CN107652588A - A kind of ferroelectric polymers based dielectric film, and its production and use - Google Patents
A kind of ferroelectric polymers based dielectric film, and its production and use Download PDFInfo
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- CN107652588A CN107652588A CN201710938349.3A CN201710938349A CN107652588A CN 107652588 A CN107652588 A CN 107652588A CN 201710938349 A CN201710938349 A CN 201710938349A CN 107652588 A CN107652588 A CN 107652588A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 77
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 229910002706 AlOOH Inorganic materials 0.000 claims abstract description 24
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 27
- 238000009987 spinning Methods 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 22
- 238000010041 electrostatic spinning Methods 0.000 claims description 19
- 238000007731 hot pressing Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 10
- 238000010791 quenching Methods 0.000 claims description 10
- 230000000171 quenching effect Effects 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 abstract description 29
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 71
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000013049 sediment Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910017920 NH3OH Inorganic materials 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 230000005621 ferroelectricity Effects 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 2
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/20—Dielectrics using combinations of dielectrics from more than one of groups H01G4/02 - H01G4/06
- H01G4/206—Dielectrics using combinations of dielectrics from more than one of groups H01G4/02 - H01G4/06 inorganic and synthetic material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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Abstract
The present invention relates to a kind of ferroelectric polymers based dielectric film, and its production and use.The ferroelectric polymers based dielectric film of the present invention contains vinylidene hexafluoropropylene copolymer P (VDF co HFP) and inorganic matter AlOOH, wherein, with volume percentage, both proportionings are (100 x) %P (VDF co HFP)-x%AlOOH, 0<x≤10.The ferroelectric polymers based dielectric film of the present invention has high breakdown field strength, high energy storage density and a high energy storage efficiency, and leadless environment-friendly, has excellent energy-storage property, suitable for high density energy storage field.
Description
Technical field
The present invention relates to a kind of ferroelectric polymers based dielectric film, and its production and use, belong to dielectric material
Material field.
Background technology
Dielectric capacitor is main passive storage device, has the power of quick charge/discharge rates and superelevation close
Degree, is widely used in electronic circuit, it is possible to achieve the work(such as separated by direct communication, coupling, bypass, filtering, resonant tank, energy conversion
Energy.But its relatively low energy storage density turns into the bottleneck that it further develops and applied.Commercialized polymer matrix electricity is situated between at present
Material such as BOPP energy storage density only~2J/cm3, one or two low quantity compared with electrochemical capacitor or battery
Level.Therefore, the study hotspot that the dielectric substance with high energy storage density is always this area is explored.
Ceramic-like dielectric has a big dielectric constant and higher disruptive field intensity, but with thin polymer film dielectric phase
Than its disruptive field intensity is still not high enough, and volume is big, non-flexible so that ceramic-like dielectric is limited in some application fields
System, and polymer-based dielectric film then has the characteristics that flexible, small volume, is adapted to future device and minimizes, be integrated
Deng requirement.
The 2J/cm more than commercial BOPP film is had been realized in polymer-based dielectric film at present3Energy storage it is close
Degree.Wherein representative material is such as：P (VDF-co-CTFE) film that Z.C.Zhang et al. is prepared using solwution method, should
Energy storage density of the material under 400MV/m field strength about 7~10J/cm3, M.R.Gadinski and B.Chu et al. pass through list respectively
Axle pulling method improves the disruptive field intensity of such film to 600~700MV/m, while energy storage density is improved to 20J/cm3Left and right.
But the solwution method that these materials use in preparation process is suitable for application in large-scale production.Therefore, exploitation has height
Disruptive field intensity, high energy storage density and it is easy to the polymer-based dielectric thin film dielectric material of production to turn into the current urgency in this area
Compel task.
The content of the invention
Problems to be solved by the invention
It is an object of the invention to provide a kind of ferroelectric polymers based dielectric film, and its production and use.This hair
Bright ferroelectric polymers based dielectric film has high breakdown field strength, high energy storage density and high energy storage efficiency, preparation method letter
It is single feasible, it is easy to produce.
The solution used to solve the problem
The present invention provides a kind of ferroelectric polymers based dielectric film, and the thin dielectric film contains vinylidene-hexafluoro
Propylene copolymer P (VDF-co-HFP) and inorganic matter AlOOH, wherein, with volume percentage, both proportionings are (100-
X) %P (VDF-co-HFP)-x%AlOOH, 0<x≤10.
