CN103779089A - Gel polymer dielectric and preparation method for the same, super capacitor and application thereof - Google Patents
Gel polymer dielectric and preparation method for the same, super capacitor and application thereof Download PDFInfo
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Abstract
This invention provides poly (partial fluorine ethylene - hexafluoropropylene) gel polymer dielectric and a preparation method for the same, a super capacitor and application thereof. The gel polymer dielectric comprises active fillers, poly-vinylidene-fluoride-hexafluoropropylene, and organic ionic liquid electrolyte, wherein the weight ratio of the active fillers to the poly-vinylidene-fluoride-hexafluoropropylene is 3-20:100. The preparation method comprises steps of preparing slurry materials, preparing gel polymer electrolyte membrane, and preparing gel polymer electrolyte. The super capacitor comprises the gel polymer dielectric. The gel polymer dielectric disclosed by the invention has high mechanical strength, high conductivity, low cost, simple preparation method technology, mature technology, high yield and efficiency, and reduced production cost. The super capacitor containing the gel polymer electrolyte has high yield, low production cost, and excellent electrochemical performance, and expands wide application of the super capacitor.
Description
Technical field
The invention belongs to electrochemical power source technical field, be specifically related to a kind of gel polymer electrolyte and preparation method thereof, ultracapacitor and application thereof.
Background technology
Ultracapacitor is a kind of novel energy device between rechargeable battery and capacitor, have that volume is little, capacity is large, charging rate is fast, have extended cycle life, the advantage such as discharging efficiency is high, operating temperature range is wide, good reliability and contaminant-free maintenance-free, it is a kind of novel, efficient, practical energy accumulating device, thereby be widely used in military field, device for mobile communication, computer, and the AC-battery power source of electric automobile etc.
Ultracapacitor working electrolyte is divided into aqueous electrolyte, organic liquid electrolyte and polymer dielectric.The decomposition voltage of aqueous electrolyte is low, thereby studies less.The advantage of now widely used liquid organic electrolyte is that conductivity is high, but inflammable owing to containing, volatile organic solvent, it discharges fuel gas in charge and discharge process, particularly under some unconventional condition of work, (discharge and recharge as high-power, super-charge super-discharge etc.) produces large calorimetric meeting and accelerates the generation of gas, cause inner pressure of battery to increase, Leakage Gas, blast even on fire, thereby there is serious potential safety hazard.
At present, in order to overcome the above-mentioned defect of organic liquid electrolyte, solid gel polymer dielectric is developed in this area.This solid polymer electrolyte because thering is safety, without leaking, leakage current is little, can arbitrary shape etc. the studied persons of advantage pay attention to and apply.But under solid polymer electrolyte room temperature, conductivity is lower by (10
-5~ 10
-4s/cm), can not meet the characteristic of lithium ion battery high current charge-discharge, cause its application to be restricted.
In order to overcome the defect that solid polymer electrolyte conductivity is low, the current gel polymer electrolyte that occurred, this gel polymer electrolyte has advantages of liquid electrolyte and solid electrolyte, can improve the security performance of electric conductivity and the raising liquid electrolyte of solid polymer electrolyte.But it is that its mechanical strength is low that gel polymer electrolyte exists a major defect, therefore, the industrialization that has restricted this gel polymer electrolyte is produced, and causes the production cost of existing gel polymer electrolyte high.Mainly can improve to a certain extent at present the mechanical strength of polymer dielectric by means such as copolymerization, grafting generation cross-linked copolymer, dopen Nano metal oxides.But effect is not very desirable, battery rate of finished products is not high.In addition, existing gel polymer electrolyte improves limited to electric conductivity, is not well positioned to meet demand and the range of application of market expanding day.
Summary of the invention
The object of the embodiment of the present invention is to overcome the above-mentioned deficiency of prior art, and gel polymer electrolyte that a kind of mechanical strength and conductance are high, cost is low and preparation method thereof is provided.
Another object of the embodiment of the present invention is to provide a kind of ultracapacitor and application thereof that comprises gel polymer electrolyte.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A kind of gel polymer electrolyte, contains active filler, poly-(vinylidene fluoride-hexafluoropropylene), organic ion liquid electrolyte; Wherein, the ratio of active filler and poly-(vinylidene fluoride-hexafluoropropylene) weight is 3 ~ 20:100.
