TWI589610B - 聚電解質與儲能元件 - Google Patents
聚電解質與儲能元件 Download PDFInfo
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- TWI589610B TWI589610B TW103145220A TW103145220A TWI589610B TW I589610 B TWI589610 B TW I589610B TW 103145220 A TW103145220 A TW 103145220A TW 103145220 A TW103145220 A TW 103145220A TW I589610 B TWI589610 B TW I589610B
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- polyelectrolyte
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- 229920000867 polyelectrolyte Polymers 0.000 title claims description 72
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- 239000003792 electrolyte Substances 0.000 claims description 26
- 238000004146 energy storage Methods 0.000 claims description 21
- 239000004014 plasticizer Substances 0.000 claims description 17
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 8
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000011244 liquid electrolyte Substances 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 5
- 239000003990 capacitor Substances 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000446 fuel Substances 0.000 claims description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- JWJGFXCGGDFFHW-UHFFFAOYSA-N dibutyl benzene-1,2-dicarboxylate;phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O.CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC JWJGFXCGGDFFHW-UHFFFAOYSA-N 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 229920000642 polymer Polymers 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 16
- 150000002500 ions Chemical class 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 8
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 7
- 238000012983 electrochemical energy storage Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- -1 poly(p-hydroxystyrene) copolymer Polymers 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229920000106 Liquid crystal polymer Polymers 0.000 description 4
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- GRFNSWBVXHLTCI-UHFFFAOYSA-N 1-ethenyl-4-[(2-methylpropan-2-yl)oxy]benzene Chemical compound CC(C)(C)OC1=CC=C(C=C)C=C1 GRFNSWBVXHLTCI-UHFFFAOYSA-N 0.000 description 3
