CN114411334A - Capacitor film and preparation method and application thereof - Google Patents
Capacitor film and preparation method and application thereof Download PDFInfo
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- CN114411334A CN114411334A CN202210051294.5A CN202210051294A CN114411334A CN 114411334 A CN114411334 A CN 114411334A CN 202210051294 A CN202210051294 A CN 202210051294A CN 114411334 A CN114411334 A CN 114411334A
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- 239000003990 capacitor Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 42
- 239000002033 PVDF binder Substances 0.000 claims abstract description 27
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 239000000835 fiber Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 238000007731 hot pressing Methods 0.000 claims abstract description 18
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 17
- 238000010791 quenching Methods 0.000 claims abstract description 15
- 230000000171 quenching effect Effects 0.000 claims abstract description 15
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 14
- 239000002798 polar solvent Substances 0.000 claims abstract description 9
- 239000010408 film Substances 0.000 claims description 36
- 239000010409 thin film Substances 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 230000005684 electric field Effects 0.000 claims description 6
- 229920000131 polyvinylidene Polymers 0.000 claims description 6
- 229920005594 polymer fiber Polymers 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 2
- 238000001523 electrospinning Methods 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000004146 energy storage Methods 0.000 abstract description 20
- 230000015556 catabolic process Effects 0.000 abstract description 14
- 238000005191 phase separation Methods 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 30
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 10
- 239000004926 polymethyl methacrylate Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 208000012886 Vertigo Diseases 0.000 description 6
- 238000009987 spinning Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000205 poly(isobutyl methacrylate) Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Classifications
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/4318—Fluorine series
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/44—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
-
- 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
- H01G4/06—Solid dielectrics
- H01G4/14—Organic dielectrics
- H01G4/16—Organic dielectrics of fibrous material, e.g. paper
-
- 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
- H01G4/06—Solid dielectrics
- H01G4/14—Organic dielectrics
- H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose
-
- 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
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Power Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a capacitor film and a preparation method and application thereof. The first aspect of the present invention provides a method for preparing a capacitor film, comprising the steps of: dissolving a PVDF-based polymer and a polymer shown in a formula 1 in a polar solvent to prepare a mixed solution; carrying out electrostatic spinning treatment on the mixed solution to obtain a composite fiber non-woven fabric; and carrying out hot pressing treatment, heat treatment and cold quenching treatment on the composite fiber non-woven fabric in sequence to obtain the capacitor film. According to the preparation method provided by the invention, the polymer shown in the formula 1 is added into the PVDF-based polymer, and after electrostatic spinning, hot pressing, heat treatment and cold quenching treatment, a phase separation structure can be formed automatically, so that the mechanical property and the electrical property of the composite polymer are improved, and the capacitor film has higher breakdown field strength and energy storage density.
Description
Technical Field
The invention relates to a capacitor film, a preparation method and application thereof, and relates to the technical field of capacitor films.
Background
The capacitor is sometimes required to operate under high voltage and high temperature environment, so the requirement on the breakdown field intensity of the capacitor dielectric is high, particularly in the construction of future urban power grids, overhead lines are gradually replaced by high-voltage cables, and the capacitor dielectric is required to have excellent high-voltage resistance, mechanical property and aging resistance.
The PVDF-based capacitor film is a commonly used capacitor medium at present, but the energy storage density is low, the breakdown field strength is still concentrated at 500MV/m, and more attention is paid to how to improve the energy storage density and the breakdown field strength of the PVDF-based capacitor film.
Disclosure of Invention
The invention provides a capacitor film and a preparation method thereof, which are used for improving the energy storage density and the breakdown field strength of a PVDF-based capacitor film.
The first aspect of the present invention provides a method for preparing a capacitor film, comprising the steps of:
dissolving a PVDF-based polymer and a polymer shown in a formula 1 in a polar solvent to prepare a mixed solution; carrying out electrostatic spinning treatment on the mixed solution to obtain a composite fiber non-woven fabric; carrying out hot pressing treatment, heat treatment and cold quenching treatment on the composite fiber non-woven fabric in sequence to obtain the capacitor film;
in formula 1, R is saturated alkyl, n is a positive integer greater than 0, and the molecular weight of the polymer in formula 1 is 30000-150000.
