CN108752612A - High energy storage dielectric composite material preparation method based on PMMA sandwich structures - Google Patents
High energy storage dielectric composite material preparation method based on PMMA sandwich structures Download PDFInfo
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
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Abstract
The present invention relates to the high energy storage dielectric composite material preparation methods based on PMMA sandwich structures.Existing single layer composite electrical property promotes unobvious.Poly methyl methacrylate particle is dissolved in polar solvent by the method for the present invention first, forms PMMA solution；Surface active is carried out to the antiferroelectric ceramics filler that grain size is 1~100nm with activator, surface modification is carried out to ceramic packing with coupling agent；It adds a polymer in polar solvent, forms polymer solution；The ceramic packing that surface is modified is added in polymer solution, forms suspension；PMMA solution is coated on basement membrane, suspension is coated after dry, PMMA solution is coated with after dry, forms the film of three-decker after dry；Through melting, quenching, hot-pressing processing, finished film is obtained.The polymeric layer of upper and lower surface of the present invention improves disruptive field intensity, and composite material middle layer improves dielectric constant and dielectric displacement, while the advantages of take into account two kinds of materials, improves film performance.
Description
Technical field
The invention belongs to technical field of material, and in particular to a kind of high energy storage dielectric based on PMMA sandwich structures
Composite material and preparation method thereof.
Background technology
With the fast development of science and technology, high density capacitors have obtained widely answering in electric power, electronics industry
With.Capacitor is as a kind of basic passive device and energy storage device, in advanced electronics and such as fixed power grid of electric system, electricity
Sub- weapon, hybrid vehicle etc. play an important role, and using the polymer of high electric strength as matrix, dielectric is added
The filler of function admirable integrates the advantage of two-phase or multiphase material respectively, to which the high energy storage density that acquisition prepares capacitor is situated between
Composite, such Research Thinking, it has also become the hot spot of Recent study.However it although is achieved on high-k
Huge success, but they are as high energy storage medium, and the Science and Technology challenge in many practical applications is still unresolved.
Composite material is combined with each other by the method for physics or chemistry by two or more material or component, can not only
Retain the property of one-component material, additionally it is possible to produce the new features that one-component does not have.Capacitor requirement has Gao Jie
The characteristics of electric constant, high breakdown field strength, low dielectric loss and high energy storage density, and composite material is due to high-quality, Yi Jia
The advantages that work, toughness are high, at low cost becomes the first choice of dielectric material, and wherein polymer has high breakdown field strength, high Young
The characteristics of modulus, has higher dielectric constant, therefore the two is incorporated in although its disruptive field intensity of ceramic packing is relatively low
Together, the advantage for giving full play to the two, can be obtained high-performance composite materials.
Common polymer has：The fluorine-containing object such as PVDF, P (VDF-CTFE), P (VDF-HFP) and PE, PVA, PAN,
The linear polymers such as BOPP, PSAN, PMMA, wherein polymethyl methacrylate (PMMA) due to having higher disruptive field intensity by
Scholar studies extensively, and antiferroelectric ceramics, such as PbZrO3、PbZrTiO3And PLZT, PLZST and the PZST pottery of La doping
Porcelain etc., due to higher dielectric constant, becoming the preferred material of high density capacitors medium filler in recent years.But
It is that the composite material is that its disruptive field intensity improves unobvious using bottleneck, causes energy storage density to be promoted little, reason is first
First it is that the interface compatibility between organic matrix and inorganic particulate is poor, easy tos produce fault of construction；Next is to obtain
High-k, often use high volume content ceramic particle, this cause the mechanics of composite material and breakdown performance substantially under
Drop.
Antiferroelectric ceramics disperses in a polymer solution, and the size of particle has directly the electrical property of composite material
Influence.In general, filler particles size is smaller, and particle disperses evenly in a polymer solution, and is formed with matrix
Interfacial effect it is more notable, interface compatibility is more preferable, however to improve filler dispersibility in the polymer, and filler often needs
To pass through surface modification to handle, ceramics are handled using coupling agent, such as KH550, dopamine, make its surface attachment base
Group.
Invention content
The present invention provides a kind of base to overcome single layer composite electrical property in the prior art to promote unconspicuous disadvantage
In the high energy storage dielectric composite material preparation method of PMMA sandwich structures.
