CN102924732A - Method for preparing polyvinylidene fluoride (PVDF)-hexafluoropropylene (HFP) modification membrane of high energy density through hot pressing cross linking - Google Patents
Method for preparing polyvinylidene fluoride (PVDF)-hexafluoropropylene (HFP) modification membrane of high energy density through hot pressing cross linking Download PDFInfo
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- 238000004132 cross linking Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000007731 hot pressing Methods 0.000 title claims abstract description 24
- 239000012528 membrane Substances 0.000 title claims abstract description 17
- 229920002981 polyvinylidene fluoride Polymers 0.000 title abstract description 6
- 239000002033 PVDF binder Substances 0.000 title abstract 4
- 230000004048 modification Effects 0.000 title abstract 4
- 238000012986 modification Methods 0.000 title abstract 4
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims abstract description 77
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 21
- 238000001291 vacuum drying Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000004146 energy storage Methods 0.000 claims description 41
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000011159 matrix material Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000013557 residual solvent Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 abstract description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 abstract description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 2
- 239000011218 binary composite Substances 0.000 abstract 2
- 239000000463 material Substances 0.000 description 26
- 238000005303 weighing Methods 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 6
- 230000005684 electric field Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 4
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 4
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication 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
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
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Abstract
The invention discloses a method for preparing a polyvinylidene fluoride (PVDF)-hexafluoropropylene (HFP) modification membrane of high energy density through hot pressing cross linking. The method comprises steps of dissolving cross linking agents benzoyl peroxide (BPO) and PVDF-HFP by using a solvent, preparing a transparent uniform solution, pouring the solution to a dispersed uniform BPO/PVDF-HFP binary composite material on the normal temperature condition, removing a residual solution through vacuum drying, placing the BPO/PVDF-HFP binary composite material in a tablet press, and on certain temperature and pressure conditions, preparing the PVDF-HFP cross linking modification membrane through the hot pressing cross linking. The method is simple in process, an expensive ultraviolet light cross linking method or an expensive electron irradiation method is not used, the energy density of the prepared cross linking modification membrane is improved and the dielectric loss is reduced.
Description
Technical field
The present invention relates to novel energy-storing material technology field, relate in particular to the method for the PVDF-HFP modified membrane of the crosslinked preparation high energy storage density of a kind of hot pressing.
Background technology
Along with the continuous growth of dielectric materials in electric capacity, message memory and sensor demand, development high energy storage density and high-power energy storage material help to develop and have the novel capacitor material that cost is low, volume is little, lightweight and specific power is large and be applied in the industry.Wherein, vinylidene fluoride copolymers has the excellent performance such as high specific inductivity and Gao Nai breaking down field strength, fast charging and discharging speed, low cost and good stability because of it, be the best energy storage material of control and stored charge and electric energy, in the hyundai electronics power system is used, play an important role.The large I of electrical power storage density of material is calculated by (1) formula.
Wherein, U
eBe the energy storage density of material, E is the disruptive field intensity of material, and D is electricdisplacement.
This shows, the method that improves the energy storage density of material has two kinds: (1) improves the electricdisplacement of material, namely improves the polarizability of material.The factor that affects the electropolarization size of material has a lot.So that vinylidene (VDF)-R 1216 (HFP) multipolymer (PVDF-HFP) is as example, the PVDF-HFP chemical structure is-(CH
2-CF
2)
n-(CF
2-CFCF
3)
m-, C-F key on its main chain is larger than C-H or the C-C polarity on the main chain of polyethylene (PE) and Biaxially oriented polypropylene film (BOPP) (BOPP), be easier to occur dipole polarization under electric field action, its electricdisplacement is also larger, therefore the energy storage density of PVDF-HFP is higher than PE and BOPP.Secondly, the PVDF-HFP crystal property that VDF content is higher is good, and wherein the domain structure size is larger, is difficult for occuring the orientation upset in electric field, namely is difficult for being oriented polarization in electric field, and its electricdisplacement is smaller.If the size by suitable way modulation PVDF-HFP domain structure diminishes domain structure, make its domain structure in electric field, be easy to upset, its electricdisplacement will become greatly, and the energy storage density of material also improves thereupon.(2) the anti-breaking down field strength of raising material.According to formula (2):
（2）
Wherein,
Be permittivity of vacuum,
Be the measured specific inductivity of material, Em is the anti-disruptive strength of material.From formula as can be known, the energy storage density of material is directly proportional with the quadratic power of anti-disruptive strength.Therefore, improve the anti-disruptive strength of material, can increase substantially the energy storage density of material.