- AMKGKYQBASDDJB-UHFFFAOYSA-N 9$l^{2}-borabicyclo[3.3.1]nonane Chemical compound C1CCC2CCCC1[B]2 AMKGKYQBASDDJB-UHFFFAOYSA-N 0.000 description 3
- FEJUGLKDZJDVFY-UHFFFAOYSA-N 9-borabicyclo[3.3.1]nonane Substances C1CCC2CCCC1B2 FEJUGLKDZJDVFY-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- FPEQNDQUWPJCKZ-UHFFFAOYSA-N 9-borabicyclo[3.3.1]nonane Chemical compound C1CCC2CCCC1B2.C1CCC2CCCC1B2 FPEQNDQUWPJCKZ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- WNTGVOIBBXFMLR-UHFFFAOYSA-N bicyclo[3.3.1]nonane Chemical compound C1CCC2CCCC1C2 WNTGVOIBBXFMLR-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNCXPJFPCAYUGJ-UHFFFAOYSA-N dilithium bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].[Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F HNCXPJFPCAYUGJ-UHFFFAOYSA-N 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000002090 nanochannel Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F12/22—Oxygen
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/04—Oxidation
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- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/22—Oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/08—Isoprene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
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- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
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- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
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- H—ELECTRICITY
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- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
- H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/60—Liquid electrolytes characterised by the solvent
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/64—Liquid electrolytes characterised by additives
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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Description
本發明是有關於一種儲能技術,且特別是有關於一種適用於儲能元件的聚電解質。
隨著人們對於高功率和高能量密度的鋰二次電池需求不斷地提高,越來越多研究單位致力於提升其安全性及穩定性。又由於人們對於攜帶型電子產品依賴度提升,並且期望增加電化學儲能裝置於車輛、不斷電系統等的應用,鋰二次電池的安全性又必須進一步被嚴格要求,特別是用於高空飛行的飛機或是太空梭等。目前對於安全性的相關研究通常專注於發展阻燃添加劑、固態電解質或是新電解液系統等,這些都是為了要改善液態電解液的種種問題並增加電化學儲能元件的熱穩定性,並且期望能有效降低或是完全不使用高揮發性、易燃的有機溶劑。
