur the obvious diffraction peak respectively diffraction angle 2 θ=5 ° and 8 °.But in the XRD figure spectrum of PVDF-HFP/Na-MMT polymeric film and PVDF-HFP/OMMT polymeric film, but do not observe the characteristic diffraction peak of montmorillonite, the montmorillonite of explanation in these two kinds of polymeric films exists with the limellar stripping state, this is because the molecular chain of PVDF-HFP enters the sheet interlayer of montmorillonite, thereby makes the lamella of polynite be strutted so that peel off.
The polymeric film that is obtained in embodiment 1-2 and the Comparative Examples 1 is studied the structure in configuration of surface, pore size distribution and the hole of polymeric film by high resolving power field emission scanning electron microscope (Zeiss, LEO 1515).
Fig. 2 is followed successively by the form by SEM observed PVDF-HFP polymeric film, PVDF-HFP/Na-MMT polymeric film and PVDF-HFP/OMMT polymeric film under identical multiplying power from left to right.As can be seen from the figure, the polymeric film that contains the layered nano-structure montmorillonite is with respect to the PVDF-HFP polymeric film, and the aperture obviously diminishes, and the connectedness in the quantity in hole, hole and homogeneity have improved greatly.The connection that an amount of hole can be supported between competent liquid electrolyte and the Kong Yukong in the polymeric film can guarantee ion migration fast in film, thereby makes polymeric film at room temperature have the sub-performance of diversion fast.
Embodiment 3
With 1.0M LiPF
6Be dissolved in organic solvent ethyl-carbonate (EC), diethyl carbonate (DEC) (EC: DEC=1: 1v/v).The PVDF-HFP/Na-MMT polymeric film with vesicular structure that makes is immersed in 6h obtains porous semi-solid state ionogen in the solution.Then, blot the solution that remains in the film surface, finally obtain porous PVDF-HFP/Na-MMT semi-solid state ionogen with filter paper.
Embodiment 4
With 1.0M LiPF
6Be dissolved in organic solvent ethyl-carbonate (EC), diethyl carbonate (DEC) (EC: DEC=1: 1v/v).The PVDF-HFP/OMMT polymeric film with vesicular structure that makes is immersed in 6h obtains porous semi-solid state ionogen in the solution.Then, blot the solution that remains in the film surface, finally obtain porous PVDF-HFP/OMMT semi-solid state ionogen with filter paper.
Comparative Examples 3
With 1.0M LiPF
6Be dissolved in organic solvent ethyl-carbonate (EC), diethyl carbonate (DEC) (EC: DEC=1: 1v/v).Flooding the PVDF-HFP polymeric film with vesicular structure that makes wherein, 6h obtains porous semi-solid state ionogen.Then, blot the solution that remains in the film surface, finally obtain porous PVDF-HFP semi-solid state ionogen with filter paper.
By synchronous thermogravimetric analyzer DSC-TGA (DSC: dsc; TGA: thermogravimetric analyzer) (TA instruments Q-600) analyzes polymeric film, the multipolymer in the Comparative Examples 2 and embodiment 3-4 in embodiment 1-2, the Comparative Examples 1, the semi-solid state ionogen in the Comparative Examples 3 to thermal stability.Experiment condition: 10 ℃/min of temperature rise rate, sweep limit: room temperature-500 ℃.
Fig. 3 is the thermogravimetric analysis result curve.The melt temperature of pure PVDF-HFP is 159 ℃, but as can be seen from the figure: the polymeric film that provides in embodiment 1-2, the Comparative Examples 1 and the thermostability of the multipolymer in the Comparative Examples 2 are up to 400 ℃.Simultaneously, the initial degradation temperature of polymeric film that has added the silicate of nanometer laminated structure descends to some extent, and 5% weight loss is arranged approximately, and this phenomenon can be decomposed owing to the organic group between the silicate layer of nanometer laminated structure.The semi-solid state ionogen loses since 90 ℃ of weight, shows that the polymeric film that has absorbed liquid electrolyte all is stable at 0-90 ℃.In addition, between temperature range 100-200 ℃, tangible weight loss has appearred in the polymeric film that has absorbed liquid electrolyte, and the decomposition of the liquid electrolyte in the polymeric film pore texture is described.Another phenomenon: all semi-solid state ionogen are between 100-200 ℃, and weight loss all is about 50%, show that apertured polymeric film can absorb the liquid electrolyte of high level.
Study the electrolytical ionic conductivity of semi-solid state in embodiment 3-4 and the Comparative Examples 3 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, S is the area of film, R
bBe the solution body impedance that records by alternating-current impedance experiment to stainless steel/semi-solid state ionogen/stainless steel battery.The alternating-current impedance experiment is all carried out on the CHI660 electrochemical workstation.AC amplitude is 10mV, and range of frequency is 0.1Hz to 100kHz.
