CN101323692A - Polymer-based high energy storage density material and preparing method thereof - Google Patents
Polymer-based high energy storage density material and preparing method thereof Download PDFInfo
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- CN101323692A CN101323692A CNA200810116165XA CN200810116165A CN101323692A CN 101323692 A CN101323692 A CN 101323692A CN A200810116165X A CNA200810116165X A CN A200810116165XA CN 200810116165 A CN200810116165 A CN 200810116165A CN 101323692 A CN101323692 A CN 101323692A
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Abstract
The invention discloses a polymer-based material with high energy storage density and a preparation method thereof, pertaining to the technical field of the preparation of dielectric materials and energy storage materials. The polymer-based material with high energy storage density comprises carbon nanotube materials and polymer matrix materials, both of which are modified with organics by a chemical method in the proportions of 3 wt percent to 10 wt percent, and has the effects of good compatibility with the matrix, reduction in the leakage current density and dielectric loss of the materials and improvement of the dielectric constant and breakdown field strength of the materials. The matrix material is polystyrene which is dissolved with ethyl acetate and then blended with modified carbon nanotube solution; the solution is then cast into a mould and the mould is formed by hot pressing and shaped by cold pressing. The polymer-based material with high energy storage density of the invention is characterized by good insulation, low density, excellent flexibility, low cost and easy processing, and can be applied to dielectric materials of electronic devices of information technologies, dielectric projects, electrostatic storage and capacitors.
Description
Technical field
The invention belongs to dielectric materials and energy storage material preparing technical field, be particularly related to a kind of polymer-based high energy storage density material and preparation method thereof, specifically, the nano composite material that relates to the high energy storage density that contains modified carbon nano-tube, have good insulating, density is low, snappiness is good, low-cost and easily processing, can be applicable to information technology electron device, dielectric engineering and electrostatic energy storage and capacitors dielectrics.
Background technology
Fast development of information technology makes electron device stride forward fast to the direction of " little, little, light ", and the electrical condenser of preparation high energy storage density will be one of effective way that reduces electron device volume, quality, cost.Polymer matrix composite because possess good insulating, density is low, snappiness is good, low-cost and easy advantage such as processing and enjoy high praise in hyundai electronics and dielectric engineering.
According to the dielectric physics theory, the maximum energy storage density of dielectric materials can be expressed as Ue=0.5 ε
0ε
rE
d 2, here, ε
0Be meant permittivity of vacuum, ε
rBe relative permittivity, E
dIt is the breaking down field strength of material.Self-evident, improve the ability of the store electrical energy of the electrical condenser of forming by dielectric medium, the specific inductivity and the breaking down field strength of only managing to improve medium just can realize.A kind of method is to dose the inorganic nano-filler with high-k to improve dielectric properties, for example barium titanate (BaTiO
3), silicon-dioxide (SiO
2), zirconium dioxide (ZrO
2) and titanium dioxide (TiO
2) etc.But shortcomings such as this class material exists density is big, pore is many, snappiness difference and limit its use.Another kind method is to dose conductive filler material, and as carbon nanotube, metal (gold and silver, aluminium, copper, nickel etc.) nanoparticle utilizes near its phenomenon that specific inductivity is undergone mutation the seepage flow threshold value to improve the dielectric properties of matrix material.Simultaneously, loss, the leakage conductance of matrix material also increase, and make breaking down field strength significantly descend.
Therefore, need that a kind of cost of exploitation is low, density is little, the polymer-based carbon dielectric composite material of in light weight, handling ease and high energy storage density.
Summary of the invention
The purpose of this invention is to provide a kind of polymer-based high energy storage density material and preparation method thereof, it is characterized in that described polymer-based high energy storage density material is by being that body material is formed in the ratio of 3～10wt% by chemical process with organism modified carbon nanotube material and fragrant olefin polymer.
The preparation of described modified carbon nanotube material is to utilize the method for in-situ polymerization to coat an organic electronic on the carbon nanotube wall to intercept nanometer layer, formation is nuclear with the carbon nanotube, organic layer is the core/shell structure material of shell, concrete grammar is that 0.5～3 milligram of carbon nanotube is added 1～5ml organic modifiers, 0.1 in the dispersion agent of the initiator of～3 grams and 4～8 grams or the mixture of emulsifying agent, and in inert atmosphere, under ultrasonic or agitation condition, reacted 0.5～10 hour down at-5～5 ℃, forming after drying with the carbon nanotube is nuclear, and organic layer is the nucleocapsid structure material of shell.
Described body material is that polystyrene is dissolved in fully and stirs into homogeneous solution in the ethyl acetate solution.
The preparation of described matrix material: with modified carbon nano-tube and body material by the mixed of 3～10wt%, stir after, carry out solution casting, the normal temperature film forming, again at 150～180 ℃, hot pressing moulding in 20 minutes under the condition of 10～20MPa, the typing of colding pressing at last is prepared into the matrix material of high energy storage density, obtains the high energy storage density dielectric composite material.
Described organic modifiers is the pyrroles, analytical pure.
Described initiator is an ammonium persulphate, analytical pure.
Described emulsifying agent is the hexadecyl benzene sulfonic acid sodium salt, analytical pure.