According to the ferroelectric polymers based dielectric film of the present invention, the thickness of the film is 5~30 μm, preferably 6~
20μm。
According to the ferroelectric polymers based dielectric film of the present invention, the pattern of the inorganic matter AlOOH is two-dimensional layer.
The present invention also provides a kind of preparation method of the ferroelectric polymers based dielectric film according to the present invention, and its feature exists
In comprising the following steps：
Step 1), by by comprising Al salt alkaline solution carry out hydro-thermal reaction, obtain inorganic matter AlOOH；
Step 2), the inorganic matter AlOOH and the vinylidene fluoride-hexafluoropropylene copolymer P (VDF-co-HFP) pressed
Proportioning mixes in organic solvent, obtains electrostatic spinning liquid；
Step 3), by the electrostatic spinning liquid carry out high-voltage electrostatic spinning, obtain non-woven fabric-like spinning body；
Step 4), by the non-woven fabric-like spinning body carry out hot pressing, carry out cold quenching after naturally cooling to room temperature, obtain ferroelectricity
Polymer-based dielectric film.
According to the preparation method of the ferroelectric polymers based dielectric film of the present invention, alkaline solution in the step 1)
PH ＞ 8.
According to the preparation method of the ferroelectric polymers based dielectric film of the present invention, in the step 1), 150~240
2~24 hours are incubated at DEG C and carries out hydro-thermal reaction.
According to the preparation method of the ferroelectric polymers based dielectric film of the present invention, in the step 3), high-pressure electrostatic is spun
Positive and negative voltage difference >=5kV of silk, collect rotating speed >=200 turn/min of wheel, solution fltting speed >=1mL/h.
According to the preparation method of the ferroelectric polymers based dielectric film of the present invention, in the step 4), by the nonwoven
Cloth-like spinning body hot pressing 20~100 minutes under 100~500 DEG C, 400~600dpi pressure.
According to the preparation method of the ferroelectric polymers based dielectric film of the present invention, the non-woven fabric-like spinning body is carried out
Hot pressing, after naturally cooling to room temperature, after 150~250 DEG C are incubated 2~20 minutes, cold quenching is carried out at 0 DEG C.
A kind of purposes according to the ferroelectric polymers based dielectric film of the present invention in electrical equipment.
The effect of invention
Ferroelectric polymers based dielectric film provided by the present invention has high breakdown field strength, high energy storage density and high storage
Can efficiency, and leadless environment-friendly, there is excellent energy-storage property, suitable for high density energy storage.Meanwhile ferroelectricity provided by the present invention
Polymer-based dielectric film has less dielectric loss concurrently, is that one kind can be applied to a variety of electrical equipments, such as embedded
The material in the fields such as capacitor, electrostatic energy storage component, pulse power element.
Brief description of the drawings
The structural representation of Fig. 1 polymer-based dielectric capacitors.
The inorganic matter AlOOH prepared in Fig. 2 embodiments 1 transmission electron microscope (TEM) figure
The inorganic matter AlOOH prepared in Fig. 3 embodiments 1 XRD.
The energy storage density of the polymer-based dielectric film prepared in Fig. 4 embodiments 1 and comparative example 1.
The dielectric constant of the polymer-based dielectric film prepared in Fig. 5-1 embodiments 1 and comparative example 1
The dielectric loss of the polymer-based dielectric film prepared in Fig. 5-2 embodiments 1 and comparative example 1.
Description of reference numerals
1- dielectric capacitors, 2- electrodes, 3- polymer-based dielectric films
Embodiment
The present invention provides a kind of ferroelectric polymers based dielectric film, and the thin dielectric film contains vinylidene-hexafluoro
Propylene copolymer P (VDF-co-HFP) and inorganic matter AlOOH, wherein, with volume percentage, both proportionings are (100-
X) %P (VDF-co-HFP)-x%AlOOH, 0<X≤10, preferably 1~5, within the above range, ferroelectric polymers have good
Flexibility.
Compared with other ferroelectric polymers, such as PVDF etc., after monomer hexafluoropropene HFP and vinylidene VDF combined polymerizations
The P (VDF-co-HFP) of generation, there is longer and narrower ferroelectric hysteresis loop, be fluorine-containing ferroelectric polymers PVDF excellent substitute.
The present invention improves the breakdown environment inside ferroelectric polymers by adding inorganic matter AlOOH, can reach raising
The purpose of ferroelectric polymers disruptive field intensity.The ferroelectric polymers based dielectric film disruptive field intensity at room temperature of the present invention >=
400kV/mm, when x is more preferably 1<x<When 3, the disruptive field intensity of ferroelectric polymers based dielectric film of the invention at room temperature
≥600kV/mm。
The ferroelectric polymers based dielectric film of the present invention, wherein, the thickness of the film is 5~30 μm, preferably 6~
20 μm, the thickness range and the equipment for producing thin film of existing industrial quarters maturation and the matching of technique are preferable.
