CN107154512B - A kind of polymer dielectric and its preparation and application with self-healing function - Google Patents
A kind of polymer dielectric and its preparation and application with self-healing function Download PDFInfo
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- CN107154512B CN107154512B CN201710311578.2A CN201710311578A CN107154512B CN 107154512 B CN107154512 B CN 107154512B CN 201710311578 A CN201710311578 A CN 201710311578A CN 107154512 B CN107154512 B CN 107154512B
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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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- 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
Abstract
The invention discloses a kind of polymer dielectric with self-healing function and its preparation and application, wherein it is block copolymer that this, which has the polymer dielectric of self-healing function, and chemical structural formula is as follows.The present invention is improved by structure to polymer dielectric key and composition etc., and uses corresponding preparation method, can effectively solve the problem that polymer dielectric is easy to produce crackle, causes the problem of battery short circuit compared with prior art.Wherein (5~20) x:y=: 100, n=3~20.
Description
Technical field
The invention belongs to lithium ion battery electrolyte materials field, more particularly, to a kind of with self-healing function
Polymer dielectric and its preparation and application, the polymer dielectric are the block copolymers of kind of the UPy of structure containing Quadrupolar hydrogen bond,
It is total to that is, Quadrupolar hydrogen bond structure UPy-MA, Poly (PEG-MA) presoma polymerize the block to be formed through reversible addion-fragmentation chain transfer
Polymer electrolyte matter.
Background technique
Electrolyte in lithium ion battery is an important factor for influencing performance of lithium ion battery as a kind of critical material.Mesh
Preceding lithium battery is widely applied still based on liquid electrolyte, but liquid electrolyte is because containing a large amount of inflammable and explosive, volatile
Organic solvent proposes stern challenge to the security performance of lithium ion battery.Solid lithium ion electrolyte phase is for liquid electricity
The good security performance of Xie Zhiyou, especially polymer dielectric can be rationally designed according to different performance requirements,
So as to assign electrolyte multiple functions.Relative to liquid electrolyte, polymer dielectric also has preferable mechanical performance.With
Upper advantage makes developing direction of the polymer dielectric as electrolyte.
Although polymer dielectric has many advantages, toughness is poor, is easily broken during the work time, so as to
Battery short circuit can be caused and generate safety accident.Have if it can design a kind of polymer dielectric with self-healing function
It hopes and solves this problem.After crackle occurs, self-healing function that material assigns can be spontaneously by crack forming mechanism, thus can be with
Effectively avoid the safety problem generated by battery short circuit.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the purpose of the present invention is to provide one kind to have self-healing function
Can polymer dielectric and its preparation and application, wherein passing through the progress such as structure to the polymer dielectric key and composition
Improve, and use corresponding preparation method, can effectively solve the problem that compared with prior art polymer dielectric be easy to produce crackle,
The problem of causing battery short circuit, the present invention are by Quadrupolar hydrogen bond structure UPy-MA, polyethylene glycol monomethyl ethermethacrylic acid esters
PEG-MA polymerize to form UPy-MA-Poly (PEG-MA) block copolymer by reversible addion-fragmentation chain transfer, and the polymer
The UPy-MA of the structure containing Quadrupolar hydrogen bond can form two molecule dimers in structure, to realize self-healing.In addition, the present invention passes through
The overall flow technique for controlling the polymer dielectric preparation method (including the reactant species in each reaction step and is matched
Than, reaction temperature and reaction time etc.), accordingly make the polymer dielectric meet specified chemical structure, is applied to lithium ion
When battery, there is good conductivity and mechanical performance, after polymer occurs crackle or is crushed, can be repaired automatically,
To solve the safety problem that polymer dielectric occurs by crackle short circuit, and improve the service life of lithium battery.
To achieve the above object, according to one aspect of the present invention, a kind of polymer with self-healing function is provided
Electrolyte, which is characterized in that the polymer dielectric is block copolymer, and chemical structural formula is as follows:
It is wherein preferred, x:y=(5~20): 100, n=3~20.