Adopt the ultraviolet light cross-linking method can greatly improve the energy storage density of vinylidene fluoride copolymers film.(X.Z. Chen. et al. Greatly Enhanced Energy Density and Patterned Films Induced by Photo Cross-Linking of Poly(vinylidene fluoride-chlorotrifluoroethylene[J]. Macromolecular Rapid Communication. October 2012. Vol.32. 94-99. Online ISSN 1521-3927.)。Its principle is that photo-crosslinking is introduced more polycrystal-noncrystal interface, so that more electric charge distributes in polymkeric substance and stores, polarizability has improved nearly one times, and the energy storage density of vinylidene fluoride copolymers film greatly improves.But owing to adopting the method for photo-crosslinking, there are the shortcomings such as poor stability, price of photocrosslinking agent, cause the manufacturing cost of material to improve.Adopt electron irradiation that a large amount of defectives is incorporated in the multipolymer, the size of modulation ferroelectric domain makes original normal ferroelectrics change ferroelectric relaxation body into, and the energy storage density of material has improved.(Q.M. Zhang. et al. Giant Electrostriction and Relaxor Ferroelectric Behavior in Electron-Irradiated Poly(vinylidene fluoride-trifluoroethylene) Copolymer[J]. Science. June 1998. Vol.280. pages 2101 and 2104. Online ISSN 1095-9203.) 。But the dosage of an irradiation is few, and to stability and the poor reproducibility of structural modulation, is unfavorable for industrial scale operation.
Summary of the invention
Problem for above-mentioned prior art existence, the method that the purpose of this invention is to provide the PVDF-HFP modified membrane of the crosslinked preparation high energy storage density of a kind of hot pressing, adopt different content initiator B PO, it is benzoyl peroxide, the crosslinked PVDF-HFP of hot pressing, the cross-linking modified film energy storage density of prepared PVDF-HFP improves, dielectric loss reduces, and the method for the invention technique is simple, can effectively improve the energy storage density of material, avoid simultaneously with adopting expensive optical cross-linking method, electron irradiation method.
For reaching described purpose, the technical scheme that the present invention takes is: the method for the PVDF-HFP modified membrane of the crosslinked preparation high energy storage density of a kind of hot pressing comprises the steps:
A. the preparation of the binary matrix material solution of crosslinking agent B PO/PVDF-HFP: PVDF-HFP is dissolved in N, dinethylformamide, being mixed with concentration is 0.04g/ml, then adds the crosslinking agent B PO of different crosslinked ratios, stirs at normal temperatures the solution of transparent homogeneous.
B. remove solvent: solution casting described in the steps A in the tetrafluoroethylene mould, is dried in baking oven first at normal temperatures, continue oven dry in vacuum drying oven again, guaranteeing does not wherein have residual solvent, namely obtains the binary matrix material of crosslinking agent B PO/PVDF-HFP.
C. hot pressing crosslinking reaction: the described binary matrix material of step B is positioned in the tabletting machine crosslinked, crosslinked to guarantee that BPO and PVDF-HFP can fully react generation, make thickness and be about 20 ~ 30
The cross-linking modified film of the PVDF-HFP of high energy storage density.
The molar percentage of HFP among the PVDF-HFP described in the steps A is 2.5% ~ 30%, and the preferred monomers mol ratio is: n
VDF: n
HFP=97.5:2.5.
PVDF-HFP described in the steps A and crosslinking agent B PO mass ratio are: 100:5 ~ 15.
The built-in temperature of compressing tablet described in the step C is that 200 ℃, pressure are 5Mpa.
Crosslinking time is no less than 2h described in the step C, and is crosslinked to guarantee that BPO and PVDF-HFP can fully react generation.
