CN102504450B - High-dielectric-constant polymer-potassium salt composite film material and preparation method thereof - Google Patents

High-dielectric-constant polymer-potassium salt composite film material and preparation method thereof Download PDF

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CN102504450B
CN102504450B CN 201110346427 CN201110346427A CN102504450B CN 102504450 B CN102504450 B CN 102504450B CN 201110346427 CN201110346427 CN 201110346427 CN 201110346427 A CN201110346427 A CN 201110346427A CN 102504450 B CN102504450 B CN 102504450B
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sylvite
composite film
film material
pvdf
polymer
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朱基亮
朱波
曾子繁
孙平
汪忠兴
郑茂梅
王明松
刘静
朱建国
肖定全
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Sichuan University
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Abstract

The invention relates to a high-dielectric-constant polymer-potassium salt composite film material and a preparation method thereof. The method comprises: calculating the required amount of the polymer which is polyvinylidene fluoride and the required amount of the potassium slat according to a designed volume percentage ratio; adding an organic solvent into the mixed powder of the polyvinylidene fluoride and the potassium slat after mixing and ball milling, and dissolving the polyvinylidene fluoride by using a magnetic stirrer; after the polyvinylidene fluoride is dissolved, shaking the mixed solution by using ultrasonic waves till the potassium salt dispersed in the mixed solution uniformly; pouring the mixed solution onto a glass sheet to cast the mixed solution, evaporating the organic solvent at a constant temperature and obtaining a composite film; heating the composite film to obtain a composite material sample with a thickness of about 60 to 120 micrometers; and sputtering a metal electrode onto the surface of the sample, and thus obtaining the polyvinylidene fluoride-potassium salt composite film material with a relative dielectric constant of 10<2> to 10<4>. The film material is expected to be widely used in electronic industry and can be used as an energy storage capacitor and the like.

Description

The polymkeric substance of high-k-sylvite composite film material and preparation method thereof
Technical field
The present invention relates to a kind of composite film material and technology of preparing thereof, particularly composite film material of a kind of polymer poly vinylidene (PVDF) with high-k and sylvite and preparation method thereof, belong to the dielectric composite material field.
Background technology
High dielectric material, due to its good dielectric properties, has a wide range of applications on solid-state capacitor, microwave-medium element, as: dynamic RAM, high power capacitor etc.And high dielectric ceramic, as CaCu 3ti 4o 12because its good dielectric properties have obtained paying attention to widely.But, although high dielectric ceramic has good dielectric properties, larger fragility arranged and need high preparation temperature, thereby having limited its application, particularly the application on unicircuit has been subject to larger restriction.
And high dielectric polymer matrix composite has certain toughness and far below ceramic preparation temperature, and have far above the specific inductivity of general polymer and more and more paid close attention to.The Nan Cewen seminar of Tsing-Hua University in 2000 has reported the PVDF-Ni matrix material with high-k, and its specific inductivity is 400, is less than 10 specific inductivity far above pure PVDF, and this seminar has also reported Ni-BaTiO afterwards 3/ PVDF three-phase composite material, its specific inductivity is up to 800; 2005, the silver-epoxy resin composite material of the people such as Lai Qi report also had 300 specific inductivity; And the people such as the Q.M.Zhang of Pennsylvania State University are reporting that multiple all-polymer matrix material has the specific inductivity that is greater than 1000 under 1kHz in recent years.But the specific inductivity of these polymer composites is still far below the specific inductivity of high dielectric ceramic.
In recent years, the emphasis for the research of composite material with high dielectric constant remains the body material.Yet, along with the miniaturization of modern device development and integrated, with respect to the body material, more frivolous mould material has shown its distinctive superiority.2007, the people such as Chen have reported and added acetylene black (AB) in PVDF, take DMF as solvent, and the PVDF/AB composite film material that adopts dip-coating method to make has about 50 specific inductivity under 1kHz, but this compares larger gap in addition with high dielectric ceramic and block composite material.
So, a kind of have can be with the specific inductivity of high dielectric ceramic comparable or higher high-k, and preparation technology is simple, raw material is easy to get, with low cost, high-k composite film material and the technology of preparing thereof of can the big area film forming and being easy to scale operation need to be developed as early as possible, and this is task of the present invention place just also.
