CN107658500A - A kind of original position prepares method and the application of flexible lithium ion battery polymer dielectric - Google Patents
A kind of original position prepares method and the application of flexible lithium ion battery polymer dielectric Download PDFInfo
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Abstract
A kind of original position prepares method and the application of flexible lithium ion battery polymer dielectric, and polymer is prepared into polymeric substrates perforated membrane first；Then ion liquid functionalization monomer, not ionic liquids monomer, crosslinking agent, thermal initiator, ionic liquid and lithium salts are stirred and is prepared into water white transparency precursor solution；Polymeric substrates perforated membrane is immersed in precursor solution again, then the polymeric substrates perforated membrane for being soaked with precursor solution 10 ~ 24 h is reacted into inert atmosphere in 60 ~ 80 DEG C, is formed in situ polymer dielectric.Secondary lithium battery of the present invention using gel-type polymer as electrolyte has good chemistry and electrochemical stability, and security performance greatly improves.It is in-situ cross-linked to can be very good to simplify preparation technology, the compatibility of electrolyte and electrode is lifted, interface impedance is reduced, is particularly suitable for that variously-shaped thin battery is made.
Description
Technical field
The invention belongs to technical field of lithium batteries, is related to lithium ion battery electrolyte materials and the electricity using the electrolyte
Pond.
Background technology
Polymer lithium secondary battery has higher than energy, has a safety feature and the advantages that processing characteristics is excellent by people
Extensive concern.Compared with traditional liquid lithium ionic cell, polymer lithium secondary battery removes and maintains high voltage, high specific energy
Measure, have extended cycle life, green and memory-less effect the advantages that outside, while overcome that liquid lithium ion battery is existing to be leaked
The safety issues such as liquid, on fire or even blast.Polymer lithium secondary battery shell can also use aluminum-plastic composite membrane to be used as packaging,
It is more flexible in design.In light weight due to aluminum-plastic composite membrane, polymer lithium secondary battery is significantly super on gravimetric specific energy
Liquid lithium ion battery is crossed.Due to it is above-mentioned notable the advantages of, polymer lithium secondary battery is in future electronic consumer field
Liquid lithium ion battery will progressively be substituted.
Polymer dielectric film is not only the important component of polymer lithium secondary battery, and determines battery performance
One of key factor.In polymer lithium secondary battery, polymer dielectric film requires uniform microcellular structure, high hole
Gap rate, good ionic conductivity and excellent mechanical strength and stable electrode/electrolyte membrane interface property.
At present, the preparation of pore type electrolyte is mostly first to produce polymer film, then by microporous barrier Electolyte-absorptive
Activation, its specific film-forming method have：Natural the tape casting：The slurry for being made into polymer and clang salt etc. is narrow from one with certain speed
The height of seam outflow, control pressure and slit, the certain film of thickness, width is formed, it is coiled after drying；Casting：Make even whole
Glass plate is carrier, wherein the shallow slot of setting area, thickness not etc..Injection slurries are allowed to flow, and then flatly dry.Remove
There are print roll coating method and slit extrusion coated method outside this, wherein print roll coating method is come control accuracy with scraper；And slit
Extrusion coated rule is to use the mould for having special streamline with slit and intracavitary, and slurry is controlled by coating thickness sensor etc.
Flow processed.But the method for this manufacture perforated membrane has complex manufacturing, operation cycle long, high to equipment and environmental requirement
And the shortcomings of substantial amounts of extractant is needed in poration process.Therefore, develop that excellent performance, preparation technology be simple, operability
Strong and green polymer dielectric film has become one of focus of scientific research and technological development.
Liquid electrolyte is mainly filled in polymer matrix inside story by lithium ion battery polymer electrolyte at present, is prepared
Gel type electrolyte mechanical resistance it is bad, while using direct combination method prepare electrolyte liquid content it is few, liquid
Easily leakage, from the assembling procedure very complicated for being prepared into battery of electrolyte.