The semi-solid state electrolytical ac impedance spectroscopy of Fig. 4 for providing by EIS test implementation example 3-4 and Comparative Examples 3 under the room temperature.Learn by test result: PVDF-HFP, PVDF-HFP/Na-MMT and the electrolytical impedance of PVDF-HFP/OMMT semi-solid state are 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 that discloses by the present invention prepares 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 is abundant, it is strong to absorb the liquid electrolyte ability, and the surface of film and the back side are microvoid structure all, make to have high ionic conductivity under the polymer dielectric room temperature thereby make ion transport can run through whole polymeric film.
By assembling stainless steel/semi-solid state ionogen/lithium metal battery, adopt cyclic voltammetry to study PVDF-HFP/OMMT semi-solid state electrolyte electrochemical stability window among the embodiment 4, stainless steel is a working electrode, lithium is supporting electrode and reference electrode.The linear time base sweep experiment is all carried out on the CHI660 electrochemical workstation.
The cyclic voltammetric result in 10 weeks of PVDF-HFP/OMMT semi-solid state electrolyte circulation that Fig. 5 provides for embodiment 4.As can be seen from the figure: porous polymer electrolyte first all anodic stabilization voltage windows show that up to 4.8V electrochemical decomposition is impossible generation being lower than 4.8V.In second week, electrochemical stability strengthens, and the dielectric film stabilized voltage arrives 5V.The electrochemical stability voltage of bibliographical information PVDF-HFP film is about 4.38V.This result shows that clearly the electrochemical stability of the apertured polymeric film that 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 assorted peak residual and other do not occur when voltage is low shows that all the nanometer polymer film purity that this preparation method makes is very high.
Embodiment 5
With tertiary cathode active material S/PAN/Mg
0.6Ni
0.4O, binding agent PVDF, electrically conductive material KB mix according to 8: 1: 1 mass ratio, add N-Methyl pyrrolidone as solvent, the slurry that obtains is coated on the plus plate current-collecting body nickel foam by the scraper coating technique, 50 ℃ of following vacuum-drying 24h, make positive plate at the tabletting machine lower sheeting, with the metallic lithium is negative pole, and porous PVDF-HFP/Na-MMT semi-solid state ionogen is arranged between positive pole and the cathode of lithium, splashes into 2 and contains 1M LiPF
6EC/DEC solution after, in being full of the glove box of argon gas, be assembled into the CR2032 button cell.
Embodiment 6
With tertiary cathode active material S/PAN/Mg
0.6Ni
0.4O, binding agent PVDF, electrically conductive material KB mix according to 8: 1: 1 mass ratio, add N-Methyl pyrrolidone as solvent, the slurry that obtains is coated on the plus plate current-collecting body nickel foam by the scraper coating technique, 50 ℃ of following vacuum-drying 24h, make positive plate at the tabletting machine lower sheeting, with the metallic lithium is negative pole, and porous PVDF-HFP/OMMT semi-solid state ionogen is arranged between positive pole and the cathode of lithium, splashes into 2 and contains 1M LiPF
6EC/DEC solution after, in being full of the glove box of argon gas, be assembled into the CR2032 button cell.
The at room temperature initial voltage pattern that discharges and recharges for 5 times of the battery that Fig. 6 provides for embodiment 6, voltage range is 1.5-3V, charge-discharge velocity is 0.2C.
Comparative Examples 4
With tertiary cathode active material S/PAN/Mg
0.6Ni
0.4O, binding agent PVDF, electrically conductive material KB mix according to 8: 1: 1 mass ratio, add N-Methyl pyrrolidone as solvent, the slurry that obtains is coated on the plus plate current-collecting body nickel foam by the scraper coating technique, 50 ℃ of following vacuum-drying 24h, make positive plate at the tabletting machine lower sheeting, with the metallic lithium is negative pole, and porous PVDF-HFP semi-solid state ionogen is arranged between positive pole and the cathode of lithium, splashes into 2 and contains 1M LiPF
6EC/DEC solution after, in being full of the glove box of argon gas, be assembled into the CR2032 button cell.
In order to detect the performance of battery, the battery in embodiment 5-6 and the Comparative Examples 4 is carried out charge-discharge test.When discharging and recharging, voltage range is 1.0-3.0V, and discharge rate is 0.2C.
Fig. 7 and Fig. 8 be respectively provide in embodiment 5-6 and the Comparative Examples 4 250 week of battery circulation back enclosed pasture efficient and loading capacity to the synoptic diagram of cycle index.The good capability retention and the reversibility that adopt the battery of apertured polymeric film all to embody, the enclosed pasture efficient after 250 weeks of circulation be near 100%, and the loading capacity that contains the polymer dielectric of nano layered silicate has obviously increased.The initial loading capacity of the battery that embodiment 5 and 6 provides is identical, yet the battery among the embodiment 5 promptly adopts the loading capacity of the battery of PVDF-HFP/Na-MMT nanometer polymer film to have decay, after 60 weeks of circulation, the capacity of the battery in the loading capacity of battery and the Comparative Examples 4 is identical.And the battery that adopts PVDF-HFP/OMMT nanometer polymer film among the embodiment 8 has shown very high loading capacity and it is very slow to decay after having experienced long circulation, and the cell container after 250 weeks of circulation still approaches the loading capacity first of battery in the Comparative Examples 4.Concrete, lithium-sulfur cell shows initial specific storage up to 950mAh/gr (with respect to the content of sulphur), and capacity still remains on 650mAh/gr after 250 weeks of circulation, and the enclosed pasture efficient in 250 weeks is 100%.
