CN106349613A - Composite thin film material with high energy density and low dielectric loss and method for preparing composite thin film material - Google Patents
Composite thin film material with high energy density and low dielectric loss and method for preparing composite thin film material Download PDFInfo
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Abstract
The invention relates to a composite thin film material with high energy density and low dielectric loss and a method for preparing the composite thin film material. Nanofibers with one-dimensional special structures are dispersed in polymer matrixes to obtain the composite thin film material. The nanofibers with the one-dimensional special structures are BaTiO3@Al2O3, and polymers are polyvinylidene fluoride (PVDF). The volume percent of the BaTiO3@Al2O3 with the one-dimensional special structures is 2.1-8 vol.%, and the volume percent of the polymers PVDF is 97.9-92 vol.%. The composite thin film material is prepared from the BaTiO3@Al2O3 with the one-dimensional special structures and the polymers PVDF according to certain volume ratios by the aid of spin-coating technologies. The composite thin film material and the method have the advantages that the composite thin film material prepared by the aid of the method is low in dielectric loss, high in energy density, good in flexibility and suitable for preparing capacitors with high energy density, embedded capacitors and high-power electrostatic storage energy materials, and the like.
Description
Technical field
The present invention relates to functional material preparing technical field, especially relate to a kind of high-energy-density, low-dielectric loss multiple
Close thin-film material and preparation method thereof.
Background technology
With social continuous progress, the fast development of electronic devices and components, people are close to the lightweight of material, storage energy
The service life of degree and period requires more and more higher.High dielectric constant compound film material is in embedded capacitor, electric stress
The dielectric power storage aspect of the electronic apparatus such as control, electric motor car and high energy storage device has important utilization.For example in high dielectric
Application in terms of electronic devices and components energy storage for the composite film material, has high dielectric constant, high breakdown field to material requirements
By force.And piezoelectric ceramics has high dielectric constant, its toughness, disruptive field intensity are relatively low；Polymer has high disruptive field intensity, excellent
Toughness；The two is combined and can get high-dielectric composite material.Enjoy the Biaxially oriented polypropylene (bopp) of researcher concern
Kynoar (pvdf) its dielectric constant is both less than 10, and the dielectric constants of Barium metatitanate. are very remote, may be when compound
Wait and occur that the erroneous matching of dielectric properties leads to the reduction of combination property.In order to solve the above problems, a novelty
Structure design can complement each other respective deficiency, relatively high dielectric constant can be maintained, and big breakdown field can be kept
By force, it is finally reached high storage energy density.
(volume ratio is below 5%) can significantly improve at low concentrations for experiment and theoretical verified one-dimensional material
The storage energy density of dielectric composite film material.Because it is big etc. that one-dimensional nanostructured has big draw ratio, specific surface area
Advantage.For example, generally, when the concentration of the one-dimensional material such as barium titanate nano fiber, barium strontium titanate nanofiber is more than 7%,
Its composite film material relatively easily punctures.Because the fault of construction (as pore) of the high composite film material of content leading to
The locality electric field concentration of composite increases and reduces disruptive field intensity.Meanwhile, the toughness of this material also decreases.For understanding
Determine this problem, an effective method is by suitable polymer surfaces functionalization filler, or by " graft to " side
Method is grafted to filler surface polymer chain, and " graft from " method is grafted to filler surface organic monomer.This polymerization
Surface layer not only can mitigate the reunion of filler, but also can limit movement between the filler of polymer for the electric charge.Therefore,
The disruptive field intensity of composite material film has obtained further improvement.But the method be disadvantageous in that unnecessary monomer or
Person's polymer does not allow easy-clear to affect the raising of the disruptive field intensity of material.The surface of nano-particle has very big energy, in system
Standby composite is easy reunion.Modifying interface is an effective way improving nano-filled thing.