The content of the invention
It is an object of the invention to propose that a kind of electrospun membrane in situ for preparing supports flexible lithium ion battery polymer electrolysis
The method of matter, and the application in the polymer battery comprising the polymer dielectric is prepared.Overcome existing polymer electrolytic
Matter prepares that time-consuming, process route is complicated, the introducing of the residual containing organic solvent, impurity so that technological process is simplified, required sets
Standby reduction, activity time are shortened, production efficiency improves, while reduces cost, improve the liquid-keeping property of polymer.The technique system
Standby polymer dielectric solidification electrolyte content is very high, this cause electrolytic conductivity high and polymer Li-ion battery it is each
Kind performance is also improved.
A kind of method that original position prepares flexible lithium ion battery polymer dielectric, as follows.
（1）Polymer dissolving is prepared into homogeneous solution in a solvent, the mass fraction of polymer is 10-20%, and high pressure is quiet
It is electrospun to polymeric substrates perforated membrane.
（2）By ion liquid functionalization monomer, not ionic liquids monomer, crosslinking agent, thermal initiator, ionic liquid and lithium
Salt, which stirs, prepares water white transparency precursor solution, and wherein concentration of the lithium salts in ionic liquid is 0.3 ~ 1M, thermal initiator
For 0.5 ~ 5wt% of monomer, not ionic liquids monomer and ion liquid functionalization monomer:Crosslinking agent quality ratio is 5:1, nonionic
Liquid monomer:The mol ratio of ion liquid functionalization monomer is 1:1 ~ 40, preferably 3:7.
（3）Polymeric substrates perforated membrane is immersed in 0.1-2h in precursor solution, then will be soaked with precursor solution
Polymeric substrates perforated membrane reacts 10 ~ 24 h in inert atmosphere in 60 ~ 80 DEG C, monomer occurs freely in the presence of initiator
Base polymerisation, ionic liquid is coated in the hole of segment, is formed in situ polymer dielectric.
Described ion liquid functionalization monomer and ionic liquid are more than one or both of imidazole type.
Described crosslinking agent is the monomer containing two or more double bonds, is glycol diacrylate, polyethylene glycol two
It is more than one or both of methacrylate, ethoxylated trimethylolpropane triacrylate.
Described thermal initiator is azo-initiator and peroxide type initiators, preferably azodiisobutyronitrile and peroxide
Change dibenzoyl.
Described polymeric substrates perforated membrane includes polypropylene（PP）, polyethylene（PE）, polyamide（PA）, polyvinyl chloride
（PVC）, Kynoar（PVDF）, Kynoar hexafluoropropene（PVDF-HFP）Etc. electrospun membrane.
Described polymeric substrate film can be changed by the method that blending and spray are spun to its compatibility, mechanical property etc.
Property.
Described preparation method need not add organic solvent, and contact of the electrode with electrolyte is good.
Application of the present invention in the polymer battery comprising the polymer dielectric is prepared, as follows：
Assembled first in the way of positive pole/polymeric substrates perforated membrane/negative pole, it is more that precursor solution then is injected into polymeric substrates
On pore membrane, treat that precursor solution infiltrates polymeric substrates perforated membrane 0.1-2h, then 60 ~ 80 DEG C of reactions 10 ~ 24 in inert atmosphere
H, polymeric substrates perforated membrane is solidified into gel mould, be assembled into button and soft-package battery.
Advantages of the present invention：Secondary lithium battery using gel-type polymer as electrolyte has well chemical and electric
Chemical stability.Traditional carbonates electrolyte is replaced using ionic liquid simultaneously, security performance greatly improves.Gel-type gathers
The ionic conductivity of polymer electrolyte is higher than total solids electrolyte, is advantageous to the migration of lithium ion, and it is in-situ cross-linked can be with
Simplify preparation technology well, lift the compatibility of electrolyte and electrode, reduce interface impedance, be particularly suitable for being made variously-shaped
Thin battery.
Brief description of the drawings
Fig. 1 is the SEM figures for implementing PVDF-HFP electrospun membranes in 1.