The reaction mechanism of the crosslinked PVDF-HFP of crosslinking agent B PO hot pressing of the present invention is as follows:
The first step: crosslinking agent B PO decomposes the free agent of generation;
Second step: the hydrogen atom on the main chain is captured in free agent, produces the chain free radical;
The 3rd step: the chain free radical coupling stops, and obtains the cross-linking modified film of PVDF-HFP.
The method of the invention can change the PVDF-HFP crystalline structure shown in Fig. 1-4, the crosslinked while also changes the size on PVDF-HFP polarity farmland, so that PVDF-HFP produces the polarity farmlands that are easy to polarize more, the polarity of material is switching little, under identical current field condition, the upset ability of the polarizability of material and electricdomain improves widely, therefore the energy storage density of PVDF-HFP also improves thereupon.
PVDF-HFP and crosslinking agent B PO mass percent are 100:5 ~ 15 in the cross-linking modified film of the PVDF-HFP that the method for the invention makes, can be applicable to prepare the electric capacity of high energy storage density, low-dielectric loss, help to develop and have the novel capacitor material that cost is low, volume is little, lightweight and specific power is large.Beneficial effect of the present invention: 1. the inventive method is simple, and used linking agent low price obtains the cross-linking modified film of PVDF-HFP of high energy storage density.When strength of electric field was 250MV/m, the polarizability of pure PVDF-HFP was 3.22, and energy storage density is 5.82 J/cm
3, and the polarizability of the cross-linking modified film of the prepared PVDF-HFP of the present invention is 5.09, energy storage density is up to 7.51 J/cm
3, energy storage density has improved 29%.2. can effectively reduce the dielectric loss of PVDF-HFP, its dielectric loss is from original 5.27% reduction by 3.33%, and its dielectric loss has reduced by 58%.
Description of drawings
The domain structure of the crosslinked front PVDF-HFP of Fig. 1 the method for the invention;
The domain structure of the crosslinked rear PVDF-HFP of Fig. 2 the method for the invention;
The polarization of the crosslinked front and back PVDF-HFP of Fig. 3 the method for the invention;
The energy density curve of the crosslinked front and back PVDF-HFP of Fig. 4 the method for the invention.
Embodiment
The following examples will specify the preparation process of cross-linking modified film and the performance test process of corresponding material.
Embodiment 1:
Taking by weighing respectively the 1.00g molecular weight is 30 ~ 400,000, the mol ratio of vinylidene and R 1216 is that the vinylidene fluoride-hexafluoropropylene copolymer PVDF-HFP of 97.5:2.5 and 0.050g crosslinking agent B PO are dissolved in and fill 25 milliliters of N in the multipolymer, in the tool plug conical flask shape of the 50ml of dinethylformamide, stirring device with magnetic force under normal temperature mixes to the solution that becomes transparent homogeneous, mentioned solution is cast on the tetrafluoroethylene mould, in baking oven, dry at normal temperatures first, continue oven dry in vacuum drying oven again, guaranteeing does not wherein have residual solvent, can obtain the binary matrix material of crosslinking agent B PO/PVDF-HFP.Taking by weighing the binary matrix material that quality is about 0.035g is positioned between two pads, be that 200 ℃, pressure are under the condition of 5Mpa in temperature, adopt the crosslinked 2h of powder compressing machine 769YP-15A hot pressing, to guarantee can crosslinking reaction occuring fully with crosslinking agent B PO and PVDF-HFP, make thickness and be about 20 ~ 30
The cross-linking modified film of the PVDF-HFP of high energy storage density.
Embodiment 2:
Taking by weighing respectively the 1.00g molecular weight is 30 ~ 400,000, the mol ratio of vinylidene and R 1216 is that the vinylidene fluoride-hexafluoropropylene copolymer PVDF-HFP of 97.5:2.5 and 0.100g crosslinking agent B PO are dissolved in and fill 25 milliliters of N in the multipolymer, in the tool plug conical flask shape of the 50ml of dinethylformamide, stirring device with magnetic force under normal temperature mixes to the solution that becomes transparent homogeneous, mentioned solution is cast on the tetrafluoroethylene mould, in baking oven, dry at normal temperatures first, continue oven dry in vacuum drying oven again, guaranteeing does not wherein have residual solvent, can obtain the binary matrix material of crosslinking agent B PO/PVDF-HFP.Taking by weighing the binary matrix material that quality is about 0.035g is positioned between two pads, be that 200 ℃, pressure are under the condition of 5Mpa in temperature, adopt the crosslinked 2h of powder compressing machine 769YP-15A hot pressing, to guarantee can crosslinking reaction occuring fully with crosslinking agent B PO and PVDF-HFP, make thickness and be about 20 ~ 30
The cross-linking modified film of the PVDF-HFP of high energy storage density.