Another one improves energy density, the effective approach of dielectric loss is to introduce on the implant surface of high-k
The cushion of one low relative dielectric constant, for example: silicon dioxide, zirconium dioxide, titanium dioxide, aluminium oxide etc..Cushion
Effect can mitigate dielectric constant between polymer and implant, reduce the interfacial polarization between implant and polymer and improve
Disruptive field intensity；It can in addition contain play an insulating effect, thus alleviating the long-pending of the interface charge between polymer and filler
Tired, reduce dielectric loss.Therefore developing the composite film material that a kind of pliability is good, energy density is high and dielectric loss is low becomes
Extremely important.
Present invention employs the one-dimensional batio with superior dielectric performance3@al2o3Nanofiber is as filler, al2o3Tool
There is suitable dielectric constant to be 10, the difference of dielectric constant between filler polymer can be reduced；Another aspect al2o3Have
Excellent insulating properties.And use the one-dimensional batio of electrostatic spinning one-step method preparation structure at present3@al2o3Nanofiber, and conduct
The composite film material of filler can keep higher energy density and low loss simultaneously.Presently relevant technical scheme report
Very few.
Content of the invention
The purpose of the present invention is exactly to provide a kind of high-energy-density, low to overcome the defect that above-mentioned prior art exists
Dielectric loss composite film material and preparation method thereof.
A kind of high-energy-density proposed by the present invention, low-dielectric loss composite film material, this composite film material is by one
The nanofiber dispersion of dimension special construction forms in polymer nature, and the nanofiber of described one-dimensional special construction is
batio3@al2o3Nanofiber, polymer is Kynoar (pvdf)；Wherein, the batio of one-dimentional structure3@al2o3Nanowire
The shared percent by volume of dimension is 2.1-8 vol.%, and the percent by volume shared by polymer pvdf is 97.9-92 vol.%.Adopt
With the technology of spin coating by the batio of one-dimentional structure3@al2o3Nanofiber and polymer pvdf are prepared into THIN COMPOSITE membrane material in proportion
Material；Prepared composite film material thickness is 6-25 μm.
In the present invention, described batio3@al2o3Nanofiber, its a diameter of 150-300 nm, length is 2-20 μm.
In the present invention, described batio3@al2o3Nanofiber is the batio modified by dopamine3@al2o3Nanowire
Dimension.
High-energy-density proposed by the present invention, the preparation method of low-dielectric loss composite film material, specifically comprise the following steps that
(1) electrostatic spinning technique is adopted to prepare batio3@al2o3Nanofiber；
(2) batio being obtained with dopamine modifying processing step (1)3@al2o3Nanofiber；
(3) batio of the surface modification that step (2) is obtained3@al2o3Nanofiber is placed in n, in n- dimethylformamide, surpasses
Sound 3-10 min, then magnetic agitation 2-3 h, form stable suspension d；
(4) in step (3) gained suspension d add pvdf, at 40-60 DEG C magnetic agitation be completely dissolved to pvdf obtain molten
Liquid e；;
(5) solution e is dropped in and laminated film is prepared on the ito glass of spin coating instrument, wherein the rotating speed of spin coating instrument is 3000 revs/min
Clock, spin-coating time is 30 seconds；It is vacuum dried 10 h at this laminated film is placed in 60-80 DEG C, remove organic solvent, be combined
Thin film a；
(6) in order to remove the defect in laminated film a (such as pore, surface impurity, flatness etc.), laminated film a is placed in
It is incubated 10-20 min at 190-230 DEG C, be subsequently placed into mixture of ice and water and carry out Quenching Treatment, at 40-80 DEG C, 5-10h is dried,
Obtain the composite film material of high-quality.
