CN105623156A - Polymer-based hybrid membrane and preparation method and application thereof - Google Patents

Polymer-based hybrid membrane and preparation method and application thereof Download PDF

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CN105623156A
CN105623156A CN201511006121.8A CN201511006121A CN105623156A CN 105623156 A CN105623156 A CN 105623156A CN 201511006121 A CN201511006121 A CN 201511006121A CN 105623156 A CN105623156 A CN 105623156A
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polymer
based carbon
hybridized film
modified ceramic
carbon hybridized
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宋宇
郑斌
沈洋
南策文
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Shenzhen Research Institute Tsinghua University
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Shenzhen Research Institute Tsinghua University
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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Abstract

The invention discloses a polymer-based hybrid membrane and a preparation method and application thereof. The polymer-based hybrid membrane is prepared from modified ceramic particle-doped polymers which comprise, by mass, 5%-30% of modified ceramic particles and 70%-95% of the polymers, and the surfaces of the modified ceramic particles are provided with organic modified layers formed through modification of a surface modifier. The polymer-based hybrid membrane is prepared from the modified ceramic particle-doped polymers, and by doping the modified ceramic particles, the dielectric constant is increased, and the energy storage density is increased. Compared with a traditional polymer-based material, the maximum energy storage density of the polymer-based hybrid membrane can reach 15 kJ/L, and the energy storage density is high.