固態電解質中的聚電解質為陰離子或陽離子以共價鍵結於高分子的重複單元上,又稱單離子導體(Single Ion Conductor,SIC)。由於陰離子或陽離子固定於高分子鏈上,此離子並不會造
成濃度梯度變化,減低鹽類沉積於電極或隔離膜的可能性,延長元件循環特性。
上述聚電解質雖然可以抑制鋰金屬的沉積穿刺,增加鋰電池安全性,並且在尺寸及形狀上可彈性製備,適用於各種鋰電池,但其較差的離子導電度(固態高分子電解質為~10-5S/cm,單離子導體為~10-6S/cm)一直阻礙其應用與商業化。
本發明的聚電解質包括第一鏈段以及第二鏈段,其中第一鏈段結構為式(1)與式(2)中至少之一;第二鏈段結構為式(3)與式(4)中至少之一。
本發明的另一聚電解質包括第一鏈段、第二鏈段以及第三鏈段,且所述第三鏈段在所述第一鏈段與所述第二鏈段之間。
其中,第一鏈段結構為上式(1)與式(2)中至少之一,第二鏈段結構為上式(3)與上式(4)中至少之一,而第三鏈段結構為式(5)。
本發明的儲能元件則包括上述聚電解質,其中聚電解質是藉由混合、塗佈、包覆或添加,應用於所述儲能元件內。
基於上述,藉由本發明的聚電解質,能減少儲能元件中易揮發、易燃的電解液的使用,甚至完全不用。而且,在室溫下不含任何電解液的情形下,本發明的聚電解質仍然具有~10-5S/cm的離子導電度,且在具有少量電解液的情形下可以有~10-4S/cm的離子導電度。這種聚電解質可應用於電化學儲能元件,有效排除或降低電解液的使用,大幅提升電化學儲能元件的特性。
為讓本發明的上述特徵和優點能更明顯易懂,下文特舉實施例,並配合所附圖式作詳細說明如下。
100‧‧‧儲能元件
圖1是依照本發明的一實施例的一種儲能元件的示意圖。
圖2是實驗例一的核磁共振氫譜圖。
圖3是實驗例一中含塑化劑的聚電解質的TEM切片照片。
圖4是實驗例二的凝膠滲透層析圖。
圖5是實驗例二的核磁共振氫譜圖。
圖6是實驗例二中不含塑化劑和電解液的聚電解質之TEM切片照片。
圖7是實驗例三的未接液晶反應物之聚電解質的凝膠滲透層析圖。
圖8是實驗例三的未接液晶反應物之聚電解質的核磁共振氫譜圖。
圖9是實驗例三的含液晶反應物之聚電解質的核磁共振氫譜圖。
圖10是實驗例三的含液晶反應物之聚電解質的核磁共振氫譜圖。
圖11是實驗例三之末端官能基分別為PIOSCLCN、PIOSCLC6和PIOSCLC的聚電解質的TEM切片照片。
圖12是實驗例四的凝膠滲透層析圖。
圖13是實驗例四的核磁共振氫譜圖。
圖14是實驗例四中不含塑化劑和電解液的聚電解質的TEM切片照片。
本揭露的聚電解質包括第一鏈段以及第二鏈段,其中第一鏈段結構為式(1)與式(2)中至少之一;第二鏈段結構為式(3)與式
(4)中至少之一。所述第一鏈段的分子量(MW)例如在10000~90000之間;所述第二鏈段的分子量例如在10000~30000之間。
在本實施例中,第一鏈段負責提供聚電解質的機械強度和阻水氧特性,可選擇式(1)的結構或式(2)的結構,也可同時有式
(1)與式(2)的結構;第二鏈段則負責提供聚電解質的離子傳導,可選擇式(3)的結構或式(4)的結構,也可同時有式(3)與式(4)的結構。如此一來,聚電解質會微相分離(microphase separation)而形成具有奈米等級有序的自組裝微結構。
本揭露的另一種聚電解質是在上述第一鏈段與上述第二鏈段之間還有一第三鏈段,且第三鏈段之結構為式(5)。在本實施例中,第三鏈段的分子量例如在10000~20000之間。
在本實施例中,第三鏈段在第一與第二鏈段間,主要能讓第二鏈段遠離第一鏈段,讓第二鏈段不受第一鏈段的牽制,可以有更大的自由擺動空間,進而提升聚電解質的離子傳導度。
由於本揭露的上述聚電解質均可進行微相分離而形成奈米等級有序的自組裝微結構。而且在聚電解質內的第一鏈段所形成的主架構提供了高分子的機械強度與阻止水、氣穿透的功能;離子傳導通道則負責傳遞離子。至於聚電解質內的第二鏈段是由具有磺酸根、磷酸根或羧酸根等基團的部分(Moiety)以共價鍵結,
固定於主鏈上而不會移動,因此可大幅提升離子遷移係數。另外,由於離子僅能於奈米通道中移動,所形成的金屬沉積也會被限制於其中,而減少金屬晶枝穿刺的可能。
而且,在本揭露的上述聚電解質中,如果添加不同比例的塑化劑、高介電係數溶劑或液態電解液,也被發現有助於離子傳導度的提升。舉例來說,塑化劑可為鄰苯二甲酸二(2-乙基己基)酯(bis(2-ethylhexyl)phthalate,BEHP)、鄰苯二甲酸二丁酯(Dibutyl phthalate,DBP)、鄰苯二甲酸二異丁酯(Diisobutyl phthalate,DIBP)等,高介電係數溶劑可為碳酸丙烯酯(Propylene carbonate,PC)、碳酸乙烯酯(Ethylene carbonate,EC)、碳酸二乙酯(Diethyl carbonate,DEC)、碳酸二甲酯(Dimethyl carbonate,DEC)、碳酸甲基乙基酯(Ethyl methyl carbonate,EMC)等,液態電解液可為電解質(即鋰鹽)LiPF6、LiBF4、LiClO4、LiTFSI(雙三氟甲磺醯亞胺鋰鹽)等溶於前述高介電係數溶劑中所形成的液態電解液。
