CN106898813A - A kind of solid electrolyte, solid electrolyte membrane and its manufacture method and lithium secondary battery - Google Patents
A kind of solid electrolyte, solid electrolyte membrane and its manufacture method and lithium secondary battery Download PDFInfo
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- CN106898813A CN106898813A CN201510955695.3A CN201510955695A CN106898813A CN 106898813 A CN106898813 A CN 106898813A CN 201510955695 A CN201510955695 A CN 201510955695A CN 106898813 A CN106898813 A CN 106898813A
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- solid electrolyte
- ion liquid
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- liquid polymer
- polymer
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 55
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 239000012528 membrane Substances 0.000 title claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 80
- 239000007788 liquid Substances 0.000 claims abstract description 58
- -1 nitrile compounds Chemical class 0.000 claims abstract description 39
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 30
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 18
- 150000002825 nitriles Chemical class 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- OEICGMPRFOJHKO-UHFFFAOYSA-N 2-(ethoxymethylidene)propanedinitrile Chemical compound CCOC=C(C#N)C#N OEICGMPRFOJHKO-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 229920006391 phthalonitrile polymer Polymers 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims description 4
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 claims description 4
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 description 45
- 239000003792 electrolyte Substances 0.000 description 41
- 239000007787 solid Substances 0.000 description 19
- 230000004087 circulation Effects 0.000 description 18
- 150000002466 imines Chemical class 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 229910010710 LiFePO Inorganic materials 0.000 description 13
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000009477 glass transition Effects 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000013019 agitation Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 238000003475 lamination Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 229910000813 Li/LiFePO4 Inorganic materials 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical group C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 229910052794 bromium Inorganic materials 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 239000002608 ionic liquid Substances 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical class C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 4
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 230000004224 protection Effects 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000012790 confirmation Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- GOKUDEWVRNZXDZ-UHFFFAOYSA-N 1-bromo-3-(3-bromopropoxy)propane Chemical class BrCCCOCCCBr GOKUDEWVRNZXDZ-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- MMYKTRPLXXWLBC-UHFFFAOYSA-N 1-bromo-2-ethoxyethane Chemical class CCOCCBr MMYKTRPLXXWLBC-UHFFFAOYSA-N 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-butylbenzenesulfonamide Chemical compound CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JAMFGQBENKSWOF-UHFFFAOYSA-N bromo(methoxy)methane Chemical compound COCBr JAMFGQBENKSWOF-UHFFFAOYSA-N 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 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 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
The present invention provides a kind of solid electrolyte, solid electrolyte membrane and its manufacture method and lithium secondary battery.The solid electrolyte includes ion liquid polymer, nitrile compounds and lithium salts.The battery that solid electrolyte of the invention is formed has extraordinary specific discharge capacity and excellent cycle performance under high charge-discharge magnification (such as 0.5C and 1.0C), is highly suitable as battery and uses, and is particularly suitable for lithium secondary battery and uses.
Description
Technical field
The present invention relates to a kind of solid electrolyte, solid electrolyte membrane and its manufacture method and lithium secondary battery.
Background technology
Electrolyte is the important component in electrochemical device.At present, the electrolyte of lithium secondary battery is main by organic
Solvent and lithium salts composition, and organic solvent low boiling point, flash-point are low, inflammable volatile, greatly influence the safety of lithium secondary battery
Property；Meanwhile, with the expansion of lithium secondary battery application field, the rate capability and power density of battery are also improved constantly, organic
The potential safety hazard that electrolyte is brought also is protruded increasingly.
Produced by organic electrolyte catch fire, explode, the potential safety hazard such as leakage seriously constrains high-energy-density lithium ion
The development of battery.Therefore, it is subject to high safety, polymer dielectric flexible, that the advantages such as lithium dendrite growth can be suppressed
Extensive concern.However, polymer dielectric generally existing conductivity at room temperature is relatively low at present, electrode/polymer dielectric
The problems such as interface impedance is excessive, limits its practical application in lithium ion battery.
Secondary lithium batteries solid polyelectrolyte is due to that with good mechanical performance and high security, can prevent electricity
Solution liquid leakage, and without barrier film, caused extensive concern.However, the room-temperature ion conductance of most polymers solid electrolyte
Rate relatively low (10-5~10-6S cm-1), limit its practical application.So far, people take some tactful its ion-conductances of enhancing
Conductance, for example adulterate filler, polymer blending, copolymerization and crosslinking etc., however, ionic conductivity is still not ideal enough.
Ionic liquid has a series of excellent spies such as substantially non-volatile, heat resistance is high, nonflammable, electrochemical stability is good
Property, itself and lithium salts are combined and are applied in lithium secondary battery as electrolyte, the security of battery can be improved.So far,
Ionic liquid of the prior art there are single centre cationic ion liquid and double center cation ionic liquids.However, should
Class electrolyte is still liquid phase presence in the lithium secondary battery, can't resolve the leakage problem of battery, it is difficult to ensure the peace of battery
Full property and stability.
Nitrile compounds have highly polar, and it has the ability of the good various lithium salts of dissolving.
For example, research finds the electrolyte of succinonitrile/bis- (trimethyl fluoride sulfonyl) imine lithium system, its ion at room temperature
Electrical conductivity is up to 10-3S cm-1(Nature materials,2004,3,476-481)。
Also there is the electrolyte that succinonitrile is introduced in polymeric matrix, for example, electrolyte includes polyacrylonitrile
The electrolyte of (Electrochemistry Communications, 2008,10,1912-1915) and succinonitrile；Including crust
Electrolyte of plain (Journal of Membrane Science, 2014,468,149-154) and succinonitrile etc..
Recently, researcher also develops and uses situ synthesis techniques to prepare a kind of electrolysis of nitrile full solid state polymer
Matter (Advanced Energy Materials, 2015,5,1500353).Such polymer dielectric is ethylized by by nitrile
Polyvinyl alcohol (PVA-CN) monomer forms precursor in being dissolved in succinonitrile all solid state electrolyte, and then precursor is immersed into polypropylene
Prepared by in-situ polymerization being carried out in nitrile electrospinning fibre film network.But when it is applied to lithium secondary battery, battery is in room temperature and low
Charge-discharge magnification (0.1C) under specific discharge capacity be also possible that but carrying with charge-discharge magnification (such as 0.5C and 1.0C)
Height, its specific discharge capacity is greatly lowered.
So an urgent demand can develop obtained lithium secondary battery specific discharge capacity under charge-discharge magnification high
Do not reduce, the electrolyte of the cycle performance also become reconciled with specific discharge capacity high under charge-discharge magnification high.
For the electrolyte of lithium secondary battery, can guarantee that the battery has electric discharge ratio high under charge-discharge magnification high
Capacity and excellent cycle performance it is critical that.