According to the preparation method provided by the invention, the polymer shown in the formula 1 is added into the PVDF-based polymer, and after electrostatic spinning, hot pressing, heat treatment and cold quenching treatment, a phase separation structure can be formed automatically, the mechanical property and the electrical property of the composite polymer are improved, so that the capacitor film has higher breakdown field strength and energy storage density.
Fig. 1 is a schematic flow chart of a preparation method according to an embodiment of the present invention, and as shown in fig. 1, the method specifically includes the following steps:
step 1, dissolving a PVDF-based polymer and a polymer shown in a formula 1 in a polar solvent to prepare a mixed solution;
the PVDF-based polymer refers to a polymer obtained by polymerizing vinylidene fluoride in a polymerization monomer, and specifically includes one or more of polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (P (VDF-HFP)), polyvinylidene fluoride-trifluoroethylene (P (VDF-TrFE)), polyvinylidene fluoride-chlorotrifluoroethylene (P (VDF-CTFE)), and poly (vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene) (P (VDF-TrFE-CTFE)), and has the following structures, wherein x and y respectively represent polymerization degrees and are positive integers greater than 0, and the molecular weight of the PVDF-based polymer is 30000-150000:
the polymer represented by formula 1 is obtained by polymerizing isobutyl alkylacrylate, for example, polyisobutyl methacrylate, polyisobutyl polyethylacrylate, etc., having a molecular weight of 30000-150000; further, the polymer shown in formula 1 is polyisobutyl methacrylate (p (ibma)), and the polymerization methods of the PVDF-based polymer and the polymer shown in formula 1 can adopt the conventional technical means in the art, and the details of the present invention are not repeated herein.
Dissolving PVDF-based polymer and the polymer shown in formula 1 in a certain mass ratio in a polar solvent, and stirring to obtain a mixed solution, wherein the mixed solution is used for further regulating the capacitor filmThe breakdown field strength and the energy storage density of the capacitor film can reach 830MV/m and the energy storage density reaches 21J-cm when the mass ratio of the PVDF-based polymer to the polymer shown in the formula 1 is 10/1 through experiments-3The performance is excellent; the polar solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, acetone and dimethyl sulfoxide, and a mixed solution with the mass fraction of 0.01-0.5% is prepared.
the method comprises the following steps of (1) carrying out electrostatic spinning treatment on a mixed solution, wherein the electrostatic spinning is used as a fiber manufacturing process, the mixed solution is subjected to jet spinning by using a strong electric field to obtain polymer fibers, and a composite fiber non-woven fabric is obtained by a fiber collecting device;
in the electrostatic spinning treatment process, the diameter of the fiber and the thickness of the composite fiber non-woven fabric can be effectively controlled by controlling parameters, specifically, the voltage difference of the electric field is 1-20kV, the fiber cannot be formed when the voltage difference is lower than 1kV, and the instrument is damaged when the voltage difference is higher than 20 kV; the advancing speed of the injector is 0.1-3mL/h, the vertical distance between the outlet of the needle head of the injector and the roller, namely the spinning distance is 20-40cm, the rotating speed of the roller is 50-300r/min, the electrostatic spinning treatment can be finished after the spinning of the mixed solution is finished, and the thickness of the composite fiber non-woven fabric can be controlled by controlling the spinning time.
Step 3, carrying out hot-pressing treatment, heat treatment and cold quenching treatment on the composite fiber non-woven fabric in sequence to obtain the capacitor film;
carrying out hot-pressing treatment on the composite fiber non-woven fabric obtained in the step 2 to form a film-shaped material at high temperature and high pressure; during the hot-pressing treatment, the temperature of the hot-pressing treatment is controlled to be 100-.
