CN109411810A - A kind of fluorescent type polyurethane solid electrolyte and its dielectric film and lithium battery - Google Patents
A kind of fluorescent type polyurethane solid electrolyte and its dielectric film and lithium battery Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
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- Y02E60/10—Energy storage using batteries
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- 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
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Abstract
The present invention proposes a kind of fluorescent type polyurethane solid electrolyte and its dielectric film and lithium battery, the solid electrolyte include fluorescence type polyurethane 20-95% and lithium salts 5-80% by weight percentage.The preparation method of its dielectric film includes: that fluorescence type polyurethane and lithium salts are dissolved in solvent to obtain casting solution, and the casting solution is formed a film up to the dielectric film.Electrolyte of the present invention is used as matrix using fluorescence type polyurethane, assigns the high ionic conductivity of solid electrolyte and strong fluorescence, can not only carry out fluorescence identifying and detection, and be used for can light-emitting electronic devices preparation.
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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| Application Number | Priority Date | Filing Date | Title |
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| CN201811397859.5A CN109411810A (en) | 2018-11-22 | 2018-11-22 | A kind of fluorescent type polyurethane solid electrolyte and its dielectric film and lithium battery |
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| CN111440289A (en) * | 2020-03-27 | 2020-07-24 | 中山大学 | Polyurethane, polyurethane solid electrolyte, and preparation method and application thereof |
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| CN110240689A (en) * | 2019-06-21 | 2019-09-17 | 齐鲁工业大学 | A kind of preparation of selfreparing polyurethane ionic conductor and application |
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