The method of the present invention is as follows：
Polymetylmethacrylate grain dissolution in polar solvent, is stirred well to completely molten by step (1)
Solution forms PMMA solution；1~200g PMMA particles are added in every liter of polar solvent.
The polar solvent is the analysis pure solvent of DMF, NMP or DMAC.
Step (2) carries out surface active with activator to ceramic packing, then carries out surface to ceramic packing with coupling agent
It is modified；Lipophilic group is adhered on the ceramic packing surface that surface is modified, and disperses in a polymer solution evenly.
The ceramic packing is nanoscale antiferroelectric ceramics filler, and grain size R is 1~100nm, passes through solid phase method, hydro-thermal
Method or sol-gal process prepare.Ceramic packing size is small enough to the contact area between increase filler and polymer,
It is easy to scatter in the polymer, and then promotes the dielectric properties of film.
The material of the antiferroelectric ceramics filler is PbZrO3、PbZrTiO3And La doping PLZT, PLZST or
One kind in PZST ceramic materials.La doping concentrations are using the conventional prior art.
The activator be a concentration of 5~30% hydrogen peroxide, a concentration of 10~30% hydrochloric acid or a concentration of 0.1~
The sodium hydroxide solution of 1mol/L.
The coupling agent is the KH550 solution or solid dopamine of 98% concentration.The KH550 solution of 98% concentration and solid
Body dopamine is customary commercial.
The specific method of surface active is that ceramic packing is added in activator, and ratio is 5~200g/L, is fully stirred
It mixes, sonic oscillation, recycles 1~20 time, then washed with absolute ethyl alcohol, dry 1~20h at 50~100 DEG C.
Surface be modified specific method be that the ceramic packing after surface active is added in absolute ethyl alcohol, ratio be 5~
200g/L is added the coupling agent that quality is ceramic packing 0.1~20%, is sufficiently stirred, sonic oscillation, recycles 1~20 time, 50
Dry 1~20h, takes out ceramic packing at~100 DEG C.
Step (3) is added a polymer in polar solvent, is sufficiently stirred, until being completely dissolved, forms clear
Polymer solution；5~200g polymer is added in every liter of polar solvent.
The polymer is Kynoar (PVDF) or P (VDF-CTFE), P (VDF-TrFE), P based on PVDF
(VDF-CTFE-TrFE), one kind in P (VDF-HFP).
The polar solvent is the analysis pure solvent of DMF, NMP or DMAC.
The ceramic packing that surface is modified by step (4) is added in polymer solution, is sufficiently stirred oscillation, is formed stable
1~80g ceramic packings are added in suspension, every liter of polymer solution.
Step (5) first by step (1) prepare PMMA solution using the tape casting be coated in basement membrane on, coating thickness be 1~
50 μm, then dry 12~600min, PMMA layers of formation the first at 50~120 DEG C；The suspension again prepared by step (4) applies
It overlays on the first PMMA layers, coating thickness is 1~50 μm, continues dry 12~600min, forms ceramic packing layer；By step
(1) the PMMA solution prepared is coated on ceramic packing layer, and coating thickness is 1~50 μm, is continued dry 12~600min, is formed
2nd PMMA layers；The film with three-decker is finally removed from basement membrane.
Film is melted 10~600min by step (6) at 150~250 DEG C, is put into -196~0 DEG C of low temperature immediately after
3~60min of quenching treatment in environment, obtains composite film material.
Step (7) hot pressing under 180~250 DEG C of temperature, 0.2~100Mpa pressure, obtains composite film material and obtains into
Product film.
The present invention will first form the first layer of sandwich structure in PMMA solution curtain coatings to basement membrane, then by filler and polymer
Mixing suspension be added on basement membrane and form the second layer, finally add PMMA solution and form third layer, by hot-pressing processing system
For at laminated film.Film stands a period of time through being immediately placed under low temperature after high-temperature fusion.By this quenching heat treatment it
After can effectively improve its electrical property.
The present invention is punctured using the compound system that nanoscale antiferroelectric ceramics particle and polymer form as middle layer with height
The linear dielectrical polymer of electric field strength is upper and lower layer surface, and design is prepared for a kind of laminated film of sandwich structure,
The linear dielectric polymer layer of middle upper and lower surface can improve the disruptive field intensity of film, and composite material can be carried as middle layer
The advantages of dielectric constant of high film and dielectric displacement, the thin-film material of preparation takes into account two kinds of materials simultaneously, improve the total of film
Body performance.
