CN109411810A - Fluorescent polyurethane-based solid electrolyte, electrolyte membrane thereof and lithium battery - Google Patents
Fluorescent polyurethane-based solid electrolyte, electrolyte membrane thereof and lithium battery Download PDFInfo
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- CN109411810A CN109411810A CN201811397859.5A CN201811397859A CN109411810A CN 109411810 A CN109411810 A CN 109411810A CN 201811397859 A CN201811397859 A CN 201811397859A CN 109411810 A CN109411810 A CN 109411810A
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- fluorescent
- type polyurethane
- solid electrolyte
- fluorescent type
- fluorescence
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 93
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 93
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 59
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 17
- 239000003792 electrolyte Substances 0.000 title abstract description 11
- 239000012528 membrane Substances 0.000 title abstract description 6
- 238000005266 casting Methods 0.000 claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 16
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 53
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- 239000004417 polycarbonate Substances 0.000 claims description 21
- 229920000515 polycarbonate Polymers 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 13
- 150000002009 diols Chemical class 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 239000004970 Chain extender Substances 0.000 claims description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229940051250 hexylene glycol Drugs 0.000 claims description 8
- SVTBMSDMJJWYQN-UHFFFAOYSA-N hexylene glycol Natural products CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 125000005442 diisocyanate group Chemical group 0.000 claims description 6
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 6
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 6
- 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 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 150000003384 small molecules Chemical class 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 210000000170 cell membrane Anatomy 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical group CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 238000012546 transfer Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 5
- OURRXQUGYQRVML-AREMUKBSSA-N [4-[(2s)-3-amino-1-(isoquinolin-6-ylamino)-1-oxopropan-2-yl]phenyl]methyl 2,4-dimethylbenzoate Chemical compound CC1=CC(C)=CC=C1C(=O)OCC1=CC=C([C@@H](CN)C(=O)NC=2C=C3C=CN=CC3=CC=2)C=C1 OURRXQUGYQRVML-AREMUKBSSA-N 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 235000016804 zinc Nutrition 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229920001109 fluorescent polymer Polymers 0.000 description 1
- -1 hexa-methylene diisocyanate Ester Chemical class 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明提出一种荧光型聚氨酯基固态电解质及其电解质膜和锂电池，所述固态电解质按重量百分比包括荧光型聚氨酯20‑95％和锂盐5‑80％。其电解质膜的制备方法包括：将荧光型聚氨酯和锂盐溶解于溶剂中得到铸膜液，将所述铸膜液成膜即得所述电解质膜。本发明所述电解质采用荧光型聚氨酯作为基体，赋予固态电解质高的离子电导率和强的荧光性，不仅可以进行荧光识别和检测，而且用于可发光电子器件的制备。
The present invention provides a fluorescent polyurethane-based solid electrolyte, an electrolyte membrane thereof, and a lithium battery. The solid electrolyte includes 20-95% of fluorescent polyurethane and 5-80% of lithium salt by weight. The preparation method of the electrolyte membrane includes: dissolving fluorescent polyurethane and lithium salt in a solvent to obtain a casting solution, and forming a membrane from the casting solution to obtain the electrolyte membrane. The electrolyte of the invention adopts fluorescent polyurethane as the matrix, which endows the solid electrolyte with high ionic conductivity and strong fluorescence, which can not only perform fluorescence identification and detection, but also be used for the preparation of light-emitting electronic devices.
Description
Technical field
The present invention relates to technical field of lithium batteries more particularly to a kind of fluorescent type polyurethane solid electrolyte and its electrolysis
Plasma membrane and lithium battery.
Background technique
Lithium ion battery has many advantages, such as energy density high, long service life and memory-less effect, be widely used in mobile phone,
In the electronic equipments such as computer, digital camera, unmanned plane, robot and motion bracelet.In addition, lithium ion battery is in new-energy automobile
Field is also well used as main energy storage device.However the preparation of current lithium ion battery mainly uses liquid
Organic bath, there are volatile, easy firing, the easily security risks such as leakage and explosive, restrict the development of lithium ion battery.For
The safety problem of lithium ion battery is solved, people prepare all-solid lithium-ion battery using solid polymer electrolyte, avoid
Liquid electrolyte bring safety problem.And polyurethane is because having unique Soft hard segment structure, hard section can mention for electrolyte
For mechanical performance, soft segment can be chosen as the matrix of polymer dielectric with conducting lithium ions.Fluorescent polymer materials are because of it simultaneously
Good optical property, is widely used in production and living.
