CN108752812A - A kind of nanocomposite of high-k low conductivity - Google Patents
A kind of nanocomposite of high-k low conductivity Download PDFInfo
- Publication number
- CN108752812A CN108752812A CN201810504583.XA CN201810504583A CN108752812A CN 108752812 A CN108752812 A CN 108752812A CN 201810504583 A CN201810504583 A CN 201810504583A CN 108752812 A CN108752812 A CN 108752812A
- Authority
- CN
- China
- Prior art keywords
- graphene
- composite material
- organic
- film
- organic molecule
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Abstract
This technology invention belongs to dielectric composite material field, is related to a kind of new method preparing the nanocomposite films with high-k and low conductivity.Dielectric material is in microelectronics domain, it is still a technological difficulties including suffering from the material for being widely applied, but obtaining high dielectric constant, extremely low conductance and low-dielectric loss in feed-through capacitor, organic field effect tube, organic thin layer electroluminescent device, the application of electric field controls and electrical energy storage device.The present invention is combined using small size graphene and aromatic series organic molecule, is filled in polymer, has been prepared nanocomposite films, has 104The high-k of the order of magnitude and 10‑8The low conductivity of the order of magnitude effectively advances the application range of dielectric material, improves the performance of material.By adsorbing organic molecule on the surface of graphene, the stacking of graphene film and the formation of conductive network are hindered, can inhibit conductivity again while improving the conductivity of composite material.Material molding is simple, superior performance, is conducive to industrialized production.
Description
Technical field：
The invention belongs to dielectric composite material fields, and in particular to a kind of organic small using small size graphene, aromatic series
Molecule and Kynoar can be used in prepare the nanocomposite with high-k and low conductivity, diaphragm type
Capacitor improves energy density.
Background technology：
High dielectric material has very important application in electronics and electromechanics trade, is especially used in high energy-storage capacitor
On.The formula of the electric energy of calculable capacitor storage is W=CV2/ 2, wherein capacitance C is directly proportional to capacitor dielectric constant, so
The energy storage capacity of the certain capacitor of size is determined by the dielectric constant of capacitor under identical voltage V.
Effect of the high dielectric constant material in terms of energy storage and electric field homogenizing so that it has in electrical technology field
Significance.Compound by material obtains new high dielectric constant work(new material, has important science and practical significance.
The method for preparing high dielectric constant material at present is mainly the following：1. high dielectric material ceramics are added in the polymer
Grain；2. conductive agent is added in the polymer, theory is oozed by Chongqing so that the dielectric constant of material oozes Near Threshold in Chongqing and reaches most
Big value.
These methods can improve the dielectric constant values of material, but high-dielectric-constant ceramics particle is added in polymer and makes
Standby dielectric material has extremely serious defect, including functive addition is excessive causes material flexibility very poor, material proportion
Amount is big, material poor processability and the defects of cannot reach high-k.And it can be very in conductive particle addition polymer
Just reach huge dielectric constant numerical value when small addition to be promoted, but since the formation of the conductive network when threshold value is oozed in Chongqing is led
Cause the dielectric loss of material also very big.Therefore, the shape of conductive network in conductive particle can effectively be obstructed by finding a kind of method
At being to solve the problems, such as this key point.
Graphene be one kind by carbon atom with sp2The two-dimension nano materials that the mode of hydridization is constituted have excellent physics
And chemical property.It was found in 2004, was initially to obtain single-layer graphene by removing high quality graphite method with adhesive tape.
The preparation method of graphene is broadly divided into two classes：Wet chemistry method and gas-phase reaction method.Process for preparing graphenes by chemical vapour deposition produces
Rate is low and severe reaction conditions, needs vacuum environment.And Hummer ' the s methods in wet chemistry method, i.e., graphite powder is subjected to oxygen
Change stripping, then the graphene oxide of monoatomic layer restored, have price low and is easy to the advantage of preparation of industrialization,
Therefore it is widely used among the research and development of ultracapacitor.But the graphene after restoring is easy to attract each other and be stacked into stone again
Ink sheet, and oxygen-containing functional group removal is not thorough and causes conductivity low, and these are all unfavorable for graphene being applied to high dielectric,
In low conductance composite material film.