Maximum feature of the invention is to use sandwich structure, and wherein upper layer and lower layer uses purely linear dielectric PMMA solution
Coating, does not add any inorganic filler, can significantly promote disruptive field intensity, and middle layer is molten using polymer and ceramic packing mixing
Liquid coats, which there is higher dielectric constant and dielectric displacement, the two to be combined together, and laminated film has fully taken into account two kinds of materials
The advantage of material improves the overall performance of film.By adjusting antiferroelectric ceramics granule content, it can fully compare form film
The performances such as dielectric constant, dielectric loss, breakdown strength, dielectric displacement.The present invention is to quenched film using at high temperature hot pressing
It manages, after polymer melting, under pressure, keeps the gap inside film closer, help to promote disruptive field intensity.
Description of the drawings
Fig. 1 is the dielectric constant and dielectric loss schematic diagram of the composite film material；
Fig. 2 is the ferroelectric hysteresis loop figure of the composite film material；
Fig. 3 is energy storage density and loss figure under the different field strength of the composite film material.
Specific implementation mode
Step of the present invention is described further with reference to the accompanying drawings and examples.
Embodiment 1.
Step (1) according to every liter of 100g ratio, by polymetylmethacrylate grain dissolution DMF analyze it is pure
It in solvent, is stirred well to and is completely dissolved, form PMMA solution.
Step (2) uses solid phase method to prepare grain size R as 10nm, material PbZrO3The antiferroelectric ceramics of ceramic material is filled out
Material.
Ceramic packing is added in a concentration of 20% hydrogen peroxide, additional proportion 100g/L is sufficiently stirred, and ultrasound is shaken
It swings, recycles 10 times, then washed with absolute ethyl alcohol, dry 10h, completes the surface active to ceramic packing at 80 DEG C.
Ceramic packing after surface active is added in absolute ethyl alcohol, ratio 100g/L, quality is added and is filled out for ceramics
The solid dopamine of material 10%, is sufficiently stirred, sonic oscillation, recycles 10 times, and the dry 10h at 80 DEG C completes surface and is modified；It takes
Go out ceramic packing.
Kynoar (PVDF) is added in the analysis pure solvent of DMF by step (3) according to the ratio of every liter of 100g,
It is sufficiently stirred, until being completely dissolved, forms the polymer solution of clear.
The ceramic packing of surface modification is added in polymer solution, fully stirs according to the ratio of every liter of 50g by step (4)
Oscillation is mixed, stable suspension is formed.
The PMMA solution that step (5) is first prepared step (1) is coated in using the tape casting on basement membrane, and coating thickness is 30 μ
M, then dry 30min, PMMA layers of formation the first at 100 DEG C；The suspension again prepared by step (4) is coated in the first PMMA
On layer, coating thickness is 20 μm, continues dry 20min, forms ceramic packing layer；PMMA solution coating prepared by step (1)
On ceramic packing layer, coating thickness is 30 μm, continues dry 30min, PMMA layers of formation the 2nd；Tool is finally removed from basement membrane
There is the film of three-decker.
Film is melted 300min by step (6) at 200 DEG C, is put into immediately after in -196 DEG C of low temperature environments at quenching
3min is managed, composite film material is obtained.
Step (7) hot pressing under 200 DEG C of temperature, 50Mpa pressure, obtains composite film material and obtains finished film.
From Fig. 1, Fig. 2, Fig. 3：Dielectric constant of the composite high-performance dielectric material of the sandwich structure at 100Hz
13.4 can be reached, loss is 0.08 or so, and in terms of energy storage, and under 375MV/m field strength, the releasable energy density of film is
6.8 μ C/cm2, corresponding release efficiency are 60%, have high energy storage, low-loss feature.
Embodiment 2.
Step (1) according to every liter of 50g ratio, by polymetylmethacrylate grain dissolution NMP analyze it is pure molten
It in agent, is stirred well to and is completely dissolved, form PMMA solution.