Fig. 2 is the SEM figures for implementing gel-type polymer electrolyte in 1.
Fig. 3 is the SEM figures for implementing PET electrospun membranes in 2.
Fig. 4 is the SEM figures for implementing gel-type polymer electrolyte in 2.
Fig. 5 is the SEM figures for implementing blending electrospun membrane in 3.
Fig. 6 is the SEM figures for implementing gel-type polymer electrolyte in 3.
Fig. 7 is positive electrode and the electrolyte sectional view in situ prepared.
Embodiment
The invention provides a kind of gel-type polymer electrolyte, the gel-type polymer electrolyte contain substrate skeleton and
The ion transmission phase being filled in skeleton, the ion transmission mutually include the polymer and liquid electrolyte that can transmit ion.Institute
Stating polymer is polymerized under certain condition in the presence of initiator by monomer.
Substrate skeleton includes LITHIUM BATTERY barrier film, non-woven fabrics and static spinning membrane, and wherein LITHIUM BATTERY barrier film is selected from polypropylene
（PP）, polyethylene diagrams（PE）And its composite membrane, such as Celgand 2400, Celgard 2325, the barrier films of Celgard 2340；
Non-woven fabrics is selected from PP, PET（PET）, PE, the non-woven fabrics such as cellulose；Static spinning membrane is selected from polyvinylidene fluoride
Alkene (PVDF), PET（PET）, Kynoar-hexafluoropropene（PVDF-HFP）, polystyrene（PS）、
Polyphenylene oxide（PPO）, polyoxyethylene（PEO）, polyacrylonitrile（PAN）, polystyrene and polyimides（PI）Mixing electrostatic spinning
The electrospun membranes such as film.
LITHIUM BATTERY membrane thicknesses are 20-30um, and nonwoven thickness selects 20-30um, and electrostatic spinning film thickness selects 10-
80um.Basilar memebrane is optimized fracture, curling occur when being not only avoided that using static spinning membrane as substrate, moreover it is possible to optimization electrolysis
The ionic conductivity of matter, impedance is reduced, improve the mechanical resistance of battery.
Ion transmission phase in polymer be polymerized by double bond containing monomer, the monomer for can carry out free radical or from
The ionic liquid monomer with unsaturated bond of son polymerization.
Crosslinking agent is the acrylic ester monomer containing two or more double bonds, such as glycol diacrylate, poly- second two
Alcohol dimethylacrylate, ethoxylated trimethylolpropane triacrylate.
The ionic liquid for imidazoles of ionic liquid selection, its structure are：
Wherein R1, R2For alkyl chain, X-For anion, such as tetrafluoroborate（BF4 -）Hexafluoro-phosphate radical（PF6 -）, thiocyanate
（SCN-）With fluorinated amide (CF3CF2SO2)2N-(CF3SO2)2N-.Initiator selects thermal initiator, such as azo-initiator：It is even
Nitrogen bis-isobutyronitrile, ABVN；Peroxide type initiators：Cumyl peroxide, peroxidating two acyl diphenyl peroxide
Formyl.In addition, the lithium salts used in the present invention is LiBF4（LiBF4）, lithium hexafluoro phosphate（LiPF6）, lithium perchlorate
（LiClO4）, hexafluoroarsenate lithium（LiAsF6）, trifluoromethanesulfonic acid lithium（LiCF3SO3）, it is double（Trifyl）Imine lithium（LiN
(SO2CF3)2）, double fluorine Huang imide lis（LiFSI）, tetraphenylboronic acid lithium（LiBOB）, it is double（Five fluorine ethylsulfonyls）Imine lithium
（LiN(SO2C2F5)2）In one or more of mixtures, wherein with anion close with selected ionic liquid and bear from
The larger lithium salts of son has bigger contribution to obtain the more polymer dielectric of high-lithium ion transport number and lithium ion conductivity.