In the present invention, step (1) adopts electrostatic spinning technique to prepare batio3@al2o3Nanofiber, specifically comprises the following steps that
(1.1) barium titanate nano particle being prepared with hydro-thermal method (a diameter of 50nm, bt nps) is dispersed in ethanol
(ch3ch2Oh ultrasonic 30 min in), barium titanate nano particle is 2:1, magnetic agitation 5 h at room temperature with the mass ratio of ethanol,
Form solution a;By aluminum isopropylate. (c9h21alo3) it is added to ethanol (ch3ch2Oh, in), aluminum isopropylate. with the mass ratio of ethanol is
1:2, then magnetic agitation 1 h at 600 DEG C, until c9h21alo3It is dissolved completely in ch3ch2In oh, obtain solution b, will obtain
Solution b stand 2 h at room temperature；Pvp is added to ethanol (ch3ch2Oh, in), pvp is 1:4 with the mass ratio of ethanol, then
Magnetic agitation 30 min at temperature is for 30-80 DEG C, until pvp is dissolved completely in ch3ch2In oh, obtain solution c, by obtain
Solution c stands 2 h at room temperature；Solution b after solution a, the standing and solution c after standing is pressed the mass ratio mixing of 1:1:4,
Magnetic agitation 1-3 h at room temperature, obtain one transparent, clarification, stable colloid solution, finally by this colloid solution in room temperature
Lower standing 1 day, that is, obtain electrostatic spinning precursor solution；
(1.2) electrostatic spinning preparing precursor solution is added in the needle tubing of electrostatic spinning, then carries out electrostatic spinning,
Obtain (pvp+c9h21alo3+ bt nps) for presoma fiber.
(1.3) by (pvp+c obtaining9h21alo3+ bt nps) it is the fiber of presoma dry 20 at 90 DEG C
H, the fiber of dried presoma is placed in alumina dry pot and is placed in Muffle furnace, rises to for 5 DEG C/min according to heating rate
700 DEG C of insulation 3h, are finally cooled to room temperature, obtain the batio of one-dimentional structure3@al2o3Nanofiber.
In the present invention, described in step (2), use dopamine modification batio3@al2o3Nanofiber, concrete steps are such as
Under:
By the one-dimensional batio preparing3@al2o3Nanofiber adds the tris-hcl buffer solution ultrasonic disperse 20 of ph=8.5
min；Add aqueous dopamine solution, the concentration controlling aqueous dopamine solution is 0.015 mol/l, and then magnetic force stirs at room temperature
Mix 24 h, subsequently centrifugation, repeatedly washing, control centrifugal rotational speed is 4000 turns/min, be dried 10 in 80 DEG C of vacuum drying ovens
H, obtains the modified batio of dopamine3@al2o3Nanofiber.
Compared with prior art, the invention has the advantages that
Filler of the present invention is one-dimensional batio3@al2o3Nanofiber, prepared by this one dimension fibre one-step method.One
Dimension batio3@al2o3Nanofiber has big draw ratio, compares with granule and has lower surface energy, can subtract further
Little reunion in polymer nature, thus affect disruptive field intensity and the energy density of this laminated film.And at low concentrations may be used
With the dielectric properties of bigger raising composite film material, because it has big dipole polarization.In order to improve filler further
Compatibility, present invention application dopamine is to one-dimensional batio3@al2o3Nanofiber has carried out modification.The present invention passes through association
Same-action, obtains good effect.Composite film material prepared by the present invention has light weight, flexible, energy storage density
High the features such as, is it is adaptable to capacitor, high-power electrostatic energy storage material.
