CN103804708A - Poly(vinylidene fluoride-hexafluoropropenyl) gel polymer film as well as preparation and application thereof - Google Patents
Poly(vinylidene fluoride-hexafluoropropenyl) gel polymer film as well as preparation and application thereof Download PDFInfo
- Publication number
- CN103804708A CN103804708A CN201210457302.2A CN201210457302A CN103804708A CN 103804708 A CN103804708 A CN 103804708A CN 201210457302 A CN201210457302 A CN 201210457302A CN 103804708 A CN103804708 A CN 103804708A
- Authority
- CN
- China
- Prior art keywords
- pvdf
- polyvinylidene difluoride
- polymer film
- base
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a poly(vinylidene fluoride-hexafluoropropenyl) gel polymer film as well as a preparation and an application thereof. The preparation method comprises: mixing poly(vinylidene fluoride-hexafluoropropene), an organic solvent and metal oxide nano particles, adding a plasticizer, and stirring to obtain a paste, wherein, the consumption ratio of the poly(vinylidene fluoride-hexafluoropropene), the organic solvent, the metal oxide nano particles to the plasticizer is 1g: 20-30mL: 0.4-0.6g: 0.5-2.0g; and casting and drying the paste to obtain the poly(vinylidene fluoride-hexafluoropropenyl) gel polymer film. The polymer film is further soaked into an electrolyte for 5 to 60 minutes to obtain a poly(vinylidene fluoride-hexafluoropropenyl) gel polymer electrolyte. The poly(vinylidene fluoride-hexafluoropropenyl) gel polymer electrolyte modified by the metal oxide nano particles has relatively high conductivity, mechanical strength and application performance and is high in safety and environment-friendly, and the preparation method is simple.
Description
Technical field
The present invention relates to electrochemical field, relate in particular to a kind of polyvinylidene difluoride (PVDF)-R 1216 base gelatin polymer film and its preparation method and application.
Background technology
Along with the development of various new forms of energy, the miniaturization development of portable electric appts and the widespread demand of electromobile to large-capacity high-power chemical power source.A kind of research and development of the novel battery material with high-rate charge-discharge capability become of crucial importance.But safety problem is the bottleneck of the large capacity of restriction, high power lithium ion cell application always.Wherein, the problem such as burning, blast that leakage, ionogen oxidation decomposition and the thermal runaway etc. that now widely used liquid electrolyte produces cause is the main potential safety hazard of battery.
The advantage of the liquid electrolyte of current routine is that specific conductivity is high, but inflammable owing to containing, volatile organic solvent, it discharges inflammable gas in charge and discharge process, particularly under some unconventional working conditions, (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, gas leakage, blast even on fire, thereby there is serious potential safety hazard.The studied persons of advantage such as polymer electrolyte lithium-ion battery is safe because having, nothing is leaked, leakage current is little pay attention to.Because specific conductivity under solid polymer electrolyte room temperature is lower by (10
-5~ 10
-4s/cm), use application to be restricted, thereby gel polymer electrolyte become research emphasis.
Gel polymer electrolyte is made up of polymkeric substance, small molecule solvent (softening agent) and inorganic salt etc., conventionally turned into forming by chemically crosslinked isogel between Van der Waals force and polymkeric substance, there is the processing characteristics that polymkeric substance is good, and contain liquid electrolyte, and there is high conductivity at room temperature, can serve as barrier film, replace liquid electrolyte, and because polymkeric substance has thermoplasticity, plastic, make gel polymer electrolyte there is good application prospect in the field such as lithium ion battery, electrical condenser.But due to the existence of small-molecule substance, make the shortcomings such as gel polymer electrolyte exists chemistry, electrochemical stability, thermostability and mechanical property is poor.
Summary of the invention
Given this, the present invention aims to provide a kind of polyvinylidene difluoride (PVDF)-R 1216 base gelatin polymer film and its preparation method and application.The present invention further provides a kind of polyvinylidene difluoride (PVDF)-R 1216 base gel polymer electrolyte and preparation method thereof.Described polymer dielectric is take polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gelatin polymer film as base material, and it,, by after metal oxide nanoparticles modification, possesses higher specific conductivity, and security is good, environmental friendliness.Preparation method's technical process provided by the invention is simple.