, can be with addition to containing lithium salts and liquid plasticizer among gel-type polymer electrolyte provided by the invention
Add other additives, such as vinylene carbonate（VC）The additive for generating stable SEI films can be promoted to cause positive and negative
The stable SEI films of the Surface Creation of pole, improve ionic liquid and acted on for the gel-type polymer electrolyte of plasticizer with both positive and negative polarity
Cyclical stability, so as to improve the life-span of battery.
Present invention also offers a kind of preparation method of gel-type polymer electrolyte, this method includes：（1）Will polymerization list
Body（Not ionic liquids monomer, ion liquid functionalization monomer, crosslinking agent）Rectification and purification, remove moisture and other impurities；（2）Will
Initiator and porous Electrospun film dry 24h in 40 DEG C of vacuum drying chamber and remove moisture；（3）In inert atmosphere glove box
In；The stirring of ion liquid functionalization monomer, not ionic liquids monomer, crosslinking agent, thermal initiator, ionic liquid and lithium salts is equal
Even to prepare water white transparency precursor solution, wherein concentration of the lithium salts in ionic liquid is 0.3 ~ 1M, and thermal initiator is monomer
0.5 ~ 5wt%, not ionic liquids monomer and ion liquid functionalization monomer:Crosslinking agent quality ratio is 5:1, not ionic liquids monomer:
The mol ratio of ion liquid functionalization monomer is 1:1 ~ 4, preferably 3:7.（5）The basilar memebrane of precursor solution will be impregnated with inertia
Heat cure is molded in atmosphere.
The present invention also provides a kind of gel type polymer batteries, and the battery includes positive pole, negative pole and gel-type polymer electricity
Xie Zhi, battery are assembled into sandwich structure by the order of positive pole/gel-type polymer electrolyte/negative pole, and electrolyte used is
The present invention provides gel-type polymer electrolyte.
The positive pole of polymer battery is formed in the present invention includes plus plate current-collecting body and the electrode being supported on plus plate current-collecting body
Material, described plus plate current-collecting body can be aluminium foil, and the positive active material can be LiFePO4、LiCoO2、LiNiO2、
LiMn2O2And LiAlO2In one or more, content of the positive active material on the plus plate current-collecting body is 80-95%；Institute
Stating negative pole includes negative current collector and is supported on the electrode material of negative current collector, the collector of the negative pole can be copper foil and
Aluminium foil, the negative electrode active material can be lithium metal, lithium alloy, lithium titanate, graphite or carbon fiber, and negative electrode active material is negative
Shared ratio is 80-95% in the material of pole.
Present invention also offers a kind of preparation method of gel type polymer batteries：（1）Using perforated substrate film as Obstruct membrane,
Assembled according to the order of positive pole, perforated membrane, negative pole, make lamination soft-package battery, stay one side mouth not seal.（2）By precursor liquid
It is injected into laminated batteries, makes its complete wetting porous septum, is placed on certain temperature in baking oven and polymerize 6-24h so that be single
Body polymerization is complete, forms water white transparency, the gel with certain viscosity.（3）Battery is dried and encapsulated, folding electricity is made
Pond.
The present invention will be described further by following examples.
Present case is used to illustrate polymer dielectric provided by the invention and preparation method thereof.
Embodiment 1.
（1）The preparation of static spinning membrane.
By PVDF-HFP（MW=4×105g mol-1）Stirring and dissolving is in VAcetone:VN-N dimethylformamides=3:Match somebody with somebody in 1 mixed solution
Put the polymer solution that mass fraction is 15%.Above-mentioned polymer solution is added in 5mL syringe, using syringe pump
Polymer solution is promoted, setting injection rate is 1.2 mLh-1, using device of the high voltage direct current generator as high-voltage electrostatic field,
Cylindrical drum adjusts voltage, voltage is arranged to 18 kV, roller as receiver board according to the concentration of polymer solution and viscosity
Rotating speed is 500 r s-1, the vertical range of roller to needle point is 15 cm.After the completion of spinning, film is placed on 40oC is dried in vacuo
24 h are dried in case and obtain required electrostatic spinning film.