Brief description
Fig. 1 is to prepare one-dimentional structure batio3@ al2o3(a) scanning electron microscope (sem) (b) x-ray of nanofiber
Diffraction (xrd) analyzes collection of illustrative plates；
Fig. 2 is the amine-modified batio of bar3@ al2o3Regional High Resolution transmission picture (tem)；
Fig. 3 is batio3@ al2o3The batio amine-modified with DOPA3@ al2o3Infrared spectrogram；
Fig. 4 is the laminated film digital pictures of high tenacity.Wherein: (a) is the composite film material of high-quality, after (b) is curling
High-quality composite film material.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1: the features such as composite film material prepared by the present invention has light weight, flexible, energy storage density is high,
1. prepare one-dimentional structure batio3@al2o3Nanofiber, its preparation method is as follows: the titanium that (1) will be prepared with hydro-thermal method
Sour barium nano-particle (diameter about 50-100 nm, bt nps) is dispersed in ethanol (ch3ch2Oh, in), its mass ratio is 2:1, ultrasonic
30 min, magnetic agitation 5 h at room temperature, form solution a;By aluminum isopropylate. (c9h21alo3) it is added to ethanol
(ch3ch2Oh), its mass ratio is 1:2, then magnetic agitation 1 h at 60 0 DEG C, until c9h21alo3It is dissolved completely in
ch3ch2In oh, obtain solution b, the solution obtaining b is stood 2 h at room temperature;Pvp is added ethanol (ch3ch2Oh in),
Pvp is 1:4, then magnetic agitation 30 min at temperature is for 30-80 DEG C with the mass ratio of ethanol, until pvp is dissolved completely in
ch3ch2In oh, obtain solution c, the solution obtaining c is stood 2 h at room temperature；By solution a, the solution b after standing and solution c
It is the ratio mixing of 1:1:4 in mass ratio, magnetic agitation 1-3 h at room temperature, the colloid obtaining a transparent clear stable is molten
This colloid solution is finally stood 1 day, that is, obtains electrostatic spinning precursor liquid by liquid at room temperature；
(2) precursor solution preparing is added in the needle tubing of electrostatic spinning, then carry out electrostatic spinning, obtain (pvp+
c9h21alo3+ bt nps) for presoma fiber；
(3) by (pvp+c obtaining9h21alo3+ bt nps) for presoma fiber at 90 DEG C be dried 20 h, will do
Dry good precursor fibre is placed in alumina dry pot and is placed in Muffle furnace, rises to 700 DEG C of guarantors according to programming rate for 5 DEG C/min
Warm 3h, is finally cooled to room temperature and obtains one-dimentional structure batio3@al2o3Nanofiber, as shown in Figure 1；
2nd, modified one-dimentional structure batio3@al2o3Nanofiber, its step is as follows: by the one-dimensional batio preparing3@al2o3Receive
Rice fiber adds tris-hcl buffer solution ultrasonic disperse 20 min of ph=8.5；Add dopamine, wherein dopamine is water-soluble
The concentration of liquid is 0.015 mol/l, then magnetic agitation 24 h at room temperature, subsequently centrifugation, repeatedly wash, its centrifugal rotational speed is
4000 turns/min, finally 80 DEG C vacuum drying oven be dried 10 h obtain the modified batio of dopamine3@al2o3Nanowire
Dimension, as shown in Figure 2；Fig. 3 further demonstrates dopamine success modification batio3@al2o3Nanofiber.
3rd, by the batio of 0.172g surface modification3@al2o3Nanofiber is placed in n, in n- dimethylformamide, ultrasonic 3-
10 min, then magnetic agitation 2-3 h, form stable suspension d；
4th, add 2g pvdf in suspension d, magnetic agitation is completely dissolved to pvdf and obtains solution e at 40-60 DEG C;
5th, solution e is dropped in and laminated film is prepared on the ito glass of spin coating instrument, wherein the rotating speed of spin coating instrument is 3000 revs/min
Clock, spin-coating time is 30 seconds；It is vacuum dried 10 h at this laminated film is placed in 60-80 DEG C, remove organic solvent, be combined
Thin film a；
6th, in order to remove the defect in laminated film a (such as pore, surface impurity, flatness etc.), laminated film a is placed in 190-
It is incubated 10-20 min at 230 DEG C, be subsequently placed into mixture of ice and water and carry out Quenching Treatment, 5-10h is dried at 40-80 DEG C, obtains final product
To the composite film material of high-quality, as shown in Figure 4 (a)；We also can be seen that the laminated film of high-quality has well simultaneously
Toughness, as shown in Figure 4 (b).