First aspect, the invention provides the preparation method of a kind of polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gelatin polymer film, comprises the following steps:
(1) under the protection of rare gas element, by polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)), organic solvent and metal oxide nanoparticles mix and blend 1 ~ 4h, add softening agent, continue to stir 12 ~ 36h, obtain slurry, wherein, the amount ratio of described polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)), described organic solvent, described metal oxide nanoparticles and described softening agent is 1g:20 ~ 30mL:0.4 ~ 0.6g:0.5 ~ 2.0g;
(2) step (1) gained slurry is poured on substrate, after vacuum-drying, obtains polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gelatin polymer film.
Step of the present invention (1) is for preparing the process of slurry after polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)), organic solvent, softening agent and described metal oxide nanoparticles are mixed according to a certain ratio.
Preferably, the weight-average molecular weight of described polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) is 30 ~ 800,000.Polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) has good physical strength, thermostability and chemical stability, can improve mechanical property and the stability of prepared gel electrolyte as the base material of gel polymer electrolyte.
Preferably, described metal oxide nanoparticles is TiO
2, MgO, Al
2o
3or ZnO.
Preferably, the particle diameter of described metal oxide nanoparticles is 10nm ~ 60nm.
Preferably, described rare gas element is nitrogen or argon gas.
Preferably, described organic solvent is acetone, acetonitrile or tetrahydrofuran (THF) (THF).
Preferably, described softening agent is dibutyl phthalate, m-phthalic acid dibutylester or dibutyl terephthalate.
Adding of metal oxide nanoparticles, can make polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) the base gelatin polymer film preparing there is good pore space structure, not only there are a large amount of micropores on surface, and also having many interconnective micropores in lower face, these pore space structures will be conducive to improve electrolytical specific conductivity.Meanwhile, metal oxide nanoparticles can serve as polymer crosslinking center, and macromolecular chain is intertwined more closely, thereby improves polymeric film and electrolytical mechanical property.
Step (2) is the dry process that obtains polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gelatin polymer film of slurry cast final vacuum prepared by step (1).In the structure of gained polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gelatin polymer film, there are a large amount of micropores, be conducive to finally improve electrolytical specific conductivity.
Preferably, described vacuum-drying is vacuum-drying 24 ~ 48h at 60 ~ 100 ℃.
Preferably, pressure when described vacuum-drying is 0.01MPa.Vacuum tightness in drying process is more high better.
Preferably, described substrate is sheet glass or polyfluortetraethylene plate.
Preferably, the thickness of described polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gelatin polymer film is 15 ~ 60 μ m.
Second aspect, the invention provides a kind of polyvinylidene difluoride (PVDF)-R 1216 base gelatin polymer film, adopts preparation method as described in first aspect to make.
The third aspect, the invention provides the application of polyvinylidene difluoride (PVDF)-R 1216 base gelatin polymer, as the application of ionogen base material, as follows:
The invention provides a kind of polyvinylidene difluoride (PVDF)-R 1216 base gel polymer electrolyte, described ionogen comprises the polyvinylidene difluoride (PVDF)-R 1216 base gelatin polymer film described in second aspect and is adsorbed on the electrolytic solution on described polymeric film.
Preferably, described electrolytic solution is by LiBF4 (LiBF
4), propylene carbonate (PC) and Methyl ethyl carbonate (EMC) composition.
Preferably, described propylene carbonate (PC): the volume ratio of Methyl ethyl carbonate (EMC) is 1:2 ~ 1:6.
Preferably, described LiBF4 (LiBF
4) volumetric molar concentration be 0.3 ~ 1.5mol/L.
Fourth aspect, the invention provides polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) the base method for preparing gel polymer electrolyte as described in the third aspect, comprises the following steps:
In inert atmosphere, polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gelatin polymer film is dipped in to 5 ~ 60min in electrolytic solution, obtains polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gel polymer electrolyte.