Description

Polymer-based carbon hybridized film and its preparation method and application
Technical field
The present invention relates to field of new, particularly relate to a kind of polymer-based carbon hybridized film and its preparation method and application.
Background technology
In recent years, people are devoted to develop the polymer matrix composite with relatively high dielectric property. On the one hand, ceramic condenser has extremely high specific inductivity, but the higher sintering temperature of ceramic dielectic makes, and its complex process, power consumption are big and snappiness is poor. On the other hand, currently used high voltage capacitor mainly uses the pure macromolecular materials such as polypropylene (PP) as dielectric layer, these materials have very high breaking down field strength (��300kV/mm), but due to its specific inductivity very low (relative permittivity is 2��3), the electrical condenser energy storage density adopting pure macromolecular material to manufacture is low (1��2kJ/L).
Summary of the invention
Based on this, it is necessary to polymer-based carbon hybridized film providing a kind of energy storage density higher and its preparation method and application.
A kind of polymer-based carbon hybridized film, the material of described polymer-based carbon hybridized film is the particle doped polymkeric substance of modified ceramic;
In described polymer-based carbon hybridized film, the mass percentage of described modified ceramic particle is 5%��30%, and the mass percentage of described polymkeric substance is 70%��95%;
There is the organically-modified layer formed through surface-modifying agent modification on the surface of described modified ceramic particle.
In an embodiment, at least one that described polymkeric substance is selected from polyvinylidene difluoride (PVDF), polypropylene, polyester, polyphenylene sulfide, epoxy resin and polyimide;
Described modified ceramic particle is barium titanate, strontium-barium titanate and CaCu3Ti4O12In at least one formed through surface-modifying agent modification;
Described surface-modifying agent is Dopamine HCL, silane coupling agent or titanate coupling agent.
In an embodiment, the particle diameter of described modified ceramic particle is 50nm��500nm, and the thickness of described organically-modified layer is 1nm��5nm.
In an embodiment, the thickness of described polymer-based carbon hybridized film is 5 ��m��50 ��m.
The preparation method of a kind of above-mentioned polymer-based carbon hybridized film, it is characterised in that, comprise the steps:
After polymkeric substance and modified ceramic uniform particles being mixed, heating and melting obtains mixing raw material, and wherein, in described mixing raw material, the mass percentage of described modified ceramic particle is 5%��30%, and the mass percentage of described polymkeric substance is 70%��95%;
Casting films is obtained after the described mixing raw material of melting is carried out curtain coating;
Described casting films is stretched successively and shapes, obtain work in-process film; And
Described work in-process film is carried out trimming and rolling, obtains described polymer-based carbon hybridized film.
In an embodiment, described modified ceramic particle is obtained by following operation: ceramic particle is placed in the surface modification agent solution that concentration is 0.001mol/L��0.01mol/L, after processing 8h��24h, obtains described modified ceramic particle at 60 DEG C��90 DEG C;
The solute of described surface modification agent solution is Dopamine HCL, silane coupling agent or titanate coupling agent.
In an embodiment, the described described mixing raw material to melting obtains being operating as of casting films after carrying out curtain coating: be close to casting roller after being extruded by the described mixing raw material of melting, and under the rotation and traction of casting roller, curtain coating forms described casting films.
In an embodiment, described described casting films stretched successively and shapes, obtain being operating as of work in-process film: carry out stretching and shaping through preheat roll, fixing draw roll, mobile draw roll, lehr rollers and cooling roller successively by described casting films, described casting films thickness subtracts thin simultaneously, obtains the uniform work in-process film of thickness.
A kind of composite hybridization film, comprises the first organic membrane of stacking successively and above-mentioned polymer-based carbon hybridized film.
In an embodiment, also comprise the 2nd organic membrane, described first organic membrane, described polymer-based carbon hybridized film and described 2nd organic membrane stacking successively.
The material of this kind of polymer-based carbon hybridized film is the particle doped polymkeric substance of modified ceramic, by the doping of modified ceramic particle, it is to increase specific inductivity, adds energy storage density simultaneously. Compared with traditional polymer-based material, the energy storage density of this kind of polymer-based carbon hybridized film is the highest can reach 15kJ/L (8kJ/L��15kJ/L), and energy storage density is higher.
This kind of polymer-based carbon hybridized film can be widely used in the high-power electrostatic energy storage devices such as electrical condenser.
Accompanying drawing explanation
Fig. 1 is the schema of the preparation method of the polymer-based carbon hybridized film of an enforcement mode.
Embodiment
Mainly in conjunction with the drawings and the specific embodiments polymer-based carbon hybridized film and its preparation method and application is further explained explanation below.
Implementing a polymer-based carbon hybridized film for mode, material is the particle doped polymkeric substance of modified ceramic.
In polymer-based carbon hybridized film, the mass percentage of modified ceramic particle is 5%��30%, and the mass percentage of polymkeric substance is 70%��95%.
There is the organically-modified layer formed through surface-modifying agent modification on the surface of modified ceramic particle.
Preferably, at least one that polymkeric substance is selected from polyvinylidene difluoride (PVDF), polypropylene, polyester, polyphenylene sulfide, epoxy resin and polyimide.
Modified ceramic particle is barium titanate, strontium-barium titanate and CaCu3Ti4O12In at least one formed through surface-modifying agent modification.
Surface-modifying agent can be Dopamine HCL, silane coupling agent or titanate coupling agent. Silane coupling agent can be KH-550, KH-560, etc. Titanate coupling agent can be TMC-101, TMC-TTS, etc.
Preferably, the particle diameter of modified ceramic particle is 50nm��500nm, and the thickness of the organically-modified layer of modified ceramic particle surface is 1nm��5nm.
Preferably, the thickness of polymer-based carbon hybridized film is 5 ��m��50 ��m.
The material of this kind of polymer-based carbon hybridized film is the particle doped polymkeric substance of modified ceramic, by the doping of modified ceramic particle, it is to increase specific inductivity, adds energy storage density simultaneously. Compared with traditional polymer-based material, the energy storage density of this kind of polymer-based carbon hybridized film is the highest can reach 15kJ/L, and energy storage density is higher.
In addition, this kind of polymer-based carbon hybridized film, by doping modified ceramic particle, specific inductivity improves 3 times on the basis of polymeric matrix, dielectric loss remains on the lower level of tan �� < 5%, and breaking down field strength also remains on higher level (> 200kV/mm).
This kind of polymer-based carbon hybridized film can be widely used in the high-power electrostatic energy storage devices such as electrical condenser.
The preparation method of above-mentioned polymer-based carbon hybridized film as shown in Figure 1, comprises the steps:
S10, polymkeric substance and modified ceramic uniform particles are mixed after, be heated to 200 DEG C��400 DEG C and make polymer melt, obtain mixing raw material.
The operation of polymkeric substance and the mixing of modified ceramic uniform particles can be completed by the mode of spiral feeding, and polymkeric substance and modified ceramic particle feed in raw material from main spout and side spout respectively.
In mixing raw material, the mass percentage of modified ceramic particle is 5%��30%, and the mass percentage of polymkeric substance is 70%��95%.
There is the organically-modified layer formed through surface-modifying agent modification on the surface of modified ceramic particle.
Preferably, at least one that polymkeric substance is selected from polyvinylidene difluoride (PVDF), polypropylene, polyester, polyphenylene sulfide, epoxy resin and polyimide.
Modified ceramic particle is barium titanate, strontium-barium titanate and CaCu3Ti4O12In at least one formed through surface-modifying agent modification.
Concrete, modified ceramic particle is obtained by following operation: ceramic particle is placed in the surface modification agent solution that concentration is 0.001mol/L��0.01mol/L, after processing 8h��24h, obtains described modified ceramic particle at 60 DEG C��90 DEG C.
Surface-modifying agent can be Dopamine HCL, silane coupling agent or titanate coupling agent. Silane coupling agent can be KH-550, KH-560, etc. Titanate coupling agent can be TMC-101, TMC-TTS, etc.
Preferably, the particle diameter of modified ceramic particle is 50nm��500nm, and the thickness of the organically-modified layer of modified ceramic particle surface is 1nm��5nm.
The mixing raw material of S20, the melting obtained by S10 obtains casting films after carrying out curtain coating.
In S20, obtaining being operating as of casting films after mixing raw material is carried out curtain coating: be close to casting roller after being extruded by the mixing raw material of melting, under the rotation and traction of casting roller, curtain coating forms described casting films.
S30, the casting films obtained by S20 stretch successively and shape, and obtain work in-process film.
In S30, casting films is stretched successively and shapes, obtain being operating as of work in-process film: carrying out stretching and shaping through preheat roll, fixing draw roll, mobile draw roll, lehr rollers and cooling roller successively by casting films, casting films thickness subtracts thin simultaneously, obtains the uniform work in-process film of thickness.
The temperature of preheat roll can be 120 DEG C��300 DEG C.
S40, the work in-process film obtained by S30 carry out trimming and rolling, obtain polymer-based carbon hybridized film.
The operation of rolling can be: completes automatic winding through tension control device.
Obtained polymer-based carbon hybridized film requires evenly, continuously with without obvious defect.
The thickness of obtained polymer-based carbon hybridized film is 5 ��m��50 ��m, and after trimming, fabric width can reach 30cm.
The preparation method of this kind of polymer-based carbon hybridized film, simple and reliable, serialization, the integration that can realize polymer-based carbon hybridized film are produced, the material of obtained polymer-based carbon hybridized film is the particle doped polymkeric substance of modified ceramic, by the doping of modified ceramic particle, improve specific inductivity, add energy storage density simultaneously. Compared with traditional polymer-based material, the energy storage density of this kind of polymer-based carbon hybridized film is the highest can reach 15kJ/L (8kJ/L��15kJ/L), and energy storage density is higher.
The invention also discloses a kind of composite hybridization film, comprise the first organic membrane of stacking successively and above-mentioned polymer-based carbon hybridized film.
The one that the material of the first organic membrane is selected from polyvinylidene difluoride (PVDF), polypropylene, polyester, polyphenylene sulfide, epoxy resin and polyimide.
Preferably, this kind of composite hybridization film comprises the 2nd organic membrane, the first organic membrane, polymer-based carbon hybridized film and the 2nd organic membrane stacking successively.
The one that the material of the 2nd organic membrane is selected from polyvinylidene difluoride (PVDF), polypropylene, polyester, polyphenylene sulfide, epoxy resin and polyimide.
This kind of composite hybridization film can by the first organic membrane with obtain together with attaching under roll-in with the traction of casting roller at rubber roll after polymer-based carbon hybridized film stacking.
The thickness of this kind of composite hybridization film can be 10 ��m��50 ��m.
This kind of composite hybridization film is by by the first organic membrane and polymer-based carbon hybridized film stacking, considerably increasing the breaking down field strength of composite hybridization film, it is possible to be widely used in the high-power electrostatic energy storage devices such as electrical condenser.
The above embodiment only have expressed one or more enforcement modes of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to patent scope of the present invention. , it is also possible to make some distortion and improvement, it should be appreciated that for the person of ordinary skill of the art, without departing from the inventive concept of the premise these all belong to protection scope of the present invention. Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (10)