Embodiment 2:
1. prepare one-dimentional structure batio3@al2o3Nanofiber, its preparation method is as follows: the titanium that (1) will be prepared with hydro-thermal method
Sour barium nano-particle (diameter about 50-100 nm, bt nps) is dispersed in ethanol (ch3ch2Oh, in), its mass ratio is 2:1, ultrasonic
30 min, magnetic agitation 5 h at room temperature, form solution a;By aluminum isopropylate. (c9h21alo3) it is added to ethanol
(ch3ch2Oh), its mass ratio is 1:2, then magnetic agitation 1 h at 60 0 DEG C, until c9h21alo3It is dissolved completely in
ch3ch2In oh, obtain solution b, the solution obtaining b is stood 2 h at room temperature;Pvp is added ethanol (ch3ch2Oh in),
Pvp is 1:4, then magnetic agitation 30 min at temperature is for 30-80 DEG C with the mass ratio of ethanol, until pvp is dissolved completely in
ch3ch2In oh, obtain solution c, the solution obtaining c is stood 2 h at room temperature；By solution a, the solution b after standing and solution c
It is the ratio mixing of 1:1:4 in mass ratio, magnetic agitation 1-3 h at room temperature, the colloid obtaining a transparent clear stable is molten
This colloid solution is finally stood 1 day, that is, obtains electrostatic spinning precursor liquid by liquid at room temperature；
(2) precursor solution preparing is added in the needle tubing of electrostatic spinning, then carry out electrostatic spinning, obtain (pvp+
c9h21alo3+ bt nps) for presoma fiber；
(3) by (pvp+c obtaining9h21alo3+ bt nps) for presoma fiber at 90 DEG C be dried 20 h, by drying
Good precursor fibre is placed in alumina dry pot and is placed in Muffle furnace, rises to 700 DEG C of insulations according to programming rate for 5 DEG C/min
3h, is finally cooled to room temperature and obtains one-dimentional structure batio3@al2o3Nanofiber；
2nd, modified one-dimentional structure batio3@al2o3Nanofiber, its step is as follows: by the one-dimensional batio preparing3@al2o3Receive
Rice fiber adds tris-hcl buffer solution ultrasonic disperse 20 min of ph=8.5；Add dopamine, wherein dopamine is water-soluble
The concentration of liquid is 0.015 mol/l, then magnetic agitation 24 h at room temperature, subsequently centrifugation, repeatedly wash, its centrifugal rotational speed is
4000 turns/min, finally 80 DEG C vacuum drying oven be dried 10 h obtain the modified batio of dopamine3@al2o3Nanowire
Dimension.
3rd, by the batio of 0.301g surface modification3@al2o3Nanofiber is placed in n, in n- dimethylformamide, ultrasonic 3-
10 min, then magnetic agitation 2-3 h, form stable suspension d；
4th, add 2g pvdf in suspension d, magnetic agitation is completely dissolved to pvdf and obtains solution e at 40-60 DEG C;
5th, solution e is dropped in and laminated film is prepared on the ito glass of spin coating instrument, wherein the rotating speed of spin coating instrument is 3000 revs/min
Clock, spin-coating time is 30 seconds；It is vacuum dried 10 h at this laminated film is placed in 60-80 DEG C, remove organic solvent, be combined
Thin film a；
6th, in order to remove the defect in laminated film a (such as pore, surface impurity, flatness etc.), laminated film a is placed in 190-
It is incubated 10-20 min at 230 DEG C, be subsequently placed into mixture of ice and water and carry out Quenching Treatment, 5-10h is dried at 40-80 DEG C, obtains final product
Composite film material to high-quality.