Described electrolytic solution is contained in the glove box that is full of rare gas element.
Preferably, rare gas element is nitrogen or argon gas.
Above-mentioned steps, for polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gelatin polymer film is dipped in to 5 ~ 60min in electrolytic solution, obtains the process of polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gel polymer electrolyte of metal oxide nanoparticles modification.
Adding of metal oxide nanoparticles, can make polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gelatin polymer film there is good pore space structure, not only there are a large amount of micropores on surface, and also having many interconnective micropores in lower face, these pore space structures will be conducive to improve electrolytical specific conductivity.Meanwhile, metal oxide nanoparticles can serve as polymer crosslinking center, and macromolecular chain is intertwined more closely, thereby improves the mechanical property of polymer dielectric.
The preparation method and corresponding ionogen and the preparation method that the invention provides a kind of polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gelatin polymer film, have following beneficial effect:
(1) polyvinylidene difluoride (PVDF)-R 1216 provided by the invention (P (VDF-HFP)) base gel polymer electrolyte, after metal oxide nanoparticles modification, possesses higher specific conductivity, nanoparticle can serve as polymer crosslinking center simultaneously, macromolecular chain is intertwined more closely, thereby improve polymeric film and electrolytical mechanical property, and safety performance is high, has good power density, life-span and specific storage;
(2) polyvinylidene difluoride (PVDF)-R 1216 provided by the invention (P (VDF-HFP)) base method for preparing gel polymer electrolyte is simple and quick, possesses low cost, and the feature such as environmental friendliness;
(3) polyvinylidene difluoride (PVDF)-R 1216 provided by the invention (P (VDF-HFP)) base gel polymer electrolyte can be used as the solid state electrolyte of lithium ion battery.
Embodiment
The following stated is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Embodiment mono-
Polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gelatin polymer film and corresponding electrolyte preparation method, comprise the following steps:
(1) in the flask of 1L, adding respectively 20g weight-average molecular weight is 500,000 polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)), 400mL acetonitrile and 10gTiO
2(particle diameter is 35nm) stirred 2h and made to mix under the protection of nitrogen, adds 20g dibutyl phthalate, continues to stir 26h, obtains slurry;
(2) slurry step (1) being made is poured on clean sheet glass, vacuum-drying 48h at 60 ℃, pressure when dry is 0.01MPa, obtains polyvinylidene difluoride (PVDF)-R 1216 that thickness is 30 μ m (P (VDF-HFP)) base gelatin polymer film.
(3) polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gelatin polymer film step (2) being made immerses 35min in electrolytic solution, and electrolytic solution is made up of LiBF4, PC and EMC, and the volume ratio of PC and EMC is 1:4, LiBF
4volumetric molar concentration be 1mol/L, electrolytic solution is contained in the glove box that is full of argon gas, takes out and obtain polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gel polymer electrolyte.
Embodiment bis-
Polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gelatin polymer film and corresponding electrolyte preparation method, comprise the following steps:
(1) in the flask of 1L, adding respectively 20g weight-average molecular weight is that 300,000 polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)), 600mL acetone and 8gMgO(particle diameter are 10nm), under the protection of nitrogen, stirring 1h makes to mix, add 10g m-phthalic acid dibutylester, continue to stir 36h, obtain slurry;
(2) slurry step (1) being made is poured on clean sheet glass, vacuum-drying 24h at 80 ℃, pressure when dry is 0.01MPa, obtains polyvinylidene difluoride (PVDF)-R 1216 that thickness is 15 μ m (P (VDF-HFP)) base gelatin polymer film.
(3) polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gelatin polymer film step (2) being made immerses 60min in electrolytic solution, and electrolytic solution is by LiBF
4, PC and EMC composition, the mass ratio of PC and EMC is 1:2, LiBF
4volumetric molar concentration be 0.3mol/L, electrolytic solution is contained in the glove box that is full of argon gas, takes out and obtain polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gel polymer electrolyte.