Embodiment 3:
Taking by weighing respectively the 1.00g molecular weight is 30 ~ 400,000, the mol ratio of vinylidene and R 1216 is that the vinylidene fluoride-hexafluoropropylene copolymer PVDF-HFP of 97.5:2.5 and 0.150g linking agent benzoyl peroxide are dissolved in and fill 25 milliliters of N in the multipolymer, in the tool plug conical flask shape of the 50ml of dinethylformamide, stirring device with magnetic force under normal temperature mixes to the solution that becomes transparent homogeneous, mentioned solution is cast on the tetrafluoroethylene mould, in baking oven, dry at normal temperatures first, continue oven dry in vacuum drying oven again, guaranteeing does not wherein have residual solvent, can obtain the binary matrix material of crosslinking agent B PO/PVDF-HFP.Taking by weighing the binary matrix material that quality is about 0.035g is positioned between two pads, be that 200 ℃, pressure are under the condition of 5Mpa in temperature, adopt the crosslinked 2h of powder compressing machine 769YP-15A hot pressing, to guarantee can crosslinking reaction occuring fully with crosslinking agent B PO and PVDF-HFP, make thickness and be about 20 ~ 30
The cross-linking modified film of the PVDF-HFP of high energy storage density.
The prepared cross-linking modified film properties index of PVDF-HFP of above-described embodiment is as shown in the table, the detection method that adopts is: the material clip that will detect is in two metal masks, and the aperture is 2.8mm, and is fixing, place ion film plating instrument SBC-12, keep certain vacuum tightness to carry out sputter.About sputtering current 4mA, sputtering time is about 8min, sputter thickness 30 ~ 40nm, and the area on film two sides is about 0.0615cm
2Adopt Changzhou with sending us the TH2828/A/S of Subsidiary Company instrument by cable, the loading test voltage is 1.0V, test frequency: 100 ~ 1000000HZ.Dielectric loss according to formula and the cross-linking modified film of calculating:
Wherein, be the dielectric loss of material, be the dielectric imaginary part of material, be the dielectric real part;
Adopt ferroelectric tester RT6000HVS, test voltage scope 0-10000V can record the ferroelectric hysteresis loop of PVDF-HFP, and the recycling formula calculates the energy storage density of the cross-linking modified film of PVDF-HFP;
When test frequency is 1000Hz, record the dielectric loss of the cross-linking modified film of PVDF-HFP; When strength of electric field is 250MV/m, record polarizability and energy storage density.
Wherein Comparative Examples 1 is that polyvinylidene difluoride (PVDF)-R 1216 of 0.035g is 200 ℃ in temperature for directly taking by weighing quality, and pressure is to adopt powder compressing machine 769YP-15A hot pressing 2h under the condition of 5Mpa, and the thickness that makes is about the PVDF-HFP film of 20 ~ 30 μ m.
Shown in table 1 and Fig. 1-4, for the method for the invention is simple, polarizability, the energy storage density of the cross-linking modified film of prepared PVDF-HFP improve greatly, effectively reduce the dielectric loss of PVDF-HFP simultaneously.
The performance index of table 1 PVDF-HFP modified membrane
| Energy storage density | Polarizability | Dielectric loss | |
| J/cm 3 | μc/cm 2 | ||
| Embodiment 1 | 6.24 | 3.67 | 4.50% |
| |
6.88 | 4.19 | 3.81% |
| |
7.51 | 5.09 | 3.33% |
| Comparative Examples 1 | 5.82 | 3.22 | 5.27% |
Claims (8)
1. the method for the PVDF-HFP modified membrane of the crosslinked preparation high energy storage density of hot pressing adopts the crosslinked PVDF-HFP of different content crosslinking agent B PO hot pressing, makes cross-linking modified film PVDF-HFP.