The ferroelectric polymers based dielectric film of the present invention, wherein, in the film, the pattern of the inorganic matter AlOOH
For two-dimensional layer, the pattern is advantageous to improve the disruptive field intensity of film, so as to increase energy storage density.By regulate and control spinning technique and
Heat pressing process can regulate and control distributions of the inorganic matter AlOOH in ferroelectric polymers, so as to realize the adjustability of energy storage density.
Energy storage density under the ferroelectric polymers based dielectric film room temperature of the present invention is more than 5J/cm3, preferably 21~
26J/cm3.It is higher than pure ferroelectric polymers to the addition of the dielectric constant of the polymer of inorganic matter, while basic keep not is lost
Become.
The present invention also provides a kind of preparation method according to ferroelectric polymers based dielectric film of the present invention, its
In, comprise the following steps：
Step 1), by by comprising Al salt alkaline solution carry out hydro-thermal reaction, obtain inorganic matter AlOOH；
Step 2), the inorganic matter AlOOH and the vinylidene fluoride-hexafluoropropylene copolymer P (VDF-co-HFP) pressed
Proportioning mixes in organic solvent, obtains electrostatic spinning liquid；
Step 3), by the electrostatic spinning liquid carry out high-voltage electrostatic spinning, obtain non-woven fabric-like spinning body；
Step 4), by the non-woven fabric-like spinning body carry out hot pressing, carry out cold quenching after naturally cooling to room temperature, obtain ferroelectricity
Polymer-based dielectric film.
The preparation method of the ferroelectric polymers based dielectric film of the present invention, wherein, the alkaline solution in the step 1)
The preferred ＞ 8 of pH.Meanwhile in the step 1), 2~24 hours are incubated at 150~240 DEG C and carries out hydro-thermal reaction.
The preparation method of the ferroelectric polymers based dielectric film of the present invention, wherein, in the step 1), hydro-thermal reaction
Afterwards, reaction product is washed to neutrality and dried.
The preparation method of the ferroelectric polymers based dielectric film of the present invention, wherein, in the step 2), in order to mix
It is even, it is stirred 12~24 hours.
The preparation method of the ferroelectric polymers based dielectric film of the present invention, wherein, the organic solvent in the step 2)
For acetone, N,N-dimethylformamide (DMF) or DMAC N,N' dimethyl acetamide (DMA).
The preparation method of the ferroelectric polymers based dielectric film of the present invention employs method of electrostatic spinning, and this method is advantageous to
The thin polymer film of special sandwich construction is prepared, wherein, in the step 3), positive and negative voltage difference >=5kV of high-voltage electrostatic spinning,
Collect rotating speed >=200 turn/min of wheel, solution fltting speed >=1mL/h.The proportion of solute (gram) and solution (milliliter) is
1:4.12~1:Between 7.83.
The preparation method of the ferroelectric polymers based dielectric film of the present invention, wherein, in the step 4), by the nonwoven
Cloth-like spinning body hot pressing 20~100 minutes under 100~500 DEG C, 400~600dpi pressure.
The preparation method of the ferroelectric polymers based dielectric film of the present invention, wherein, the non-woven fabric-like spinning body is entered
Row hot pressing, after naturally cooling to room temperature, after 150~250 DEG C are incubated 2~20 minutes, cold quenching is carried out at 0 DEG C, is advantageous to polymerize
Thing obtains preferable energy storage density.
The present invention also provides a kind of purposes of ferroelectric polymers based dielectric film of the present invention in electric elements.
The electric elements are embedded capacitor, electrostatic energy storage component or pulse power element.
Embodiment
Embodiment 1
Respectively by AlCl3·6H2O、NaOH、NH3OH is configured to concentration 1M solution in deionized water, then by NaOH
And NH3OH mixed solutions progressively slowly instill AlCl3In solution, solution is transferred to behind pH value=10 of solution poly-
In the reactor of tetrafluoroethene liner, 17 hours are incubated in the baking oven at 200 DEG C, sediment is obtained after Temperature fall, is spent
Ionized water and ethanol rinse sediment repeatedly, and until pH value is in neutrality, the sediment after drying is according to 98.32vol%P (VDF-
Co-HFP) -1.68vol%AlOOH (x=1.68) carries out dispensing, and it is standby that spinning solution is made after 12 hours using acetone as stirring solvent
With.The proportion of solute (gram) and solution (milliliter) is 1:5.