And a kind of preparation method of above-mentioned gel polymer electrolyte, comprises the steps:
To gather (vinylidene fluoride-hexafluoropropylene) and be dissolved in organic solvent, then add active filler according to the ratio of active filler and poly-(vinylidene fluoride-hexafluoropropylene) weight, at 30 ~ 50 ℃, be uniformly mixed, obtain slurry;
Described slurry is coated in substrate, and vacuumize, obtains gel polymer electrolyte film;
Under the protection of dry inert gas, it is that the organic ion liquid electrolyte of 0.5～1.5mol/L is flooded 10～60min that described gel polymer electrolyte film is placed in to concentration, takes out and obtains described gel polymer electrolyte.
And, a kind of ultracapacitor, described ultracapacitor comprises above-mentioned gel polymer electrolyte.
And, the application of above-mentioned ultracapacitor in communication apparatus, computer, electric automobile and military field.
It is substrate that above-mentioned method for preparing gel polymer electrolyte adopts P (VDF-HFP) polymer, and in this substrate dispersed activity filler, effectively strengthen this gel polymer electrolyte film conductivity, improved the mechanical strength of this gel polymer electrolyte film and the ability of absorbed electrolyte simultaneously.After gel polymer electrolyte film is soaked in electrolyte, can be effectively by electrolyte absorption and be retained in this gel polymer electrolyte film, thereby effectively raise the electric conductivity of this gel polymer electrolyte.
Above-mentioned method for preparing gel polymer electrolyte only need be filled out P (VDF-HFP) polymer and activity to be mixed with on request slurry, then applies film forming, impregnated in organic ion liquid electrolyte.Its technique is simple, technology maturation, and rate of finished products and production efficiency are high, effectively reduce production cost.
Above-mentioned ultracapacitor, due to the gel polymer electrolyte that adopts said method to prepare, because this gel polymer electrolyte has high conductance, thereby has effectively improved ultracapacitor chemical property, as high rate performance.The high-mechanical property that this gel polymer electrolyte has and low production cost, effectively improved the rate of finished products of this ultracapacitor, reduced the production cost of ultracapacitor, produces thereby make this ultracapacitor can realize industrialization.
There is excellent chemical property just because of this ultracapacitor, thereby effectively expanded the range of application of above-mentioned ultracapacitor.Application by this ultracapacitor in communication apparatus, computer, electric automobile and military field.
Accompanying drawing explanation
Fig. 1 is inventive embodiments method for preparing gel polymer electrolyte process chart.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the present invention provides a kind of mechanical strength and conductance is high, cost is low gel polymer electrolyte.This gel polymer electrolyte contains active filler, poly-(vinylidene fluoride-hexafluoropropylene), organic ion liquid electrolyte; Wherein, the ratio of the weight of active filler and poly-(vinylidene fluoride-hexafluoropropylene) is 3 ~ 20:100.
Particularly, the weight average molecular weight of above-mentioned poly-(vinylidene fluoride-hexafluoropropylene) is preferably 300,000 ~ 800,000.The solvent resistance of poly-(vinylidene fluoride-hexafluoropropylene) is better, has good film forming and thermal stability and electrochemical stability, and compared with other polymeric matrixs, this P (VDF-HFP) has lower degree of crystallinity and fusing point.Set it as the matrix of this gel polymer electrolyte, under active filler acting in conjunction, give the good electrochemical stability performance of this gel polymer electrolyte and mechanical performance and higher ionic conductivity, and better with the contact of electrode.
Active filler is Li
10geP
2s
12, Li
3n, LiAlO
2, at least one in AgI; The particle diameter of active filler is 100 ~ 5000 nanometers.After above-mentioned active filler adds and stirs, it is dispersed, and forms uniform slurry with P (VDF-HFP).
Organic ion liquid electrolyte comprises the first component and second component, the first component is the one in N-butyl-N-methylmorpholine tetrafluoroborate, N-methoxy ethyl-N-methylmorpholine tetrafluoroborate preferably, and second component is the one in acetonitrile, propene carbonate preferably; Also, in this organic ion liquid electrolyte take N-butyl-N-methylmorpholine tetrafluoroborate or N-methoxy ethyl-N-methylmorpholine tetrafluoroborate as solute, take the one in acetonitrile or propene carbonate acetonitrile as solvent.This concentration of electrolyte is 0.5-1.5mol/L.