Step (2) uses hydro-thermal method to prepare grain size R as 5nm, material PbZrTiO3The antiferroelectric ceramics of ceramic material is filled out
Material, ceramic packing is added in a concentration of 5% hydrogen peroxide, and additional proportion 50g/L is sufficiently stirred, sonic oscillation, cycle
It 5 times, is then washed with absolute ethyl alcohol, dry 1h, completes the surface active to ceramic packing at 100 DEG C；
Ceramic packing after surface active is added in absolute ethyl alcohol, ratio 50g/L, addition quality is ceramic packing
The KH550 solution of 1% 98% concentration, is sufficiently stirred, sonic oscillation, recycles 5 times, and the dry 1h at 100 DEG C completes surface and changes
Property；Take out ceramic packing.
For step (3) according to the ratio of every liter of 50g, the analysis that the P (VDF-CTFE) based on PVDF is added to NMP is pure molten
It in agent, is sufficiently stirred, until being completely dissolved, forms the polymer solution of clear.
The ceramic packing of surface modification is added in polymer solution, fully stirs according to the ratio of every liter of 20g by step (4)
Oscillation is mixed, stable suspension is formed.
The PMMA solution that step (5) is first prepared step (1) is coated in using the tape casting on basement membrane, and coating thickness is 50 μ
M, then dry 60min, PMMA layers of formation the first at 120 DEG C；The suspension again prepared by step (4) is coated in the first PMMA
On layer, coating thickness is 30 μm, continues dry 30min, forms ceramic packing layer；PMMA solution coating prepared by step (1)
On ceramic packing layer, coating thickness is 50 μm, continues dry 60min, PMMA layers of formation the 2nd；Tool is finally removed from basement membrane
There is the film of three-decker.
Film is melted 600min by step (6) at 150 DEG C, is put into immediately after in -120 DEG C of low temperature environments at quenching
30min is managed, composite film material is obtained.
Step (7) hot pressing under 180 DEG C of temperature, 100Mpa pressure, obtains composite film material and obtains finished film.
Embodiment 3.
Step (1) according to every liter of 200g ratio, by polymetylmethacrylate grain dissolution DMAC analyze it is pure
It in solvent, is stirred well to and is completely dissolved, form PMMA solution.
Step (2) use sol-gal process prepare grain size R for 50nm, material be La adulterate PLZT ceramic materials anti-iron
Ceramic packing is added in a concentration of 30% hydrogen peroxide by electroceramics filler, and additional proportion 200g/L is sufficiently stirred, and is surpassed
Sound oscillation is recycled 20 times, is then washed with absolute ethyl alcohol, and dry 20h, completes the surface active to ceramic packing at 50 DEG C；
Ceramic packing after surface active is added in absolute ethyl alcohol, ratio 200g/L, quality is added and is filled out for ceramics
The solid dopamine of material 0.1%, is sufficiently stirred, sonic oscillation, recycles 20 times, and the dry 20h at 50 DEG C completes surface and is modified；
Take out ceramic packing.
For step (3) according to the ratio of every liter of 5g, the analysis that the P (VDF-TrFE) based on PVDF is added to DMAC is pure molten
Agent is sufficiently stirred, until being completely dissolved, forms the polymer solution of clear.
The ceramic packing of surface modification is added in polymer solution, fully stirs according to the ratio of every liter of 1g by step (4)
Oscillation is mixed, stable suspension is formed.
The PMMA solution that step (5) is first prepared step (1) is coated in using the tape casting on basement membrane, and coating thickness is 10 μ
M, then dry 300min, PMMA layers of formation the first at 50 DEG C；The suspension again prepared by step (4) is coated in the first PMMA
On layer, coating thickness is 50 μm, continues dry 600min, forms ceramic packing layer；PMMA solution coating prepared by step (1)
On ceramic packing layer, coating thickness is 15 μm, continues dry 180min, PMMA layers of formation the 2nd；Finally removed from basement membrane
Film with three-decker.
Film is melted 480min by step (6) at 160 DEG C, is put into quenching treatment in 0 DEG C of low temperature environment immediately after
60min obtains composite film material.
Step (7) hot pressing under 190 DEG C of temperature, 50Mpa pressure, obtains composite film material and obtains finished film.
Embodiment 4.
Step (1) according to every liter of 1g ratio, by polymetylmethacrylate grain dissolution DMF analyze it is pure molten
It in agent, is stirred well to and is completely dissolved, form PMMA solution.