The uniform spinning body of polymer nanocomposite silk is prepared using high-voltage electrostatic spinning.The parameter of the high-voltage electrostatic spinning
For：Positive and negative voltage difference 6kV；300 revs/min of roller rotating speed, solution fltting speed 1mL per hour.
After spinning terminates, film is at 200 DEG C, and hot pressing 60 minutes, are then naturally cooling to room temperature under 500dpi.After hot pressing
Film is incubated 10 minutes after cold quenching at 0 DEG C in the environment of 240 DEG C, obtains ferroelectric polymers based dielectric film, is designated as thin
Film -1.
About 10 μm of the thickness of obtained film -1, the performance of the polymer-based dielectric film at 25 DEG C are：
Under 1KHz, dielectric constant and dielectric loss are respectively 10 and 0.04, disruptive field intensity 615kV/mm, energy storage density 24J/cm3。
Embodiment 2
Respectively by AlCl3·6H2O、NaOH、NH3OH is configured to concentration 1M solution in deionized water, then by NaOH
And NH3OH mixed solutions progressively slowly instill AlCl3In solution, solution is transferred to behind pH value=10 of solution poly-
In the reactor of tetrafluoroethene liner, 17 hours are incubated in the baking oven at 200 DEG C, sediment is obtained after Temperature fall, is spent
Ionized water and ethanol rinse sediment repeatedly, and until pH value is in neutrality, the sediment after drying is according to 90vol%P (VDF-co-
HFP) -10vol%AlOOH (x=10) carries out dispensing, and it is standby that spinning solution is made after 12 hours using acetone as stirring solvent.Solute
The proportion of (gram) and solution (milliliter) is 1:5.
The uniform spinning body of polymer nanocomposite silk is prepared using high-voltage electrostatic spinning.The parameter of the high-voltage electrostatic spinning
For：Positive and negative voltage difference 6kV；300 revs/min of roller rotating speed, solution fltting speed 1mL per hour.After spinning terminates, film exists
200 DEG C, 500dpi pressures hot pressing 60 minutes, then it is naturally cooling to room temperature.Film after hot pressing is incubated in the environment of 240 DEG C
After cold quenching at 0 DEG C, ferroelectric polymers based dielectric film is obtained, is designated as film -2 within 10 minutes.
About 9.8 μm of the thickness of obtained film -2, the performance of the polymer-based dielectric film at 25 DEG C are：
Under 1KHz, dielectric constant and dielectric loss are respectively 16 and 0.047, disruptive field intensity 620kV/mm, energy storage density 13J/
cm3。
Embodiment 3
Respectively by AlCl3·6H2O、NaOH、NH3OH is configured to concentration 1M solution in deionized water, then by NaOH
And NH3OH mixed solutions progressively slowly instill AlCl3In solution, solution is transferred to behind pH value=10 of solution poly-
In the reactor of tetrafluoroethene liner, 17 hours are incubated in the baking oven at 200 DEG C, sediment is obtained after Temperature fall, is spent
Ionized water and ethanol rinse sediment repeatedly, and until pH value is in neutrality, the sediment after drying is according to 93vol%P (VDF-co-
HFP) -7vol%AlOOH (x=7) carries out dispensing, and it is standby that spinning solution is made after 12 hours using acetone as stirring solvent.Solute
The proportion of (gram) and solution (milliliter) is 1:5.
The uniform spinning body of polymer nanocomposite silk is prepared using high-voltage electrostatic spinning.The parameter of the high-voltage electrostatic spinning
For：Positive and negative voltage difference 6kV；300 revs/min of roller rotating speed, after the 1mL spinning per hour of solution fltting speed terminates, film is 200
DEG C, 500dpi pressures hot pressing 60 minutes, then it is naturally cooling to room temperature.Film after hot pressing is incubated 10 in the environment of 240 DEG C
Minute after cold quenching at 0 DEG C, obtains ferroelectric polymers based dielectric film, is designated as film -3.