Fluorescence type polyurethane mostly uses two kinds of preparation methods, and one is directly polyurethane is blended with fluorescent powder, China is specially
Sharp CN106634527A reports a kind of bi-component no-solvent polyurethane fluorescent paint and preparation method thereof and application method, by first
(polyalcohol, thickener, disappears at fluorescent powder component (solventfree resin, fluorescent powder, thickener, defoaming agent and levelling agent) with second component
Infusion and levelling agent) it is mixed according to certain mass ratio, the fluorescence that the fluorescence polyurethane of this method preparation being directly blended issues
Dispersion is uneven, and unstable, and fluorescent material content is too high, relatively high to environment and cost requirement.Another kind is by polyurethane
It is copolymerized with fluorescent monomer, it is aqueous poly- that Chinese patent CN103254396A reports a kind of fluorescent type based on chromophore in dihydric alcohol
Fluorescent dihydric alcohol is reacted to obtain by urethane and preparation method thereof directly as reactant with isocyanates, macromolecular polyol
The fluorescent type aqueous polyurethane molecular weight of the fluorescence polyurethane of copolymerization, this method preparation is lower, is not directed in lithium cell electrolyte
In application.Chinese patent CN201510606971 reports a kind of composite modified aqueous polyurethane solid electrolyte of kaolin,
Kaolin hydrophilic modifying is added in aqueous polyurethane emulsion, then the solid electrolyte prepared with lithium perchlorate doping, it should
The electrolyte of method preparation does not have fluorescence property.Chinese patent CN104779415A report a kind of lithium battery solid electrolyte and
The polymer that silane coupling agent and polyethylene glycol crosslinked react is mixed the solid state electrolysis formed with lithium salts by solid lithium battery
Matter, the solid electrolyte do not have fluorescence property.Traditional polyurethane solid electrolyte mainly uses polyethylene glycol or poly- third
Glycol is prepared as primary raw material, that there is also conductivity is low for the polyurethane of this kind of polyether-type, to lithium from solvability it is limited etc.
Disadvantage, polycarbonate glycol is stronger to the solvability of lithium salts due to higher dielectric constant, but at present by poly- carbonic acid
Report of the polyurethane of ester preparation for solid electrolyte is less.
Summary of the invention
Technical problems based on background technology, the present invention propose a kind of fluorescent type polyurethane solid electrolyte and its
Furthermore the preparation method of dielectric film and dielectric film also proposed the lithium battery using the dielectric film.The electrolyte is adopted
It uses fluorescence type polyurethane as matrix, assigns the high ionic conductivity of solid electrolyte and strong fluorescence, can not only carry out
Fluorescence identifying and detection, and for can light-emitting electronic devices preparation.
A kind of fluorescent type polyurethane solid electrolyte proposed by the present invention, the solid electrolyte wrap by weight percentage
Include fluorescence type polyurethane 20-95% and lithium salts 5-80%.