It is that La adulterates the anti-of PLZST ceramic materials that step (2), which uses sol-gal process to prepare grain size R as 100nm, material,
Ceramic packing is added in a concentration of 10% hydrochloric acid by ferroelectric ceramic fillers, and additional proportion 10g/L is sufficiently stirred, ultrasound
Oscillation is recycled 1 time, is then washed with absolute ethyl alcohol, and dry 2h, completes the surface active to ceramic packing at 50 DEG C；
Ceramic packing after surface active is added in absolute ethyl alcohol, ratio 10g/L, addition quality is ceramic packing
The KH550 solution of 0.1% 98% concentration, is sufficiently stirred, sonic oscillation, recycles 1 time, and dry 2h, completes surface at 50 DEG C
It is modified；Take out ceramic packing.
P (VDF-CTFE-TrFE) based on PVDF is added to point of DMF by step (3) according to the ratio of every liter of 200g
It analyses in pure solvent, is sufficiently stirred, until being completely dissolved, form the polymer solution of clear.
The ceramic packing of surface modification is added in polymer solution, fully stirs according to the ratio of every liter of 80g by step (4)
Oscillation is mixed, stable suspension is formed.
The PMMA solution that step (5) is first prepared step (1) is coated in using the tape casting on basement membrane, and coating thickness is 50 μ
M, then dry 600min, PMMA layers of formation the first at 50 DEG C；The suspension again prepared by step (4) is coated in the first PMMA
On layer, coating thickness is 20 μm, continues dry 300min, forms ceramic packing layer；PMMA solution coating prepared by step (1)
On ceramic packing layer, coating thickness is 50 μm, continues dry 600min, PMMA layers of formation the 2nd；Finally removed from basement membrane
Film with three-decker.
Film is melted 360min by step (6) at 180 DEG C, is put into quenching treatment in -20 DEG C of low temperature environments immediately after
45min obtains composite film material.
Step (7) hot pressing under 210 DEG C of temperature, 25Mpa pressure, obtains composite film material and obtains finished film.
Embodiment 5.
Step (1) according to every liter of 10g ratio, by polymetylmethacrylate grain dissolution NMP analyze it is pure molten
It in agent, is stirred well to and is completely dissolved, form PMMA solution.
Step (2) use solid phase method prepare grain size R for 1nm, material be La adulterate PZST ceramic materials antiferroelectric ceramics
Ceramic packing is added in a concentration of 20% hydrochloric acid by filler, and additional proportion 20g/L is sufficiently stirred, and sonic oscillation follows
Ring 3 times, is then washed with absolute ethyl alcohol, and dry 3h, completes the surface active to ceramic packing at 60 DEG C；
Ceramic packing after surface active is added in absolute ethyl alcohol, ratio 20g/L, addition quality is ceramic packing
5% solid dopamine, is sufficiently stirred, sonic oscillation, recycles 3 times, and the dry 3h at 60 DEG C completes surface and is modified；Take out pottery
Porcelain filling.
For step (3) according to the ratio of every liter of 20g, the analysis that the P (VDF-HFP) based on PVDF is added to NMP is pure molten
Agent is sufficiently stirred, until being completely dissolved, forms the polymer solution of clear.
The ceramic packing of surface modification is added in polymer solution, fully stirs according to the ratio of every liter of 10g by step (4)
Oscillation is mixed, stable suspension is formed.
The PMMA solution that step (5) is first prepared step (1) is coated in using the tape casting on basement membrane, and coating thickness is 1 μ
M, then dry 12min, PMMA layers of formation the first at 50 DEG C；The suspension again prepared by step (4) is coated in the first PMMA
On layer, coating thickness is 1 μm, continues dry 12min, forms ceramic packing layer；PMMA solution prepared by step (1) is coated in
On ceramic packing layer, coating thickness is 1 μm, continues dry 12min, PMMA layers of formation the 2nd；Finally being removed from basement membrane has
The film of three-decker.
Film is melted 60min by step (6) at 210 DEG C, is put into quenching treatment in -50 DEG C of low temperature environments immediately after
30min obtains composite film material.
Step (7) hot pressing under 220 DEG C of temperature, 10Mpa pressure, obtains composite film material and obtains finished film.