From the above mentioned, it is substrate that above-mentioned method for preparing gel polymer electrolyte adopts P (VDF-HFP) polymer, and in this substrate dispersed activity filler, effectively strengthen this gel polymer electrolyte film conductivity, improved the mechanical strength of this gel polymer electrolyte film and the ability of absorbed electrolyte simultaneously.After gel polymer electrolyte film is soaked in electrolyte, can be effectively by electrolyte absorption and be retained in this gel polymer electrolyte film, thereby effectively raise the electric conductivity of this gel polymer electrolyte.By the further selection to P (VDF-HFP), active filler and organic ion liquid electrolyte, can significantly improve conductivity and the mechanical performance of this gel polymer electrolyte.
Correspondingly, the embodiment of the present invention provides method for preparing gel polymer electrolyte in the simple above-described embodiment of a kind of technique.As shown in Figure 1, it comprises the steps: in the method technological process
S01: the preparation of slurry: will gather (vinylidene fluoride-hexafluoropropylene) and be dissolved in organic solvent, add active filler according to the ratio of active filler and poly-(vinylidene fluoride-hexafluoropropylene) weight again, at 30 ~ 50 ℃, be uniformly mixed, obtain slurry;
S02: the preparation of gel polymer electrolyte film: the slurry in step S01 is coated in substrate, and vacuumize, obtains gel polymer electrolyte film;
S03: the preparation of gel polymer electrolyte: under the protection of dry inert gas; it is that the organic ion liquid electrolyte of 0.5～1.5mol/L is flooded 10～60min that described gel polymer electrolyte film is placed in to concentration, takes out and obtains described gel polymer electrolyte.
Particularly, in above-mentioned steps S01, P (VDF-HFP), active filler as described above, in order to save length, do not repeat them here.
Organic solvent is more than one in 1-METHYLPYRROLIDONE, DMF, acetonitrile, ethanol.This organic solvent can effectively make to gather (vinylidene fluoride-hexafluoropropylene) and effectively dissolve, and prepare dispersed and stable viscous paste, when this viscous paste is carried out to lower step coated plate processing, can make this contain poly-(vinylidene fluoride-hexafluoropropylene) viscous paste is uniformly coated in substrate, make the gel polymer electrolyte film even thickness forming, soak and adsorb the equilibrium of electrolyte ability.Certainly, the application can also be dissolved with other energy well known in the art the organic solvent of poly-(vinylidene fluoride-hexafluoropropylene).
Preferably, as the preferred embodiment of the present invention, in this step S01, the viscous paste of preparation poly-(vinylidene fluoride-hexafluoropropylene) preferably carries out in the environment of Buchholz protection that is dried inertia, concrete method is: in the environment of the Buchholz protection of dry inertia, to gather (vinylidene fluoride-hexafluoropropylene) is dissolved in organic solvent, be that 3 ~ 20:100 adds inorganic filler according to the ratio of active filler and poly-(vinylidene fluoride-hexafluoropropylene) weight again, at 30 ~ 50 ℃, be uniformly mixed, making to gather (vinylidene fluoride-hexafluoropropylene) dissolves completely, to form uniform and stable viscous paste.In this embodiment; the object of carrying out in the environment containing the Buchholz protection that is formulated in dry inertia of the viscous paste of poly-(vinylidene fluoride-hexafluoropropylene) is in order to prevent that airborne moisture is by the viscous paste absorption containing poly-(vinylidene fluoride-hexafluoropropylene), thereby affects the performance that obtains gel polymer electrolyte film after the stability of this viscous paste and coated plate.
In above-mentioned steps S02, preparation in step S01 is coated in to suprabasil mode containing viscous paste and can adopts mode well known in the art to be coated in substrate.Wherein, the glass plate of substrate preferred smooth cleaning, this substrate can also be selected other conventional substrates of this area certainly.Like this, the gel polymer electrolyte film even thickness that drying forms after processing, stable electrochemical property, sound construction, mechanical strength is high.Slurry be coated in suprabasil amount be preferably drying process after to thicknesses of layers be 50～200 μ m.This preferred thickness can effectively improve transmission performance and the mechanical performance of gel polymer electrolyte to electric charge, thereby improves chemical property and the rate of finished products of the ultracapacitor that hereinafter contains this gel polymer electrolyte.