The content of the invention
Defect of the present inventor existing for above-mentioned prior art, to ion liquid polymer and nitrile
Combination of compound etc. has made intensive studies, and develops of the invention comprising ion liquid polymer, nitrile compounds and lithium salts
Solid electrolyte, solid electrolyte membrane and its manufacture method and lithium secondary battery.
The present invention provides a kind of solid electrolyte, comprising ion liquid polymer, nitrile compounds and lithium salts.
In described solid electrolyte of the invention, the ion liquid polymer be selected from following formula (1) polymer and
One kind of the polymer of following formula (2)：
Wherein in formula (1), n is 1000≤n≤4000；
Wherein in formula (2), m is 50≤m≤2000；R1It is hydrogen atom or the straight-chain aliphatic alkyl of C1-C10；R2It is C1-
The straight-chain aliphatic alkyl or ether of C10；
B in formula (1) and (2)-It is BF4 -、PF6 -Or (CF3SO2)2N-。
The R2Ether be：-CH2OCH3、-CH2CH2OCH3、-CH2CH2OCH2CH3、-CH2CH2OCH2CH2CH3Or-
CH2CH2CH2OCH3。
The nitrile compounds are selected from malononitrile, succinonitrile, ethoxy methylene malononitrile, para-Phthalonitrile, isophthalic two
One kind in formonitrile HCN, phthalonitrile and 4- fluorine phthalic nitriles.
The nitrile compounds are ethoxy methylene malononitrile or succinonitrile.
The lithium salts is LiY；Wherein Y-It is BF4 -、PF6 -Or (CF3SO2)2N-。
The mass ratio of the ion liquid polymer and the nitrile compounds is 1:0.1~1:2.0.
The mass ratio of the ion liquid polymer and the lithium salts is 1:0.1~1:1.0.
The present invention also provides a kind of dielectric film, and the dielectric film contains foregoing solid electrolyte.
The present invention also provides a kind of manufacture method of the dielectric film of aforesaid electrolyte, and the manufacture method includes following step
Suddenly：
(1) it is, 1 according to the mass ratio of ion liquid polymer and nitrile compounds:0.1~1:2.0 and ionic liquid
The mass ratio of polymer and lithium salts is 1:0.1~1:1.0 ratio by the ion liquid polymer, the nitrile compounds with
And the lithium salts dissolving is in a solvent, uniform mixing is obtained mixed liquor；
(2), the mixed liquor obtained by step (1) is coated in template, solid electrolyte membrane is obtained.
The present invention also provides a kind of lithium secondary battery, contains foregoing solid electrolyte membrane.
Technique effect
In the present invention, a kind of combination of the new component of solid electrolyte is provide not only, but also it is new there is provided these
The specific proportioning of component, and prior art and its conventional polymer matrix phase ratio, so that its battery fills in the height of 0.5C and 1.0C
There is extraordinary specific discharge capacity and excellent cycle performance under discharge-rate.
Furthermore, electrolyte of the invention is in amorphous state, with low glass transition temperature (<- 80 DEG C), be conducive to electricity
The motion of pond lithium ion, also makes battery of the invention have extraordinary electric discharge ratio under the high charge-discharge magnification of 0.5C and 1.0C
Capacity and excellent cycle performance.
Brief description of the drawings
Fig. 1 is the ion liquid polymer obtained in embodiment 11H NMR spectra (deuterated solvents：Deuterated acetone).
Fig. 2 is the Li/LiFePO formed with the solid electrolyte obtained by embodiment 14Battery is in different discharge and recharges times
Specific discharge capacity and cycle performance figure under rate (0.1C, 0.5C and 1.0C).
Fig. 3 is the ion liquid polymer obtained in embodiment 21H NMR spectra (deuterated solvents：Deuterated dimethyl is sub-
Sulfone).
Fig. 4 is the Li/LiFePO formed with the solid electrolyte obtained by embodiment 24Battery is in different discharge and recharges times
Specific discharge capacity and cycle performance figure under rate (0.1C, 0.5C and 1.0C).
Fig. 5 is the ion liquid polymer obtained in embodiment 31H NMR spectra (deuterated solvents：Deuterated dimethyl is sub-
Sulfone).
Fig. 6 is the Li/LiFePO formed with the solid electrolyte obtained by embodiment 34Battery is in different discharge and recharges times
Specific discharge capacity and cycle performance figure under rate (0.1C, 0.5C and 1.0C).
Fig. 7 is the Li/LiFePO formed with the solid electrolyte obtained by embodiment 44Battery is in different discharge and recharges times
Specific discharge capacity and cycle performance figure under rate (0.1C, 0.5C and 1.0C).
Specific embodiment
The present invention provides a kind of solid electrolyte, and the electrolyte includes ion liquid polymer, nitrile compounds and lithium salts.
Foregoing ion liquid polymers is selected from the one kind in the polymer of the polymer of following formula (1) and following formula (2)：
Wherein in formula (1), n is 1000≤n≤4000.
Wherein in formula (2), m is 50≤m≤2000；R1It is hydrogen atom or the straight-chain aliphatic alkyl of C1-C10；R2It is C1-
The straight-chain aliphatic alkyl or ether of C10.
B in formula (1) and (2)-It is BF4 -、PF6 -Or (CF3SO2)2N-。
The straight-chain aliphatic alkyl of foregoing C1-C10 is, for example,：Methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptan
Base, octyl group, nonyl, decyl.
The straight-chain aliphatic alkyl of aforementioned linear aliphatic alkyl preferably C1-C5, is exemplified by：Methyl, ethyl, propyl group,
Butyl, amyl group.
Foregoing R2Ether be, for example,：-CH2OCH3、-CH2CH2OCH3、-CH2CH2OCH2CH3、-CH2CH2OCH2CH2CH3、
Or-CH2CH2CH2OCH3, preferably-CH2CH2OCH3Or-CH2CH2OCH2CH3。
R1Preferably hydrogen atom or methyl.
R2Preferably methyl, ethyl or-CH2CH2OCH3Ether.
The preparation method of foregoing ion liquid polymers can be following manufacture method.
The manufacture method of the ion liquid polymer of formula (1) can use such as document A.-L.Pont,
R.Marcilla, I.De Meatza, H.Grande, D.Mecerreyes, power technology journal (Journal of Power
Sources) the manufacture method described in (2009,188,558-563).
The ion liquid polymer of the polymer of formula (1) can be obtained by following manufacture method：
The PDDA aqueous solution (concentration is 20.00 mass %) is dissolved in deionized water, is stirred
Mix to form the solution containing PDDA.
Another to dissolve in deionized water lithium salts, stirring forms the solution containing lithium salts.
According to the mol ratio 1 of PDDA and lithium salts:1.2~1:2.0 ratio is obtained foregoing
Two solution carry out mixed preparing, stirring reaction 2~8 hours has solid to generate, solid is collected by filtration, then be washed with deionized water
Wash, untill washings is detected without halide anion with silver nitrate, be finally vacuum dried 12~48 hours, so that formula is obtained
(1) ion liquid polymer.