About 10.65 μm of the thickness of obtained film -3, the performance of the polymer-based dielectric film at 25 DEG C are：
Under 1KHz, dielectric constant and dielectric loss are respectively 21 and 0.04, disruptive field intensity 469kV/mm, energy storage density 9.7J/
cm3。
Comparative example 1
By P (VDF-co-HFP) powders of purchase according to every gram of solute corresponding 5 milliliters of mixed organic solvents (acetone and diformazans
The mixture of base formamide (DMF)) mixing after, at room temperature stir 12-24 hours, it is fully dissolved.Spun using high-pressure electrostatic
Silk prepares the uniform spinning body of polymer nanocomposite silk.The parameter of the high-voltage electrostatic spinning is：Positive and negative voltage difference 6kV；Roller turns
300 revs/min of speed, solution fltting speed 1mL per hour.After spinning terminates, at 200 DEG C, 500dpi pressure hot pressing 60 divides film
Clock, then it is naturally cooling to room temperature.Film after hot pressing is incubated 10 minutes after cold quenching at 0 DEG C in the environment of 240 DEG C, obtains
Ferroelectric polymers based dielectric film, is designated as film -4.
About 10 μm of the thickness of obtained film -4, the performance of the polymer-based dielectric film at 25 DEG C are：
Under 1KHz, dielectric constant and dielectric loss are respectively 9 and 0.03, and disruptive field intensity is about 400kV/mm, energy storage density 7.8J/
cm3。
Performance test
Round metal electrode is prepared by vacuum deposition method on sample thin film -1~4, and tests its properties.
Dielectric properties：Tested using electric impedance analyzer (Agilent company of the U.S., E4990A).
Disruptive field intensity and ferroelectric hysteresis loop：Using ferroelectricity tester (Radiant Tech., Precision Premier
II) tested, energy storage density and energy storage efficiency are calculated by ferroelectric hysteresis loop and obtained.
Claims (10)
1. a kind of ferroelectric polymers based dielectric film, it is characterised in that the thin dielectric film contains vinylidene-hexafluoro third
Alkene copolymer P (VDF-co-HFP) and inorganic matter AlOOH, wherein, with volume percentage, both proportionings are (100-x) %P
(VDF-co-HFP)-x%AlOOH, 0<x≤10.
2. ferroelectric polymers based dielectric film according to claim 1, it is characterised in that the thickness of the film is 5
~30 μm, preferably 6~20 μm.
3. ferroelectric polymers based dielectric film according to claim 1 or 2, it is characterised in that the inorganic matter AlOOH
Pattern be two-dimensional layer.
4. a kind of preparation method of ferroelectric polymers based dielectric film according to any one of claims 1 to 3, its feature
It is, comprises the following steps：
Step 1), by by comprising Al salt alkaline solution carry out hydro-thermal reaction, obtain inorganic matter AlOOH；
Step 2), by the inorganic matter AlOOH and the vinylidene fluoride-hexafluoropropylene copolymer P (VDF-co-HFP) by proportioning
Mix in organic solvent, obtain electrostatic spinning liquid；
Step 3), by the electrostatic spinning liquid carry out high-voltage electrostatic spinning, obtain non-woven fabric-like spinning body；
Step 4), by the non-woven fabric-like spinning body carry out hot pressing, carry out cold quenching after naturally cooling to room temperature, obtain ferroelectric polymer
Thing based dielectric film.
5. the preparation method of ferroelectric polymers based dielectric film according to claim 4, it is characterised in that the step
1) the pH ＞ 8 of the alkaline solution in.
6. the preparation method of the ferroelectric polymers based dielectric film according to claim 4 or 5, it is characterised in that described
In step 1), 2~24 hours are incubated at 150~240 DEG C and carries out hydro-thermal reaction.
7. the preparation method of the ferroelectric polymers based dielectric film according to any one of claim 4~6, its feature exist
In in the step 3), positive and negative voltage difference >=5kV of high-voltage electrostatic spinning collects rotating speed >=200 turn/min of wheel, and solution pushes away
Enter speed >=1mL/h.
8. the preparation method of the ferroelectric polymers based dielectric film according to any one of claim 4~7, its feature exist
In, in the step 4), by the film under 100~500 DEG C, 400~600dpi pressure hot pressing 20~100 minutes.
9. the preparation method of the ferroelectric polymers based dielectric film according to any one of claim 4~8, its feature exist
In, the non-woven fabric-like spinning body is subjected to hot pressing, after naturally cooling to room temperature, after 150~250 DEG C are incubated 2~20 minutes,
Cold quenching is carried out at 0 DEG C.
A kind of 10. use of the ferroelectric polymers based dielectric film in electrical equipment according to any one of claims 1 to 3
On the way.
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| CN114989464A (en) * | 2022-06-02 | 2022-09-02 | 华东师范大学 | PVDF/PMMA composite film and preparation method thereof |
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