In this step S02, vacuum drying temperature is preferably 70 ℃～100 ℃, is preferably 24～48 hours drying time; Vacuum degree can be 0.01MPa, if certain conditions permit, vacuum degree is more high better.This preferred drying condition, can effectively remove the organic solvent in viscous paste, can further improve the correlated performance of this gel polymer electrolyte film simultaneously, as the absorption property to electrolyte etc.
In above-mentioned steps S03, the operation that gel polymer electrolyte film is immersed in electrolyte is preferably carried out in the environment of argon gas or other inert gas shieldings, as carried out in the glove box that is full of argon gas.The Buchholz protection object of dry inertia is in order to prevent that airborne moisture from together being adsorbed wherein by gel polymer electrolyte film in company with electrolyte, thereby guarantees the electric property of gel polymer electrolyte.Gel polymer electrolyte film is in electrolyte after fully adsorbing, and electrolyte is adsorbed and is fixed in this gel polymer electrolyte film, thereby forms mechanical strength and the high gel polymer electrolyte of conductance.
In this step S03, organic ion liquid electrolyte comprises the first component and second component, the first component is selected from the one in N-butyl-N-methylmorpholine tetrafluoroborate, N-methoxy ethyl-N-methylmorpholine tetrafluoroborate, and second component is selected from the one in acetonitrile, propene carbonate; Also, in this organic ion liquid electrolyte take N-butyl-N-methylmorpholine tetrafluoroborate or N-methoxy ethyl-N-methylmorpholine tetrafluoroborate as solute, take the one in acetonitrile or propene carbonate acetonitrile as solvent.This concentration of electrolyte is 0.5-1.5mol/L.
Poly-(vinylidene fluoride-hexafluoropropylene) base method for preparing gel polymer electrolyte of above-described embodiment only need stir poly-(vinylidene fluoride-hexafluoropropylene), active filler and organic solvent, effectively strengthen the mechanical strength of gel polymer electrolyte film, effectively improved the ability of this gel polymer electrolyte film absorbed electrolyte simultaneously; Then be coated in the dry gel polymer electrolyte film that obtains on smooth plates matrix, again dielectric film is immersed in electrolyte, can effectively organic ion liquid electrolyte be absorbed and be retained in this gel polymer electrolyte film, thereby effectively raise the electric conductivity of this gel polymer electrolyte; Taking-up is done to obtain poly-(vinylidene fluoride-hexafluoropropylene) base gel polymer electrolyte after surface treatment.The not high and not high defect of existing gel polymer electrolyte conductance of effective like this mechanical strength that has overcome existing gel polymer electrolyte.In addition, this method for preparing gel polymer electrolyte technique is simple, technology maturation, and rate of finished products and efficiency are high, effectively reduce production cost.
The embodiment of the present invention also provides a kind of ultracapacitor, and this ultracapacitor comprises gel polymer electrolyte mentioned above.
Particularly, the preparation method of ultracapacitor is as follows:
Step S04. prepares gel polymer electrolyte: this gel polymer electrolyte is gel polymer electrolyte preparation method be by mentioned earlier prepared from;
Step S05. prepares battery core: step S04 is prepared to gel polymer electrolyte and stack gradually according to electrode/gel polymer electrolyte/electrode overlapped way, make battery core;
Step S06. encapsulated capacitor: step S05 is prepared to battery core and pack in capacitor casing, sealing, makes ultracapacitor.
Encapsulated capacitor method in above-mentioned steps S05 in the preparation method of electrode and the preparation method of battery core and step S06 all can be according to the method preparation of this area routine.In addition, the battery core in step S05 can be circular or other shapes that need according to different ultracapacitors.