The lithium salts is：Two (trimethyl fluoride sulfonyl) imine lithiums, lithium hexafluoro phosphate etc..
The viscosity average molecular weigh M of the ion liquid polymer of formula (1) of the inventionvIt is 3.0 × 105~5.0 × 106g
mol-1(polymethyl methacrylate is used as standard specimen).
The confirmation method of the ion liquid polymer (1) is1H NMR spectras.
The manufacture method of the ion liquid polymer of formula (2) can using such as document K.Yin, Z.X.Zhang,
L.Yang, S.-i.Hirano, power technology journal (Journal of Power Sources) (2014,258,150-154) institute
The manufacture method of record.
The ion liquid polymer of the polymer of formula (2) can be obtained by following manufacture method：
The first step：By the dissolving of olefin-containing unsaturated group imidazoles monomer in a solvent, monomer mass is accounted for initiator
0.2~1.0% ratio adds initiator, carries out Raolical polymerizable.Under the protection of the protective gas such as argon gas, 60~90
Stirring reaction 6~12 hours at reflux at DEG C, solid to be had is generated, washed with solvent after filtering, at 60~90 DEG C
Vacuum drying 12~48 hours, is obtained the polymer containing glyoxaline structure.
Olefin-containing unsaturated group imidazoles monomer：Can be 1- vinyl imidazoles, 1- allyl imidazoles etc..
Polymerization initiator：Azodiisobutyronitrile, ABVN, azo-bis-iso-dimethyl.
Solvent：Toluene, benzene, tetrahydrofuran, acetone etc..
The molecular weight of obtained polymer：Its viscosity average molecular weigh MvIt is 1.0 × 104~5.0 × 105g mol-1(poly- methyl
Methyl acrylate is used as standard specimen).
Second step：By the polymer obtained by the first step containing glyoxaline structure and halogenated hydrocarbons or halogen ether in molar ratio 1:
1.5~1:In a solvent, stirring reaction 24~72 hours at 40~80 DEG C, vacuum distillation removes solvent for 2.0 dissolvings, collects solid
Body, is washed 3 times with absolute ether, and rotary evaporation removes ether, is vacuum dried 12~48 hours, obtains anionic ion containing halogen
Liquid polymers.
Solvent therein is：N,N-dimethylformamide, methyl alcohol etc..
The halogenated hydrocarbons：Bromoethane, N-Propyl Bromide, NBB etc..
The halogen ether：2- bromo-ethyl-methyl ethers, bromomethyl methyl ether, 2- bromoethyl ethylethers etc..
The molecular weight of the obtained liquid polymers of anionic ion containing halogen：Its viscosity average molecular weigh MvIt is 1.0 × 105~
5.0×106g mol-1(polymethyl methacrylate is used as standard specimen).
3rd step：The liquid polymers of anionic ion containing halogen and lithium salts that second step is obtained in molar ratio 1:1.2~
1:In deionized water, stirring reaction 2~8 hours has solid to generate, and solid is collected by filtration, then be washed with deionized water for 2.0 dissolvings
Wash, until washings with silver nitrate detect be free of halide anion, finally vacuum drying obtain within 12~48 hours formula (2) from
Sub- liquid polymers.
The lithium salts is：Two (trimethyl fluoride sulfonyl) imine lithiums, lithium hexafluoro phosphate etc..
The viscosity average molecular weigh M of the ion liquid polymer of formula (2) of the inventionvIt is 1.0 × 105~5.0 × 106g
mol-1(polymethyl methacrylate is used as standard specimen).
The confirmation method of the ion liquid polymer is1H NMR spectras.
The viscosity average molecular weigh M of ion liquid polymer of the inventionvIt is 1.0 × 105~5.0 × 106g mol-1(poly- methyl
Methyl acrylate is used as standard specimen).
The confirmation method of the ion liquid polymer：1H NMR spectras.
Foregoing nitrile compounds of the invention are selected from malononitrile, succinonitrile, ethoxy methylene malononitrile, terephthaldehyde
One kind in nitrile, isophthalodinitrile, phthalonitrile and 4- fluorine phthalic nitriles, preferably ethoxy methylene malononitrile or
Succinonitrile.
Foregoing nitrile compounds can be obtained for common manufacturing method, it is also possible to directly be bought from market.
For example, the succinonitrile in nitrile compounds used by the present invention can be used by Fujian Chuangxin Science and Technology Development Co., Ltd.
The succinonitrile of production.
Malononitrile of the invention, ethoxy methylene malononitrile, para-Phthalonitrile, isophthalodinitrile, phthalonitrile, with
And 4- fluorine phthalic nitrile also can be used the nitrile compounds produced by Aladdin company, directly be bought as commodity.
The lithium salts of the invention is LiY；Wherein Y-It is BF4 -、PF6 -Or (CF3SO2)2N-。
I.e. the present invention used by lithium salts be LiBF4, lithium hexafluoro phosphate, two (trimethyl fluoride sulfonyl) imine lithiums,
Using the lithium salts produced by gloomy field chemical industry (Zhangjiagang) Co., Ltd, directly bought as commodity.
The mass ratio of the ion liquid polymer and the nitrile compounds is 1:0.1~1:2.0, preferably 1：0.3
~1：1.5.If the mass ratio of the nitrile compounds is less than 0.3, dielectric film chemical property is bad；If the nitrile
The mass ratio of compound can cause that dielectric film is too viscous and intactly cannot be stripped down from mould more than 1.5.
The mass ratio of the ion liquid polymer and the lithium salts is 1:0.1~1:1.0, preferably 1：0.3~1：
0.8。
The present invention also provides a kind of dielectric film, contains foregoing solid electrolyte.
The present invention also provides a kind of manufacture method of aforesaid electrolyte film, and the manufacture method comprises the following steps：
(1) it is 1 according to the mass ratio of ion liquid polymer and nitrile compounds:0.1~1:2.0 (preferably 1：0.3~
1：1.5) and ion liquid polymer and lithium salts mass ratio be 1:0.1~1:1.0 (preferably 1：0.3~1：0.8) ratio
By the dissolving of the ion liquid polymer, the nitrile compounds and the lithium salts in a solvent, uniform mixing is obtained mixed example
Close liquid；
(2) mixed liquor obtained by step (1) is coated in template, solid electrolyte membrane is obtained.
Solid electrolyte of the invention is applied in the lithium secondary battery, i.e., the present invention also provides a kind of lithium secondary battery, should
Battery contains foregoing ion liquid polymer solid electrolyte membrane.
Solid electrolyte of the invention is preferably used in Li/LiFePO4In battery.
The preparation of battery and assemble method：
Argon gas protection glove box in by the positive pole cap of battery, positive plate, obtained dielectric film, negative plate,
Negative pole cap forms lamination according to order stacking placement from top to bottom, lamination then is placed on into punching press on stamping machine so that electricity
The mutually closed lock jail of the both positive and negative polarity cap in pond, so far lithium secondary battery preparation of the invention is completed.