Embodiment 6.
Step (1) according to every liter of 20g ratio, by polymetylmethacrylate grain dissolution DMAC analyze it is pure
It in solvent, is stirred well to and is completely dissolved, form PMMA solution.
Step (2) uses hydro-thermal method to prepare grain size R as 20nm, material PbZrTiO3The antiferroelectric ceramics of ceramic material
Ceramic packing is added in a concentration of 30% hydrochloric acid by filler, and additional proportion 30g/L is sufficiently stirred, and sonic oscillation follows
Ring 15 times, is then washed with absolute ethyl alcohol, and dry 1h, completes the surface active to ceramic packing at 80 DEG C；
Ceramic packing after surface active is added in absolute ethyl alcohol, ratio 30g/L, addition quality is ceramic packing
The KH550 solution of 3% 98% concentration, is sufficiently stirred, sonic oscillation, recycles 15 times, and the dry 1h at 80 DEG C completes surface and changes
Property；Take out ceramic packing.
For step (3) according to the ratio of every liter of 150g, the analysis that the P (VDF-CTFE) based on PVDF is added to DMAC is pure
It in solvent, is sufficiently stirred, until being completely dissolved, forms the polymer solution of clear.
The ceramic packing of surface modification is added in polymer solution, fully stirs according to the ratio of every liter of 30g by step (4)
Oscillation is mixed, stable suspension is formed.
The PMMA solution that step (5) is first prepared step (1) is coated in using the tape casting on basement membrane, and coating thickness is 5 μ
M, then dry 120min, PMMA layers of formation the first at 60 DEG C；The suspension again prepared by step (4) is coated in the first PMMA
On layer, coating thickness is 5 μm, continues dry 120min, forms ceramic packing layer；PMMA solution coating prepared by step (1)
On ceramic packing layer, coating thickness is 5 μm, continues dry 120min, PMMA layers of formation the 2nd；Tool is finally removed from basement membrane
There is the film of three-decker.
Film is melted 45min by step (6) at 220 DEG C, is put into quenching treatment in -80 DEG C of low temperature environments immediately after
10min obtains composite film material.
Step (7) hot pressing under 230 DEG C of temperature, 1Mpa pressure, obtains composite film material and obtains finished film.
Embodiment 7.
Step (1) according to every liter of 5g ratio, by polymetylmethacrylate grain dissolution DMF analyze it is pure molten
It in agent, is stirred well to and is completely dissolved, form PMMA solution.
Step (2) uses solid phase method to prepare grain size R as 2nm, material PbZrO3The antiferroelectric ceramics of ceramic material is filled out
Material, ceramic packing is added in the sodium hydroxide solution of a concentration of 0.1mol/L, and additional proportion 200g/L is sufficiently stirred,
Sonic oscillation is recycled 2 times, is then washed with absolute ethyl alcohol, and dry 12h, completes the surface active to ceramic packing at 60 DEG C；
Ceramic packing after surface active is added in absolute ethyl alcohol, ratio 200g/L, quality is added and is filled out for ceramics
The solid dopamine of material 20%, is sufficiently stirred, sonic oscillation, recycles 12 times, and the dry 12h at 60 DEG C completes surface and is modified；It takes
Go out ceramic packing.
Kynoar (PVDF) is added in the analysis pure solvent of DMF by step (3) according to the ratio of every liter of 60g,
It is sufficiently stirred, until being completely dissolved, forms the polymer solution of clear.
The ceramic packing of surface modification is added in polymer solution, fully stirs according to the ratio of every liter of 40g by step (4)
Oscillation is mixed, stable suspension is formed.
The PMMA solution that step (5) is first prepared step (1) is coated in using the tape casting on basement membrane, and coating thickness is 2 μ
M, then dry 15min, PMMA layers of formation the first at 60 DEG C；The suspension again prepared by step (4) is coated in the first PMMA
On layer, coating thickness is 4 μm, continues dry 30min, forms ceramic packing layer；PMMA solution prepared by step (1) is coated in
On ceramic packing layer, coating thickness is 2 μm, continues dry 15min, PMMA layers of formation the 2nd；Finally being removed from basement membrane has
The film of three-decker.