Embodiment tri-
Polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gelatin polymer film and corresponding electrolyte preparation method, comprise the following steps:
(1) in the flask of 1L, adding respectively 20g weight-average molecular weight is 800,000 polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)), 500mL tetrahydrofuran (THF) and 12gAl
2o
3(particle diameter is 60nm) stirred 4h and made to mix under the protection of nitrogen, adds 40g dibutyl terephthalate, continues to stir 12h, obtains slurry;
(2) slurry step (1) being made is poured on clean sheet glass, vacuum-drying 30h at 100 ℃, pressure when dry is 0.01MPa, obtains polyvinylidene difluoride (PVDF)-R 1216 that thickness is 60 μ m (P (VDF-HFP)) base gelatin polymer film.
(3) polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gelatin polymer film step (2) being made immerses 5min in electrolytic solution, and electrolytic solution is made up of LiBF4, PC and EMC, and the mass ratio of PC and EMC is 1:6, LiBF
4volumetric molar concentration be 1.5mol/L, electrolytic solution is contained in the glove box that is full of argon gas, takes out and obtain polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gel polymer electrolyte.
Embodiment tetra-
Polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gelatin polymer film and corresponding electrolyte preparation method, comprise the following steps:
(1) in the flask of 1L, adding respectively 20g weight-average molecular weight is that 600,000 polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)), 450mL acetone and 12gZnO(particle diameter are 20nm), under the protection of nitrogen, stirring 3h makes to mix, add 30g m-phthalic acid dibutylester, continue to stir 25h, obtain slurry;
(2) slurry step (1) being made is poured on clean sheet glass, vacuum-drying 30h at 70 ℃, pressure when dry is 0.01MPa, obtains polyvinylidene difluoride (PVDF)-R 1216 that thickness is 45 μ m (P (VDF-HFP)) base gelatin polymer film.
(3) polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gelatin polymer film step (2) being made immerses 40min in electrolytic solution, and electrolytic solution is by LiBF
4, PC and EMC composition, the mass ratio of PC and EMC is 1:3, LiBF
4volumetric molar concentration be 0.8mol/L, electrolytic solution is contained in the glove box that is full of argon gas, takes out and obtain polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gel polymer electrolyte.
Comparative example
For the unmodified polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gelatin polymer film and the corresponding electrolyte preparation method that contrast, comprise the following steps:
(1) in the flask of 1L, adding respectively 20g weight-average molecular weight is 600,000 polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) and 450mL acetone, under the protection of nitrogen, stirring 3h makes to mix, add 30g m-phthalic acid dibutylester, continue to stir 25h, obtain slurry;
(2) slurry step (1) being made is poured on clean sheet glass, vacuum-drying 30h at 70 ℃, pressure when dry is 0.01MPa, and obtaining thickness is unmodified polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gelatin polymer film of 45 μ m.
(3) polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gelatin polymer film step (2) being made immerses 40min in electrolytic solution, and electrolytic solution is made up of LiBF4, PC and EMC, and the mass ratio of PC and EMC is 1:3, LiBF
4volumetric molar concentration be 0.8mol/L, electrolytic solution is contained in the glove box that is full of argon gas, takes out and obtain unmodified polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gel polymer electrolyte.
Test implementation example
For polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) the base gelatin polymer film and the corresponding electrolytical application performance that illustrate prepared by the present invention, provide following testing method and data:
(1) specific conductivity test: the ionogen that adds preparation between two stainless steel blocking electrodes, form polymer dielectric blocking electrode system, do ac impedance measurement, obtain the complex impedance orthographic plan of 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 (σ) between relation:
σ=d/(S×R
b)
Can calculate ionic conductivity, thickness, S that wherein d is polymer dielectric are the contact area of polymer dielectric and electrode.
The specific conductivity of test implementation example one ~ tetra-polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gel polymer electrolyte of preparation and unmodified polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gel polymer electrolyte of comparative example as stated above, data are in table 1.