As present invention further optimization, the polymer dielectric is mainly by Quadrupolar hydrogen bond structure UPy-MA and poly-
The block copolymer that glycol monoethyl ether methacrylate PEG-MA reacts, wherein
The molecular structure of the Quadrupolar hydrogen bond structure UPy-MA is as follows:
Preferably, the molecular structure of the polyethylene glycol monomethyl ethermethacrylic acid esters PEG-MA is as follows:
The relative molecular mass of the polyethylene glycol monomethyl ethermethacrylic acid esters PEG-MA is 200~1000.
It is another aspect of this invention to provide that the present invention provides a kind of preparations with self-healing function polymer dielectric
Method, which comprises the following steps:
(1) 2- amino-4-hydroxy -6- methylpyrimidine is added in solvent and is dissolved by heating, it is different that methacrylic acid is then added
Cyanaoethyl methacrylate reacts under stirring condition, reaction product through precipitating, filter and obtain Quadrupolar hydrogen bond structure UPy-MA after dry；
(2) by polyethylene glycol monomethyl ethermethacrylic acid esters, initiator, chain transfer agents and solvent by deoxygenation and
After water, heating reaction obtains Poly (PEG-MA) presoma；
(3) by the Quadrupolar hydrogen bond structure Upy-MA that the step (1) the obtains and Poly that the step (2) obtains
(PEG-MA) presoma is mixed together uniformly with initiator and solvent, and after deoxygenation and water, heating reaction obtains UPy-
MA-Poly (PEG-MA) block copolymer；
(4) UPy-MA-Poly (PEG-MA) that the step (3) obtains is dissolved in organic solvent, lithium salts is added and stirs
After mixing uniformly, casting film is dried to obtain the polymer dielectric with self-healing function.
As present invention further optimization, in the step (1),
The molecular structure of the 2- amino-4-hydroxy -6- methylpyrimidine are as follows:
The molecular structure of the isocyanatoethyl are as follows:
The molecular structure of the Quadrupolar hydrogen bond structure UPy-MA are as follows:
The reaction temperature of the reaction is 80~180 DEG C, and the reaction time is 3~30 minutes.
As present invention further optimization, in the step (2),
The molecular structure of the polyethylene glycol monomethyl ethermethacrylic acid esters are as follows:
The relative molecular mass of the polyethylene glycol monomethyl ethermethacrylic acid esters is 200~1000；
The molecular structure of Poly (PEG-MA) presoma are as follows:
The initiator is that oil-soluble radical closes initiator, and the amount of the initiator is poly glycol monomethyl ether methyl
0.1~1mol% of acrylate；The chain-transferring agent is two thio naphthoic acid isobutyronitrile esters, two thio phenyl first of 4- cyanopentanoic acid
Acid, any one in 2- (dodecyl trithiocarbonic acid ester group) -2- isobutyric acid, the amount of the chain-transferring agent is polyethylene glycol
0.2~5mol% of monomethyl ether metacrylic acid ester.
As present invention further optimization, in the step (2), the reaction temperature of the reaction is 50~100 DEG C, institute
Stating the reaction time is 10~30 hours；
The solvent is tetrahydrofuran, N,N-dimethylformamide, any one in acetonitrile.
As present invention further optimization, in the step (3), UPy-MA-Poly (PEG-MA) block copolymerization
The molecular structure of object are as follows:
The initiator is that oil-soluble radical closes initiator；The amount of the initiator is before the Poly (PEG-MA)
Drive 1~10mol% of body；The amount of the Quadrupolar hydrogen bond structure UPy-MA is corresponding with the Poly (PEG-MA) presoma
5~30mol% of polyethylene glycol monomethyl ethermethacrylic acid esters.