Invention content：
This technology invention utilizes the stacking and conduction of small size graphene absorption organic molecule obstruction graphene film for the first time
Network forms this method to prepare high-k material of low conductivity.As shown in Figure 1, using π-π interactions in graphite
The nonconducting aromatic series organic molecule of alkene adsorption.The graphene sheet layer of such non-functionalized processing is being packed into polymer
After medium, since the covering of organic molecule plays drop even if graphene film after contacting with each other, can also inhibit the conduction of electronics
The effect of low conductivity.This preparation method is simple and efficient, and can be prepared on a large scale.
Chemical raw material used in the present invention is cheap and common, and preparation process is simply pollution-free, and thin film preparation process can meet
Large-scale production demand.
Preparation process includes the following steps：
1) small pieces graphene is prepared using improved ultrasonic wave added Hummer ' s methods, specific steps include the pre- of expanded graphite
The cleaning and concentration of oxidation and ultrasonic disperse, oxidation of the pre-oxidation graphene under ultrasound, and pre-oxidation graphene.
2) dissolving in dimethylformamide (DMF), stirring by the graphene oxide of concentration and specific organic molecule
With graphene oxide the pi-conjugated absorption of π-occurs for 24 hours organic molecules that can make containing phenyl ring.It is washed repeatedly with DMF solvent
Product removes the organic molecule not adsorbed with graphene, centrifugal concentrating product.
3) obtained product is uniformly mixed with the Kynoar (PVDF) being dissolved in DMF, mechanical agitation 2h, ultrasound
Disperse 30min, is put into the gas for vacuumizing in vacuum drying oven and being dissolved in 2h discharge solution, solution-cast is being coated with releasing agent
After in the mold of polytetrafluoroethylene (PTFE), it is placed in 40 DEG C of baking ovens dry 12h, it is spare to take film off.
4) 3) film in a manner of facing face two prepared in opened to after putting together hot pressing forms a film under hot press, is taken advantage of
Heat removes film, trims spare behind corner.
5) by the film two sides deposited metal film of acquisition, flat capacitor device is prepared.
The present invention prepares Kynoar/graphene nanocomposite material using graphene absorption organic molecule, this
Technical solution major advantage is：
1) absorption of graphene and organic molecule does not need hydro-thermal reaction and other reaction conditions, is stirred at room temperature i.e.
It can react
2) absorption of graphene and organic molecule can effectively hinder graphene film stacking and composite material in it is conductive
The formation of network.Ordinary circumstance is that the conductivity of composite material can increasing and increase with carbon material loading.We use
The method that organic molecule covers graphene, can significantly inhibit conductivity.As shown in Fig. 2, being in graphene mass fraction
Conductivity is 10 when 5%-9The order of magnitude.
3) preparation is simple, raw material cost is low, be easily enlarged production and prepares large-sized composite material film.
4) properties of product are superior, and dielectric constant is high, conductance is low, dielectric loss is small, 5% graphene content as shown in Figure 3
Sample.
Description of the drawings
Attached drawing 1 using the graphene that organic molecule is modified be added in polymer in conjunction with and the dielectric composite material for preparing show
It is intended to.
The content of graphene and the relation curve of conductivity in PVDF polymer of the attached drawing 2 containing functionalization graphene.
A kind of dielectric properties example of the graphene-based PVDF composite materials containing 5% mass percent of attached drawing 3.
Specific implementation mode：
The present invention is further elaborated below in conjunction with example, but the invention is not limited in specific embodiments.
1) small pieces graphene is prepared with ultrasonic wave added Hummer ' s methods, raw material use the expanded graphite powder of 12000 mesh
Body.
2) the small pieces graphene concentrated solution obtained in (1) taking-up is dissolved into DMF, dihydroxy diphenyl ether is added, to ammonia
One kind in base phenol, diaminodiphenyl sulfide, diaminonaphthalene, stirs evenly.Three times with DMF solution centrifuge washing by solution
It is spare after concentration collection survey concentration after removing unreacted organic molecule
3) PVDF is dissolved in DMF, with (2) in absorption organic molecule graphene material mix be made into graphene/
PVDF solution, mechanical agitation 2h, ultrasonic disperse 30min are put into the gas for vacuumizing in vacuum drying oven and being dissolved in 2h discharge solution,
By solution-cast in the mold for the polytetrafluoroethylene (PTFE) for being coated with releasing agent after, be placed in 40 DEG C of baking ovens dry 12h, take film off
It is spare
4) film in a manner of facing face two prepared in (3) opened to after putting together hot pressing forms a film under hot press,
It removes film while hot, trims spare behind corner
5) in the film two sides deposited metal film of acquisition, it is used as flat capacitor device and uses.