Summary of the invention
Purpose of the present invention be exactly to provide that a kind of preparation technology is simple, raw material is easy to get, with low cost, can the big area film forming and be easy to scale operation there is high-k and than the preparation method of the polymer poly vinylidene (PVDF) of low-dielectric loss-sylvite composite film material, the method is that polymer P VDF is prepared into to mixture with sylvite by design volume mark ratio, then mixture is prepared into to the composite film material of high-k; The composite film material that described method obtains under 1kHz its relative permittivity up to 10 2～10 4, the specific inductivity that is less than 100 far above existing composite film material.
For realizing above-mentioned purpose of the present invention, the present invention is that the technical scheme that adopts following measures to form realizes:
The invention provides the preparation method of a kind of polymer poly vinylidene with high-k-sylvite composite film material, comprise successively following processing step:
(1) by polymer poly vinylidene (PVDF) and the Volume fraction 100-x of sylvite according to design: x calculates institute's expense, and the scope of x described in its ratio is 1～99;
(2) according to the institute's expense calculated in step (1), with the good PVDF of electronic balance weighing and sylvite, then they are packed in ball grinder, take dehydrated alcohol as medium, on conventional ball mill, ball milling became mixed powder after 4～12 hours, the mixed powder taking-up is placed in to thermostatic drying chamber and dries;
(3) in the PVDF obtained in step (2) and the mixed powder of sylvite, add 10～50ml organic solvent to obtain mixing liquid, and stir this mixing liquid with magnetic stirring apparatus under 60～100 ℃, PVDF in its liquid is fully dissolved, adopt again sonic oscillation to sylvite to be dispersed in and dissolve in liquid, obtain composite fluid;
(4) composite fluid obtained in step (3) slowly is poured on clean clean smooth sheet glass and makes its curtain coating even, again described sheet glass is placed in to thermostatic drying chamber, at 60～120 ℃ of temperature, drying is 2～12 hours, make organic solvent evaporation, the PVDF-sylvite composite membrane that acquisition thickness is 60～120 microns;
(5) composite membrane obtained in step (4) is placed in to retort furnace, utilize temperature controller to set intensification, insulation, cooling process, at 80～240 ℃ of temperature, thermal treatment is 30～480 minutes, with the rate of temperature fall of 20 ℃/h cool to room temperature at the uniform velocity, make the polymer P VDF-sylvite composite film material sample with high-k afterwards;
(6) the polymer P VDF-sylvite composite film material sample surfaces obtained in step (5) is passed through to metal electrode in the ion sputtering instrument sputter, it after standing 24 hours, is tested to its dielectric properties in air.
In technique scheme, described sylvite is salt of wormwood (K 2cO 3).
In technique scheme, described organic solvent is DMF (DMF).
In technique scheme, the metal electrode used during described ion sputtering instrument sputter is gold electrode.
The polymer P VDF-sylvite composite film material prepared according to preparation method of the present invention, this composite film material has high dielectric constant, and its volume fraction at sylvite is that relative permittivity under 4～16,1kHz is up to 10 2～10 4.
The present invention compared with prior art has following characteristics and useful technique effect:
1, preparation method's technique of the present invention is simple, raw materials used be easy to get and with low cost, and required equipment is simple, and technological process is also simple, is convenient to scale operation.
2, the prepared polymer poly vinylidene of preparation method of the present invention-sylvite composite film material has higher specific inductivity, it is compared with the specific inductivity of common high dielectric ceramic, not only have higher specific inductivity, also take into account snappiness and extremely low preparation temperature preferably.
3, the prepared polymer poly vinylidene of preparation method of the present invention-sylvite composite film material is compared with common body material, is more suitable for miniaturization and integrated device production requirements.
4, the prepared polymer poly vinylidene of preparation method of the present invention-sylvite composite film material, owing to having higher specific inductivity, therefore can be applied in the middle of the production of energy storage capacitor.
The accompanying drawing explanation
Fig. 1 is the profile scanning electron microscope pattern of the prepared polymer poly vinylidene of the embodiment of the present invention 1-salt of wormwood composite film material sample; As can be seen from the figure, its thickness of the composite film material of gained is about 80 microns, and the composite membrane thickness is even, has fabulous compactness.
Embodiment
Below the present invention is described in further detail with specific embodiment, but and do not mean that any restriction to protection domain of the present invention.