As present invention further optimization, in the step (3), the reaction temperature of the reaction is 50~100 DEG C, institute
Stating the reaction time is 10~30 hours；The solvent is tetrahydrofuran, N,N-dimethylformamide, any one in acetonitrile.
As present invention further optimization, the step (4) lithium salts is lithium perchlorate, LiBF4, hexafluoro
The one or more of lithium phosphate, bis trifluoromethyl sulfimide lithium；The organic solvent is tetrahydrofuran, acetonitrile, N, N- diformazan
Any one in base formamide, dimethyl sulfoxide；The molar ratio of ethyoxyl is 1:5~1:20 in the lithium salts and polymer；
The polymer dielectric with self-healing function is film, and the thickness of the film is preferably 50~300 microns.
Another aspect according to the invention, the present invention provides the above-mentioned polymer dielectrics with self-healing function in lithium
The application of ion battery.
Contemplated above technical scheme through the invention, compared with prior art, due to by by Quadrupolar hydrogen bond structure
For the block copolymer of UPy-MA and polyethylene glycol monomethyl ethermethacrylic acid esters PEG-MA composition as polymer dielectric, this is poly-
UPy-MA structure can assign the self-healing performance of electrolyte in polymer electrolyte, and PEG-MA structure then assigns electrolyte and leads lithium ion
Function, this 2 kinds of functions play a role simultaneously i.e. so that the polymer dielectric have self-repair function.The present invention has self-healing
Functional polymer electrolyte phase is closed for conventional polymer electrolyte, can effectively overcome traditional electrolyte matter property more crisp, tough
Property poor disadvantage, to can avoid leading to safety accident caused by battery short circuit because electrolyte is broken.It is provided by the invention
Electrolyte can be realized self-regeneration, while electrolyte lithium ion conductance with higher when crackle occurs or destroys
Rate.
In general, designed above technical scheme can achieve the following beneficial effects through the invention:
(1) present invention uses RAFT method (that is, reversible addion-fragmentation chain transfer polymerization) by Quadrupolar hydrogen bond structure Upy-MA
Block copolymer is formed with Poly (PEG-MA) forerunner's precursor reactant.At present with Quadrupolar hydrogen bond structure UPy-MA and polyethyleneglycol first
The block copolymer that ether metacrylic acid ester is formed is used as, and there is self-healing function polymer dielectric not yet to appear in the newspapers.Two points
The characteristics of sub- Upy can form dimer, form this reversible hydrogen bond by Quadrupolar hydrogen bond imparts UPy structure with self-healing
Function.After crackle occurs for polymer, the association that reversible Quadrupolar hydrogen bond is formed by means of UPy-MA can be by crack healing.
(2) provided by the invention to have self-healing function polymer dielectric in lithium battery polymer dielectric use process
Middle generation crackle or it is broken after can healed cracks or breakage, can effectively avoid the safety problem caused by short circuit.
(3) its self-healing principle of self-healing function polymer dielectric that has of the invention is to contain quadruple in polymer architecture
The UPy-MA of hydrogen bond structure can form two molecule dimers, the molecular structure of dimer are as follows:
(4) present invention prepares the chemical synthesis formula of Quadrupolar hydrogen bond structure UPy-MA monomer are as follows:
(5) present invention prepares the chemical synthesis formula of UPy-MA-Poly (PEG-MA) block copolymer are as follows:
(6) method for preparing polymer electrolytes of the present invention, reaction condition is mild, and operating method is relatively simple,
High conversion rate, and can be by selecting the PEG-MA of different molecular weight to regulate and control the conductivity and mechanical performance of polymer.
The present invention passes through the overall flow technique for controlling the polymer dielectric preparation method, each anti-particularly by controlling
Reactant species and proportion in step, reaction temperature and reaction time etc. are answered, meet the polymer dielectric special
Determine chemical structure, when being applied to lithium ion battery, after polymer occurs crackle or is crushed, can be repaired automatically, thus
The safety problem that polymer dielectric occurs by crackle short circuit is solved, and improves the service life of lithium battery.