Above-mentioned ultracapacitor, due to the gel polymer electrolyte that adopts said method to prepare, because this gel polymer electrolyte has high conductance, thereby has effectively improved the chemical property of ultracapacitor, as high rate performance.The high-mechanical property that this gel polymer electrolyte has and low production cost, effectively improved the rate of finished products of this ultracapacitor, reduced the production cost of ultracapacitor, produces thereby make this ultracapacitor can realize industrialization.This ultracapacitor preparation method technology maturation in addition, condition is easily controlled, and qualification rate is high.
The embodiment of the present invention further provides the range of application of above-mentioned ultracapacitor, and this range of application comprises communication apparatus, computer, electric automobile, electronic product etc.
Illustrate below the aspects such as above-mentioned gel polymer electrolyte and preparation method thereof, ultracapacitor and application thereof by multiple embodiment.
Embodiment 1
Poly-(vinylidene fluoride-hexafluoropropylene) base gel polymer electrolyte and preparation method thereof, this preparation method comprises the steps:
S11: the preparation of slurry: poly-10g (vinylidene fluoride-hexafluoropropylene) (weight average molecular weight 500,000) is dissolved in about 30g 1-METHYLPYRROLIDONE, stirs, and be the Li of 5000 nanometers to adding 0.9g particle diameter in system
10geP
2s
12, and be warmed up to 40 ℃ to system and be uniformly mixed, obtain uniform slurry.
S12: the preparation of gel polymer electrolyte film: the slurry obtaining is coated on clean glass plate equably, after dry under 100 ℃, 0.01MPa vacuum again, obtain poly-(vinylidene fluoride-hexafluoropropylene) base gel polymer electrolyte film of the doping active filler of thickness approximately 120 μ m.
S13: the preparation of gel polymer electrolyte: dried gel polymer electrolyte film is put into the glove box that is full of argon gas, and be immersed in 40min in the organic ion liquid electrolyte of 1.2mol/L, this organic ion liquid electrolyte is take N-butyl-N-methylmorpholine tetrafluoroborate as electrolyte, take acetonitrile as solvent.After taking-up, obtain poly-(vinylidene fluoride-hexafluoropropylene) base gel polymer electrolyte of active filler doping by the il electrolyte that filter paper blots film surface.
Embodiment 2
Poly-(vinylidene fluoride-hexafluoropropylene) base gel polymer electrolyte and preparation method thereof, this preparation method comprises the steps:
S21: the preparation of slurry: poly-10g (vinylidene fluoride-hexafluoropropylene) (weight average molecular weight 300,000) is dissolved in about 10g DMF, stirs, and be the Li of 2450 nanometers to adding 0.5g particle diameter in system
3n, and be warmed up to 50 ℃ to system and be uniformly mixed, uniform slurry obtained.S22: the preparation of gel polymer electrolyte film: the slurry obtaining is coated on clean glass plate equably, after dry under 90 ℃, 0.01MPa vacuum again, obtain poly-(vinylidene fluoride-hexafluoropropylene) base gel polymer electrolyte film of the doping active filler of thickness approximately 50 μ m.
S23: the preparation of gel polymer electrolyte: dried gel polymer electrolyte film is put into the glove box that is full of argon gas, and be immersed in 60min in the organic ion liquid electrolyte of 0.5mol/L, this organic ion liquid electrolyte is take N-methoxy ethyl-N-methylmorpholine tetrafluoroborate as electrolyte, take acetonitrile as solvent.After taking-up, obtain poly-(vinylidene fluoride-hexafluoropropylene) base gel polymer electrolyte of active filler doping by the il electrolyte that filter paper blots film surface.
Embodiment 3
Poly-(vinylidene fluoride-hexafluoropropylene) base gel polymer electrolyte and preparation method thereof, this preparation method comprises the steps:
S31: the preparation of slurry: poly-10g (vinylidene fluoride-hexafluoropropylene) (weight average molecular weight 700,000) is dissolved in about 40g acetonitrile, stirs, and be the LiAlO of 100 nanometers to adding 1.2g particle diameter in system
2, and be warmed up to 45 ℃ to system and be uniformly mixed, obtain uniform slurry.S32: the preparation of gel polymer electrolyte film: the slurry obtaining is coated on clean glass plate equably, after dry under 80 ℃, 0.01MPa vacuum again, obtain poly-(vinylidene fluoride-hexafluoropropylene) base gel polymer electrolyte film of the doping active filler of thickness approximately 160 μ m.