Above-mentioned used positive pole cap, positive plate, negative plate, negative pole cap etc. are in addition to dielectric film of the invention
Battery component, all can be used known method obtained by associated batteries part, also can by it is various sale sellers obtain.
The measure of molecular weight：
Viscosity average molecular weigh method of testing：
Using polymethyl methacrylate as standard specimen, using the viscosity [η] of determination of ubbelohde viscometer polymer, then pass through
Formula [η]=KMv(wherein K represents broadening factor, and its value is relevant with temperature, polymer, solvent property, MvRepresent and glue equal molecule
Amount, the viscosity of [η] representation polymer) obtain viscosity average molecular weigh Mv。
The glass transition temperature T of electrolyte of the inventiongMeasure：
Enter using differential scanning calorimetry (DSC) method and using TA Instruments Q2000 type derivatographs
Row is determined.Secondary cycle is generally carried out, using the 2nd DSC curve data of circulation, glass transition temperature is obtained：First will
Electrolyte sample is cooled to -80 DEG C from room temperature, and then constant temperature 10 minutes be warming up to 200 DEG C, constant temperature 5 with 10 DEG C/min of speed
Minute, then -80 DEG C are cooled to 10 DEG C/min of speed, as the 1st circulation.Aforesaid operations are repeated to be followed as the 2nd time for 1 time
Ring.
The measure of the ionic conductivity of electrolyte of the invention：
The ionic conductivity of electrolyte is tested using AC impedence method, and instrument is CHI600D electrochemical workstations.Will
Testing sample with：The composition order of stainless steel electrode/electrolyte/stainless steel electrode constitutes simulated battery, then to the simulated battery
Ac impedance measurement is carried out at 25 DEG C.Before test, simulated battery is stood into 1h, frequency range 1Hz in each temperature spot constant temperature
~100KHz, AC amplitude 5mV.Conductivity Calculation formula is as follows：
R is electrolyte body impedance (Ω) in formula, and L represents the thickness (cm) of dielectric film, and S represents having for dielectric film
Effect area (cm2)。
The specific discharge capacity of battery is measured in the following manner：
The electrolyte of gained is made battery, the battery is placed in 25 DEG C of temperature, with the voltage model of 2.5-4.0V
Enclose and 0.1C, 0.5C or 1.0C constant current by its discharge and recharge, using CT2001A (Lan Bo test equipments Co., Ltd of Wuhan City,
LAND battery test systems-CT2001A) charging/discharging apparatus determine battery discharge capacity and untill being recycled to 10 times first
Discharge capacity.
The computing formula of specific discharge capacity：
Specific discharge capacity (mAh g-1The quality (g) of active material in)=actual discharge capacity (mAh)/positive plate.
The data of the cycle performance figure in accompanying drawing are obtained：
Using the data of specific discharge capacity obtained above as ordinate, circulation is made using cycle-index as abscissa
Performance map.
Embodiment
The following examples are further illustrated to of the invention, but are not limited the scope of the invention.
Embodiment 1
The preparation of poly- (dimethyldiallylammonium two (trimethyl fluoride sulfonyl) imines) base solid electrolyte
The preparation of poly- (dimethyldiallylammonium two (trimethyl fluoride sulfonyl) imines) ion liquid polymer：
The PDDA of 20.00g is added in 250.00mL beakers
The aqueous solution (20 mass %) (Aldrich product) and 100.00mL deionized waters, magnetic agitation 1 hour are contained with being formed
The solution of PDDA.
Two (trimethyl fluoride sulfonyl) imine lithiums of 8.52g (29.68mmol) are sequentially added in another 50.00mL beaker
(gloomy field chemical industry (Zhangjiagang) Co., Ltd product) and 10.00mL deionized waters, magnetic agitation are allowed to be completely dissolved, and formation contains
The solution of two (trimethyl fluoride sulfonyl) imine lithiums.
Foregoing two kinds of solution is mixed, ion exchange 2 hours has solid to generate, solid is collected by filtration, is washed with water and washs one
Untill washings detects not chloride ion-containing with silver nitrate, finally vacuum drying obtains ionic liquid in 72 hours at 105 DEG C
Polymer poly (dimethyldiallylammonium two (trimethyl fluoride sulfonyl) imines), its structural formula is：
The viscosity average molecular weigh of the ion liquid polymer is 2.11 × 106g mol-1。
The chemical constitution of the ion liquid polymer is used1H NMR spectras are characterized, as shown in Figure 1.
As can be seen that spectrogram result is consistent with desired structure.
The preparation of electrolyte：
To the poly- (dimethyldiallylammonium two (trimethyl fluoride sulfonyl) added in single necked round bottom flask obtained by 1.00g
Imines), add 20.00g acetone, magnetic agitation dissolving, the succinonitrile for adding 1.00g (to create the prosperous limited public affairs of scientific and technological development in Fujian
Department's product) and 0.50g bis- (trimethyl fluoride sulfonyl) imine lithium (gloomy field chemical industry (Zhangjiagang) Co., Ltd product), the magnetic at 25 DEG C
Power stirring mixing obtains poly- (dimethyldiallylammonium two (trimethyl fluoride sulfonyl) Asia of transparent homogeneous mixed liquor after 12 hours
Amine) electrolyte.
The preparation of dielectric film：
The transparent homogeneous electrolyte of gained is coated in polytetrafluoroethylene (PTFE) template, then 48 is vacuum dried at 30 DEG C
Hour, obtain dielectric film.Dielectric film glass transition temperature TgIt is that, less than -80 DEG C, ionic conductivity is at 25 DEG C
5.74×10-4S cm-1。
The preparation of battery：
LiFePO4 (LiFePO will be contained4) as the positive plate of positive electrode, obtained dielectric film, with lithium (Li)
Lamination is formed according to order stacking placement from top to bottom as the negative plate of negative material, then lamination is placed on stamping machine
Punching press, obtains Li/LiFePO4Battery.
By obtained Li/LiFePO4Battery carries out constant current charge-discharge survey under 25 DEG C, the voltage range of 2.5-4.0V
Examination, 10 circulations of each test under 0.1C, 0.5C and 1.0C charge-discharge magnifications.
The determination data result of embodiment 1 is summarised in 2~table of table 3 and Fig. 1~2.
Embodiment 2
The system of poly- (1- (2- methoxy ethyls) -3- vinyl imidazoles two (trimethyl fluoride sulfonyl) imines) base solid electrolyte
It is standby
Poly- (1- (2- methoxy ethyls) -3- vinyl imidazoles two (trimethyl fluoride sulfonyl) imines) ion liquid polymer
Prepare：
(1) using 1- vinyl imidazoles as reaction monomers, azodiisobutyronitrile as initiator, toluene as reaction dissolvent,
Raolical polymerizable is carried out, wherein initiator accounts for the 0.5% of monomer mass.At Ar atmosphere protections, 65 DEG C, it is stirred at reflux anti-
Answer 8 hours.Solid to be had is generated, and is washed with acetone after filtering, is vacuum dried 24 hours at 75 DEG C, obtains polyvinyl miaow
Azoles.