1. a polymer-based carbon hybridized film, it is characterised in that, the material of described polymer-based carbon hybridized film is the particle doped polymkeric substance of modified ceramic;
In described polymer-based carbon hybridized film, the mass percentage of described modified ceramic particle is 5%��30%, and the mass percentage of described polymkeric substance is 70%��95%;
There is the organically-modified layer formed through surface-modifying agent modification on the surface of described modified ceramic particle.
2. polymer-based carbon hybridized film according to claim 1, it is characterised in that, at least one that described polymkeric substance is selected from polyvinylidene difluoride (PVDF), polypropylene, polyethylene terephthalate, polyphenylene sulfide, epoxy resin and polyimide;
Described modified ceramic particle is barium titanate, strontium-barium titanate and CaCu3Ti4O12In at least one formed through surface-modifying agent modification;
Described surface-modifying agent is Dopamine HCL, silane coupling agent or titanate coupling agent.
3. polymer-based carbon hybridized film according to claim 1, it is characterised in that, the particle diameter of described modified ceramic particle is 50nm��500nm, and the thickness of described organically-modified layer is 1nm��5nm.
4. polymer-based carbon hybridized film according to claim 1, it is characterised in that, the thickness of described polymer-based carbon hybridized film is 5 ��m��50 ��m.
5. the preparation method of a polymer-based carbon hybridized film as according to any one of Claims 1 to 4, it is characterised in that, comprise the steps:
After polymkeric substance and modified ceramic uniform particles are mixed, it is heated to 200 DEG C��400 DEG C and makes polymer melt, obtain mixing raw material, wherein, in described mixing raw material, the mass percentage of described modified ceramic particle is 5%��30%, and the mass percentage of described polymkeric substance is 70%��95%;
Casting films is obtained after the described mixing raw material of melting is carried out curtain coating;
Described casting films is stretched successively and shapes, obtain work in-process film; And
Described work in-process film is carried out trimming and rolling, obtains described polymer-based carbon hybridized film.
6. polymer-based carbon hybridized film according to claim 5, it is characterized in that, described modified ceramic particle is obtained by following operation: ceramic particle is placed in the surface modification agent solution that concentration is 0.001mol/L��0.01mol/L, after processing 8h��24h at 60 DEG C��90 DEG C, obtain described modified ceramic particle;
The solute of described surface modification agent solution is Dopamine HCL, silane coupling agent or titanate coupling agent.
7. polymer-based carbon hybridized film according to claim 5, it is characterized in that, the described described mixing raw material to melting obtains being operating as of casting films after carrying out curtain coating: be close to casting roller after being extruded by the described mixing raw material of melting, and under the rotation and traction of casting roller, curtain coating forms described casting films.
8. polymer-based carbon hybridized film according to claim 5, it is characterized in that, described described casting films stretched successively and shapes, obtain being operating as of work in-process film: carry out stretching and shaping through preheat roll, fixing draw roll, mobile draw roll, lehr rollers and cooling roller successively by described casting films, described casting films thickness subtracts thin simultaneously, obtains the uniform work in-process film of thickness.
9. a composite hybridization film, it is characterised in that, comprise the first organic membrane of stacking successively and the polymer-based carbon hybridized film as according to any one of Claims 1 to 4.
10. composite hybridization film according to claim 9, it is characterised in that, also comprise the 2nd organic membrane, described first organic membrane, described polymer-based carbon hybridized film and described 2nd organic membrane stacking successively.
CN201511006121.8A 2015-12-28 2015-12-28 Polymer-based hybrid membrane and preparation method and application thereof Pending CN105623156A (en)