Detailed description of the invention
Fig. 1 is the nmr spectrum of the Quadrupolar hydrogen bond structure UPy-MA prepared in the embodiment of the present invention 1, and abscissa is to change
Displacement study；
Fig. 2 is the infrared spectrogram of UPy-MA-Poly (PEG-MA) block copolymer prepared in the embodiment of the present invention 1,
Abscissa is wave number (cm-1)；
Fig. 3 is that the conductivity of the polymer dielectric prepared in the embodiment of the present invention 1 varies with temperature figure；
Fig. 4 is the self-healing procedure chart after the polymer dielectric film cutting prepared in the embodiment of the present invention 1.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
Self-healing polymer in the present invention is by Quadrupolar hydrogen bond structure UPy-MA, polyethylene glycol monomethyl ethermethacrylic acid esters
PEG-MA polymerize to form UPy-MA, Poly (PEG-MA) block copolymer, molecular structure by reversible addion-fragmentation chain transfer
Are as follows:
Wherein it is preferred to x:y=(5~20): 100, n=3~20.
Correspondingly, this has self-repair function method for preparing polymer electrolytes, may comprise steps of:
1) synthesis of Quadrupolar hydrogen bond structure UPy-MA monomer:
2- amino-4-hydroxy -6- methylpyrimidine is added in solvent and is dissolved by heating, methacrylic acid isocyano group is then added
Ethyl ester reacts under stirring condition, reaction product through precipitating, suction filtration, it is dry after obtain Quadrupolar hydrogen bond structure UPy-MA.
2) synthesis of Poly (PEG-MA) presoma:
By polyethylene glycol monomethyl ethermethacrylic acid esters, initiator, chain transfer agents, solvent after deoxygenation and water, add
Thermal response obtains Poly (PEG-MA) presoma.
3) synthesis of Poly (Upy-MA)-co-Poly (PEG-MA) block copolymer:
It is Poly (PEG-MA) presoma that obtained Quadrupolar hydrogen bond structure Upy-MA and step 2) are obtained, initiator, molten
Agent is uniformly mixed, and after deoxygenation and water, heating reaction obtains UPy-MA-Poly (PEG-MA) block copolymer.
4) preparation of self-healing polymer dielectric:
The UPy-MA-Poly (PEG-MA) that step 3) obtains is dissolved in organic solvent, lithium salts is added after mixing evenly,
Casting film is dried to obtain the polymer dielectric with self-healing function.
The molecular structure of the step 1) 2- amino-4-hydroxy -6- methylpyrimidine are as follows:
The molecular structure of the polyethylene glycol monomethyl ethermethacrylic acid esters are as follows:
The molecular structure of the Quadrupolar hydrogen bond structure UPy-MA are as follows:
The chemical synthesis formula of the Quadrupolar hydrogen bond structure UPy-MA are as follows:
Preferably, the step 1) heating temperature is 80~180 DEG C, and the reaction time is 3~30 minutes.
Preferably, the molecular weight of the step 2) polyethylene glycol monomethyl ethermethacrylic acid esters is 200~1000.
Preferably, the step 2) initiator is that oil-soluble radical closes initiator.
Preferably, the amount of the initiator is the 0.1 of PEG-MA monomer (that is, polyethylene glycol monomethyl ethermethacrylic acid esters)
~1mol%；The chain-transferring agent is two thio naphthoic acid isobutyronitrile esters, 4- cyanopentanoic acid dithiobenzoic acid, 2- (dodecane
Base trithiocarbonic acid ester group) any one in -2- isobutyric acid；The amount of the chain-transferring agent is PEG-MA monomer (that is, poly- second two
Alcohol monomethyl ether metacrylic acid ester) 0.2~5mol%.
Preferably, the step 2) reaction temperature is 50~100 DEG C, and the reaction time is 10~30 hours.
Preferably, the step 2) solvent is tetrahydrofuran, n,N-Dimethylformamide, any one in acetonitrile.