Polyvinyl imidazol viscosity average molecular weigh MvIt is 3.39 × 105g mol-1。
(2) the 2- bromo-ethyl-methyl ethers (63.83mmol) of the polyvinyl imidazol obtained by 4.00g and 8.90g are dissolved
In the DMF of 60.00mL, stirring reaction 48 hours at 60 DEG C, vacuum distillation removes solvent, collects solid
Body, is washed 3 times with absolute ether, rotary evaporation remove ether, be vacuum dried 24 hours, obtain it is poly- (1- (2- methoxy ethyls)-
3- vinyl imidazoles bromine).
Poly- (1- (2- methoxy ethyls) -3- vinyl imidazoles bromine) viscosity average molecular weigh MvIt is 5.62 × 105g mol-1。
(3) by poly- (1- (2- the methoxy ethyls) -3- vinyl imidazoles bromine) and 5.17g obtained by 3.50g
(18.02mmol) two (trimethyl fluoride sulfonyl) imine lithium (gloomy field chemical industry (Zhangjiagang) Co., Ltd product) is dissolved in 20.00mL
In deionized water, magnetic agitation 6 hours, have solid to generate at room temperature, and solid is collected by filtration, then are washed with deionized, directly
Detected with silver nitrate to washings and be free of halide anion, finally vacuum drying obtains ion liquid polymerization in 24 hours at 75 DEG C
Thing is poly- (1- (2- methoxy ethyls) -3- vinyl imidazoles two (trimethyl fluoride sulfonyl) imines), and its structural formula is：
The chemical constitution of the ion liquid polymer is used1H NMR spectras are characterized, as shown in Figure 3.As can be seen that spectrogram
Result is consistent with desired structure.
The viscosity average molecular weigh M of the ion liquid polymervIt is 7.32 × 105g mol-1。
The preparation of electrolyte：
To poly- (1- (2- the methoxy ethyls) -3- vinyl imidazoles two added in single necked round bottom flask obtained by 1.00g
(trimethyl fluoride sulfonyl) imines), 20.00g acetone is added, magnetic agitation dissolving adds the ethoxymeyhylene the third two of 0.60g
(gloomy field chemical industry (Zhangjiagang) Co., Ltd produces for nitrile (Aladdin Products) and 0.50g bis- (trimethyl fluoride sulfonyl) imine lithium
Product), magnetic agitation obtains poly- (1- (2- methoxy ethyls) -3- of transparent homogeneous mixed liquor after mixing 12 hours at 25 DEG C
Vinyl imidazole two (trimethyl fluoride sulfonyl) imines) electrolyte.
The preparation of dielectric film：
The transparent homogeneous electrolyte of gained is coated in polytetrafluoroethylene (PTFE) template, then 48 is vacuum dried at 25 DEG C
Hour, obtain dielectric film.Dielectric film glass transition temperature TgIt is that, less than -80 DEG C, ionic conductivity is at 25 DEG C
2.98×10-4S cm-1。
The preparation of battery：
LiFePO4 (LiFePO will be contained4) as the positive plate of positive electrode, obtained dielectric film, with lithium (Li)
Lamination is formed according to order stacking placement from top to bottom as the negative plate of negative material, then lamination is placed on stamping machine
Punching press, obtains Li/LiFePO4Battery.
By obtained Li/LiFePO4Battery carries out constant current charge-discharge survey under 25 DEG C, the voltage range of 2.5-4.0V
Examination, 10 circulations of each test under 0.1C, 0.5C and 1.0C charge-discharge magnifications.
The determination data result of embodiment 2 is summarised in 2~table of table 3 and Fig. 3~4.
Embodiment 3
The preparation of poly- (1- (2- methoxy ethyls) -3- vinyl imidazoles hexafluorophosphoric acid) base solid electrolyte
The preparation of poly- (1- (2- methoxy ethyls) -3- vinyl imidazoles hexafluorophosphoric acid) ion liquid polymer：
(1) using 1- vinyl imidazoles as reaction monomers, azodiisobutyronitrile as initiator, toluene as reaction dissolvent,
Raolical polymerizable is carried out, wherein initiator accounts for the 0.5% of monomer mass.At Ar atmosphere protections, 65 DEG C, it is stirred at reflux anti-
Answer 8 hours.Solid to be had is generated, and is washed with acetone after filtering, is vacuum dried 24 hours at 75 DEG C, obtains polyvinyl miaow
Azoles.
Polyvinyl imidazol viscosity average molecular weigh MvIt is 3.39 × 105g mol-1。
(2) the 2- bromo-ethyl-methyl ethers (63.83mmol) of the polyvinyl imidazol obtained by 4.00g and 8.90g are dissolved
In the DMF of 60.00mL, stirring reaction 48 hours at 60 DEG C, vacuum distillation removes solvent, collects solid
Body, is washed 3 times with absolute ether, rotary evaporation remove ether, be vacuum dried 24 hours, obtain it is poly- (1- (2- methoxy ethyls)-
3- vinyl imidazoles bromine).
Poly- (1- (2- methoxy ethyls) -3- vinyl imidazoles bromine) viscosity average molecular weigh MvIt is 5.62 × 105g mol-1。
(3) by poly- (1- (2- the methoxy ethyls) -3- vinyl imidazoles bromine) and 2.74g obtained by 3.50g
(18.02mmol) lithium hexafluoro phosphate (gloomy field chemical industry (Zhangjiagang) Co., Ltd product) is dissolved in the deionized water of 20.00mL,
Magnetic agitation 6 hours, have solid to generate at room temperature, and solid is collected by filtration, then are washed with deionized, until washings nitre
Sour silver detection is free of halide anion, and finally vacuum drying obtains poly- (1- (the 2- first of ion liquid polymer for 24 hours at 75 DEG C
Epoxide ethyl) -3- vinyl imidazoles hexafluorophosphoric acid), its structural formula is：
The chemical constitution of the ion liquid polymer is used1H NMR spectras are characterized, as shown in Figure 5.As can be seen that spectrogram
Result is consistent with desired structure.
The viscosity average molecular weigh M of the ion liquid polymervIt is 6.35 × 105g mol-1。
The preparation of electrolyte：
To poly- (1- (2- the methoxy ethyls) -3- vinyl imidazole hexafluoros added in single necked round bottom flask obtained by 1.00g
Phosphoric acid), 20.00g acetone is added, magnetic agitation dissolving adds ethoxy methylene malononitrile (the Aladdin company of 0.60g
Product) and 0.40g lithium hexafluoro phosphates (gloomy field chemical industry (Zhangjiagang) Co., Ltd product) magnetic agitation mixing at 25 DEG C it is 12 small
When after obtain poly- (1- (2- the methoxy ethyls) -3- vinyl imidazoles hexafluorophosphoric acid) electrolyte of transparent homogeneous mixed liquor.