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CN105906967A (en) * 2016-06-13 2016-08-31 吴江佳亿电子科技有限公司 Low-loss composite thin film medium changeable capacitor material and preparation method thereof
CN106065132A (en) * 2016-06-13 2016-11-02 吴江佳亿电子科技有限公司 A kind of composite polystyrene capacitor material and preparation method thereof
CN106317944A (en) * 2016-08-25 2017-01-11 黄渭国 Method for improving permittivity of capacitor film
CN107099106A (en) * 2017-04-25 2017-08-29 晶锋集团股份有限公司 A kind of polysiloxane grafted barium strontium titanate/polyvinylidene fluoride composite material of high dielectric and preparation method thereof
CN107116874A (en) * 2017-04-24 2017-09-01 浙江永盛薄膜科技有限公司 A kind of temperature control semiconductor BOPET polyester base films and its production technology
CN108059767A (en) * 2017-12-19 2018-05-22 会通新材料股份有限公司 A kind of high-k PP composite material and preparation method thereof
CN108117693A (en) * 2017-12-28 2018-06-05 清远市普塞呋磷化学有限公司 A kind of open air high voltage electric elements halogen-free anti-flaming polypropylene material and preparation method thereof
CN109233099A (en) * 2018-08-24 2019-01-18 全球能源互联网研究院有限公司 A kind of membrane capacitance high dielectric constant polypropylene/ceramic composite and preparation method thereof
CN109943090A (en) * 2019-01-30 2019-06-28 东莞理工学院 A kind of barium titanate/heat stable resin compound dielectric film and preparation method thereof
CN110885581A (en) * 2018-09-10 2020-03-17 宁波其兰文化发展有限公司 Wear-resistant composite conductive coating and preparation method thereof
CN111024273A (en) * 2019-12-27 2020-04-17 浙江清华柔性电子技术研究院 Pressure sensor with temperature stability and preparation method thereof
CN111044207A (en) * 2019-12-30 2020-04-21 浙江清华柔性电子技术研究院 Pressure sensor and preparation method thereof
CN113948251A (en) * 2021-10-19 2022-01-18 广东电网有限责任公司 Insulation structure of superconducting cable
CN114196108A (en) * 2021-12-08 2022-03-18 丹阳新华美塑料有限公司 Modified polypropylene film material for capacitor and preparation method thereof