S33: the preparation of gel polymer electrolyte: dried gel polymer electrolyte film is put into the glove box that is full of argon gas, and be immersed in 30min in the organic ion liquid electrolyte of 0.8mol/L, this organic ion liquid electrolyte is take N-butyl-N-methylmorpholine tetrafluoroborate as electrolyte, take propene carbonate as solvent.After taking-up, obtain poly-(vinylidene fluoride-hexafluoropropylene) base gel polymer electrolyte of active filler doping by the il electrolyte that filter paper blots film surface.
Embodiment 4
Poly-(vinylidene fluoride-hexafluoropropylene) base gel polymer electrolyte and preparation method thereof, this preparation method comprises the steps:
S41: the preparation of slurry: poly-10g (vinylidene fluoride-hexafluoropropylene) (weight average molecular weight 800,000) is dissolved in about 20g ethanol, stir, and be the AgI of 500 nanometers to adding 1.5g particle diameter in system, and be warmed up to 30 ℃ to system and be uniformly mixed, obtain uniform slurry.
S42: the preparation of gel polymer electrolyte film: the slurry obtaining is coated on clean glass plate equably, after dry under 70 ℃, 0.01MPa vacuum again, obtain poly-(vinylidene fluoride-hexafluoropropylene) base gel polymer electrolyte film of the doping active filler of thickness approximately 200 μ m.
S43: the preparation of gel polymer electrolyte: dried gel polymer electrolyte film is put into the glove box that is full of argon gas, and be immersed in 10min in the organic ion liquid electrolyte of 1.5mol/L, this organic ion liquid electrolyte is take N-methoxy ethyl-N-methylmorpholine tetrafluoroborate as electrolyte, take propene carbonate as solvent.After taking-up, obtain poly-(vinylidene fluoride-hexafluoropropylene) base gel polymer electrolyte of active filler doping by the il electrolyte that filter paper blots film surface.
Embodiment 5
Poly-(vinylidene fluoride-hexafluoropropylene) base gel polymer electrolyte and preparation method thereof, this preparation method comprises the steps:
S11: the preparation of slurry: poly-10g (vinylidene fluoride-hexafluoropropylene) (weight average molecular weight 400,000) is dissolved in about 8g 1-METHYLPYRROLIDONE, stirs, and be the Li of 4000 nanometers to adding 0.3g particle diameter in system
10geP
2s
12, and be warmed up to 40 ℃ to system and be uniformly mixed, obtain uniform slurry.
S12: the preparation of gel polymer electrolyte film: the slurry obtaining is coated on clean glass plate equably, after dry under 100 ℃, 0.01MPa vacuum again, obtain poly-(vinylidene fluoride-hexafluoropropylene) base gel polymer electrolyte film of the doping active filler of thickness approximately 50 μ m.
S13: the preparation of gel polymer electrolyte: dried gel polymer electrolyte film is put into the glove box that is full of argon gas, and be immersed in 40min in the organic ion liquid electrolyte of 0.5mol/L, this organic ion liquid electrolyte is take N-butyl-N-methylmorpholine tetrafluoroborate as electrolyte, take acetonitrile as solvent.After taking-up, obtain poly-(vinylidene fluoride-hexafluoropropylene) base gel polymer electrolyte of active filler doping by the il electrolyte that filter paper blots film surface.
Embodiment 6
Poly-(vinylidene fluoride-hexafluoropropylene) base gel polymer electrolyte and preparation method thereof, this preparation method comprises the steps:
S21: the preparation of slurry: poly-10g (vinylidene fluoride-hexafluoropropylene) (weight average molecular weight 600,000) is dissolved in about 30g DMF, stirs, and be the Li of 3000 nanometers to adding 2g particle diameter in system
3n, and be warmed up to 50 ℃ to system and be uniformly mixed, uniform slurry obtained.
S22: the preparation of gel polymer electrolyte film: the slurry obtaining is coated on clean glass plate equably, after dry under 90 ℃, 0.01MPa vacuum again, obtain poly-(vinylidene fluoride-hexafluoropropylene) base gel polymer electrolyte film of the doping active filler of thickness approximately 195 μ m.