The preparation of dielectric film：
The transparent homogeneous electrolyte of gained is coated in polytetrafluoroethylene (PTFE) template, then 48 is vacuum dried at 30 DEG C
Hour, obtain dielectric film.Dielectric film glass transition temperature TgIt is that, less than -80 DEG C, ionic conductivity is at 25 DEG C
1.08×10-4S cm-1。
The preparation of battery：
LiFePO4 (LiFePO will be contained4) as the positive plate of positive electrode, obtained dielectric film, with lithium (Li)
Lamination is formed according to order stacking placement from top to bottom as the negative plate of negative material, then lamination is placed on stamping machine
Punching press, obtains Li/LiFePO4Battery.
The determination data result of embodiment 3 is summarised in 2~table of table 3 and Fig. 5~Fig. 6.
Embodiment 4
Except the weight ratio of the polymer of embodiment 1 and succinonitrile is changed into 1:Beyond 1.5, other all with embodiment
1 equally forms electrolyte and dielectric film and battery.
Dielectric film glass transition temperature TgIt is that, less than -80 DEG C, ionic conductivity is 3.56 × 10 at 25 DEG C-4S
cm-1。
The determination data result of the electrolyte of embodiment 4 is summarised in 2~table of table 3 and Fig. 7.
Embodiment 5
Except the weight ratio of the polymer of embodiment 2 and ethoxy methylene malononitrile is changed into 1:Beyond 0.3, its
He forms electrolyte and dielectric film in the same manner as in Example 2.
Dielectric film glass transition temperature TgIt is that, less than -80 DEG C, ionic conductivity is 1.01 × 10 at 25 DEG C-4S
cm-1。
The determination data result of embodiment 5 is summarised in table 2.
Comparative example
The composition and relative production of the electrolyte of comparative example, refer to citation《Advanced Energy
Materials》(2015,5,1500353)。
Its electrolyte is constituted：Polyacrylonitrile (J＆KScientific Ltd. products), nitrile ethylization polyvinyl alcohol (Shin-
Etsu Chemical products), succinonitrile (Aladdin Products) and LiTFSI lithium salts (TCI Products).Nitrile ethylizes
Polyvinyl alcohol:Succinonitrile:LiTFSI=5:83:10 (mass ratioes).Ion of the invention is not used and contained in a comparative example
Liquid polymers.
Polyacrylonitrile as matrix, nitrile ethylization polyvinyl alcohol are prepared as linked and succinonitrile, lithium salts are compound
Go out polymer dielectric, the electrolyte of gained is applied to Li/LiFePO4In battery.
At 25 DEG C, with the voltage range of 2.4~4.2V under, with 0.1C constant current charge-discharges determine battery electric discharge specific volume first
It is 155mAh g to measure-1, specific discharge capacity is 150mAh g after 10 circulations-1, and the specific discharge capacity point under 0.5C and 1.0C
Wei not 125mAh g-1With 98mAh g-1And specific discharge capacity is respectively 120mAh g after 10 circulations-1With 85mAh g-1。
They are combined and prepare solid electrolyte, electrolyte ionic conductivity at 25 DEG C is 4.49 × 10-4Scm-1。
Its result is represented in 2~table of table 3.
Table 1
Fig. 2 is the Li/LiFePO formed with the solid electrolyte obtained by embodiment 14Battery is in different discharge and recharges times
Specific discharge capacity and cycle performance figure under rate (0.1C, 0.5C and 1.0C).
Battery carries out constant current charge-discharge, first discharge specific capacity with the multiplying power of 0.1C, 0.5C and 1.0C respectively at 25 DEG C
Respectively 150mAh g-1, 132mAh g-1With 121mAh g-1, specific discharge capacity is respectively 152mAh g after 10 circulations-1,
130mAh g-1With 116mAh g-1。
Fig. 4 is the Li/LiFePO formed with the solid electrolyte obtained by embodiment 24Battery is in different discharge and recharges times
Specific discharge capacity and cycle performance figure under rate (0.1C, 0.5C and 1.0C).
Battery carries out constant current charge-discharge, specific discharge capacity difference with the multiplying power of 0.1C, 0.5C and 1.0C respectively at 25 DEG C
It is 135mAh g-1(0.1C), 129mAh g-1(0.5C) and 119mAh g-1(1.0C), specific discharge capacity difference after 10 circulations
It is 143mAh g-1(0.1C), 128mAh g-1(0.5C) and 113mAh g-1(1.0C)。
Fig. 6 is the Li/LiFePO formed with the solid electrolyte obtained by embodiment 34Battery is in different discharge and recharges times
Specific discharge capacity and cycle performance figure under rate (0.1C, 0.5C and 1.0C).
Battery carries out constant current charge-discharge with the multiplying power of 0.1C, 0.5C and 1C respectively at 25 DEG C, and specific discharge capacity is respectively
132mAh g-1(0.1C), 128mAh g-1(0.5C) and 112mAh g-1(1.0C), specific discharge capacity is respectively after 10 circulations
138mAh g-1(0.1C), 126mAh g-1(0.5C) and 110mAh g-1(1.0C)。
Fig. 7 is the Li/LiFePO formed with the solid electrolyte obtained by embodiment 44Battery is in different discharge and recharges times
Specific discharge capacity and cycle performance figure under rate (0.1C, 0.5C and 1.0C).
Battery carries out constant current charge-discharge with the multiplying power of 0.1C, 0.5C and 1C respectively at 25 DEG C, and specific discharge capacity is respectively
145mAh g-1(0.1C), 127mAh g-1(0.5C) and 116mAh g-1(1.0C), specific discharge capacity is respectively after 10 circulations
146mAh g-1(0.1C), 126mAh g-1(0.5C) and 111mAh g-1(1.0C)。
Aforementioned data is summarised in table 2 below and table 3.
Table 2
Embodiment 1~5 is in amorphous state, only glass transition temperature, does not have fusing point.
Comparative example is crystalline polymer, there is fusing point.
The Li/LiFePO of table 34Battery discharge specific capacity compares
As known from Table 3, in the solid electrolyte institute by embodiments of the invention 1, embodiment 2, embodiment 3 and embodiment 4
In the battery of formation, the first discharge specific capacity under the charge-discharge magnification of 0.5C is all in 125mAh g-1More than, it is electric discharge high
Specific capacity.Even if under the high charge-discharge magnification of 1.0C, the first discharge specific capacity of the battery of embodiment 1~4 is also all in 112mAh
g-1More than.
And in a comparative example, although its first discharge specific capacity is 125mAh g under the charge-discharge magnification of 0.5C-1But,
Its first discharge specific capacity is reduced to 100mAh g under the high charge-discharge magnification of 1.0C-1Hereinafter, it is 98mAh g-1, it is impossible to just
Often work.