Preferably, synthesize includes Fluorescent dihydric alcohol, the fluorescent type in the chain extender raw material of the fluorescence type polyurethane
The structural formula of dihydric alcohol are as follows:
Preferably, synthesize includes polycarbonate glycol, the poly- carbon in the polyol starting material of the fluorescence type polyurethane
Acid esters dihydric alcohol is preferably 1,5-PD and 1, the copolymer of polycarbonate diol of 6- hexylene glycol, it is preferable that its molecular weight is
1000-3000。
1,5-PD and 1,6- hexylene glycol copolymer of polycarbonate diol can be used that well known to a person skilled in the art one
As method be prepared, directly commercially, such as 1,5-PD and 1 can also be may be selected to be, the poly- carbon of 6- hexylene glycol
Acid esters diol copolymer CROMOGENIA PC21 or 1,5-PD and 1,6- hexylene glycol copolymer of polycarbonate diol
CROMOGENIA PC22。
Preferably, the method for synthesizing the fluorescence type polyurethane includes: to mix diisocyanate, polycarbonate glycol
Uniformly, it is stirred to react 3-4h after being warming up to 80-100 DEG C, then common small molecule dihydric alcohol chain extension is added after being cooled to 60-70 DEG C
Agent, Fluorescent dihydric alcohol and catalyst are stirred to react 1-2h at 60-80 DEG C, then cure 10-24h at 110-120 DEG C, obtain
To the fluorescence type polyurethane；Preferably, the diisocyanate is isophorone diisocyanate, hexa-methylene diisocyanate
Ester, toluene di-isocyanate(TDI), 4,4'- methyl diphenylene diisocyanate, one in 4,4'- dicyclohexyl methyl hydride diisocyanate
Kind is a variety of；Preferably, the common small molecule glycol chain extender is diglycol, in 1,4-butanediol, ethylene glycol
It is one or more；It is highly preferred that the catalyst is stannous octoate, in di-n-butyltin dilaurate, organic zinc, organo-bismuth
It is one or more.
Preferably, it synthesizes in the fluorescence type polyurethane, diisocyanate, polycarbonate glycol, common small molecule two
The molar ratio of first alcohol chain extender, Fluorescent dihydric alcohol and catalyst is 1:1.8-2.2:0.8-1.1:0.01-0.1:0.005-
0.02。
Preferably, the lithium salts is lithium perchlorate, lithium hexafluoro phosphate, LiBF4, double trifluoromethanesulfonimides
One or more of lithium.
The present invention also proposes the method that above-mentioned fluorescent type polyurethane solid electrolyte prepares dielectric film, comprising: will be glimmering
Light type polyurethane and lithium salts, which are dissolved in solvent, obtains casting solution, and the casting solution is formed a film up to the dielectric film.
Preferably, the method for preparing dielectric film includes: that fluorescence type polyurethane and lithium salts are dissolved in acetone, and stirring is equal
It is even to obtain casting solution, the casting solution is cast on polyfluortetraethylene plate, drying and forming-film, obtains the dielectric film.
The invention also proposes the fluorescent type polyurethane solid electrolytes of the above-mentioned method preparation for preparing dielectric film
Film.
Present invention further propose that a kind of solid lithium battery comprising anode pole piece and positive electrode active materials and cathode
Pole piece and negative electrode active material are equipped with above-mentioned fluorescent type polyurethane solid electrolyte between anode pole piece and cathode pole piece
Film.
Compared with prior art, the present invention has the advantage that
(1) fluorescence type polyurethane can be generated with lithium salts in a kind of fluorescent type polyurethane solid electrolyte provided by the invention
The solid electrolyte of fluorescent quenching effect, preparation can be used for fluorescence identifying and detection；
(2) select 4'- in a kind of fluorescent type polyurethane solid electrolyte provided by the invention (to N, N- dihydroxy ethyl)
Anilino- -3,2':6', 3 "-terpyridyl imparts solid electrolyte fluorescence property as fluorescent monomer small molecule chain extender,
It is set to can be used for the preparation of light-emitting electronic devices；
(3) it is soft segment that polycarbonate is selected in a kind of fluorescent type polyurethane solid electrolyte provided by the invention, is being protected
The good mechanical performance of electrolyte is imparted while demonstrate,proving ionic conductivity, the superperformance for fluorescent type lithium ion battery provides
Precondition.
Detailed description of the invention
Fig. 1 is the fluorescence intensity of fluorescent type polyurethane solid electrolyte membrane described in 1-5 of the embodiment of the present invention.