因此,本揭露的聚電解質在室溫、不含任何溶劑或電解液的情形下,離子導電度都大於10-5S/cm。而在少量的電解液吸附(<30wt%)時,則有10-4S/cm的離子傳導度。
圖1是依照本發明的一實施例的一種儲能元件的示意圖。
在圖1中的儲能元件100只是示意圖,其可為鋰離子一次電池、鋰離子二次電池、電容器、超級電容器、燃料電池、金屬硫電池、或金屬空氣電池等。而本揭露的聚電解質可藉由混合、塗佈、包覆或添加等方式應用於儲能元件100內。
以下列舉一些實驗例來驗證本發明的功效,但本發明並不侷限於以下的內容。
實驗例一
依照下面合成流程,在-78℃下、四氫呋喃(THF)溶劑中加入100μl的仲丁基鋰(sec-butyllithium,sec-BuLi)(1.3M in cyclohexane)和12.88ml的苯乙烯單體,攪拌反應15分鐘,之後在同一溫度下加入4.17ml的對叔丁氧基苯乙烯(p-tert-butoxystyrene)單體,反應三天,以無水甲醇終止反應,並沉澱析出聚苯乙烯和PtBuOS(poly(p-tert-butoxystyrene))共聚高分子。
取此高分子12g溶於1,4-二噁烷(1,4-dioxane),並加入7.1ml 37wt%的鹽酸(HCl)水溶液,升溫至60℃反應兩天,再將高分子沉澱於正己烷中,並以純水反復清洗,可得去保護的聚(對羥基苯乙烯)(poly(p-hydroxystyrene))共聚高分子。
取去保護的共聚高分子10g溶於THF,升溫到60℃後加入3.6g氫化鉀(KH),反應2小時,再加入5.36g的1,3-丙磺酸內酯(1,3-propanesultone),反應24小時,以甲醇清洗後,產物分別加入過量的TBAOH(tetrabutylammonium hydroxide)、1.5M硫酸水溶液,最後再以1M LiOH水溶液清洗得最終聚電解質。
然後利用凝膠滲透層析(Gel permeation chromatography,GPC)比對PS標準品,發現兩鏈段分子量分別為Mw90000和30000(估算a、b分別約為865及717),氫譜核磁共振儀(1H-Nuclear Magnetic Resonance spectroscopy)也證實了兩鏈段的比例,請見圖2。然後添加不同量的塑化劑:鄰苯二甲酸二丁酯(Dibutyl phthalate,DBP)幫助成膜。對乾膜進行量測,但因乾膜並無法測量到離子導電度,所以進一步將其浸潤到電解液(1M LiClO4 in EC/PC)的濕膜進行鋰離子導電度量測,結果顯示於下表一。
由表一可以知道,濕膜離子導電度1.2×10-5~4.1×10-5
S/cm,含浸量為10.8wt%~30.8wt%。圖3顯示含塑化劑的聚電解質的TEM切片照片,可觀察實驗例一的聚電解質會微相分離成球狀結構。
實驗例二
依照下面合成流程,在-78℃下、THF溶劑中加入70μl的仲丁基鋰(sec-BuLi)(1.3M in cyclohexane)和5ml的苯乙烯單體,攪拌反應15分鐘,之後在同一溫度下加入2.67ml的異戊二烯單體,再升溫至-30℃反應三天,以無水甲醇終止反應,並沉澱析出聚苯乙烯和聚(1,2或3,4-異戊二烯)共聚高分子。
取此高分子1.5g溶於THF中,於-15℃下加入40ml的9-硼雙環[3.3.1]壬烷(9-borabicyclo(3.3.1)nonane)(簡稱9-BBN[0.5M in THF]),升溫至55℃反應兩天,再冷卻至-25℃,加入1ml甲醇攪拌反應30分鐘後,加入0.46g 6N的NaOH和4ml 30% H2O2水溶液反應2小時,再升溫到55℃反應1小時,待兩相分層後,將上層溶液沉澱於0.25M的NaOH水溶液中,過濾可得異戊二烯雙鍵水解成氫氧基共聚高分子。
取水解完的共聚高分子0.5g溶於THF,升溫到60℃後加入0.6g KH,反應2小時,再加入0.37ml的1,3-丙磺酸內酯(1,3-propanesultone),反應8小時,以甲醇清洗後,產物分別加入過量的TBAOH(tetrabutylammonium hydroxide)、1.5M硫酸水溶液,最後再以1M LiOH水溶液清洗得最終聚電解質(R代表CH3或H)。
利用GPC比對PS標準品,發現兩鏈段分子量分別為Mw50000、20000(請見圖4與下表二)(估算c、d分別約為480及294)。氫譜核磁共振儀也證實了兩鏈段的比例,如圖5所示。
然後添加不同量塑化劑DBP幫助成膜,再對乾膜進行鋰離子導電度量測,結果顯示於下表三。
由表三可知,實驗例二的聚電解質在室溫且無添加任何
塑化劑或電解液的情形下,就可達到導電度2.8×10-5S/cm;而添加5~20wt%的DPB乾膜離子導電度提升至4.0×10-5S/cm以上。
另外,對不添加塑化劑的聚電解質進行測試,得到僅含浸電解液(1M LiClO4 in EC/PC),導電度提升至23×10-5S/cm,含浸量為22wt%。圖6顯示不含塑化劑和電解液的聚電解質之TEM切片照片,並可觀察實驗例二的聚電解質會微相分離成柱狀結構。