Preferably, the step 3) initiator is that oil-soluble radical closes initiator；The amount of the initiator is Poly
(PEG-MA) 1~10mol% of presoma；The amount of the Quadrupolar hydrogen bond structure UPy-MA is poly glycol monomethyl ether metering system
5~30mol% of acid esters.
Preferably, the step 3) reaction temperature is 50~100 DEG C, and the reaction time is 10~30 hours.
Preferably, the step 3) solvent is tetrahydrofuran, n,N-Dimethylformamide, any one in acetonitrile.
Preferably, the step 4) lithium salts is lithium perchlorate, LiBF4, lithium hexafluoro phosphate, bis trifluoromethyl sulphonyl
The one or more of imine lithium；The organic solvent is tetrahydrofuran, in acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide
Any one；
Preferably, the molar ratio of the step 4) lithium salts and ethyoxyl in polymer is 1:5~1:20.
In addition, UPy-MA-Poly (PEG-MA) the block copolymer polymer film being prepared in the present invention, the electrolysis
The thickness of matter film is preferably 50~300 microns.
The following are specific embodiments.
Embodiment 1
By 2.0g 2- amino-4-hydroxy -6- methylpyrimidine addition 30mL tetrahydrofuran be heated to 80 DEG C dissolution, then plus
Enter 2.7g isocyanatoethyl and be water-cooled reaction solution after stirring 3 minutes, white solid precipitating is obtained, through taking out
White solid after filter, vacuum drying is UPy-MA.By 2.0g molecular weight be 200 PEG-MA monomer, 1.6mg AIBN,
5.6mg 4- cyanopentanoic acid dithiobenzoic acid, 4mL acetonitrile through freezing-vacuumize-applying argon gas recycle 3 removal systems in
Water and oxygen, after being heated to 50 DEG C of reactions 10 hours, reaction solution precipitates in n-hexane obtains the Poly (PEG- of design molecular weight
MA) presoma.
140mg Upy-MA, 2.0g Poly (PEG-MA) presoma, 3.2mg AIBN, 4mL acetonitrile are passed through into freezing-pumping
Water and oxygen in vacuum-applying argon gas circulation removal system, after being heated to 50 DEG C of reactions 10 hours, reaction solution precipitates in n-hexane
Obtain Poly (Upy-MA)-co-Poly (PEG-MA).Obtained block copolymer is dissolved in acetonitrile, by second in polymer
Oxygroup/Li molar ratio is that lithium perchlorate is added in 20:1, after stirring 10 hours at room temperature.After mixing evenly, by solution-cast in mould
In tool, first drying at room temperature 8 hours is then 24 hours dry at 70 DEG C.After completely removing the solvent in electrolyte, had
The polymer dielectric of self-healing function, the lithium ion conductivity for measuring dielectric film is 3.4 × 10 at room temperature-5S cm-1。
Embodiment 2
By 2.0g 2- amino-4-hydroxy -6- methylpyrimidine addition 30mL dimethyl sulfoxide be heated to 180 DEG C dissolution, then plus
Enter 2.7g isocyanatoethyl and be water-cooled reaction solution after stirring 30 minutes, white solid precipitating is obtained, through taking out
White solid after filter, vacuum drying is UPy-MA.By 2.0g molecular weight be 300 PEG-MA monomer, 1.6mg AIBN,
The thio naphthoic acid isobutyronitrile ester of 18.6mg bis-, 4mL N,N-dimethylformamide be chilled-vacuumize-applying argon gas recycles 3 times and goes
Except the water and oxygen in system, after being heated to 70 DEG C of reactions 15 hours, reaction solution precipitates in n-hexane obtains design molecular weight
Poly (PEG-MA) presoma.