Using SEM（SEM）Morphology analysis is carried out to obtained PVDF-HFP static spinning membranes, SEM schemes such as
Shown in Fig. 1, the static spinning membrane prepared as can be seen from this figure has equally distributed loose structure, and the fibre diameter in film
Uniformly.
（2）The preparation of polymer dielectric.
A, imidazoles of the side chain containing unsaturated double-bond is double（Trifyl）Imines ion liquid monomer（MHBIm-TFSI）
Preparation.
1.5mol is double（Trifyl）Imine lithium is added dropwise to imidazoles of the every mole of side chain containing unsaturated double-bond
Bromine monomer（MHBIm-Br）In be stirred continuously, react 12h at room temperature, there is insoluble liq precipitation, remove upper strata aqueous, it is washing, dry
It is dry, it is double to obtain imidazoles of the side chain containing unsaturated double-bond（Trifyl）Imines ion liquid monomer.
B, by monomer, azodiisobutyronitrile and porous Electrospun film 40o24h is dried in C vacuum drying chamber and removes water
Point, then mentioned component is moved into inert atmosphere glove box together, by ion liquid functionalization monomer, not ionic liquids list
Body, crosslinking agent, thermal initiator, ionic liquid and lithium salts, which stir, prepares water white transparency precursor solution, and wherein lithium salts exists
Concentration in ionic liquid is 0.8M, and thermal initiator is the 2wt% of monomer, not ionic liquids monomer and ion liquid functionalization list
Body:Crosslinking agent quality ratio is 5:1, not ionic liquids monomer:The mol ratio of ion liquid functionalization monomer is 3:7,；Will be dry
Electrospun membrane is immersed in 6h in precursor solution, then under inert gas shielding by the electrospun membrane fully infiltrated 70oC gathers
12h is closed, obtains gel-type polymer electrolyte.
Morphology analysis is carried out to obtained dielectric film using SEM, SEM is schemed as shown in Fig. 2 being electrolysed as can be seen from this figure
Plasma membrane surfaces indistinctly can see the vestige of fiber, but the loose structure of PVDF-HFP electrospun fibers films does not observe
, these holes transmit phase by ion completely fills.
Embodiment 2.
The present embodiment is used to illustrate polymer dielectric provided by the invention and preparation method thereof.
（1）The preparation of static spinning membrane.
By polyethylene terephthalate（PET inherent viscosity= 0.8dl g-1）, stirring and dissolving exists
VTrifluoroacetic acid：V dichloromethane=3:Configuration quality fraction is 10% polymer solution in 2 mixed solution.By above-mentioned polymer solution
It is added in 5 mL syringe, polymer solution is promoted using syringe pump, setting injection rate is 3 mLh-1, using direct current
Device of the high pressure generator as high-voltage electrostatic field, cylindrical drum is as receiver board, according to the concentration and viscosity of polymer solution
Voltage is adjusted, voltage is arranged to 22 kV, and the rotating speed of roller is 500 r s-1, the vertical range of roller to needle point is 15 cm.Spin
After the completion of silk, film is placed on 40o24 h are dried in C vacuum drying chambers and obtain required electrostatic spinning film.
Morphology analysis is carried out to obtained PET static spinning membranes using SEM, SEM is schemed as shown in figure 3, can from the figure
Going out the static spinning membrane of preparation has equally distributed loose structure, and the fibre diameter in film is uniform.
（2）The preparation of polymer dielectric.
A, imidazoles of the side chain containing unsaturated double-bond is double（Trifyl）The preparation of imines ion liquid monomer.
1.5mol is double（Trifyl）Imine lithium is added dropwise to imidazoles of the every mole of side chain containing unsaturated double-bond
It is stirred continuously in bromine monomer, reacts 12h at room temperature, there is insoluble liq precipitation, is removed upper strata aqueous, washing, dry, obtain side chain
Imidazoles containing unsaturated double-bond is double（Trifyl）Imines ion liquid monomer.