The foregoing is merely the preferred embodiment of the present invention, are not intended to limit the scope of the invention.Every utilization
Equivalent structure or equivalent flow shift made by present specification is directly or indirectly used in other relevant technology necks
Domain is included within the scope of the present invention.
Claims (5)
1. a kind of high-k low conductivity nanocomposite, the main graphene using small size adsorbs small point organic
Son is then added to and is prepared into that high dielectric is normal and the nanocomposite of extremely low conductivity in polymer.It is characterized in that small ruler
The preparation of very little graphene, graphene surface, which are adsorbed, organic small molecule-modified reduces the conductivity and composite material of composite material
Preparation method.
1) raw material are 12000 mesh expanded graphites, and small size graphene, tool are prepared using improved ultrasonic wave added Hummer ' s methods
Body step includes pre-oxidation and the ultrasonic disperse of expanded graphite, oxidation of the pre-oxidation graphene under ultrasound, and pre-oxidation graphite
The cleaning and concentration of alkene.
2) by the graphene oxide of concentration and dihydroxy diphenyl ether, diaminodiphenyl sulfide, para-aminophenol, m-aminophenol,
Or one kind in diaminonaphthalene, the dissolving in dimethylformamide (DMF), stirring can make organic small containing phenyl ring for 24 hours
With graphene oxide the pi-conjugated absorption of π-occurs for molecule.With DMF solvent, washed product, removing are not adsorbed with graphene repeatedly
Organic molecule.
3) obtained product is uniformly mixed with the Kynoar (PVDF) being dissolved in DMF, mechanical agitation 2h, ultrasonic disperse
30min is put into the gas for vacuumizing in vacuum drying oven and being dissolved in 2h discharge solution, solution-cast is being coated with poly- the four of releasing agent
It after in the mold of vinyl fluoride, is placed in oven and dried, then takes film off.
4) 3) film in a manner of facing face two prepared in opened to after putting together hot pressing forms a film under hot press, is taken while hot
Lower film, trim corner after it is spare.
5) film of acquisition flat capacitor device is assembled into use.
2. according to claim 1 adsorb the preparation of organic molecule and small pieces graphene to prepare graphite using graphene
Alkene/polyvinylidene fluoride composite material, it is characterised in that the raw material of the small size graphene described in step (1) are chosen and prepared
Method.
3. according to claim 1 adsorb the preparation of organic molecule and small pieces graphene to prepare graphite using graphene
Alkene/polyvinylidene fluoride composite material, it is characterised in that the selection of specific organic molecule and graphene are organic in step (1)
The pi-conjugated suction-operateds of π-occurred with such molecule in solvent.
4. according to claim 1 adsorb the preparation of organic molecule and small pieces graphene to prepare graphite using graphene
Alkene/polyvinylidene fluoride composite material, it is characterised in that graphene surface functionalization method used in step (1) enhances stone
The electrical insulation capability of black alkene lamella.