Furthermore, for cycle performance, evaluated with the decay of specific discharge capacity after 10 circulations.
Under the charge-discharge magnification of 0.5C, the attenuation ratio of embodiments of the invention 1 is 1.51%, and embodiment 2 is
0.78%, embodiment 3 is 1.56%, and embodiment 4 is 0.79%, it follows that the average attenuation ratio of embodiment 1~4 is
1.16%, even if after illustrating to be circulated at 10 times, decaying also considerably less.
And for comparative example, the attenuation ratio of specific discharge capacity is after its 10 circulation under the charge-discharge magnification of 0.5C
4.00%, more substantially, its cycle performance is poor for decay.
In addition, for the attenuation of specific discharge capacity after 10 circulations under the charge-discharge magnification of 1.0C, the present invention
Embodiment 1 attenuation ratio be 4.13%, embodiment 2 be 5.04%, embodiment 3 be 1.79%, embodiment 4 be 4.31%,
Even if it follows that after being circulated at 10 times, its attenuation ratio average value is 3.82%, only 4% or so.
And for comparative example, the attenuation ratio of specific discharge capacity is after its 10 circulation under the charge-discharge magnification of 1.0C
13.27%, clearly, its cycle performance is poor for decay.
Content is known as below by the analysis of attenuation data above：
(1), under the charge-discharge magnification of 0.5C, the battery of embodiments of the invention 1~4 circulated at 10 times after electric discharge ratio
The average value of capacity attenuation ratio is only 1.16%, few compared with the 4.00% of comparative example a lot.
(2), under the charge-discharge magnification of 1.0C, the battery that the solid electrolyte of embodiments of the invention 1~4 is formed exists
The average value of the attenuation ratio of specific discharge capacity is 3.82% after 10 circulations under the charge-discharge magnification of 1.0C, is only equivalent to ratio
The attenuation ratio (4.00%) of specific discharge capacity after 10 circulations under charge-discharge magnification compared with example 0.5C.
And the attenuation ratio of specific discharge capacity is after 10 circulations under the charge-discharge magnification of the 1.0C of comparative example
13.27%, be embodiments of the invention 1~4 the charge-discharge magnification of the 1.0C of battery that is formed of solid electrolyte under 10
3.5 times of the attenuation ratio of specific discharge capacity after secondary circulation, attenuation degree is very serious, and the cycle performance of battery is excessively poor, the electricity
It is poor that pond recycles.
That is after the battery that the solid electrolyte of embodiments of the invention 1~4 is formed is circulated at 10 times, even if 1.0C's
The decay of specific discharge capacity is smaller after 10 circulations under high charge-discharge magnification, can also be remain after being circulated at 10 times highly stable
Specific discharge capacity, as battery for, be very important.
By the foregoing specific discharge capacity to after first discharge specific capacity data and first discharge specific capacity and 10 circulations
The analysis that attenuation ratio is carried out understands that solid electrolyte of the invention and its battery are under high charge-discharge magnification (0.5C and 1.0C)
With extraordinary specific discharge capacity and excellent cycle performance, it is highly suitable as battery and uses, is particularly suitable for lithium secondary
Battery is used.
I.e. in the present invention, a kind of combination of the new component of solid electrolyte is provide not only, but also there is provided these
The specific proportioning of new component, and prior art and its conventional polymer matrix phase ratio, so that height of its battery in 0.5C and 1.0C
There is extraordinary specific discharge capacity and excellent cycle performance under charge-discharge magnification.
Furthermore, electrolyte of the invention be in amorphous state, with low-down glass transition temperature (<- 80 DEG C), favorably
In the motion of battery lithium ions, also make battery of the invention under charge-discharge magnification (0.5C and 1.0C) high, with very good
Specific discharge capacity and excellent cycle performance.
The possibility utilized in industry
Applied in lithium secondary battery, particularly in Li/LiFePO by by solid electrolyte of the invention4Lithium secondary battery
In, excellent specific discharge capacity and cycle performance is can obtain under charge-discharge magnification high.
Claims (11)
1. a kind of solid electrolyte, it is characterised in that comprising ion liquid polymer, nitrile compounds and lithium salts.
2. solid electrolyte as claimed in claim 1, it is characterised in that the ion liquid polymer is selected from following formula (1)
One kind of the polymer of polymer and following formula (2)：
Wherein in formula (1), n is 1000≤n≤4000；
Wherein in formula (2), m is 50≤m≤2000；R1It is hydrogen atom or the straight-chain aliphatic alkyl of C1-C10；R2It is C1-C10
Straight-chain aliphatic alkyl or ether；
B in formula (1) and (2)-It is BF4 -、PF6 -Or (CF3SO2)2N-。
3. solid electrolyte as claimed in claim 2, it is characterised in that the R2Ether be：-CH2OCH3、-
CH2CH2OCH3、-CH2CH2OCH2CH3、-CH2CH2OCH2CH2CH3Or-CH2CH2CH2OCH3。
4. solid electrolyte as claimed in claim 1, it is characterised in that the nitrile compounds be selected from malononitrile, succinonitrile,
One kind in ethoxy methylene malononitrile, para-Phthalonitrile, isophthalodinitrile, phthalonitrile and 4- fluorine phthalic nitriles.
5. solid electrolyte as claimed in claim 4, it is characterised in that the nitrile compounds are ethoxymeyhylene the third two
Nitrile or succinonitrile.
6. solid electrolyte as claimed in claim 1, it is characterised in that the lithium salts is LiY；Wherein Y-It is BF4 -、PF6 -Or
(CF3SO2)2N-。
7. solid electrolyte as claimed in claim 1, it is characterised in that the ion liquid polymer and the nitrile chemical combination
The mass ratio of thing is 1:0.1~1:2.0.
8. solid electrolyte as claimed in claim 1, it is characterised in that the matter of the ion liquid polymer and the lithium salts
Amount is than being 1:0.1~1:1.0.
9. a kind of dielectric film, it is characterised in that contain the solid electrolyte any one of claim 1~8.
10. the manufacture method of the dielectric film described in claim 9, comprises the following steps：
(1) it is, 1 according to the mass ratio of ion liquid polymer and nitrile compounds:0.1~1:2.0 and ion liquid polymerization
The mass ratio of thing and lithium salts is 1:0.1~1:1.0 ratio is by the ion liquid polymer, the nitrile compounds and institute
State lithium salts dissolving in a solvent, uniform mixing is obtained mixed liquor；
(2), the mixed liquor obtained by step (1) is coated in template, solid electrolyte membrane is obtained.
11. a kind of lithium secondary batteries, it is characterised in that contain the solid electrolyte membrane described in claim 9.