Specific embodiment
Embodiment 1
A kind of fluorescent type polyurethane solid electrolyte, the solid electrolyte include the poly- ammonia of fluorescent type by weight percentage
Ester 95% and double trifluoromethanesulfonimide lithiums 5%；When the fluorescent type polyurethane solid electrolyte is prepared into dielectric film
It include: that fluorescence type polyurethane and double trifluoromethanesulfonimide lithiums are dissolved in acetone by above-mentioned weight percent, machinery stirs
It mixes and uniformly obtains casting solution, the casting solution is cast on polyfluortetraethylene plate, the drying and forming-film in 40 DEG C of convection ovens, i.e.,
Obtain the dielectric film；Wherein, the fluorescence type polyurethane synthesizes by the following method obtains: by 7.8g 4,4'- dicyclohexyl
Methane diisocyanate, the 1,5-PD and 1 that 30g molecular weight is 2000, the copolymer of polycarbonate diol of 6- hexylene glycol
CROMOGENIA PC22 is uniformly mixed, and 4h is stirred to react after being warming up to 80 DEG C, then 1.3g Isosorbide-5-Nitrae-fourth is added after being cooled to 70 DEG C
Glycol, 0.04g 4'- (to N, N- dihydroxy ethyl) anilino- -3,2':6', 3 "-terpyridyl and two drop stannous octoates, at 80 DEG C
Under be stirred to react 1h, transfer in 120 DEG C of baking ovens and cure 4h, obtain the fluorescence type polyurethane.
Embodiment 2
A kind of fluorescent type polyurethane solid electrolyte, the solid electrolyte include the poly- ammonia of fluorescent type by weight percentage
Ester 80% and lithium perchlorate 20%；It include: by above-mentioned when the fluorescent type polyurethane solid electrolyte is prepared into dielectric film
Fluorescence type polyurethane and lithium perchlorate are dissolved in acetone by weight percent, and mechanical stirring uniformly obtains casting solution, will be described
Casting solution is cast on polyfluortetraethylene plate, and drying and forming-film is in 40 DEG C of convection ovens to get the dielectric film；Wherein, institute
It states fluorescence type polyurethane and synthesizes by the following method and obtain: being 2000 by 6.7g isophorone diisocyanate, 30g molecular weight
The copolymer of polycarbonate diol CROMOGENIA PC22 of 1,5-PD and 1,6- hexylene glycol is uniformly mixed, and is warming up to 100 DEG C
After be stirred to react 3h, then common 1.5g diglycol, 0.2g 4'- are added after being cooled to 60 DEG C (to N, N- dihydroxy ethyl)
Anilino- -3,2':6', 3 "-terpyridyl and 2 drop di-n-butyltin dilaurates, are stirred to react 2h at 60 DEG C, transfer to
12h is cured in 120 DEG C of baking ovens, obtains the fluorescence type polyurethane.
Embodiment 3
A kind of fluorescent type polyurethane solid electrolyte, the solid electrolyte include the poly- ammonia of fluorescent type by weight percentage
Ester 60% and double trifluoromethanesulfonimide lithiums 40%；When the fluorescent type polyurethane solid electrolyte is prepared into dielectric film
It include: that fluorescence type polyurethane and double trifluoromethanesulfonimide lithiums are dissolved in acetone by above-mentioned weight percent, machinery stirs
It mixes and uniformly obtains casting solution, the casting solution is cast on polyfluortetraethylene plate, air drying forms a film to get the electrolyte
Film；Wherein, the fluorescence type polyurethane synthesizes by the following method obtains: by 7.8g 4,4'- dicyclohexyl methyl hydride diisocyanate
Ester, the 1,5-PD and 1 that 30g molecular weight is 2000, the copolymer of polycarbonate diol CROMOGENIA PC22 of 6- hexylene glycol
It is uniformly mixed, 3h is stirred to react after being warming up to 100 DEG C, then that 1.3g 1,4-butanediol, 0.2g4'- are added after being cooled to 60 DEG C is (right
N, N- dihydroxy ethyl) anilino- -3,2':6', 3 "-terpyridyl and a drop stannous octoate and a drop tin dilaurate di-n-butyls
Tin is stirred to react 1h at 80 DEG C, transfers in 120 DEG C of baking ovens and cures 4h, obtains the fluorescence type polyurethane.