The conductivity data table of table 1 gel polymer electrolyte
| Sample | Embodiment mono- | Embodiment bis- | Embodiment tri- | Embodiment tetra- | Comparative example |
| Specific conductivity (ms/cm) | 6.5 | 5.8 | 5.5 | 6.0 | 1.2 |
From table 1 data, the present invention adopts metal oxide nanoparticles modification, and the specific conductivity of polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gel polymer electrolyte and unmodified polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gel polymer electrolyte are relatively significantly improved.
(2) tensile strength test:
Polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gel polymer electrolyte that employing film stretching strength tester is prepared embodiment mono-~ tetra-and polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gel polymer electrolyte of comparative example carry out tensile strength test, the tensile strength test sample of membranaceous polymer dielectric is of a size of 3cm × 5cm, tensile strength is obtained by formula σ=G/S, wherein G is for bearing a heavy burden, S is the sectional area of polymer dielectric, σ is the tear strength of polymer dielectric, and data are in table 2.
The tensile strength data table of table 2 gel polymer electrolyte
As shown in Table 2, the present invention utilizes the more unmodified gel polymer electrolyte of tensile strength of polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) the base gel polymer electrolyte after metal oxide nanoparticles modification to improve more than 1 times, by metal oxide nanoparticles modification, the mechanical property of polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gel polymer electrolyte is significantly improved.
(3) charge-discharge test:
Gel polymer electrolyte prepared by embodiment mono-~ tetra-and comparative example is assembled into lithium ion battery, operates as follows: take 9.0g LiMn
2o
4, 0.5g acetylene black and 0.5g polyvinylidene difluoride (PVDF) (PVDF, product type is FR905), and add 20gN-methyl-2-pyrrolidone (NMP), fully be uniformly mixed, obtain slurry, slurry blade coating, on the aluminium foil cleaning through ethanol, is dried to constant weight in 80 ℃ under the vacuum condition of 0.01MPa, is then placed in 10MPa pressure lower roll and is pressed into LiMn
2o
4electrode, and be cut into anodal disk.Take anodal disk as anodal, lithium sheet is as negative pole, and the gel polymer electrolyte of respectively being prepared by embodiment mono-~ tetra-and comparative example is placed between positive and negative electrode as barrier film, and on stamping machine, button cell is made in sealing, obtains lithium ion battery.
In the voltage range of 2.5 ~ 4.2V, utilize charge-discharge test instrument to carry out 0.1C charge-discharge test to the described lithium ion battery of using respectively gel polymer electrolyte assembling prepared by embodiment mono-~ tetra-and comparative example, the amount of capacity (loading capacity) and the efficiency for charge-discharge that obtain the 10th electric discharge, data are in table 3.
The charge-discharge test data sheet of table 3 lithium ion battery
Visible, through metal oxide nanoparticles modification, the charge-discharge performance of the lithium ion battery of assembling with polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gel polymer electrolyte is significantly improved.
To sum up, adding of metal oxide nanoparticles, can make polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) base gel polymer electrolyte there is good pore space structure, not only there are a large amount of micropores on surface, and also there are many interconnective micropores in lower face, electrolytical specific conductivity be can improve, polyvinylidene difluoride (PVDF)-R 1216 (P (VDF-HFP)) mechanical property of base gel polymer electrolyte and the charge-discharge performance of lithium ion battery improved simultaneously.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (8)
1. a preparation method for polyvinylidene difluoride (PVDF)-R 1216 base gelatin polymer film, is characterized in that, comprises the following steps:
(1) under the protection of rare gas element, by polyvinylidene difluoride (PVDF)-R 1216, organic solvent and metal oxide nanoparticles mix and blend 1 ~ 4h, add softening agent, continue to stir 12 ~ 36h, obtain slurry, wherein, the amount ratio of described polyvinylidene difluoride (PVDF)-R 1216, described organic solvent, described metal oxide nanoparticles and described softening agent is 1g:20 ~ 30mL:0.4 ~ 0.6g:0.5 ~ 2.0g;
(2) step (1) gained slurry is poured on substrate, after vacuum-drying, obtains polyvinylidene difluoride (PVDF)-R 1216 base gelatin polymer film.