Embodiment 3:
1. prepare one-dimentional structure batio3@al2o3Nanofiber, its preparation method is as follows: the titanium that (1) will be prepared with hydro-thermal method
Sour barium nano-particle (diameter about 50-100 nm, bt nps) is dispersed in ethanol (ch3ch2Oh, in), its mass ratio is 2:1, ultrasonic
30 min, magnetic agitation 5 h at room temperature, form solution a;By aluminum isopropylate. (c9h21alo3) it is added to ethanol
(ch3ch2Oh), its mass ratio is 1:2, then magnetic agitation 1 h at 60 0 DEG C, until c9h21alo3It is dissolved completely in
ch3ch2In oh, obtain solution b, the solution obtaining b is stood 2 h at room temperature;Pvp is added ethanol (ch3ch2Oh in),
Pvp is 1:4, then magnetic agitation 30 min at temperature is for 30-80 DEG C with the mass ratio of ethanol, until pvp is dissolved completely in
ch3ch2In oh, obtain solution c, the solution obtaining c is stood 2 h at room temperature；By solution a, the solution b after standing and solution c
It is the ratio mixing of 1:1:4 in mass ratio, magnetic agitation 1-3 h at room temperature, the colloid obtaining a transparent clear stable is molten
This colloid solution is finally stood 1 day, that is, obtains electrostatic spinning precursor liquid by liquid at room temperature；
(2) precursor solution preparing is added in the needle tubing of electrostatic spinning, then carry out electrostatic spinning, obtain (pvp+
c9h21alo3+ bt nps) for presoma fiber；
(3) by (pvp+c obtaining9h21alo3+ bt nps) for presoma fiber at 90 DEG C be dried 20 h, by drying
Good precursor fibre is placed in alumina dry pot and is placed in Muffle furnace, rises to 700 DEG C of insulations according to programming rate for 5 DEG C/min
3h, is finally cooled to room temperature and obtains one-dimentional structure batio3@al2o3Nanofiber；
2nd, modified one-dimentional structure batio3@al2o3Nanofiber, its step is as follows: by the one-dimensional batio preparing3@al2o3Receive
Rice fiber adds tris-hcl buffer solution ultrasonic disperse 20 min of ph=8.5；Add dopamine, wherein dopamine is water-soluble
The concentration of liquid is 0.015 mol/l, then magnetic agitation 24 h at room temperature, subsequently centrifugation, repeatedly wash, its centrifugal rotational speed is
4000 turns/min, finally 80 DEG C vacuum drying oven be dried 10 h obtain the modified batio of dopamine3@al2o3Nanowire
Dimension.
3rd, by the batio of 0.432g surface modification3@al2o3Nanofiber is placed in n, in n- dimethylformamide, ultrasonic 3-
10 min, then magnetic agitation 2-3 h, form stable suspension d；
4th, add 2g pvdf in suspension d, magnetic agitation is completely dissolved to pvdf and obtains solution e at 40-60 DEG C；
5th, solution e is dropped in and laminated film is prepared on the ito glass of spin coating instrument, wherein the rotating speed of spin coating instrument is 3000 revs/min
Clock, spin-coating time is 30 seconds；It is vacuum dried 10 h at this laminated film is placed in 60-80 DEG C, remove organic solvent, be combined
Thin film a；
6th, in order to remove the defect in laminated film a (such as pore, surface impurity, flatness etc.), laminated film a is placed in 190-
It is incubated 10-20 min at 230 DEG C, be subsequently placed into mixture of ice and water and carry out Quenching Treatment, 5-10h is dried at 40-80 DEG C, obtains final product
Composite film material to high-quality.
Embodiment 4:
1. prepare one-dimentional structure batio3@al2o3Nanofiber, its preparation method is as follows: the titanium that (1) will be prepared with hydro-thermal method
Sour barium nano-particle (diameter about 50-100 nm, bt nps) is dispersed in ethanol (ch3ch2Oh, in), its mass ratio is 2:1, ultrasonic
30 min, magnetic agitation 5 h at room temperature, form solution a;By aluminum isopropylate. (c9h21alo3) it is added to ethanol
(ch3ch2Oh), its mass ratio is 1:2, then magnetic agitation 1 h at 60 0 DEG C, until c9h21alo3It is dissolved completely in
ch3ch2In oh, obtain solution b, the solution obtaining b is stood 2 h at room temperature;Pvp is added ethanol (ch3ch2Oh in),
Pvp is 1:4, then magnetic agitation 30 min at temperature is for 30-80 DEG C with the mass ratio of ethanol, until pvp is dissolved completely in
ch3ch2In oh, obtain solution c, the solution obtaining c is stood 2 h at room temperature；By solution a, the solution b after standing and solution c
It is the ratio mixing of 1:1:4 in mass ratio, magnetic agitation 1-3 h at room temperature, the colloid obtaining a transparent clear stable is molten
This colloid solution is finally stood 1 day, that is, obtains electrostatic spinning precursor liquid by liquid at room temperature；
(2) precursor solution preparing is added in the needle tubing of electrostatic spinning, then carry out electrostatic spinning, obtain (pvp+
c9h21alo3+ bt nps) for presoma fiber；
(3) by (pvp+c obtaining9h21alo3+ bt nps) for presoma fiber at 90 DEG C be dried 20 h, by drying
Good precursor fibre is placed in alumina dry pot and is placed in Muffle furnace, rises to 700 DEG C of insulations according to programming rate for 5 DEG C/min
3h, is finally cooled to room temperature and obtains one-dimentional structure batio3@al2o3Nanofiber；
2nd, modified one-dimentional structure batio3@al2o3Nanofiber, its step is as follows: by the one-dimensional batio preparing3@al2o3Receive
Rice fiber adds tris-hcl buffer solution ultrasonic disperse 20 min of ph=8.5；Add dopamine, wherein dopamine is water-soluble
The concentration of liquid is 0.015 mol/l, then magnetic agitation 24 h at room temperature, subsequently centrifugation, repeatedly wash, its centrifugal rotational speed is
4000 turns/min, finally 80 DEG C vacuum drying oven be dried 10 h obtain the modified batio of dopamine3@al2o3Nanowire
Dimension.