By 186mg Upy-MA, 2.0g Poly (PEG-MA) presoma, 3.2mg AIBN, 4mLN, dinethylformamide
Chilled-to vacuumize-applying argon gas recycles the water and oxygen in 3 removal systems, and after being heated to 70 DEG C of reactions 15 hours, reaction solution exists
Precipitating obtains Poly (Upy-MA)-co-Poly (PEG-MA) in n-hexane.
Obtained block copolymer is dissolved in acetonitrile, is that 15:1 addition is double by ethyoxyl in polymer/Li molar ratio
Lithium trifluoromethanesulp,onylimide, after stirring 10 hours at room temperature.After mixing evenly, by solution-cast in mold, first room temperature is dry
It is dry 8 hours, then 24 hours dry at 70 DEG C.After completely removing the solvent in electrolyte, obtain that there is self-healing function
Polymer dielectric, the lithium ion conductivity for measuring dielectric film is 3.3 × 10 at room temperature-5S cm-1。
Embodiment 3
By 2.0g 2- amino-4-hydroxy -6- methylpyrimidine addition 30mL dimethyl sulfoxide be heated to 120 DEG C dissolution, then plus
Enter 2.7g isocyanatoethyl, stirring after ten minutes, is water-cooled reaction solution, white solid precipitating is obtained, through taking out
White solid after filter, vacuum drying is UPy-MA.By 2.0g molecular weight be 500 PEG-MA monomer, 32.8mg AIBN,
72.8mg 2- (dodecyl trithiocarbonic acid ester group) -2- isobutyric acid, 4mL N,N-dimethylformamide be chilled-vacuumize -
Applying argon gas recycles the water and oxygen in 3 removal systems, and after being heated to 100 DEG C of reactions 30 hours, reaction solution precipitates in n-hexane
Obtain Poly (PEG-MA) presoma of design molecular weight.
By 336mg Upy-MA, 2.0g Poly (PEG-MA) presoma, 1.2mg AIBN, 4mLN, dinethylformamide
Chilled-to vacuumize-applying argon gas recycles the water and oxygen in 3 removal systems, after being heated to 100 DEG C of reactions 30 hours, reaction solution
Precipitating obtains Poly (Upy-MA)-co-Poly (PEG-MA) in n-hexane.
Obtained block copolymer is dissolved in acetonitrile, is that 10:1 is added six by ethyoxyl in polymer/Li molar ratio
Lithium fluophosphate, after stirring 10 hours at room temperature.After mixing evenly, by solution-cast in mold, first drying at room temperature 8 hours, so
It is 24 hours dry at 70 DEG C afterwards.After completely removing the solvent in electrolyte, the polymer electrolytic with self-healing function is obtained
Matter, the lithium ion conductivity for measuring dielectric film is 3.6 × 10 at room temperature-5S cm-1。
Embodiment 4
By 2.0g 2- amino-4-hydroxy -6- methylpyrimidine addition 30mL dimethyl sulfoxide be heated to 150 DEG C dissolution, then plus
Enter 2.7g isocyanatoethyl, stirring after twenty minutes, is water-cooled reaction solution, white solid precipitating is obtained, through taking out
White solid after filter, vacuum drying is UPy-MA.By 2.0g molecular weight be 950 PEG-MA monomer, 1.7mg AIBN,
11.8mg 4- cyanopentanoic acid dithiobenzoic acid, 4mL N,N-dimethylformamide be chilled-vacuumize-applying argon gas recycles 3 times
Water and oxygen in removal system, after being heated to 80 DEG C of reactions 20 hours, reaction solution precipitates in n-hexane obtains design molecular weight
Poly (PEG-MA) presoma.
By 176mg Upy-MA, 2.0g Poly (PEG-MA) presoma, 0.3mg AIBN, 4mLN, dinethylformamide
Chilled-to vacuumize-applying argon gas recycles the water and oxygen in 3 removal systems, after being heated to 100 DEG C of reactions 30 hours, reaction solution
Precipitating obtains Poly (Upy-MA)-co-Poly (PEG-MA) in n-hexane.