Embodiment 4
A kind of fluorescent type polyurethane solid electrolyte, the solid electrolyte include the poly- ammonia of fluorescent type by weight percentage
Ester 40% and double trifluoromethanesulfonimide lithiums 60%；When the fluorescent type polyurethane solid electrolyte is prepared into dielectric film
It include: that fluorescence type polyurethane and double trifluoromethanesulfonimide lithiums are dissolved in acetone by above-mentioned weight percent, machinery stirs
It mixes and uniformly obtains casting solution, the casting solution is cast on polyfluortetraethylene plate, the drying and forming-film in 50 DEG C of convection ovens, i.e.,
Obtain the dielectric film；Wherein, the fluorescence type polyurethane synthesizes by the following method obtains: by 15.7g 4, bis- hexamethylene of 4'-
Dicyclohexylmethane diisocyanate, the 1,5-PD and 1 that 30g molecular weight is 1000, the copolymer of polycarbonate diol of 6- hexylene glycol
CROMOGENIA PC21 is uniformly mixed, and 3h is stirred to react after being warming up to 100 DEG C, then 2.6g Isosorbide-5-Nitrae-fourth is added after being cooled to 60 DEG C
Glycol, 0.2g 4'- (to N, N- dihydroxy ethyl) anilino- -3,2':6', 3 "-terpyridyl and two drop organic zincs, at 80 DEG C
It is stirred to react 1h, transfers in 120 DEG C of baking ovens and cures 4h, obtains the fluorescence type polyurethane.
Embodiment 5
A kind of fluorescent type polyurethane solid electrolyte, the solid electrolyte include the poly- ammonia of fluorescent type by weight percentage
Ester 20% and double trifluoromethanesulfonimide lithiums 80%；When the fluorescent type polyurethane solid electrolyte is prepared into dielectric film
It include: that fluorescence type polyurethane and double trifluoromethanesulfonimide lithiums are dissolved in acetone by above-mentioned weight percent, machinery stirs
It mixes and uniformly obtains casting solution, the casting solution is cast on polyfluortetraethylene plate, the drying and forming-film in 40 DEG C of convection ovens, i.e.,
Obtain the dielectric film；Wherein, the fluorescence type polyurethane synthesizes by the following method obtains: by 5.2g 4,4'- dicyclohexyl
Methane diisocyanate, the 1,5-PD and 1 that 30g molecular weight is 3000, the copolymer of polycarbonate diol of 6- hexylene glycol are mixed
It closes uniformly, 3h is stirred to react after being warming up to 100 DEG C, then that 0.9g 1,4-butanediol, 0.4g 4'- are added after being cooled to 60 DEG C is (right
N, N- dihydroxy ethyl) anilino- -3,2':6', 3 "-terpyridyl and two drop organo-bismuths, be stirred to react 1h at 80 DEG C, retransfer
4h is cured into 120 DEG C of baking ovens, obtains the fluorescence type polyurethane.
Embodiment 6
A kind of fluorescent type polyurethane solid electrolyte, the solid electrolyte include the poly- ammonia of fluorescent type by weight percentage
Ester 60% and lithium hexafluoro phosphate 40%；It include: by upper when the fluorescent type polyurethane solid electrolyte is prepared into dielectric film
It states weight percent fluorescence type polyurethane and lithium hexafluoro phosphate are dissolved in acetone, mechanical stirring uniformly obtains casting solution, will
The casting solution is cast on polyfluortetraethylene plate, and drying and forming-film is in 40 DEG C of convection ovens to get the dielectric film；Its
In, the fluorescence type polyurethane synthesizes by the following method to be obtained: being by 5.5g hexamethylene diisocyanate, 30g molecular weight
The copolymer of polycarbonate diol of 2000 1,5-PD and 1,6- hexylene glycol is uniformly mixed, and is stirred to react after being warming up to 90 DEG C
3.5h, then 1.6g diglycol, 0.1g 4'- (to N, N- dihydroxy ethyl) anilino- -3,2' is added after being cooled to 65 DEG C:
6', 3 "-terpyridyl and two drop di-n-butyltin dilaurates, are stirred to react 1.5h at 70 DEG C, transfer to 110 DEG C of baking ovens
Middle curing 10h obtains the fluorescence type polyurethane.