3rd, by the batio of 0.659g surface modification3@al2o3Nanofiber is placed in n, in n- dimethylformamide, ultrasonic 3-
10 min, then magnetic agitation 2-3 h, form stable suspension d；
4th, add 2g pvdf in suspension d, magnetic agitation is completely dissolved to pvdf and obtains solution e at 40-60 DEG C;
5th, solution e is dropped in and laminated film is prepared on the ito glass of spin coating instrument, wherein the rotating speed of spin coating instrument is 3000 revs/min
Clock, spin-coating time is 30 seconds；It is vacuum dried 10 h at this laminated film is placed in 60-80 DEG C, remove organic solvent, be combined
Thin film a；
6th, in order to remove the defect in laminated film a (such as pore, surface impurity, flatness etc.), laminated film a is placed in 190-
It is incubated 10-20 min at 230 DEG C, be subsequently placed into mixture of ice and water and carry out Quenching Treatment, 5-10h is dried at 40-80 DEG C, obtains final product
Composite film material to high-quality.
Claims (6)
1. a kind of high-energy-density, low-dielectric loss composite film material are it is characterised in that this composite film material is by one-dimensional spy
The nanofiber dispersion of different structure forms in polymer nature, and the nanofiber of described one-dimensional special construction is batio3@
al2o3Nanofiber, polymer is Kynoar (pvdf)；Wherein, the batio of one-dimentional structure3@al2o3Shared by nanofiber
Percent by volume be 2.1-8 vol.%, the percent by volume shared by polymer pvdf be 97.9-92 vol.%；Using spin coating
Technology by the batio of one-dimentional structure3@al2o3Nanofiber and polymer pvdf are prepared into laminated film by certain volume ratio
Material；Prepared composite film material thickness is 6-25 μm.
2. high-energy-density according to claim 1, low-dielectric loss composite film material are it is characterised in that described
batio3@al2o3Nanofiber, its a diameter of 150-300 nm, length is 2-20 μm.
3. high-energy-density according to claim 1, low-dielectric loss composite film material are it is characterised in that described
batio3@al2o3Nanofiber is the batio modified by dopamine3@al2o3Nanofiber.
4. a kind of high-energy-density as claimed in claim 1, the preparation method of low-dielectric loss composite film material, its feature
It is, specifically comprise the following steps that
(1) electrostatic spinning technique is adopted to prepare batio3@al2o3Nanofiber；
(2) batio being obtained with dopamine modifying processing step (1)3@al2o3Nanofiber；
(3) batio of the surface modification that step (2) is obtained3@al2o3Nanofiber is placed in n, in n- dimethylformamide, surpasses
Sound 3-10 min, then magnetic agitation 2-3 h, form stable suspension d；
(4) add pvdf in step (3) gained suspension d, magnetic agitation is completely dissolved to pvdf and obtains at 40-60 DEG C
Solution e；;
(5) solution e is dropped in and laminated film is prepared on the ito glass of spin coating instrument, wherein the rotating speed of spin coating instrument is 3000 revs/min
Clock, spin-coating time is 30 seconds；It is vacuum dried 10 h at this laminated film is placed in 60-80 DEG C, remove organic solvent, be combined
Thin film a；
(6) in order to remove the defect in laminated film a (such as pore, surface impurity, flatness etc.), laminated film a is placed in
It is incubated 10-20 min at 190-230 DEG C, be subsequently placed into mixture of ice and water and carry out Quenching Treatment, at 40-80 DEG C, 5-10h is dried,
Obtain the composite film material of high-quality.