Obtained block copolymer is dissolved in acetonitrile, is that tetrafluoro is added in 8:1 by ethyoxyl in polymer/Li molar ratio
Lithium borate, after stirring 10 hours at room temperature.After mixing evenly, by solution-cast in mold, first drying at room temperature 8 hours, then
It is 24 hours dry at 70 DEG C.After completely removing the solvent in electrolyte, the polymer dielectric with self-healing function is obtained,
The lithium ion conductivity for measuring dielectric film is 3.1 × 10 at room temperature-5S cm-1。
Embodiment 5
2.0g 2- amino-4-hydroxy -6- methylpyrimidine addition 30mL acetonitrile is heated to 100 DEG C of dissolutions, is then added
2.7g isocyanatoethyl is water-cooled reaction solution after stirring 30 minutes, obtains white solid precipitating, filtered,
White solid after vacuum drying is UPy-MA.
By 2.0g molecular weight be 2000 PEG-MA monomer, 0.16mg AIBN, the thio naphthoic acid isobutyronitrile ester of 8.1mg bis-,
4mL tetrahydrofuran is chilled-vacuumize-applying argon gas recycles water and oxygen in 3 removal systems, it is heated to 60 DEG C and reacts 25 hours
Afterwards, reaction solution precipitates in n-hexane obtains Poly (PEG-MA) presoma of design molecular weight.
By 56mg Upy-MA, 2.0g Poly (PEG-MA) presoma, 0.16mg AIBN, 4mL tetrahydrofuran it is chilled-
Vacuumize-applying argon gas recycle 3 removal systems in water and oxygen, be heated to 60 DEG C reaction 25 hours after, reaction solution is in n-hexane
Middle precipitating obtains Poly (Upy-MA)-co-Poly (PEG-MA).
Obtained block copolymer is dissolved in acetonitrile, is that hexafluoro is added in 5:1 by ethyoxyl in polymer/Li molar ratio
Lithium phosphate, after stirring 10 hours at room temperature.After mixing evenly, by solution-cast in mold, first drying at room temperature 8 hours, then
It is 24 hours dry at 70 DEG C.After completely removing the solvent in electrolyte, the polymer dielectric with self-healing function is obtained,
The lithium ion conductivity for measuring dielectric film is 3.7 × 10-5S cm at room temperature-1。
Polymer dielectric in the present invention, since the monomer with Quadrupolar hydrogen bond structure assigns the selfreparing function of polymer
Can, there is good self-healing function；After crackle occurs, since the association of very strong hydrogen bond will make crack healing, from
And self-healing process occurs；Such as can be and stand 2h under the conditions of room temperature (such as 30 DEG C), as shown in figure 4, after self-healing, without bright
Aobvious crackle.
The preparation step and UPy-MA-Poly (PEG-MA) block of Poly (PEG-MA) presoma in the present invention are total
In the preparation step of polymers, used initiator is that oil-soluble radical closes initiator (such as azodiisobutyronitrile, azo
Two different heptonitriles and azo-bis-iso-dimethyl initiator etc.).Due to the polymer dielectric in the present invention can be applied to lithium from
Sub- battery, therefore lithium salts employed in preparation process of the present invention can be for lithium salts used in lithium battery in the prior art (e.g.,
Lithium perchlorate, LiBF4, lithium hexafluoro phosphate, bis trifluoromethyl sulfimide lithium one or more).In addition, of the invention
Its thickness of polymer electrolyte film with self-healing function obtained can be adjusted flexibly according to actual needs.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (7)
1. one kind has self-healing function method for preparing polymer electrolytes, which comprises the following steps:
(1) 2- amino-4-hydroxy -6- methylpyrimidine is added in solvent and is dissolved by heating, methacrylic acid isocyano group is then added
Ethyl ester reacts under stirring condition, reaction product through precipitating, filter and obtain Quadrupolar hydrogen bond structure UPy-MA after dry；
(2) by polyethylene glycol monomethyl ethermethacrylic acid esters, initiator, chain transfer agents and solvent after deoxygenation and water,
Heating reaction obtains Poly (PEG-MA) presoma；
(3) by the Quadrupolar hydrogen bond structure Upy-MA that the step (1) the obtains and Poly (PEG- that the step (2) obtains
MA) presoma is mixed together uniformly with initiator and solvent, and after deoxygenation and water, heating reaction obtains UPy-MA-
Poly (PEG-MA) block copolymer；
(4) UPy-MA-Poly (PEG-MA) that the step (3) obtains is dissolved in organic solvent, it is equal that lithium salts stirring is added
After even, casting film is dried to obtain the polymer dielectric with self-healing function.