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| CN201510955695.3A CN106898813B (en) | 2015-12-17 | 2015-12-17 | Solid electrolyte, solid electrolyte membrane and manufacturing method thereof, and lithium secondary battery |
| PCT/CN2016/110301 WO2017101849A1 (en) | 2015-12-17 | 2016-12-16 | Solid electrolyte, solid electrolyte membrane and manufacturing method therefor, and secondary battery |
| JP2018531420A JP6876050B2 (en) | 2015-12-17 | 2016-12-16 | Solid electrolyte, solid electrolyte membrane and its manufacturing method, and secondary battery |
| TW105141777A TWI771279B (en) | 2015-12-17 | 2016-12-16 | Solid electrolyte, solid electrolyte membrane, method for producing the same, and secondary battery |
| CN201680073615.4A CN108475819A (en) | 2015-12-17 | 2016-12-16 | Solid electrolyte, solid electrolyte membrane and its manufacturing method and secondary cell |
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| CN108475819A (en) * | 2015-12-17 | 2018-08-31 | 上海交通大学 | Solid electrolyte, solid electrolyte membrane and its manufacturing method and secondary cell |
| CN108807010A (en) * | 2018-08-28 | 2018-11-13 | 深圳清华大学研究院 | Dielectric film preparation method |
| CN109638350A (en) * | 2018-12-18 | 2019-04-16 | 西北工业大学 | The stable succinonitrile base solid electrolyte of a kind of pair of lithium, preparation method and applications |
| CN111446497A (en) * | 2020-04-03 | 2020-07-24 | 上海电气集团股份有限公司 | Solid electrolyte and application thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP7238304B2 (en) * | 2018-09-18 | 2023-03-14 | Tdk株式会社 | lithium secondary battery |
| FR3086806B1 (en) * | 2018-09-28 | 2020-10-23 | Commissariat Energie Atomique | PROCESS FOR PREPARING A GELIFIED ELECTROLYTE |
| CN110783624A (en) * | 2019-09-26 | 2020-02-11 | 湖南工业大学 | Preparation method of ionic gel-based composite solid electrolyte with high ionic conductivity |
| JP7124814B2 (en) * | 2019-10-28 | 2022-08-24 | トヨタ自動車株式会社 | Slurry, all-solid-state battery, and method for manufacturing all-solid-state battery |
| JPWO2022118443A1 (en) * | 2020-12-03 | 2022-06-09 | ||
| TWI751945B (en) * | 2021-04-23 | 2022-01-01 | 國立臺灣大學 | An electrolyte and its application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045806A (en) * | 2007-04-18 | 2007-10-03 | 北京科技大学 | Compound polymer electrolytic material and preparation method thereof |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3407363B2 (en) * | 1993-10-21 | 2003-05-19 | ソニー株式会社 | Polymer solid electrolyte |
| JP4318324B2 (en) * | 1996-07-17 | 2009-08-19 | 四国化成工業株式会社 | Method for preparing molten salt polymer for molten salt type polymer electrolyte and molten salt type polymer electrolyte |
| JPH10265674A (en) * | 1997-03-25 | 1998-10-06 | Mitsubishi Chem Corp | Polymer compound composite material and its production |
| US8168333B2 (en) * | 2005-07-29 | 2012-05-01 | National Research Council Of Canada | Plastic crystal electrolyte for lithium batteries |
| JP5067728B2 (en) * | 2006-03-15 | 2012-11-07 | 独立行政法人国立高等専門学校機構 | Polymer electrolyte and method for producing the same |
| JP5093656B2 (en) * | 2007-09-03 | 2012-12-12 | 国立大学法人京都大学 | Polymer solid electrolyte using ionic liquid polymer composite fine particles |
| CN101409368B (en) * | 2008-12-05 | 2010-12-01 | 北京理工大学 | Lithium secondary battery employing ion liquid type solid polymer electrolyte |
| JP2011119053A (en) * | 2009-12-01 | 2011-06-16 | Konica Minolta Holdings Inc | Electrolyte composition, and secondary battery using the same |
| CN101735542B (en) * | 2009-12-14 | 2012-09-05 | 上海交通大学 | Diblock guanidinium ionic liquid polymer electrolyte and preparation method thereof |
| KR20120000734A (en) * | 2010-06-28 | 2012-01-04 | 동우 화인켐 주식회사 | Photocurable gel polymer electrolyte composition |
| CN104031193A (en) * | 2013-03-08 | 2014-09-10 | 华中科技大学 | Polymer ion liquid electrolyte and preparation method thereof |
| CN104466240A (en) * | 2013-09-22 | 2015-03-25 | 中国科学院大学 | Ionic liquid polymer electrolyte and preparation method thereof |
| KR102163733B1 (en) * | 2013-11-29 | 2020-10-12 | 삼성전자주식회사 | Polymer electrolyte for lithium battery and lithium battery employing the same |
| CN104681865B (en) * | 2015-01-23 | 2017-07-11 | 清华大学深圳研究生院 | A kind of full solid state polymer electrolyte and its application in the battery |
| CN106898813B (en) * | 2015-12-17 | 2020-07-31 | 上海交通大学 | Solid electrolyte, solid electrolyte membrane and manufacturing method thereof, and lithium secondary battery |
-
2015
- 2015-12-17 CN CN201510955695.3A patent/CN106898813B/en active Active
-
2016
- 2016-12-16 CN CN201680073615.4A patent/CN108475819A/en active Pending
- 2016-12-16 WO PCT/CN2016/110301 patent/WO2017101849A1/en active Application Filing
- 2016-12-16 JP JP2018531420A patent/JP6876050B2/en active Active
- 2016-12-16 TW TW105141777A patent/TWI771279B/en not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045806A (en) * | 2007-04-18 | 2007-10-03 | 北京科技大学 | Compound polymer electrolytic material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| G.B. APPETECCHIA: ""Ternary polymer electrolytes containing pyrrolidinium-based polymeric ionic liquids for lithium batteries"", 《JOURNAL OF POWER SOURCES》 * |
| KUN YIN: ""An imidazolium-based polymerized ionic liquid via novel synthetic strategy as polymer electrolytes for lithium ion batteries"", 《JOURNAL OF POWER SOURCES》 * |
| 何晓燕: ""聚离子液体的合成及应用"", 《高分子通报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108475819A (en) * | 2015-12-17 | 2018-08-31 | 上海交通大学 | Solid electrolyte, solid electrolyte membrane and its manufacturing method and secondary cell |
| CN108807010A (en) * | 2018-08-28 | 2018-11-13 | 深圳清华大学研究院 | Dielectric film preparation method |
| CN109638350A (en) * | 2018-12-18 | 2019-04-16 | 西北工业大学 | The stable succinonitrile base solid electrolyte of a kind of pair of lithium, preparation method and applications |
| CN111446497A (en) * | 2020-04-03 | 2020-07-24 | 上海电气集团股份有限公司 | Solid electrolyte and application thereof |
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| JP2018537831A (en) | 2018-12-20 |
| WO2017101849A1 (en) | 2017-06-22 |
| TW201724632A (en) | 2017-07-01 |
| JP6876050B2 (en) | 2021-05-26 |
| CN108475819A (en) | 2018-08-31 |
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