B, by monomer（Ion liquid functionalization monomer/PEGDA mass ratioes are 5:1）, azodiisobutyronitrile and porous electrospinning
Silk film is 40o24h is dried in C vacuum drying chamber and removes moisture, mentioned component is then moved into inert atmosphere glove box together
In, ion liquid functionalization monomer, not ionic liquids monomer, PEGDA, thermal initiator, ionic liquid and lithium salts stir
Water white transparency precursor solution is prepared, wherein concentration of the lithium salts in ionic liquid is 0.8M, and thermal initiator is the 2wt% of monomer,
Not ionic liquids monomer:The mol ratio of ion liquid functionalization monomer is 3:7；It is molten that dry electrospun membrane is immersed in presoma
6h in liquid, then 70 under inert gas shieldingoThe electrospun membrane fully infiltrated is polymerize 12h by C, obtains gel-type polymer electricity
Xie Zhi.
Morphology analysis is carried out to obtained dielectric film using SEM, SEM is schemed as shown in figure 4, being electrolysed as can be seen from this figure
Plasma membrane surfaces indistinctly can see the vestige of fiber, but the loose structure of PET electrospun fibers films does not observe, this
Filled completely by ion transmission phase in some holes hole.
Embodiment 3.
The present embodiment is used to illustrate polymer dielectric provided by the invention and preparation method thereof.
（1）The preparation of static spinning membrane.
By PVDF-HFP（MW=4×105g mol-1）Stirring and dissolving is in VAcetone：VN-N dimethylformamides=3:Match somebody with somebody in 1 mixed solution
Put the polymer solution that mass fraction is 16%.By polyethylene glycol methacrylate-styrene polymer/PEGDA in mass ratio 5 of three arm cladodification:1
Dissolving prepares 6wt% uniform solution in acetone.Above-mentioned polymer solution is added separately in two 5mL syringe, protected
Hold two syringe needles and be in parallel position and parallel to roller, PVDF-HFP solution syringe needles are lower slightly, so that ensure can be attached on every silk
Polyethylene glycol methacrylate-styrene polymer/PEGDA of three arm cladodification, polymer solution is promoted using syringe pump, injection speed is set
Rate is 1.2mLh-1, using device of the high voltage direct current generator as high-voltage electrostatic field, cylindrical drum is as receiver board, according to poly-
Concentration and viscosity the regulation voltage of polymer solution, voltage are arranged to 18kV, and the rotating speed of roller is 500r s-1, roller to needle point
Vertical range is 15cm.After the completion of spinning, film is placed on 40oDried in C vacuum drying chambers compound quiet required for 24h is obtained
Electrospun film.
Morphology analysis is carried out to obtained PET static spinning membranes using SEM, SEM is schemed as shown in figure 5, can from the figure
Going out the static spinning membrane of preparation has equally distributed loose structure, and the fibre diameter in film is uniform, the purer PVDF- of diameter
HFP is thick and film is less likely to occur to shrink in use.
（2）The preparation of polymer dielectric.
The preparation of polymer dielectric is consistent with embodiment 1.
Morphology analysis is carried out to obtained dielectric film using SEM, SEM is schemed as shown in fig. 6, being electrolysed as can be seen from this figure
Plasma membrane surfaces indistinctly can see the vestige of fiber, but the loose structure of blending electrospun fibers film does not observe,
These holes are filled by ion transmission phase completely.
Embodiment 4.
The present embodiment is used for the preparation method for illustrating polymer dielectric and battery provided by the invention.
（1）Substrate skeleton uses PVDF-HFP electrostatic spinning films prepared by case study on implementation 1.
（2）The preparation of lithium ion cell positive.
By LiFePO4（80%）, carbon black（10%）And PVDF（10%）And a small amount of NMP mixed grindings are into homogeneous paste slurry,
Take and it is scratched to film forming on aluminium foil with scraper in right amount, dry stand-by in immigration glove box after cutting.
（3）The preparation of polymer battery.