5. according to claim 1 adsorb the preparation of organic molecule and small pieces graphene to prepare graphite using graphene
Alkene/polyvinylidene fluoride composite material, it is characterised in that in step (1) graphene and polymer uniformly mix and the solution of film
Cast molding, hot-press molding method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810504583.XA CN108752812A (en) | 2018-05-24 | 2018-05-24 | A kind of nanocomposite of high-k low conductivity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810504583.XA CN108752812A (en) | 2018-05-24 | 2018-05-24 | A kind of nanocomposite of high-k low conductivity |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108752812A true CN108752812A (en) | 2018-11-06 |
Family
ID=64006444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810504583.XA Pending CN108752812A (en) | 2018-05-24 | 2018-05-24 | A kind of nanocomposite of high-k low conductivity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108752812A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115206689A (en) * | 2022-07-07 | 2022-10-18 | 浙江理工大学 | Graphene modified material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327427A (en) * | 2014-10-23 | 2015-02-04 | 苏州华冲精密机械有限公司 | High-dielectric-constant dielectric nano composite material and preparation method thereof |
| CN106751243A (en) * | 2016-12-05 | 2017-05-31 | 西南交通大学 | The preparation method of high dielectric constant and low dielectric loss polyvinylidene fluoride composite |
| CN107706007A (en) * | 2017-10-13 | 2018-02-16 | 北京航空航天大学 | A kind of aquo-lithium ion ultracapacitor based on graphene and organic molecule |
-
2018
- 2018-05-24 CN CN201810504583.XA patent/CN108752812A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327427A (en) * | 2014-10-23 | 2015-02-04 | 苏州华冲精密机械有限公司 | High-dielectric-constant dielectric nano composite material and preparation method thereof |
| CN106751243A (en) * | 2016-12-05 | 2017-05-31 | 西南交通大学 | The preparation method of high dielectric constant and low dielectric loss polyvinylidene fluoride composite |
| CN107706007A (en) * | 2017-10-13 | 2018-02-16 | 北京航空航天大学 | A kind of aquo-lithium ion ultracapacitor based on graphene and organic molecule |
Non-Patent Citations (1)
| Title |
|---|
| YAQIONG WANG等: "Direct electrochemical DNA biosensor based on reduced grapheneoxide and metalloporphyrin nanocomposite", 《SENSORS AND ACTUATORS B: CHEMICAL》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115206689A (en) * | 2022-07-07 | 2022-10-18 | 浙江理工大学 | Graphene modified material and preparation method thereof |
| CN115206689B (en) * | 2022-07-07 | 2024-02-09 | 浙江理工大学 | Graphene modified material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Pan et al. | Highly thermal conductive epoxy nanocomposites filled with 3D BN/C spatial network prepared by salt template assisted method | |
| Lu et al. | A continuous carbon nitride polyhedron assembly for high‐performance flexible supercapacitors | |
| WO2016008290A1 (en) | Oxidized graphene nano-ribbon/polymer composite film and preparation method therefor | |
| Aghazadeh et al. | A facile route to preparation of Co 3 O 4 nanoplates and investigation of their charge storage ability as electrode material for supercapacitors | |
| Wang et al. | Highly electroconductive mesoporous activated carbon fibers and their performance in the ionic liquid-based electrical double-layer capacitors | |
| Ye et al. | Enhanced dielectric property and energy density in poly (vinylidene fluoride-chlorotrifluoroethylene) nanocomposite incorporated with graphene functionalized with hyperbranched polyethylene-graft-poly (trifluoroethyl methacrylate) copolymer | |
| CN112435867B (en) | Preparation method of flexible self-supporting MXene/CuS supercapacitor electrode material | |
| Qiu et al. | Novel polyaniline/titanium nitride nanocomposite: controllable structures and electrical/electrochemical properties | |
| CN110670107B (en) | Titanium carbide nanosheet/carbon nanotube electromagnetic shielding film and preparation method thereof | |
| CN104192836A (en) | Thermal preparation method of solution of self-supported porous graphene-based membrane | |
| CN110451615B (en) | Preparation method of metal-organic framework carbon nanotube hybrid desalination electrode | |
| CN106117521B (en) | A kind of carbyne film and preparation method and application | |
| CN102757035B (en) | Preparation method of graphene | |
| KR101381316B1 (en) | Boron doped reduced graphene oxide and method for preparation thereof | |
| JP2016056087A (en) | One kind of graphene and method of preparing the same | |
| CN107481864A (en) | It is a kind of to prepare high surface, the method for nitrogen oxygen codope carbon material and the application in ultracapacitor by raw material of organic matter | |
| CN107445148B (en) | Method for preparing functionalized graphene through ball milling | |
| Zhang et al. | Supercapacitor performance of crumpled and planar graphene materials produced by hydrogen gas reduction of graphene oxide | |
| TWI407467B (en) | Electrodes for electric double layer devices | |
| CN108752812A (en) | A kind of nanocomposite of high-k low conductivity | |
| CN110342474B (en) | Two-dimensional high-conductivity hydrogenated NbSe2Nano-film, preparation method and application thereof | |
| Yu et al. | MXene/PVA Fiber-based supercapacitor with stretchability for wearable energy storage | |
| CN105788874B (en) | A kind of composite graphite alkene paper and preparation method thereof | |
| Luo et al. | Preparation and characterization of solid electrolyte doped with carbon nanotubes and its preliminary application in NO2 gas sensors | |
| Mudila et al. | Enhanced electrocapacitive performance and high power density of polypyrrole/graphene oxide nanocomposites prepared at reduced temperature |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20181106 |