實驗例三
依照下面合成流程,在-78℃下、THF溶劑中加入100μl的仲丁基鋰(sec-BuLi)(1.3M in cyclohexane)和1.39ml的對叔丁氧基苯乙烯(p-tert-butoxystyrene)單體,攪拌反應三天,之後在同一溫度下加入3.82ml的異戊二烯單體,再升溫至-30℃反應三天,以無水甲醇終止反應,並沉澱析出聚(對羥基苯乙烯)和聚(1,2或3,4-異戊二烯)共聚高分子。
取此高分子2g溶於THF中,於-15℃下加入50ml的9-BBN[0.5M in THF],升溫至55℃反應兩天,再冷卻至-25℃,加入1ml甲醇攪拌反應30分鐘後,加入0.5g 6N的NaOH和5ml 30% H2O2水溶液反應2小時,再升溫到55℃反應1小時,待兩相分層後,將上層溶液沉澱於0.25M的NaOH水溶液中,過濾可得異戊二烯雙鍵水解成氫氧基共聚高分子。
取水解完的共聚高分子2mmol溶於THF,加入2.5mmol NaOH,攪拌反應12小時,再加入2.8mmol的含液晶反應物(或)和3mmol(10% excess)四丁基溴化銨
(tetrabutylammonium bromide,TBAB),升溫至60℃反應4天,以大量純水清洗後,再以乙醇清洗,可得液晶高分子。
取液晶高分子12g溶於1,4-二噁烷(1,4-dioxane),並加入9.82ml 85wt%的磷酸水溶液,室溫反應12小時,再將高分子沉澱於正己烷中,並以純水反覆清洗,可得去保護的液晶高分子。
取去保護的液晶高分子10.8g溶於THF,加入3.6g KH,反應1小時,再加入5.35g的1,3-丙磺酸內酯(1,3-propanesultone),升溫至60℃反應24小時,以甲醇清洗後,產物加入過量的TBAOH(tetrabutylammonium hydroxide),最後再以1.5M硫酸水溶液清洗得最終聚電解質(R代表CH3或H)。
利用GPC比對PS標準品,發現兩鏈段分子量分別為Mn10000、20000,如下表四與圖7(估算h、i分別約為57及295)。圖7中顯示的是PtBS與PtBS-b-PI,而氫譜核磁共振儀則證實了兩鏈段的比例,請見圖8。圖9和圖10則是PtBS-b-PIOBP、PtBS-b-PIOLCN與PtBS-b-PIOLC6的氫譜核磁共振儀,其可證實兩鏈段的比例。
此聚電解質酸洗後濕膜進行質子導電度量測,結果顯示於下表五。
由表五可知,實驗例三的聚電解質的質子導電度為1.01×10-2S/cm~2.33×10-2S/cm。圖11是末端官能基分別為PIOSCLCN、PIOSCLC6和PIOSCLC的聚電解質的TEM切片照片,並可觀察到此高分子會微相分離成層狀或不規則結構。
實驗例四
利用下面合成流程,在室溫下、甲苯(toluene)溶劑中加入347.9μl的仲丁基鋰(sec-BuLi)(1.3M in cyclohexane)和20ml的苯乙烯單體,攪拌反應15分鐘,之後在同一溫度下加入6.65ml的異戊二烯單體,此時溶液顏色由深紅轉為淺黃色,反應12小時後,將溫度降溫至-78℃,再將含13.28ml異戊二烯單體於THF的溶液加入其中,待溶液顏色變淺時,將反應溫度升到-30℃維持四天,以無水甲醇終止反應,並沉澱析出聚苯乙烯、聚1,4-異戊二烯和聚(1,2或3,4-異戊二烯)共聚高分子。
取此高分子4g溶於THF中,於-15℃下加入100ml的9-硼雙環[3.3.1]壬烷(9-BBN[0.5M in THF]),升溫至55℃反應兩
天,再冷卻至-25℃,加入1ml甲醇攪拌反應30分鐘後,加入2g 6N的NaOH和11ml 30% H2O2水溶液反應2小時,再升溫到55℃反應1小時,待兩相分層後,將上層溶液沉澱於0.25M的NaOH水溶液中,過濾可得異戊二烯雙鍵水解成氫氧基共聚高分子。
取水解完的共聚高分子1g溶於THF,升溫到60℃後加入0.66g KH,反應2小時,再加入0.44ml的1,3-丙磺酸內酯(1,3-propanesultone),反應8小時,以甲醇清洗後,再以1M LiOH水溶液清洗,產物分別加入過量的TBAOH(tetrabutylammonium hydroxide)、1.5M硫酸水溶液,最後再以1M LiOH水溶液清洗得最終聚電解質(R代表CH3或H)。
利用GPC比對PS標準品,發現三鏈段分子量分別為Mw40000、10000、20000,請見圖12與下表六(估算e、f、g分別約為236、148及294)。
氫譜核磁共振儀也證實了三鏈段的比例,如圖13所示。
然後添加不同量的塑化劑DBP。分別對乾膜以及浸潤到電解液(1M LiClO4的EC/PC溶液)的濕膜進行量測,結果顯示於下表七。
由表七可知,在室溫沒有添加任何塑化劑或電解液的情形下,離子導電度為4.8×10-5S/cm;不添加添加劑,僅含浸電解液導電度提升至3.2×10-4S/cm,吸液量為10wt%。而添加10wt%~20wt%的DPB乾膜離子導電度1.2×10-5~4.8×10-5S/cm,含20wt%DPB之聚電解質如含浸電解液,則離子導電度提高至3×10-4S/cm。圖14中顯示不含塑化劑和電解液的實驗例四之聚電解質的TEM切片照片,其顯示此高分子會微相分離成柱狀結構。