2. the preparation method of polyvinylidene difluoride (PVDF)-R 1216 base gelatin polymer film as claimed in claim 1, is characterized in that, in step (1), the weight-average molecular weight of described polyvinylidene difluoride (PVDF)-R 1216 is 30 ~ 800,000, and described metal oxide nanoparticles is TiO
2, MgO, Al
2o
3or ZnO, the particle diameter of described metal oxide nanoparticles is 10nm ~ 60nm.
3. the preparation method of polyvinylidene difluoride (PVDF)-R 1216 base gelatin polymer film as claimed in claim 1, it is characterized in that, in step (1), described organic solvent is acetone, acetonitrile or tetrahydrofuran (THF), and described softening agent is dibutyl phthalate, m-phthalic acid dibutylester or dibutyl terephthalate.
4. the preparation method of polyvinylidene difluoride (PVDF)-R 1216 base gelatin polymer film as claimed in claim 1, is characterized in that, in step (2), the thickness of described polyvinylidene difluoride (PVDF)-R 1216 base gelatin polymer film is 15 ~ 60 μ m.
5. polyvinylidene difluoride (PVDF)-R 1216 base gelatin polymer the film that adopts the arbitrary described preparation method of claim 1 to 4 to make.
6. polyvinylidene difluoride (PVDF)-R 1216 base gel polymer electrolyte, is characterized in that, this ionogen comprises polyvinylidene difluoride (PVDF)-R 1216 base gelatin polymer film claimed in claim 5 and is adsorbed on the electrolytic solution on described polymeric film.
7. polyvinylidene difluoride (PVDF)-R 1216 base gel polymer electrolyte as claimed in claim 6, it is characterized in that, described electrolytic solution is made up of LiBF4, propylene carbonate and Methyl ethyl carbonate, described propylene carbonate: the volume ratio of Methyl ethyl carbonate is 1:2 ~ 1:6, the volumetric molar concentration of described LiBF4 is 0.3 ~ 1.5mol/L.
8. polyvinylidene difluoride (PVDF)-R 1216 base the method for preparing gel polymer electrolyte as described in claim 6 or 7, is characterized in that, comprises the following steps:
In inert atmosphere, polyvinylidene difluoride (PVDF)-R 1216 base gelatin polymer film is dipped in to 5 ~ 60min in electrolytic solution, obtain polyvinylidene difluoride (PVDF)-R 1216 base gel polymer electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210457302.2A CN103804708A (en) | 2012-11-14 | 2012-11-14 | Poly(vinylidene fluoride-hexafluoropropenyl) gel polymer film as well as preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210457302.2A CN103804708A (en) | 2012-11-14 | 2012-11-14 | Poly(vinylidene fluoride-hexafluoropropenyl) gel polymer film as well as preparation and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103804708A true CN103804708A (en) | 2014-05-21 |
Family
ID=50702132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210457302.2A Pending CN103804708A (en) | 2012-11-14 | 2012-11-14 | Poly(vinylidene fluoride-hexafluoropropenyl) gel polymer film as well as preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103804708A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109950619A (en) * | 2019-04-12 | 2019-06-28 | 河南华瑞高新材料有限公司 | A kind of high pressure ternary lithium battery gel polymer electrolyte and preparation method thereof |
| CN110600662A (en) * | 2019-09-19 | 2019-12-20 | 湘潭大学 | Polyvinylidene fluoride-hexafluoropropylene/titanium dioxide composite membrane and preparation method and application thereof |
| WO2020119680A1 (en) * | 2018-12-14 | 2020-06-18 | 深圳先进技术研究院 | Superhydrophobic diamond-like composite layer structure and preparation method therefor |
| CN112331912A (en) * | 2020-11-09 | 2021-02-05 | 贵州梅岭电源有限公司 | Preparation method of gel electrolyte |
| CN115863753A (en) * | 2022-12-30 | 2023-03-28 | 沧州中孚新能源材料有限公司 | Gel electrolyte diaphragm and preparation method and application thereof |
-
2012
- 2012-11-14 CN CN201210457302.2A patent/CN103804708A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020119680A1 (en) * | 2018-12-14 | 2020-06-18 | 深圳先进技术研究院 | Superhydrophobic diamond-like composite layer structure and preparation method therefor |