And after the hot pressing treatment is finished, transferring the hot pressing product to a heating platform for heat treatment, wherein in the heat treatment period, PVDF in other crystal phases is converted into PVDF in a beta phase, so that the polarization of the composite material is facilitated, and the energy storage density of the composite material is improved, specifically, the heat treatment temperature is 100-300 ℃, and the time is 1-30 min.
And after the heat treatment is finished, putting the heat-treated product into ice water for cold quenching treatment to stably maintain the beta-phase PVDF formed by the heat treatment, wherein during the cold quenching treatment, the temperature of the cold quenching is controlled to be 0-10 ℃ for 1-30min, and the capacitor film can be obtained after the cold quenching is finished.
The thickness of the capacitor film prepared by the preparation method is 1-30 mu m, and the capacitor films with different thicknesses have different breakdown field strengths, so that thicker films are possibly needed in some heavy industries, but thinner films are needed on electric automobiles, and the thickness of the capacitor film can be controlled by a person skilled in the art by controlling preparation process parameters.
In conclusion, according to the preparation method provided by the invention, the polymer shown in the formula 1 is added into the PVDF-based polymer, and after electrostatic spinning, hot pressing, heat treatment and cold quenching treatment, a phase separation structure can be formed autonomously, so that the mechanical property and the electrical property of the composite polymer are improved, and the capacitor film has higher breakdown field strength and energy storage density.
In a second aspect, the present invention provides a capacitor film prepared according to any one of the above-mentioned preparation methods.
The third aspect of the present invention provides the use of the above capacitor film in an electrical device, such as an embedded capacitor, an electrostatic storage device, a pulse power device, or the like.
According to the preparation method provided by the invention, the polymer shown in the formula 1 is added into the PVDF-based polymer, and after electrostatic spinning, hot pressing, heat treatment and cold quenching treatment, a phase separation structure can be formed automatically, the mechanical property and the electrical property of the composite polymer are improved, so that the capacitor film has higher breakdown field strength and energy storage density.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic flow chart of a preparation method according to an embodiment of the present invention;
FIG. 2 is a scanning electron micrograph of a polymer fiber provided in example 1 of the present invention;
FIG. 3 is a SEM photograph of a cross-sectional structure of a capacitor thin film provided in example 1 of the present invention;
FIG. 4 is a scanning electron micrograph of a polymeric fiber according to comparative example 1 of the present invention;
FIG. 5 is a scanning electron micrograph of a cross-sectional structure of a capacitor thin film provided in comparative example 1 of the present invention;
FIG. 6 shows the energy storage density and charge/discharge efficiency of the capacitor thin films provided in examples 1 to 7 of the present invention;
fig. 7 shows the energy storage density and the charge and discharge efficiency of the capacitor films provided in comparative examples 1 to 7 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
The preparation method of the capacitor film provided by the embodiment comprises the following steps:
step 1, dissolving P (VDF-HFP) and P (iBMA) (with the molecular weight of 26 ten thousand) in a polar solvent at a mass ratio of 10/1, wherein the polar solvent comprises N, N-dimethylformamide and acetone (in a volume ratio of 3: 2), stirring for 12 hours at 60 ℃, and continuously stirring for 6 hours at room temperature to prepare a mixed solution with the mass fraction of 2.3%;
step 3, carrying out hot-pressing treatment on the composite fiber non-woven fabric, wherein the temperature of the hot-pressing treatment is 180 ℃, the pressure is 1000psi, and the time is 30 min;
and after the hot pressing treatment is finished, placing the capacitor film on a heating platform, heating the capacitor film at 200 ℃ for 5min, putting the capacitor film into water at 0 ℃, performing cold quenching for 5min, placing the capacitor film in an oven at 45 ℃, and drying water to obtain the capacitor film.
Example 2
The capacitor thin film provided in this example can be prepared by referring to example 1, except that in step 1, the mass ratio of P (VDF-HFP) to P (ibma) is 9/2.