Film is melted 20min by step (6) at 240 DEG C, is put into quenching treatment in -196 DEG C of low temperature environments immediately after
3min obtains composite film material.
Step (7) hot pressing under 240 DEG C of temperature, 0.5Mpa pressure, obtains composite film material and obtains finished film.
Embodiment 8.
Step (1) according to every liter of 150g ratio, by polymetylmethacrylate grain dissolution NMP analyze it is pure
It in solvent, is stirred well to and is completely dissolved, form PMMA solution.
Step (2) use sol-gal process prepare grain size R for 60nm, material be La adulterate PZST ceramic materials anti-iron
Ceramic packing is added in the sodium hydroxide solution of a concentration of 0.5mol/L by electroceramics filler, and additional proportion 150g/L fills
Stirring, sonic oscillation is divided to recycle 8 times, then washed with absolute ethyl alcohol, dry 12h, completes the table to ceramic packing at 50 DEG C
Face activates；
Ceramic packing after surface active is added in absolute ethyl alcohol, ratio 150g/L, quality is added and is filled out for ceramics
The KH550 solution of 98% concentration of material 5%, is sufficiently stirred, sonic oscillation, recycles 8 times, and dry 12h, completes surface at 50 DEG C
It is modified；Take out ceramic packing.
P (VDF-CTFE-TrFE) based on PVDF is added to point of NMP by step (3) according to the ratio of every liter of 120g
It analyses in pure solvent, is sufficiently stirred, until being completely dissolved, form the polymer solution of clear.
The ceramic packing of surface modification is added in polymer solution, fully stirs according to the ratio of every liter of 60g by step (4)
Oscillation is mixed, stable suspension is formed.
The PMMA solution that step (5) is first prepared step (1) is coated in using the tape casting on basement membrane, and coating thickness is 25 μ
M, then dry 240min, PMMA layers of formation the first at 80 DEG C；The suspension again prepared by step (4) is coated in the first PMMA
On layer, coating thickness is 40 μm, continues dry 480min, forms ceramic packing layer；PMMA solution coating prepared by step (1)
On ceramic packing layer, coating thickness is 35 μm, continues dry 360min, PMMA layers of formation the 2nd；Finally removed from basement membrane
Film with three-decker.
Film is melted 10min by step (6) at 250 DEG C, is put into quenching treatment in 0 DEG C of low temperature environment immediately after
60min obtains composite film material.
Step (7) hot pressing under 250 DEG C of temperature, 0.2Mpa pressure, obtains composite film material and obtains finished film.
Embodiment 9.
Step (1) according to every liter of 80g ratio, by polymetylmethacrylate grain dissolution DMAC analyze it is pure
It in solvent, is stirred well to and is completely dissolved, form PMMA solution.
Step (2) use hydro-thermal prepare grain size R for 80nm, material be La adulterate PLZST ceramic materials antiferroelectric ceramics
Ceramic packing is added in the sodium hydroxide solution of a concentration of 1.0mol/L by filler, and additional proportion 120g/L is fully stirred
It mixes, sonic oscillation, recycles 15 times, then washed with absolute ethyl alcohol, the dry 5h at 60 DEG C completes to live to the surface of ceramic packing
Change；
Ceramic packing after surface active is added in absolute ethyl alcohol, ratio 20g/L, addition quality is ceramic packing
20% solid dopamine, is sufficiently stirred, sonic oscillation, recycles 15 times, and the dry 5h at 60 DEG C completes surface and is modified；It takes out
Ceramic packing.
For step (3) according to the ratio of every liter of 20g, the analysis that the P (VDF-HFP) based on PVDF is added to DMAC is pure molten
Agent is sufficiently stirred, until being completely dissolved, forms the polymer solution of clear.
The ceramic packing of surface modification is added in polymer solution, fully stirs according to the ratio of every liter of 5g by step (4)
Oscillation is mixed, stable suspension is formed.
The PMMA solution that step (5) is first prepared step (1) is coated in using the tape casting on basement membrane, and coating thickness is 3 μ
M, then dry 20min, PMMA layers of formation the first at 80 DEG C；The suspension again prepared by step (4) is coated in the first PMMA
On layer, coating thickness is 2 μm, continues dry 12min, forms ceramic packing layer；PMMA solution prepared by step (1) is coated in
On ceramic packing layer, coating thickness is 5 μm, continues dry 45min, PMMA layers of formation the 2nd；Finally being removed from basement membrane has
The film of three-decker.