Embodiment 7
A kind of fluorescent type polyurethane solid electrolyte, the solid electrolyte include the poly- ammonia of fluorescent type by weight percentage
Ester 60% and LiBF4 40%；It include: by upper when the fluorescent type polyurethane solid electrolyte is prepared into dielectric film
It states weight percent fluorescence type polyurethane and double trifluoromethanesulfonimide lithiums are dissolved in acetone, mechanical stirring uniformly obtains
Casting solution casts in the casting solution on polyfluortetraethylene plate, and drying and forming-film is in 60 DEG C of convection ovens to get the electrolysis
Plasma membrane；Wherein, the fluorescence type polyurethane synthesizes by the following method obtains: by 4.7g toluene di-isocyanate(TDI), 30g molecular weight
Copolymer of polycarbonate diol for 2000 1,5-PD and 1,6- hexylene glycol is uniformly mixed, and is stirred after being warming up to 80 DEG C anti-
4h is answered, then 1.75g diglycol, 0.3g 4'- (to N, N- dihydroxy ethyl) anilino- -3,2' is added after being cooled to 60 DEG C:
6', 3 "-terpyridyl and a drop stannous octoate, are stirred to react 2h at 70 DEG C, transfer in 110 DEG C of baking ovens and cure 8h, obtain
To the fluorescence type polyurethane.
Embodiment 8
A kind of fluorescent type polyurethane solid electrolyte, the solid electrolyte include the poly- ammonia of fluorescent type by weight percentage
Ester 60%, double trifluoromethanesulfonimide lithiums 20% and lithium perchlorate 20%；By the fluorescent type polyurethane solid electrolyte system
It include: to be dissolved in fluorescence type polyurethane and double trifluoromethanesulfonimide lithiums by above-mentioned weight percent when at dielectric film
In acetone, mechanical stirring uniformly obtains casting solution, and the casting solution is cast on polyfluortetraethylene plate, air drying film forming,
Up to the dielectric film；Wherein, the fluorescence type polyurethane synthesizes by the following method obtains: by 7.5g 4,4'- diphenyl
Methane diisocyanate, the 1,5-PD and 1 that 30g molecular weight is 2000, the copolymer of polycarbonate diol of 6- hexylene glycol
CROMOGENIA PC22 is uniformly mixed, and 3h is stirred to react after being warming up to 100 DEG C, then 1.4g Isosorbide-5-Nitrae-fourth is added after being cooled to 60 DEG C
Glycol, 0.2g 4'- (to N, N- dihydroxy ethyl) anilino- -3,2':6', 3 "-terpyridyl and a drop tin dilaurate di-n-butyls
Tin is stirred to react 1h at 80 DEG C, transfers in 120 DEG C of baking ovens and cures 6h, obtains the fluorescence type polyurethane.
Fluorometric investigation is carried out to the dielectric film that above-described embodiment 1-5 is obtained, test results are shown in figure 1.Fluorescence is surveyed
Examination primary condition uses excitation voltage for 400V, excitation wavelength 345nm, slit width 5nm.From figure 1 it appears that with
The increase of lithium salt content, fluorescence intensity gradually weaken, this illustrates that the complexing of lithium salts and fluorescence causes fluorescence to be quenched, therefore
It can be used for the recognition detection of lithium salts distribution and spread condition in lithium ion solid electrolyte.
Conductivity test is carried out at different temperatures to the dielectric film that the above embodiments 1-5 is obtained.Test method is
AC impedence method measures the AC impedance under different temperatures by electrochemical workstation, frequency range from 100KHz to 0.01Hz,
Disturbance voltage is 10mV；Recycle formula σ=L/ (R × S) that Conductivity Results data are calculated as shown in table 1.Wherein σ be from
Electron conductivity, L are the thickness of dielectric film, and R is the resistance value of dielectric film, and S is contact of the dielectric film with stainless steel electrode
Area.The dielectric film that embodiment 1-5 is obtained it can be seen from 1 data of table has all reached electricity that can be practical at 120 DEG C or less
Conductivity, the preparation of the lithium ion battery for that can shine provide good application prospect.