In the embodiment of the present invention, electronic balance used is the FA-1104N type electronic analytical balance that upper Nereid's tech device technology company limited produces;
Magnetic stirring apparatus used is that Zhengzhou Ying Yu gives the dull and stereotyped heating of magnificent Instrument Ltd.'s production CL-200 type magnetic stirring apparatus;
Ultrasonic cleaning machine used is the KH-2200B type ultrasonic cleaning machine that Kunshan standing grain wound ultrasonic instrument company limited produces;
Ion sputtering instrument used is the SBC-12 type small ion sputtering instrument that Beijing KYKY Technology Development Co., Ltd. produces;
Thermostatic drying chamber used is that the KXH101-2A type thermostatic drying chamber that laboratory apparatus factory produces is analysed by Chinese Shanghai section;
PVDF used is that in Chengdu, fluorine chemical company limited produces.
Following examples adopt above-mentioned preparation method, processing step and processing condition to prepare polymer poly vinylidene-sylvite composite film material.
Embodiment 1:
Sylvite used is salt of wormwood (K 2cO 3), by polymer poly vinylidene (PVDF) and K 2cO 3calculate the raw material consumption according to the volume fraction ratio of 96: 4, use the electronic balance raw materials weighing; Then they are packed in ball grinder, take dehydrated alcohol as medium, on conventional ball mill, ball milling is 6 hours, and the mixed powder after ball milling is dried with thermostatic drying chamber; Then add 15ml organic solvent DMF (DMF) to obtain mixing liquid, mixing liquid is heated on magnetic stirring apparatus to 60 ℃, stir PVDF is fully dissolved; Use again the ultrasonic cleaning machine sonic oscillation to K 2cO 3be dispersed in and dissolve in liquid, obtain composite fluid; Composite fluid slowly is poured on deionized water and the clean clean smooth sheet glass of dehydrated alcohol and makes its curtain coating even, then put into thermostatic drying chamber, at 80 ℃ of temperature, drying is 8 hours, makes organic solvent evaporation, obtains polymer P VDF-sylvite composite membrane; The composite membrane of acquisition is placed in to the retort furnace be connected with temperature controller, utilize temperature controller to set intensification, insulation, cooling process: at the temperature of 220 ℃, thermal treatment is 30 minutes, then with the rate of temperature fall of 20 ℃/h cool to room temperature at the uniform velocity; Make polymer P VDF-sylvite composite film material sample, the composite membrane thickness of sample is about 80 microns; By the small ion sputtering instrument plated with gold electrode for the composite film material sample surfaces obtained, then it after standing 24 hours, is tested to the dielectric properties of gained composite film material sample under 1kHz in air.The present embodiment PVDF and K 2cO 3volume fraction is that 96: 4 its relative permittivitys of prepared composite film material are in Table 1.
Table 1
Figure BDA0000105475850000041
Embodiment 2:
Sylvite used is salt of wormwood (K 2cO 3), by polymer poly vinylidene (PVDF) and K 2cO 3calculate the raw material consumption according to the volume fraction ratio of 92: 8, use the electronic balance raw materials weighing; Then they are packed in ball grinder, take dehydrated alcohol as medium, on conventional ball mill, ball milling is 8 hours, and the mixed powder after ball milling is dried with thermostatic drying chamber; Then add 20ml organic solvent DMF (DMF) to obtain mixing liquid, mixing liquid is heated on magnetic stirring apparatus to 80 ℃, stir PVDF is fully dissolved; Use again the ultrasonic cleaning machine sonic oscillation to K 2cO 3be dispersed in and dissolve in liquid, obtain composite fluid; Composite fluid slowly is poured on deionized water and the clean clean smooth sheet glass of dehydrated alcohol and makes its curtain coating even, then put into thermostatic drying chamber, at 90 ℃ of temperature, drying is 6 hours, makes organic solvent evaporation, obtains polymer P VDF-sylvite composite membrane; The composite membrane of acquisition is placed in to the retort furnace be connected with temperature controller, utilize temperature controller to set intensification, insulation, cooling process: at the temperature of 200 ℃, thermal treatment is 90 minutes, then with the rate of temperature fall of 20 ℃/h cool to room temperature at the uniform velocity; Make polymer P VDF-sylvite composite film material sample, the composite membrane thickness of sample is about 90 microns; By the small ion sputtering instrument plated with gold electrode for the composite film material sample surfaces obtained, then it after standing 24 hours, is tested to the dielectric properties of gained composite film material sample under 1kHz in air.The present embodiment PVDF and K 2cO 3volume fraction is that 92: 8 its relative permittivitys of prepared composite film material are in Table 2.