Film is melted 35min by step (6) at 215 DEG C, is put into quenching treatment in -40 DEG C of low temperature environments immediately after
35min obtains composite film material.
Step (7) hot pressing under 200 DEG C of temperature, 80Mpa pressure, obtains composite film material and obtains finished film.
The composite high-performance dielectric material of sandwich structure of the present invention based on PMMA has high energy storage, low-loss
The characteristics of, while the preparation method being related to is simple for process, the selected prices of raw materials are low, the composite material for easily obtaining, therefore preparing
Performance is good, toughness is high, produces in enormous quantities convenient for following.
Claims (4)
1. the high energy storage dielectric composite material preparation method based on PMMA sandwich structures, it is characterised in that the specific step of this method
Suddenly it is：
Polymetylmethacrylate grain dissolution in polar solvent, is stirred well to and is completely dissolved by step (1), shape
At PMMA solution；1~200g PMMA particles are added in every liter of polar solvent；
Step (2) carries out surface active with activator to ceramic packing, and then carrying out surface to ceramic packing with coupling agent changes
Property；Take out ceramic packing；
The ceramic packing is nanoscale antiferroelectric ceramics filler, and grain size R is 1~100nm, material PbZrO3、
PbZrTiO3And one kind in PLZT, PLZST or PZST ceramic material of La doping；
The specific method of surface active is that ceramic packing is added in activator, and ratio is 5~200g/L, is sufficiently stirred, and is surpassed
Sound oscillation is recycled 1~20 time, is then washed with absolute ethyl alcohol, dry 1~20h at 50~100 DEG C；
The specific method that surface is modified is that the ceramic packing after surface active is added in absolute ethyl alcohol, and ratio is 5~200g/
L is added the coupling agent that quality is ceramic packing 0.1~20%, is sufficiently stirred, sonic oscillation, recycles 1~20 time, 50~100
Dry 1~20h at DEG C；
Step (3) is added a polymer in polar solvent, is sufficiently stirred, until being completely dissolved, forms the polymerization of clear
Object solution；5~200g polymer is added in every liter of polar solvent；
The polymer is Kynoar PVDF or P (VDF-CTFE), P (VDF-TrFE), P (VDF- based on PVDF
CTFE-TrFE), one kind in P (VDF-HFP)；
The ceramic packing that surface is modified by step (4) is added in polymer solution, is sufficiently stirred oscillation, forms stable suspension
1~80g ceramic packings are added in liquid, every liter of polymer solution；
The PMMA solution that step (5) is first prepared step (1) is coated in using the tape casting on basement membrane, and coating thickness is 1~50 μ
M, then dry 12~600min, PMMA layers of formation the first at 50~120 DEG C；The suspension again prepared by step (4) coats
On the first PMMA layers, coating thickness is 1~50 μm, continues dry 12~600min, forms ceramic packing layer；By step (1)
The PMMA solution of preparation is coated on ceramic packing layer, and coating thickness is 1~50 μm, continues dry 12~600min, forms the
Two PMMA layers；The film with three-decker is finally removed from basement membrane；
Film is melted 10~600min by step (6) at 150~250 DEG C, is put into -196~0 DEG C of low temperature environment immediately after
Middle 3~60min of quenching treatment, obtains composite film material；
Hot pressing under step (7) .180~250 DEG C temperature, 0.2~100Mpa pressure, obtains composite film material and obtains finished film.
2. the high energy storage dielectric composite material preparation method based on PMMA sandwich structures as described in claim 1, feature
It is：Polar solvent described in step (1) and (3) is the analysis pure solvent of DMF, NMP or DMAC.
3. the high energy storage dielectric composite material preparation method based on PMMA sandwich structures as described in claim 1, feature
It is：Activator described in step (2) is a concentration of 5~30% hydrogen peroxide, a concentration of 10~30% hydrochloric acid or concentration
For the sodium hydroxide solution of 0.1~1mol/L.
4. the high energy storage dielectric composite material preparation method based on PMMA sandwich structures as described in claim 1, feature
It is：Coupling agent described in step (2) is the KH550 solution or solid dopamine of 98% concentration.
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