Example 3
The capacitor thin film provided in this example can be prepared by referring to example 1, except that in step 1, the mass ratio of P (VDF-HFP) to P (ibma) is 8/3.
Example 4
The capacitor thin film provided in this example can be prepared by referring to example 1, except that in step 1, the mass ratio of P (VDF-HFP) to P (ibma) is 7/4.
Example 5
The capacitor thin film provided in this example can be prepared by referring to example 1, except that in step 1, the mass ratio of P (VDF-HFP) to P (ibma) is 6/5.
Example 6
The capacitor thin film provided in this example can be prepared by referring to example 1, except that in step 1, the mass ratio of P (VDF-HFP) to P (ibma) is 11/0.
Example 7
The capacitor thin film provided in this example can be prepared by referring to example 1, except that in step 1, the mass ratio of P (VDF-HFP) to P (ibma) is 0/11.
Comparative example 1
The method for manufacturing a capacitor thin film provided by this comparative example can refer to example 1 except that, in step 1, P (VDF-HFP) and PMMA (molecular weight 3 ten thousand 5) in a mass ratio of 10/1 are dissolved in a polar solvent to prepare a mixed solution.
Comparative example 2
The method for manufacturing a capacitor thin film provided by the present comparative example can be referred to comparative example 1 except that the mass ratio of P (VDF-HFP) to PMMA in step 1 is 9/2.
Comparative example 3
The method for manufacturing a capacitor thin film provided by the present comparative example can be referred to comparative example 1 except that the mass ratio of P (VDF-HFP) to PMMA in step 1 is 8/3.
Comparative example 4
The method for manufacturing a capacitor thin film provided by the present comparative example can be referred to comparative example 1 except that the mass ratio of P (VDF-HFP) to PMMA in step 1 is 7/4.
Comparative example 5
The method for manufacturing a capacitor thin film provided by the present comparative example can be referred to comparative example 1 except that the mass ratio of P (VDF-HFP) to PMMA in step 1 is 6/5.
Comparative example 6
The method for manufacturing a capacitor thin film provided by the present comparative example can be referred to comparative example 1 except that the mass ratio of P (VDF-HFP) to PMMA in step 1 is 11/0.
Comparative example 7
The method for manufacturing a capacitor thin film provided by the present comparative example can be referred to comparative example 1 except that the mass ratio of P (VDF-HFP) to PMMA in step 1 is 0/11.
For a clearer understanding of the invention, the polymers used in examples 1 to 7 and comparative examples 1 to 7 and their mass ratios are tabulated and shown in Table 1:
TABLE 1 polymers and mass ratios thereof used in examples 1 to 7 and comparative examples 1 to 7
| Example (P (VDF-HFP) + P (iBMA)) | Comparative example (P (VDF-HFP) + PMMA) | |
| 1 | 10/1 | 10/1 |
| 2 | 9/2 | 9/2 |
| 3 | 8/3 | 8/3 |
| 4 | 7/4 | 7/4 |
| 5 | 6/5 | 6/5 |
| 6 | 11/0 | 11/0 |
| 7 | 0/11 | 0/11 |
Scanning electron microscope test of section morphology of the composite fiber in the non-woven fabric prepared in the step 2 of the example 1 and the non-woven fabric prepared in the step 3 of the comparative example 1 was performed by using a scanning electron microscope of MWRLIN compact of Zeiss company, as shown in the fig. 2-5, respectively, it is known from comparison between the fig. 2-3 and the fig. 4-5 that, under the same mass ratio, P (iBMA) is added into PVDF-based polymer, and after electrostatic spinning, hot pressing, heat treatment and cold quenching treatment, a phase separation structure can be formed autonomously, while no phase separation structure is formed by adding PMMA.