2. having self-healing function method for preparing polymer electrolytes as described in claim 1, which is characterized in that the step
(1) in,
The molecular structure of the 2- amino-4-hydroxy -6- methylpyrimidine are as follows:
The molecular structure of the isocyanatoethyl are as follows:
The molecular structure of the Quadrupolar hydrogen bond structure UPy-MA are as follows:
The reaction temperature of the reaction is 80~180 DEG C, and the reaction time is 3~30 minutes.
3. having self-healing function method for preparing polymer electrolytes as described in claim 1, which is characterized in that the step
(2) in,
The molecular structure of the polyethylene glycol monomethyl ethermethacrylic acid esters are as follows:
The relative molecular mass of the polyethylene glycol monomethyl ethermethacrylic acid esters is 200~1000；
The molecular structure of Poly (PEG-MA) presoma are as follows:
The initiator is that oil-soluble radical closes initiator, and the amount of the initiator is poly glycol monomethyl ether metering system
0.1~1mol% of acid esters；The chain-transferring agent be two thio naphthoic acid isobutyronitrile esters, 4- cyanopentanoic acid dithiobenzoic acid,
Any one in 2- (dodecyl trithiocarbonic acid ester group) -2- isobutyric acid, the amount of the chain-transferring agent are polyethyleneglycol
0.2~5mol% of methyl ether methacrylate.
4. having self-healing function method for preparing polymer electrolytes as described in claim 1, which is characterized in that the step
(2) in, the reaction temperature of the reaction is 50~100 DEG C, and the reaction time is 10~30 hours；
The solvent is tetrahydrofuran, N,N-dimethylformamide, any one in acetonitrile.
5. having self-healing function method for preparing polymer electrolytes as described in claim 1, which is characterized in that the step
(3) in, the molecular structure of UPy-MA-Poly (PEG-MA) block copolymer are as follows:
Wherein, (5~20) x:y=: 100, n=3~20；
The initiator is that oil-soluble radical closes initiator；The amount of the initiator is described
1~the 10mol% of Poly (PEG-MA) presoma；The amount of the Quadrupolar hydrogen bond structure UPy-MA be and the Poly
(PEG-MA) 5~30mol% of the corresponding polyethylene glycol monomethyl ethermethacrylic acid esters of presoma.
6. having self-healing function method for preparing polymer electrolytes as described in claim 1, which is characterized in that the step
(3) in, the reaction temperature of the reaction is 50~100 DEG C, and the reaction time is 10~30 hours；The solvent is tetrahydro furan
It mutters, any one in N,N-dimethylformamide, acetonitrile.
7. having self-healing function method for preparing polymer electrolytes as described in claim 1, which is characterized in that the step
(4) in, the lithium salts be lithium perchlorate, LiBF4, lithium hexafluoro phosphate, bis trifluoromethyl sulfimide lithium one kind or several
Kind；The organic solvent is tetrahydrofuran, acetonitrile, N,N-dimethylformamide, any one in dimethyl sulfoxide；The lithium salts
Molar ratio with ethyoxyl in polymer is 1:5~1:20；
The polymer dielectric with self-healing function be film, the film with a thickness of 50~300 microns.
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