| CN109950619A (en) * | 2019-04-12 | 2019-06-28 | 河南华瑞高新材料有限公司 | A kind of high pressure ternary lithium battery gel polymer electrolyte and preparation method thereof |
| CN110600662A (en) * | 2019-09-19 | 2019-12-20 | 湘潭大学 | Polyvinylidene fluoride-hexafluoropropylene/titanium dioxide composite membrane and preparation method and application thereof |
| CN112331912A (en) * | 2020-11-09 | 2021-02-05 | 贵州梅岭电源有限公司 | Preparation method of gel electrolyte |
| CN112331912B (en) * | 2020-11-09 | 2021-12-21 | 贵州梅岭电源有限公司 | Preparation method of gel electrolyte |
| CN115863753A (en) * | 2022-12-30 | 2023-03-28 | 沧州中孚新能源材料有限公司 | Gel electrolyte diaphragm and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2018103129A1 (en) | Graphene-based sodium ion battery | |
| CN105140477A (en) | Silicon carbon composite material and preparation method thereof | |
| CN108232111A (en) | A kind of anode composite pole piece of solid state battery and preparation method thereof | |
| CN103633291B (en) | A kind of anode slice of lithium ion battery and preparation method | |
| CN103985840A (en) | Lithium negative electrode with functional protective layer and lithium sulfur battery | |
| CN102709597A (en) | Composite all solid-state polymer electrolyte lithium ion battery and preparation method of composite all solid-state polymer electrolyte lithium ion battery | |
| JP2018026341A (en) | Positive electrode for power storage device and power storage device | |
| CN103928668B (en) | Lithium ion battery and preparation method of anode material thereof | |
| CN103515595A (en) | Sulfur/polypyrrole-graphene composite material, preparation method thereof, battery positive electrode and lithium-sulfur battery | |
| CN103804708A (en) | Poly(vinylidene fluoride-hexafluoropropenyl) gel polymer film as well as preparation and application thereof | |
| Zhang et al. | Polydopamine blended with polyacrylic acid for silicon anode binder with high electrochemical performance | |
| CN103450498A (en) | Preparation method of polymethyl methacrylate gel electrolyte membrane, polymethyl methacrylate gel electrolyte, and preparation method of the electrolyte | |
| Lu et al. | UV-curable-based plastic crystal polymer electrolyte for high-performance all-solid-state Li-ion batteries | |
| CN105161761A (en) | Preparation method of gel polymer electrolyte and application | |
| CN104409770B (en) | Preparation method of polymer electrolyte containing allyl functionalized ionic liquid | |
| CN104781967A (en) | Active material particles, positive electrode for capacitor device, and manufacturing method for capacitor device and active material particles | |
| Xie et al. | A High‐Performance Alginate Hydrogel Binder for Aqueous Zn− Ion Batteries | |
| CN109616655B (en) | Double-layer coated lithium iron borate/nickel pyrophosphate lithium battery positive electrode material and preparation method thereof | |
| CN109167036B (en) | TiN and conductive polymer composite modified lithium ion layered ternary positive electrode material and preparation method thereof | |
| CN103680968A (en) | Gel polymer electrolyte, preparation method for the same, super capacitor and application thereof | |
| CN103682431A (en) | Gel polymer electrolyte and preparation method thereof, and electrochemical power source and application thereof | |
| CN103450493A (en) | Preparation method of polyvinyl chloride-based gel electrolyte membrane, polyvinyl chloride-based gel electrolyte, and preparation method of the electrolyte | |
| CN102709598A (en) | Compound all-solid polymer electrolyte and preparation method thereof | |
| CN103456909A (en) | Preparation method of polyvinylidene fluoride-hexafluoropropene gel electrolyte membrane, polyvinylidene fluoride-hexafluoropropene gel electrolyte and preparation method of the electrolyte | |
| CN103834153A (en) | Gel polymer electrolyte and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140521 |