Then, the cross sections of the capacitor thin films prepared in examples 1 to 7 and comparative examples 1 to 7 were coated with a copper electrode having a diameter of 3mm by evaporation, and a electromigration-electric field curve test was performed using a Premier II ferroelectric tester manufactured by Radiant Technologies at a frequency of 10Hz to obtain an electric field strength (MV/m), an electric displacement, an energy storage density (also referred to as an energy density), and a total energy density, and then the data were processed and calculated in origin and plotted to obtain an electric field strength (MV/m) and an energy density (J. cm)-3) And charge-discharge efficiency (100%), wherein the total energy density (J · cm)-3) Energy storage density + loss density, and charge-discharge efficiency (%) -energy storage density/total energy density.
FIG. 6 shows the energy storage density and the charge-discharge efficiency of the capacitor thin films provided in examples 1 to 7 of the present invention, and FIG. 7 shows the energy storage density and the charge-discharge efficiency of the capacitor thin films provided in comparative examples 1 to 7 of the present invention, as shown in FIGS. 6 to 7, it can be seen from comparison between FIGS. 6 to 7 that the capacitor thin films obtained by adding P (iBMA) to the PVDF-based polymer have higher breakdown field strength and energy density than the capacitor thin films obtained by adding PMMA in the comparative examples; according to FIG. 6It is known that the breakdown field strength of the capacitor film prepared by mixing P (VDF-HFP) with P (iBMA) is significantly improved compared with that of the capacitor film prepared by mixing P (VDF-HFP) with P (iBMA), and the breakdown field strength and the energy storage density of the capacitor film are maximized when the mass ratio of the PVDF-based polymer to the linear polymer is 10/1, the breakdown field strength is 830MV/m, and the energy storage density is 21J-cm-3However, as P (VDF-HFP) is inevitably lost under a high field, compared with P (VDF-HFP), the charging and discharging efficiency of P (VDF-HFP)/P (iBMA) (10/1) is slightly reduced, but the charging and discharging efficiency is basically kept close under the high field, which shows that the capacitor film provided by the invention has a better application prospect in energy storage devices such as high-voltage capacitors and the like.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the capacitor film is characterized by comprising the following steps:
dissolving a PVDF-based polymer and a polymer shown in a formula 1 in a polar solvent to prepare a mixed solution; carrying out electrostatic spinning treatment on the mixed solution to obtain a composite fiber non-woven fabric; carrying out hot pressing treatment, heat treatment and cold quenching treatment on the composite fiber non-woven fabric in sequence to obtain the capacitor film;
in formula 1, R is saturated alkyl, n is a positive integer greater than 0, and the molecular weight of the polymer in formula 1 is 30000-150000.
2. The method of claim 1, wherein the PVDF-based polymer comprises one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride-trifluoroethylene, polyvinylidene fluoride-chlorotrifluoroethylene, poly (vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene).
3. The method according to claim 1, wherein R is a methyl group.
4. The method according to any one of claims 1 to 3, wherein the mass ratio of the PVDF-based polymer to the polymer represented by formula 1 is 10/1.
5. The method according to claim 1, wherein the electrospinning process specifically comprises: placing the mixed solution in an injector, controlling the propelling speed of the injector to enable the mixed solution to flow out from the needle head of the injector, extending to obtain polymer fibers under the action of an electric field, and collecting the polymer fibers by using a roller to obtain the composite fiber non-woven fabric, wherein the voltage difference of the electric field is 1-20kV, the propelling speed of the injector is 0.1-3mL/h, the vertical distance between the outlet of the needle head of the injector and the roller is 20-40cm, and the rotating speed of the roller is 50-300 r/min.
6. The method as claimed in claim 1, wherein the temperature of the hot pressing is 100-200 ℃, the pressure is 200-1500psi, and the time is 5-60 min.
7. The method as claimed in claim 1, wherein the heat treatment is carried out at a temperature of 100 ℃ and 300 ℃ for a period of 1-30 min.
8. The preparation method according to claim 1, wherein the temperature of the cold quenching treatment is 0-10 ℃ and the time is 1-30 min.
9. The capacitor thin film produced by the production method according to any one of claims 1 to 8.
10. Use of the capacitor film of claim 9 in an electrical component.
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