實驗例五
同實驗例四,製作不同分子量比例的聚電解質,SII-411
的重量平均分子量分別為40000、10000、10000;SII-412的重量平均分子量分別為40000、10000、20000;SII-422的重量平均分子量分別為40000、20000、20000;SII-522的重量平均分子量分別為50000、20000、20000,其導電率如表八所示。
由表八可知不同厚度的聚電解質在室溫沒有添加任何塑化劑或電解液的情形下,離子導電度為5.3×10-5S/cm~12×10-5S/cm;不添加添加劑,僅含浸電解液導電度提升至9.8×10-5S/cm~11.6×10-5S/cm,吸液量為7.6~20wt%。
綜上所述,本發明提出的聚電解質能降低或完全不使用儲能元件中易揮發、易燃的電解液,並在室溫下不含任何電解液的情形下,仍然具有~10-5S/cm的離子導電度,而在具有少量電解液的情形下可以有~10-4S/cm的離子導電度。此種聚電解質可應用於任何電化學儲能元件,有效排除或降低電解液的使用,大幅提升電化學儲能元件的特性。
雖然本發明已以實施例揭露如上,然其並非用以限定本發明,任何所屬技術領域中具有通常知識者,在不脫離本發明的
精神和範圍內,當可作些許的更動與潤飾,故本發明的保護範圍當視後附的申請專利範圍所界定者為準。
Claims (24)
- 一種聚電解質,包括第一鏈段以及第二鏈段,其中所述第一鏈段結構為式(2):
- 如申請專利範圍第1項所述的聚電解質,其中所述第一鏈段與所述第二鏈段是交錯、重複或隨機排列。
- 如申請專利範圍第1項所述的聚電解質,其中所述第一鏈段的分子量在10000~90000之間。
- 如申請專利範圍第1項所述的聚電解質,其中所述第二鏈段的分子量在10000~30000之間。
- 如申請專利範圍第1項所述的聚電解質,其中所述第一鏈段分子重複單元y為300~900。
- 如申請專利範圍第1項所述的聚電解質,其中所述第二鏈段分子重複單元p或q為50~200。
- 如申請專利範圍第1項所述的聚電解質,其中所述聚電解 質,在室溫、不含任何溶劑或電解液的情形下,離子導電度大於10-5S/cm。
- 一種聚電解質,包括第一鏈段、第二鏈段以及第三鏈段,且所述第三鏈段在所述第一鏈段與所述第二鏈段之間,其中所述第一鏈段結構為式(2):
- 如申請專利範圍第8項所述的聚電解質,其中所述第一鏈段、所述第二鏈段與所述第三鏈段是交錯、重複或隨機排列。
- 如申請專利範圍第8項所述的聚電解質,其中所述第一鏈段的分子量在10000~90000之間。
- 如申請專利範圍第8項所述的聚電解質,其中所述第二鏈段的分子量在10000~30000之間。
- 如申請專利範圍第8項所述的聚電解質,其中所述第三鏈 段的分子量在10000~20000之間。
- 如申請專利範圍第8項所述的聚電解質,其中所述第一鏈段分子重複單元y為300~900。
- 如申請專利範圍第8項所述的聚電解質,其中所述第二鏈段分子重複單元p或q為50~200。
- 如申請專利範圍第8項所述的聚電解質,其中所述第三鏈段分子重複單元w為100~400。
- 如申請專利範圍第8項所述的聚電解質,其中所述聚電解質,在室溫、不含任何溶劑或電解液的情形下,離子導電度大於10-5S/cm。
- 一種儲能元件,包括如申請專利範圍第1~16項所述的聚電解質,其中所述聚電解質藉由混合、塗佈、包覆或添加應用於所述儲能元件內。
- 如申請專利範圍第17項所述的儲能元件,其中所述儲能元件包括鋰離子一次電池、鋰離子二次電池、電容器、超級電容器、燃料電池、金屬硫電池、或金屬空氣電池。
- 如申請專利範圍第17項所述的儲能元件,更包括於所述聚電解質中添加的塑化劑。
- 如申請專利範圍第19項所述的儲能元件,其中所述塑化劑包括鄰苯二甲酸二(2-乙基己基)酯(bis(2-ethylhexyl)phthalate,BEHP)、鄰苯二甲酸二丁酯(Dibutyl phthalate,DBP)或鄰苯二甲酸二異丁酯(Diisobutyl phthalate,DIBP)。
- 如申請專利範圍第17項所述的儲能元件,更包括於所述聚電解質中添加的高介電係數溶劑或液態電解液。
- 如申請專利範圍第21項所述的儲能元件,其中所述高介電係數溶劑包括碳酸丙烯酯(Propylene carbonate,PC)、碳酸乙烯酯(Ethylene carbonate,EC)、碳酸二乙酯(Diethyl carbonate,DEC)碳酸二甲酯(Dimethyl carbonate,DEC)或碳酸甲基乙基酯(Ethyl methyl carbonate,EMC)。
- 如申請專利範圍第21項所述的儲能元件,其中所述液態電解液包括所述高介電係數溶劑與溶於所述高介電係數溶劑的鋰鹽。
- 如申請專利範圍第23項所述的儲能元件,其中所述鋰鹽包括LiPF6、LiBF4、LiClO4或LiTFSI。
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