Imidazoles of the side chain in embodiment 1 containing unsaturated bond is double（Trifyl）Imines ion liquid monomer monomer
Rectification and purification is carried out with PEGDA, removes moisture and other impurities；By polymer monomer, azodiisobutyronitrile and porous Electrospun
Film is moved into inert atmosphere glove box together, by ion liquid functionalization monomer：PEGDA mass ratio is 5:1st, ionic liquid
And lithium salts stirs and prepares water white transparency precursor solution, wherein the weight ratio of polymerized monomer and initiator is 101, lithium salts
Concentration is 0.8M, and above material is transferred in the glass container of dried and clean into magnetic agitation into homogeneous precursor liquid；Will
PVDF-HFP electrospun membranes are cut into a diameter of 19mm disk, immerse in precursor solution, are taken out after 6h, spread over sheet
LiFePO4On positive pole, the PVDF-HFP films and the positive plate one that then infiltrate are same as 70 in inert atmosphereoC polymerize 12h, finally with lithium
Piece is negative pole, is assembled into button cell.Contact well, do not see obvious between electrolyte and electrode material prepared by in-situ method
Boundary（Fig. 7）.
Embodiment 5.
The present embodiment is used for the preparation method for illustrating polymer dielectric and battery provided by the invention.
（1）The PVDF-HFP electrostatic spinning films prepared using embodiment 1.
（2）The preparation of battery.
Positive pole：By LiFePO4（80%）, carbon black（10%）And PVDF（10%）And a small amount of NMP mixed grindings are into homogeneous paste
Slurry, take and it is scratched to film forming on aluminium foil with scraper in right amount, dry stand-by in immigration glove box after cutting.
Negative pole：For lithium metal.
（3）The preparation of battery.
Imidazoles of the side chain in embodiment 1 containing unsaturated bond is double（Trifyl）Imines ion liquid monomer monomer
Rectification and purification is carried out with PEGDA, removes moisture and other impurities；By polymer monomer, azodiisobutyronitrile and porous Electrospun
Film is moved into inert atmosphere glove box together, by ion liquid functionalization monomer：PEGDA mass ratioes are 5:1st, ionic liquid with
And lithium salts stirs and prepares water white transparency precursor solution, wherein, the weight ratio of polymerized monomer and initiator is 10:1, lithium salts
Concentration is 0.8M, and above material is transferred in the glass container of dried and clean into magnetic agitation into homogeneous precursor liquid；Will
PVDF-HFP electrospun membranes are cut into the certain rectangle of length and width, and being covered in drop has on the positive plate of precursor solution, then exists
Precursor solution is instilled on perforated membrane, after 6h fully infiltrates, PVDF-HFP films and the positive plate of precursor solution will be infiltrated together
70 in inert atmosphereoC polymerize 12h, makes monomer polymerization complete, forms water white transparency, the gel with certain viscosity, finally with
Lithium piece is negative pole, and Soft Roll flexible battery is packaged into aluminum plastic film.
The chemical property of the lithium ion battery test battery of the based solid electrolyte prepared using the present invention.According to Fig. 1
The assembled battery in inert atmosphere glove box of the structure of shown battery.Polymerized monomer using synthetically prepared imidazoles monomer,
Crosslinking agent uses PEGDA, and initiator is using the dewatered azodiisobutyronitrile purified（AIBN）, ionic liquid use
EMIM-TFSI, porous septum use PVDF-HFP electrospun membranes.
By electrolyte and monomer mole ratio 4:1, monomer is 100 with AIBN weight ratio:1 proportioning by ionic liquid, monomer,
Initiator magnetic agitation in vial is cut into 2cm into uniform precursor solution, electrospun membrane2Disk, before being immersed in
Drive in liquid solution, taken out after sealing from glove box and be placed in polymerizeing 12h in 70 DEG C of baking oven, placed into and group is carried out in glove box
Dress.