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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105906967A (en) * 2016-06-13 2016-08-31 吴江佳亿电子科技有限公司 Low-loss composite thin film medium changeable capacitor material and preparation method thereof
CN106065132A (en) * 2016-06-13 2016-11-02 吴江佳亿电子科技有限公司 A kind of composite polystyrene capacitor material and preparation method thereof
CN106317944A (en) * 2016-08-25 2017-01-11 黄渭国 Method for improving permittivity of capacitor film
CN107116874A (en) * 2017-04-24 2017-09-01 浙江永盛薄膜科技有限公司 A kind of temperature control semiconductor BOPET polyester base films and its production technology
CN107099106A (en) * 2017-04-25 2017-08-29 晶锋集团股份有限公司 A kind of polysiloxane grafted barium strontium titanate/polyvinylidene fluoride composite material of high dielectric and preparation method thereof
CN108059767A (en) * 2017-12-19 2018-05-22 会通新材料股份有限公司 A kind of high-k PP composite material and preparation method thereof
CN108117693B (en) * 2017-12-28 2020-07-21 清远市普塞呋磷化学有限公司 Halogen-free flame-retardant polypropylene material for outdoor high-voltage electrical appliance components and preparation method thereof
CN108117693A (en) * 2017-12-28 2018-06-05 清远市普塞呋磷化学有限公司 A kind of open air high voltage electric elements halogen-free anti-flaming polypropylene material and preparation method thereof
CN109233099A (en) * 2018-08-24 2019-01-18 全球能源互联网研究院有限公司 A kind of membrane capacitance high dielectric constant polypropylene/ceramic composite and preparation method thereof
CN109233099B (en) * 2018-08-24 2021-08-20 全球能源互联网研究院有限公司 High-dielectric-constant polypropylene/ceramic composite material for film capacitor and preparation method thereof
CN110885581A (en) * 2018-09-10 2020-03-17 宁波其兰文化发展有限公司 Wear-resistant composite conductive coating and preparation method thereof
CN109943090A (en) * 2019-01-30 2019-06-28 东莞理工学院 A kind of barium titanate/heat stable resin compound dielectric film and preparation method thereof
CN111024273A (en) * 2019-12-27 2020-04-17 浙江清华柔性电子技术研究院 Pressure sensor with temperature stability and preparation method thereof
CN111024273B (en) * 2019-12-27 2021-12-24 浙江清华柔性电子技术研究院 Pressure sensor with temperature stability and preparation method thereof
CN111044207A (en) * 2019-12-30 2020-04-21 浙江清华柔性电子技术研究院 Pressure sensor and preparation method thereof
CN111044207B (en) * 2019-12-30 2023-11-28 浙江清华柔性电子技术研究院 Pressure sensor and method for producing the same
CN113948251A (en) * 2021-10-19 2022-01-18 广东电网有限责任公司 Insulation structure of superconducting cable
CN113948251B (en) * 2021-10-19 2023-10-10 广东电网有限责任公司 Insulating structure of superconducting cable
CN114196108A (en) * 2021-12-08 2022-03-18 丹阳新华美塑料有限公司 Modified polypropylene film material for capacitor and preparation method thereof

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Application publication date: 20160601