Table 2
Figure BDA0000105475850000042
Embodiment 3:
Sylvite used is salt of wormwood (K 2cO 3), by polymer poly vinylidene (PVDF) and K 2cO 3calculate the raw material consumption according to the volume fraction ratio of 89: 11, use the electronic balance raw materials weighing; Then they are packed in ball grinder, take dehydrated alcohol as medium, on conventional ball mill, ball milling is 10 hours, and the mixed powder after ball milling is dried with thermostatic drying chamber; Then add 25ml organic solvent DMF (DMF) to obtain mixing liquid, mixing liquid is heated on magnetic stirring apparatus to 80 ℃, stir PVDF is fully dissolved; Use again the ultrasonic cleaning machine sonic oscillation to K 2cO 3be dispersed in and dissolve in liquid, obtain composite fluid; Composite fluid slowly is poured on deionized water and the clean clean smooth sheet glass of dehydrated alcohol and makes its curtain coating even, put into thermostatic drying chamber, at 100 ℃ of temperature, drying is 5 hours, makes organic solvent evaporation, obtains polymer P VDF-sylvite composite membrane; The composite membrane of acquisition is placed in to the retort furnace be connected with temperature controller, utilize temperature controller to set intensification, insulation, cooling process: at the temperature of 200 ℃, thermal treatment is 120 minutes, then with the rate of temperature fall of 20 ℃/h cool to room temperature at the uniform velocity; Make polymer P VDF-sylvite composite film material sample, the composite membrane thickness of sample is about 95 microns; By the small ion sputtering instrument plated with gold electrode for the composite film material sample surfaces obtained, then it after standing 24 hours, is tested to the dielectric properties of gained composite film material sample under 1kHz in air.The PVDF of the present embodiment and K 2cO 3volume fraction is that 89: 11 its relative permittivitys of prepared composite film material are in Table 3.
Table 3
Figure BDA0000105475850000051
Embodiment 4:
Sylvite used is salt of wormwood (K 2cO 3), by polymer poly vinylidene (PVDF) and K 2cO 3calculate the raw material consumption according to the volume fraction ratio of 92: 8, use the electronic balance raw materials weighing; Then they are packed in ball grinder, take dehydrated alcohol as medium, on conventional ball mill, ball milling is 10 hours, and the mixed powder after ball milling is dried with thermostatic drying chamber; Then add 30ml organic solvent DMF (DMF) to obtain mixing liquid, and mixing liquid is heated on magnetic stirring apparatus to 100 ℃, stir PVDF is fully dissolved; Use again the ultrasonic cleaning machine sonic oscillation to K 2cO 3be dispersed in and dissolve in liquid, obtain composite fluid; Composite fluid slowly is poured on deionized water and the clean clean smooth sheet glass of dehydrated alcohol and makes its curtain coating even, put into thermostatic drying chamber, at 110 ℃ of temperature, drying is 4 hours, makes organic solvent evaporation, obtains polymer P VDF-sylvite composite membrane; The composite membrane of acquisition is placed in to the retort furnace be connected with temperature controller, utilize temperature controller to set intensification, insulation, cooling process: at the temperature of 180 ℃, thermal treatment is 180 minutes, then with the rate of temperature fall of 20 ℃/h cool to room temperature at the uniform velocity; Make polymer P VDF-sylvite composite film material sample, the composite membrane thickness of sample is about 100 microns; By the small ion sputtering instrument plated with gold electrode for the composite film material sample surfaces obtained, then it after standing 24 hours, is tested to the dielectric properties of gained composite film material sample under 1kHz in air.The PVDF of the present embodiment and K 2cO 3volume fraction is that 92: 8 its relative permittivitys of prepared composite film material are in Table 4.