Claims (7)
1. a kind of method that original position prepares flexible lithium ion battery polymer dielectric, it is characterized in that as follows：
（1）Polymer dissolving is prepared into homogeneous solution in a solvent, the mass fraction of polymer is 10-20%, and high-pressure electrostatic is spun
Silk is into polymeric substrates perforated membrane；
（2）Ion liquid functionalization monomer, not ionic liquids monomer, crosslinking agent, thermal initiator, ionic liquid and lithium salts are stirred
Mix and uniformly prepare water white transparency precursor solution, wherein concentration of the lithium salts in ionic liquid is 0.3 ~ 1M, and thermal initiator is single
0.5 ~ 5wt% of body, not ionic liquids monomer and ion liquid functionalization monomer:Crosslinking agent quality ratio is 5:1, not ionic liquids
Monomer:The mol ratio of ion liquid functionalization monomer is 1:1 ~ 40, preferably 3:7；
（3）Polymeric substrates perforated membrane is immersed in 0.1-2h in precursor solution, then will be soaked with the polymerization of precursor solution
Thing substrate perforated membrane reacts 10 ~ 24 h in inert atmosphere in 60 ~ 80 DEG C, be formed in situ polymer dielectric.
2. the method that original position according to claim 1 prepares flexible lithium ion battery polymer dielectric, it is characterized in that institute
The ion liquid functionalization monomer and ionic liquid stated are more than one or both of imidazole type.
3. the method that original position according to claim 1 prepares flexible lithium ion battery polymer dielectric, it is characterized in that institute
The crosslinking agent stated is glycol diacrylate, polyethylene glycol dimethacrylate, ethoxylated trimethylolpropane 3 third
It is more than one or both of olefin(e) acid ester.
4. the method that original position according to claim 1 prepares flexible lithium ion battery polymer dielectric, it is characterized in that institute
The thermal initiator stated is azo-initiator or peroxide type initiators.
5. the method that the original position according to claim 1 or 4 prepares flexible lithium ion battery polymer dielectric, it is characterized in that
Described thermal initiator is azodiisobutyronitrile or dibenzoyl peroxide.
6. the method that original position according to claim 1 prepares flexible lithium ion battery polymer dielectric, it is characterized in that institute
The polymeric substrates perforated membrane stated includes polypropylene, polyethylene, polyamide, polyvinyl chloride, Kynoar, Kynoar six
Fluoropropene.
7. a kind of application prepared in the battery comprising polymer dielectric described in claim 1, it is characterized in that first by positive pole/
The mode of polymeric substrates perforated membrane/negative pole assembles, and then precursor solution is injected on polymeric substrates perforated membrane, forerunner
Liquid solution infiltrates complete polymeric substrates perforated membrane 0.1-2h, then reacts 10 ~ 24 h in 60 ~ 80 DEG C in inert atmosphere, makes to gather
Polymer substrates perforated membrane is solidified into gel mould, is assembled into button and soft-package battery.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768349A (en) * | 2010-01-25 | 2010-07-07 | 北京理工大学 | Ionic-liquid-base polymer electrolyte |
| CN104466240A (en) * | 2013-09-22 | 2015-03-25 | 中国科学院大学 | Ionic liquid polymer electrolyte and preparation method thereof |
| CN104638296A (en) * | 2015-01-23 | 2015-05-20 | 清华大学深圳研究生院 | Method for preparing solid polymer electrolyte lithium ion battery |
-
2017
- 2017-08-07 CN CN201710664221.2A patent/CN107658500A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768349A (en) * | 2010-01-25 | 2010-07-07 | 北京理工大学 | Ionic-liquid-base polymer electrolyte |
| CN104466240A (en) * | 2013-09-22 | 2015-03-25 | 中国科学院大学 | Ionic liquid polymer electrolyte and preparation method thereof |
| CN104638296A (en) * | 2015-01-23 | 2015-05-20 | 清华大学深圳研究生院 | Method for preparing solid polymer electrolyte lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| MINGMING QUE, ET AL.: ""Safe and flexible ion gel based composite electrolyte for lithium batteries"", 《J. MATER. CHEM. A》 * |
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