S23: the preparation of gel polymer electrolyte: dried gel polymer electrolyte film is put into the glove box that is full of argon gas, and be immersed in 60min in the organic ion liquid electrolyte of 1.5mol/L, this organic ion liquid electrolyte is take N-methoxy ethyl-N-methylmorpholine tetrafluoroborate as electrolyte, take acetonitrile as solvent.After taking-up, obtain poly-(vinylidene fluoride-hexafluoropropylene) base gel polymer electrolyte of active filler doping by the il electrolyte that filter paper blots film surface.
Comparative example:
A kind of method for preparing gel polymer electrolyte, it comprises the steps:
S51: the preparation of slurry: poly-10g (vinylidene fluoride-hexafluoropropylene) (weight average molecular weight 500,000) is dissolved in about 30g 1-METHYLPYRROLIDONE, and is warmed up to 40 ℃ of stirrings to system and obtains uniform slurry;
S52: the preparation of gel polymer electrolyte film: the slurry obtaining is coated on clean glass plate equably, after dry under 100 ℃, 0.01MPa vacuum again, obtain poly-(vinylidene fluoride-hexafluoropropylene) base gel polymer electrolyte film polymer film of thickness approximately 120 μ m;
S53: the preparation of gel polymer electrolyte: dried gel polymer electrolyte film is put into the glove box that is full of argon gas, and be immersed in 40min in the organic ion liquid electrolyte of 1.2mol/L, this organic ion liquid electrolyte is take N-butyl-N-methylmorpholine tetrafluoroborate as electrolyte, take acetonitrile as solvent.After taking-up, gathered (vinylidene fluoride-hexafluoropropylene) base gel polymer electrolyte by the il electrolyte that filter paper blots film surface.
The preparation of ultracapacitor:
The preparation of electrode: (specific area is about 1000m to take 9g active carbon
2/ g), 0.35g acetylene black and 0.5g Kynoar, and add 70gN-methyl pyrrolidone, fully stir and make it to become the slurry mixing.Then by its blade coating on the aluminium foil cleaning through ethanol, under the vacuum of 0.01MPa, 100 ℃ are dried to constant weight, and are pressed into Graphene electrodes in 10MPa pressure lower roll, and are cut into electrode disk;
The encapsulation of ultracapacitor: respectively electrode and poly-(vinylidene fluoride-hexafluoropropylene) base gel film prepared by the present embodiment 1-4 and comparative example are stacked gradually, reeled according to the stacked order of electrode/gel polymer electrolyte/electrode respectively, pack in capacitor casing sealing into.
The test of capacitance characteristic:
Utilize charge-discharge test instrument, P (VDF-HFP) base gel polymer electrolyte capacitor prepared by above-described embodiment 1～6 and comparative example is respectively used to the above-mentioned ultracapacitor assembling and carries out constant current charge-discharge test, in the electrochemical window of 0 ~ 2.7V, record than capacitance data as following table 1 with the electric current of 0.5A/g:
Table 1
Data Comparison in his-and-hers watches 1 is found, adopts the prepared P of the embodiment of the present invention (VDF-HFP) base gel polymer electrolyte to be suitable for the electrolyte of ultracapacitor, and in the electrochemical window of 2.7V, has better capacitance characteristic.And by finding that with the contrast of comparative example active filler is conducive to the raising of specific capacity.
The test of conductivity:
P (VDF-HFP) the base gel polymer electrolyte that adds respectively above-described embodiment 1～4 and comparative example to prepare between two stainless steel blocking electrodes, form polymer dielectric blocking electrode system, do ac impedance measurement, the complex impedance plane graph that obtains GPE, curve is body impedance in the intersection value of high frequency region and transverse axis.According to body impedance (R
b) and ionic conductivity (relation between ion-conductance: be related to rate figure, curve is at high frequency
b), can calculate ionic conductivity, thickness, S that wherein d is polymer dielectric film are the contact area of polymer dielectric dielectric film and electrode, conductivity test result is as table 2.
Table 2
Data by conductivity in contrast table 2 are known, and active filler doping can improve the conductivity of gel polymer electrolyte film widely.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a gel polymer electrolyte, contains active filler, poly-(vinylidene fluoride-hexafluoropropylene), organic ion liquid electrolyte; Wherein, the ratio of the weight of active filler and poly-(vinylidene fluoride-hexafluoropropylene) is 3 ~ 20:100.