5. high-energy-density according to claim 4, the preparation method of low-dielectric loss composite film material, its feature exists
In step (1) adopts electrostatic spinning technique to prepare batio3@al2o3Nanofiber, specifically comprises the following steps that
(1.1) barium titanate nano particle being prepared with hydro-thermal method (a diameter of 50nm, bt nps) is dispersed in ethanol
(ch3ch2Oh ultrasonic 30 min in), barium titanate nano particle is 2:1, magnetic agitation 5 h at room temperature with the mass ratio of ethanol,
Form solution a;By aluminum isopropylate. (c9h21alo3) it is added to ethanol (ch3ch2Oh, in), aluminum isopropylate. with the mass ratio of ethanol is
1:2, then magnetic agitation 1 h at 600 DEG C, until c9h21alo3It is dissolved completely in ch3ch2In oh, obtain solution b, will obtain
Solution b stand 2 h at room temperature；Pvp is added to ethanol (ch3ch2Oh, in), pvp is 1:4 with the mass ratio of ethanol, then
Magnetic agitation 30 min at temperature is for 30-80 DEG C, until pvp is dissolved completely in ch3ch2In oh, obtain solution c, by obtain
Solution c stands 2 h at room temperature；Solution b after solution a, the standing and solution c after standing is pressed the mass ratio mixing of 1:1:4,
Magnetic agitation 1-3 h at room temperature, obtain one transparent, clarification, stable colloid solution, finally by this colloid solution in room temperature
Lower standing 1 day, that is, obtain electrostatic spinning precursor solution；
(1.2) electrostatic spinning preparing precursor solution is added in the needle tubing of electrostatic spinning, then carries out electrostatic spinning,
Obtain (pvp+c9h21alo3+ bt nps) for presoma fiber；
(1.3) by (pvp+c obtaining9h21alo3+ bt nps) for presoma fiber at 90 DEG C be dried 20 h, will do
The fiber of dry good presoma is placed in alumina dry pot and is placed in Muffle furnace, rises to 700 DEG C according to heating rate for 5 DEG C/min
Insulation 3h, is finally cooled to room temperature, obtains the batio of one-dimentional structure3@al2o3Nanofiber.
6. high-energy-density according to claim 4, the preparation method of low-dielectric loss composite film material, its feature exists
In with dopamine modification batio described in step (2)3@al2o3Nanofiber, specifically comprises the following steps that
By the one-dimensional batio preparing3@al2o3Nanofiber adds the tris-hcl buffer solution ultrasonic disperse 20 of ph=8.5
min；Add aqueous dopamine solution, the concentration controlling aqueous dopamine solution is 0.015 mol/l, and then magnetic force stirs at room temperature
Mix 24 h, subsequently centrifugation, repeatedly washing, control centrifugal rotational speed is 4000 turns/min, be dried 10 in 80 DEG C of vacuum drying ovens
H, obtains the modified batio of dopamine3@al2o3Nanofiber.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504449A (en) * | 2011-11-01 | 2012-06-20 | 清华大学 | Polymer matrix composite membrane with high energy density and preparation method thereof |
| CN105295263A (en) * | 2015-11-11 | 2016-02-03 | 同济大学 | Polymer matrix composite and preparation method thereof |
-
2016
- 2016-09-19 CN CN201610827865.4A patent/CN106349613A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504449A (en) * | 2011-11-01 | 2012-06-20 | 清华大学 | Polymer matrix composite membrane with high energy density and preparation method thereof |
| CN105295263A (en) * | 2015-11-11 | 2016-02-03 | 同济大学 | Polymer matrix composite and preparation method thereof |
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