Table 4
Figure BDA0000105475850000061
Embodiment 5:
Sylvite used is salt of wormwood (K 2cO 3), by polymer poly vinylidene (PVDF) and K 2cO 3calculate the raw material consumption according to the volume fraction ratio of 87: 13, use the electronic balance raw materials weighing; Then they are packed in ball grinder, take dehydrated alcohol as medium, on conventional ball mill, ball milling is 12 hours, and the mixed powder after ball milling is dried with thermostatic drying chamber; Then add 35ml organic solvent DMF (DMF) to obtain mixing liquid, mixing liquid is heated on magnetic stirring apparatus to 100 ℃, stir PVDF is fully dissolved; Use again the ultrasonic cleaning machine sonic oscillation to K 2cO 3be dispersed in and dissolve in liquid, obtain composite fluid; Composite fluid slowly is poured on deionized water and the clean clean smooth sheet glass of dehydrated alcohol and makes its curtain coating even, put into thermostatic drying chamber, at 120 ℃ of temperature, drying is 2 hours, makes organic solvent evaporation, obtains polymer P VDF-sylvite composite membrane; The composite membrane of acquisition is placed in to the retort furnace be connected with temperature controller, utilize temperature controller to set intensification, insulation, cooling process: at the temperature of 160 ℃, thermal treatment is 320 minutes, then with the rate of temperature fall of 20 ℃/h cool to room temperature at the uniform velocity; Make polymer P VDF-sylvite composite film material sample, the composite membrane thickness of sample is about 120 microns; By the small ion sputtering instrument plated with gold electrode for the composite film material sample surfaces obtained, then it after standing 24 hours, is tested to the dielectric properties of gained composite film material sample under 1kHz in air.The PVDF of the present embodiment and K 2cO 3volume fraction is that 87: 13 o'clock its relative permittivitys of prepared composite film material are in Table 5.
Table 5
Figure BDA0000105475850000062

Claims (5)

1. the preparation method of the polymkeric substance with high-k-sylvite composite film material is characterized in that comprising successively following processing step:
(1) polymer poly vinylidene (PVDF) and sylvite are calculated to institute's expense according to the Volume fraction 100-x:x designed, the scope of x described in its ratio is 4～16;
(2) according to the institute's expense calculated in step (1), with the good PVDF of electronic balance weighing and sylvite, then they are packed in ball grinder, take dehydrated alcohol as medium, on conventional ball mill, ball milling became mixed powder after 4～12 hours, the mixed powder taking-up is placed in to thermostatic drying chamber and dries;
(3) in the PVDF obtained in step (2) and the mixed powder of sylvite, add 10～50ml organic solvent to obtain mixing liquid, and stir this mixing liquid with magnetic stirring apparatus under 60～100 ℃, PVDF in its liquid is fully dissolved, be dispersed in and dissolve in liquid with sonic oscillation to sylvite again, obtain composite fluid;
(4) composite fluid obtained in step (3) slowly is poured on clean clean smooth sheet glass and makes its curtain coating even, again described sheet glass is placed in to thermostatic drying chamber, at 60～120 ℃ of temperature, drying is 2～12 hours, make organic solvent evaporation, the PVDF-sylvite composite membrane that acquisition thickness is 60～120 microns;
(5) composite membrane obtained in step (4) is placed in to retort furnace, utilize temperature controller to set intensification, insulation, cooling process, at 80～240 ℃ of temperature, thermal treatment is 30～480 minutes, with the rate of temperature fall of 20 ℃/h cool to room temperature at the uniform velocity, make the polymer P VDF-sylvite composite film material sample with high-k afterwards;
(6) the polymer P VDF-sylvite composite film material sample surfaces obtained in step (5) is passed through to metal electrode in the ion sputtering instrument sputter, it after standing 24 hours, is tested to its dielectric properties in air.
2. preparation method according to claim 1, is characterized in that described sylvite is salt of wormwood (K 2cO 3).
3. preparation method according to claim 1 and 2, is characterized in that described organic solvent is DMF (DMF).
4. preparation method according to claim 1, is characterized in that the metal electrode that described ion sputtering instrument sputter is used is gold electrode.
5. the polymer P VDF-sylvite composite film material prepared according to the described either method of claim 1～4, it is characterized in that this composite film material the volume fraction of sylvite be under 4～16,1kHz relative permittivity up to 10 2～10 4.
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CN102731944A (en) * 2012-06-21 2012-10-17 四川大学 Copolymer-sylvite composite film material and its preparation method
CN104448360B (en) * 2013-09-22 2018-04-27 福建省辉锐材料科技有限公司 A kind of preparation method of piezoelectricity polyvinylidene difluoride film
CN104650373A (en) * 2015-02-04 2015-05-27 四川大学 High-dielectric-constant composite membrane material and preparation method thereof
CN104829976A (en) * 2015-05-27 2015-08-12 陕西科技大学 Method for manufacturing composite dielectric materials from polyvinylidene fluoride and end carboxyl multi-walled carbon nano-tubes

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