2. the method for the PVDF-HFP modified membrane of the crosslinked preparation high energy storage density of hot pressing according to claim 1 comprises the steps:
The preparation of the binary matrix material solution of A crosslinking agent B PO/PVDF-HFP: PVDF-HFP is dissolved in DMF, and being mixed with concentration is 0.04g/ml, then adds the crosslinking agent B PO of different crosslinked ratios, stirs at normal temperatures the solution of transparent homogeneous;
BRemove solvent: solution casting described in the steps A in the tetrafluoroethylene mould, is dried in baking oven first at normal temperatures, continue oven dry in vacuum drying oven again, guaranteeing does not wherein have residual solvent, namely obtains the binary matrix material of crosslinking agent B PO/PVDF-HFP;
CThe hot pressing crosslinking reaction: the described binary matrix material of step B is positioned in the tabletting machine crosslinked, crosslinked to guarantee that BPO and PVDF-HFP can fully react generation, make the cross-linking modified film of PVDF-HFP that thickness is about 20 ~ 30 μ m high energy storage densities.
3. the method for the PVDF-HFP modified membrane of the crosslinked preparation high energy storage density of hot pressing according to claim 2, it is characterized in that: the molar percentage of the HFP among the PVDF-HFP described in the steps A is 2.5% ~ 30%.
4. the method for the PVDF-HFP modified membrane of the crosslinked preparation high energy storage density of hot pressing according to claim 3, it is characterized in that: the monomer mole ratio among the PVDF-HFP described in the steps A is: n
VDF: n
HFP=97.5:2.5.
5. the method for the PVDF-HFP modified membrane of the crosslinked preparation high energy storage density of each described hot pressing according to claim 2-4, it is characterized in that: the PVDF-HFP described in the steps A and crosslinking agent B PO mass ratio are: 100: 5 ~ 15.
6. the method for the PVDF-HFP modified membrane of the crosslinked preparation high energy storage density of each described hot pressing according to claim 2-4 is characterized in that: the built-in temperature of compressing tablet described in the step C is that 200 ℃, pressure are 5Mpa.
7. the method for the PVDF-HFP modified membrane of the crosslinked preparation high energy storage density of hot pressing according to claim 5 is characterized in that: the built-in temperature of compressing tablet described in the step C is that 200 ℃, pressure are 5Mpa.
8. the method for the PVDF-HFP modified membrane of the crosslinked preparation high energy storage density of hot pressing according to claim 7, it is characterized in that: crosslinking time is no less than 2h described in the step C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108148210A (en) * | 2018-01-15 | 2018-06-12 | 中国科学院上海应用物理研究所 | A kind of intramolecular crosslinking polymer, preparation method and applications |
| EP3524637A1 (en) * | 2018-02-09 | 2019-08-14 | Daikin Industries, Ltd. | Fluoroelastomer composition and molded article thereof |
| US11554346B2 (en) | 2018-01-25 | 2023-01-17 | Katholieke Universiteit Leuven | Cross-linked nanofiltration membranes |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260216A (en) * | 2008-04-29 | 2008-09-10 | 哈尔滨工业大学 | PVDF-HFP base composite porous polymer membrane and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101260216A (en) * | 2008-04-29 | 2008-09-10 | 哈尔滨工业大学 | PVDF-HFP base composite porous polymer membrane and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| A. TAGUET ET AL.: "《Crosslinking in Materials Science Advances in Polymer Science》", 31 December 2005 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108148210A (en) * | 2018-01-15 | 2018-06-12 | 中国科学院上海应用物理研究所 | A kind of intramolecular crosslinking polymer, preparation method and applications |
| US11554346B2 (en) | 2018-01-25 | 2023-01-17 | Katholieke Universiteit Leuven | Cross-linked nanofiltration membranes |
| EP3524637A1 (en) * | 2018-02-09 | 2019-08-14 | Daikin Industries, Ltd. | Fluoroelastomer composition and molded article thereof |
| US11117992B2 (en) | 2018-02-09 | 2021-09-14 | Daikin Industries, Ltd. | Fluoroelastomer composition and molded article thereof |
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