Although the 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, the foregoing description is modified and/or flexible or to adopt the replacement scheme that is equal to be obvious, the essence that all can not break away from spirit of the present invention, the term that occurs among the present invention is used for can not being construed as limiting the invention the elaboration of technical solution of the present invention and understanding.
Claims (19)
1. polymeric film comprises the multipolymer of polyvinylidene difluoride (PVDF) and R 1216, and it is characterized in that: described polymeric film also comprises the silicate with laminate structure.
2. polymeric film according to claim 1 is characterized in that: described silicate comprises at least a in na-montmorillonite, the organic decoration montmorillonite.
3. polymeric film according to claim 2 is characterized in that: described organic decoration montmorillonite comprises the montmorillonite that organic quaternary ammonium salt is modified.
4. polymeric film according to claim 3 is characterized in that: described organic quaternary ammonium salt comprises at least a in two-hydroxyethyl tallow ylmethyl ammonium chloride, dimethyl diallyl ammonium chloride, octadecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethylammonium bromide, the octadecyl trimethylammonium bromide.
5. 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.
6. polymeric film according to claim 5 is characterized in that: the porosity ranges of described polymeric film is 25-75%.
7. the preparation method of a polymeric film, it is characterized in that: described preparation method comprises the steps:
1) multipolymer and the nano layered silicate with polyvinylidene difluoride (PVDF) and R 1216 is dissolved in the solvent, carries out supersound process after the mechanical stirring, forms the homogeneous film-casting liquid under the room temperature;
2) add non-solvent in film-casting liquid, mechanical stirring is cast to homogeneous phase solution on the vessel until obtaining homogeneous phase solution, treat the evaporation of solvent and non-solvent after, obtain polymeric film;
3) polymeric film is placed vacuum drying oven carry out drying treatment, to remove residual solvent and non-solvent.
8. the preparation method of polymeric film according to claim 7, it is characterized in that: described solvent is an acetone.
9. the preparation method of polymeric film according to claim 7, it is characterized in that: described non-solvent is a t-butyl methyl ether.
10. the preparation method of polymeric film according to claim 7, it is characterized in that: the multipolymer and the nano layered silicate of polyvinylidene difluoride (PVDF) and R 1216 are dissolved in the solvent, and churned mechanically time range is 8-24h.
11. the preparation method of polymeric film according to claim 7 is characterized in that: described vacuum-drying temperature range is 50-80 ℃, and time of drying, scope was 12-24h.
12. an ionogen is characterized in that: described ionogen comprises lithium salts, organic solvent and as any one described polymeric film among the claim 1-6.
13. a battery, comprise positive pole, negative pole and be located at positive pole and negative pole between ionogen, it is characterized in that: described ionogen comprises as any one described polymeric film among the claim 1-6.
14. battery according to claim 13 is characterized in that: described positive pole comprises positive electrode active materials at least, described positive electrode active materials can be reversible-deviate from embedded ion.
15. battery according to claim 13 is characterized in that: described positive pole comprises positive electrode active materials at least, and described positive electrode active materials comprises the sulfenyl material, and described sulfenyl material is selected from elementary sulfur, Li
2S
n, organic sulfide and carbon sulphur polymkeric substance (C
2S
v)
mIn at least a, wherein, n 〉=1,2.5≤v≤50, m 〉=2.
16. battery according to claim 13 is characterized in that: described positive pole comprises positive electrode active materials at least, and described positive electrode active materials comprises AB at least
xC
yD
z, wherein A is selected from least a in polypyrrole, polyacrylonitrile, the polyacrylonitrile multipolymer; 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.
17. battery according to claim 16 is characterized in that: described polyacrylonitrile multipolymer is selected from polyacrylonitrile-methylmethacrylate copolymer, at least a in polyacrylonitrile-polypyrrole multipolymer.
18. battery according to claim 16 is characterized in that: described carbon-based material is selected from least a in section's qin carbon black, acetylene black, activated carbon, Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, the Graphene.
19. battery according to claim 16 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 a; 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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| CN106532104A (en) * | 2015-09-09 | 2017-03-22 | 中国科学院大连化学物理研究所 | Gel electrolyte porous electrode for lithium-sulfur battery and preparation and application of gel electrolyte porous electrode |
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