The ionic conductivity of the dielectric film of 1 embodiment 1-5 of table preparation at different temperatures
Conductivity test equally is carried out it can be found that it is equally 120 to the dielectric film that the above embodiments 6-8 is obtained
DEG C or less all reached can be practical conductivity level.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art within the technical scope of the present invention, according to the technique and scheme of the present invention and its invents
It is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of fluorescent type polyurethane solid electrolyte, which is characterized in that the solid electrolyte includes by weight percentage
Fluorescence type polyurethane 20-95% and lithium salts 5-80%.
2. fluorescent type polyurethane solid electrolyte according to claim 1, which is characterized in that synthesize the poly- ammonia of the fluorescent type
It include Fluorescent dihydric alcohol, the structural formula of the Fluorescent dihydric alcohol in the chain extender raw material of ester are as follows:
3. fluorescent type polyurethane solid electrolyte according to claim 1 or claim 2, which is characterized in that synthesize the fluorescent type
It include polycarbonate glycol in the polyol starting material of polyurethane, the polycarbonate glycol is preferably 1,5-PD and 1,
The copolymer of polycarbonate diol of 6- hexylene glycol, it is preferable that its molecular weight is 1000-3000.
4. fluorescent type polyurethane solid electrolyte according to claim 3, which is characterized in that synthesize the poly- ammonia of the fluorescent type
The method of ester includes: to be uniformly mixed diisocyanate, polycarbonate glycol, is stirred to react 3- after being warming up to 80-100 DEG C
4h, then common small molecule glycol chain extender, Fluorescent dihydric alcohol and catalyst are added after being cooled to 60-70 DEG C, at 60-80 DEG C
Under be stirred to react 1-2h, then cure 4-12h at 110-120 DEG C, obtain the fluorescence type polyurethane；Preferably, described two is different
Cyanate is isophorone diisocyanate, hexamethylene diisocyanate, toluene di-isocyanate(TDI), 4,4'- diphenyl methane
One of diisocyanate, 4,4'- dicyclohexyl methyl hydride diisocyanate are a variety of；Preferably, the common small molecule two
First alcohol chain extender is one of diglycol, 1,4- butanediol or a variety of；It is highly preferred that the catalyst is that octanoic acid is sub-
One of tin, di-n-butyltin dilaurate, organic zinc, organo-bismuth are a variety of.
5. fluorescent type polyurethane solid electrolyte according to claim 4, which is characterized in that synthesize the poly- ammonia of the fluorescent type
In ester, diisocyanate, commonly uses small molecule glycol chain extender, Fluorescent dihydric alcohol and catalyst at polycarbonate glycol
Molar ratio is 1:1.8-2.2:0.8-1.1:0.01-0.1:0.005-0.02.
6. any one of -5 fluorescent type polyurethane solid electrolyte according to claim 1, which is characterized in that the lithium salts
For one or more of lithium perchlorate, lithium hexafluoro phosphate, LiBF4, double trifluoromethanesulfonimide lithiums.
7. the side that a kind of any one of -6 fluorescent type polyurethane solid electrolytes according to claim 1 prepare dielectric film
Method characterized by comprising fluorescence type polyurethane and lithium salts are dissolved in solvent and obtain casting solution, by the casting solution at
Film is up to the dielectric film.
8. preparing the method for dielectric film according to claim 7 characterized by comprising by fluorescence type polyurethane and lithium
Salt is dissolved in acetone, is uniformly mixing to obtain casting solution, the casting solution is cast on polyfluortetraethylene plate, drying and forming-film,
Obtain the dielectric film.
9. a kind of fluorescent type polyurethane solid state electrolysis according to the method preparation for preparing dielectric film of claim 7 or 8
Plasma membrane.
10. a kind of solid lithium battery, including anode pole piece and positive electrode active materials and cathode pole piece and negative electrode active material,
It is characterized in that, being equipped with fluorescent type polyurethane solid electrolyte described in claim 9 between anode pole piece and cathode pole piece
Film.
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