2. gel polymer electrolyte as claimed in claim 1, is characterized in that: described active filler is Li
10geP
2s
12, Li
3n, LiAlO
2, at least one in AgI.
3. gel polymer electrolyte as claimed in claim 1, is characterized in that: the particle diameter of described active filler is 100 ~ 5000 nanometers.
4. method for preparing gel polymer electrolyte as claimed in claim 1, is characterized in that: the weight average molecular weight of described poly-(vinylidene fluoride-hexafluoropropylene) is 300,000 ~ 800,000.
5. method for preparing gel polymer electrolyte as claimed in claim 1, it is characterized in that, described organic ion liquid electrolyte comprises the first component and second component, the first component is selected from the one in N-butyl-N-methylmorpholine tetrafluoroborate, N-methoxy ethyl-N-methylmorpholine tetrafluoroborate, and second component is selected from the one in acetonitrile, propene carbonate.
6. the method for preparing gel polymer electrolyte as described in claim 1 or 5, is characterized in that: the thickness of described gel polymer electrolyte film is 50 ~ 200 μ m.
7. the method for preparing gel polymer electrolyte as described in claim 1～6 any one, comprises the steps:
To gather (vinylidene fluoride-hexafluoropropylene) and be dissolved in organic solvent, then add active filler according to the ratio of active filler and poly-(vinylidene fluoride-hexafluoropropylene) weight, at 30 ~ 50 ℃, be uniformly mixed, obtain slurry;
Described slurry is coated in substrate, and vacuumize, obtains gel polymer electrolyte film;
Under the protection of dry inert gas, it is that the organic ion liquid electrolyte of 0.5～1.5mol/L is flooded 10～60min that described gel polymer electrolyte film is placed in to concentration, takes out and obtains described gel polymer electrolyte.
8. method for preparing gel polymer electrolyte as claimed in claim 7, is characterized in that: described organic solvent is at least one in 1-METHYLPYRROLIDONE, DMF, acetonitrile, ethanol.
9. a ultracapacitor, is characterized in that, described ultracapacitor comprises gel polymer electrolyte claimed in claim 8.
10. the application of ultracapacitor as claimed in claim 9 in communication apparatus, computer, electric automobile and military field.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106654369A (en) * | 2017-03-16 | 2017-05-10 | 北京化工大学 | Gel polymer electrolyte membrane of vertical membrane surface of magnetic nanorod and preparation method thereof |
| CN107369848A (en) * | 2017-07-14 | 2017-11-21 | 北京化工大学 | A kind of composite electrolyte of sandwich structure and preparation method thereof |
| CN112490023A (en) * | 2019-09-12 | 2021-03-12 | 广州汽车集团股份有限公司 | Preparation method of gel electrolyte and preparation method of super capacitor |
| CN113675008A (en) * | 2021-08-12 | 2021-11-19 | 上海奥威科技开发有限公司 | Polymer-based solid supercapacitor and preparation method and application thereof |
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2012
- 2012-10-26 CN CN201210417194.6A patent/CN103779089A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106654369A (en) * | 2017-03-16 | 2017-05-10 | 北京化工大学 | Gel polymer electrolyte membrane of vertical membrane surface of magnetic nanorod and preparation method thereof |
| CN107369848A (en) * | 2017-07-14 | 2017-11-21 | 北京化工大学 | A kind of composite electrolyte of sandwich structure and preparation method thereof |
| CN112490023A (en) * | 2019-09-12 | 2021-03-12 | 广州汽车集团股份有限公司 | Preparation method of gel electrolyte and preparation method of super capacitor |
| CN112490023B (en) * | 2019-09-12 | 2022-06-21 | 广州汽车集团股份有限公司 | Preparation method of gel electrolyte and preparation method of super capacitor |
| CN113675008A (en) * | 2021-08-12 | 2021-11-19 | 上海奥威科技开发有限公司 | Polymer-based solid supercapacitor and preparation method and application thereof |
| WO2023016579A1 (en) * | 2021-08-12 | 2023-02-16 | 上海奥威科技开发有限公司 | Polymer-based solid-state supercapacitor, and preparation method therefor and use thereof |
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