Described inert atmosphere is an argon gas.
Unusual effect of the present invention: 1. provide a kind of high energy storage density, low density, easily processing, polymer-based carbon dielectric composite material cheaply.2. a kind of lightweight is provided, easily disperses the preparation method of surface modification favorable conductive filler (modified carbon nanotube material).3. provide a kind of technology simple, be suitable for the polymer-based carbon dielectric composite material of suitability for industrialized production.
Description of drawings
Fig. 1 is the Raman spectrogram of modified carbon nano-tube (MWCNT@PPy).
Fig. 2 is the x-ray photoelectron spectroscopy figure of modified carbon nano-tube (MWCNT@PPy).
Fig. 3 is the variation relation figure (0.03,0.06,0.08,0.1MWCNT@PPy/PS matrix material) of the specific inductivity of matrix material with frequency.
Fig. 4 is the variation relation figure (0.03,0.06,0.08,0.1MWCNT@PPy/PS matrix material) of the dielectric loss of matrix material with frequency.
Fig. 5 is the variation relation figure (0.1MWCNT@PPy/PS matrix material) of the dielectric constant with temperature of matrix material.
Fig. 6 is the variation relation figure (0.1MWCNT@PPy/PS matrix material) of the leakage current density of matrix material with breaking down field strength.
Fig. 7 is the ferroelectric hysteresis loop figure (electricdisplacement-breaking down field strength figure) (0.1MWCNT@PPy/PS matrix material) of matrix material.
Embodiment
The present invention is a kind of polymer-based high energy storage density material and preparation method thereof.Preparation process is as follows:
The preparation of step (1) modified carbon nano-tube: with original position inverse emulsion polymeric method, specifically prescription is for adding 2 milligrams of carbon nanotubes in the mixture of 1.2 milliliters of pyrroles, 1.32 ammonium persulphates that restrain and the 6 hexadecyl benzene sulfonic acid sodium salts that restrain, and in the inert atmosphere argon gas, under ultrasonic or agitation condition, 0 ℃ was reacted 8 hours down, forming after drying with the carbon nanotube is nuclear, and organic layer is the nucleocapsid structure material of shell.Test result is as follows: Fig. 1 is the Raman spectrogram of MWCNT@PPy described in the step (1).As seen, 1577,1346, there is the characteristic peak of MWCNT@PPy at 1047,982 wave number places.
Fig. 2 is the x-ray photoelectron spectroscopy figure of modified carbon nano-tube described in the step (1), and wherein, the peak at 400 electron-volts of places is the characteristic peak of N element among the PPy.
The preparation of the described modified carbon nano-tube/poly styrene composite material of step (2): with 1 gram polystyrene, modified carbon nano-tube described in 3～10wt% (1), after in ethyl acetate solution, stirring, solution casting, the normal temperature film forming, at 150～180 ℃, hot-forming under the condition of 10～20MPa again, the typing of colding pressing at last is prepared into the matrix material of high energy storage density.
Described modified carbon nano-tube diameter is tens nanometers.The molecular-weight average of described polystyrene is between 20～500,000, and density is 1.06g/cm3, and the melt temperature scope is 145～155 ℃.
The electrode of the specimen of matrix material of the present invention is the method for spray plating that adopts control pressure, sputter at intermittence, and thickness is in the hundreds of nanometer range.Organic coating layer forms firm chemical conjugate key.Organic layer and macromolecule matrix have good consistency, make even carbon nanotube be dispersed in effectively in the body material, improve the processing characteristics of matrix material, improve the mechanical property and the breaking down field strength of matrix material, and the amount of filling of reduction filler, thereby the density of reduction material, and save cost.Organic layer has prevented the direct contact of conductive filler material effectively, greatly reduces the generation of leakage current and reduces dielectric loss, improves the dielectric energy storage density of matrix material.Therefore, a kind of high energy storage density, low density, easily processing, low cost, the good polymer-based carbon dielectric composite material of snappiness has successfully been obtained.Though above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Enumerating embodiment is below illustrated the present invention.
Embodiment 1
Take by weighing 1 gram polystyrene, under the agitation condition it is dissolved in the 10ml ethyl acetate solution.Take by weighing the modified carbon nano-tube described in the 0.03 gram above-mentioned steps (1) again and join ultrasound procedure (the employing 800W power that carried out in the 10ml ethyl acetate solution 0.5 hour; ultrasonic 1min; the mode of 5s intermittently); mix with the ethyl acetate solution of polystyrene then; and under argon shield; stirring at room is even; the cast film forming; room temperature is dried; behind the vacuum drying, be 150 ℃ in temperature again, pressure is to place moulding in 20 minutes in the environment of 10MPa; at last at normal temperature; place typing in 20 minutes in the non-pressurized environment, promptly obtain the matrix material (being designated as 0.03MWCNT@PPy/PS) of modified carbon nano-tube/polystyrene high energy storage density.
Take by weighing 1 gram polystyrene, under the agitation condition it is dissolved in the 10ml ethyl acetate solution.Take by weighing the modified carbon nano-tube described in the 0.06 gram above-mentioned steps (1) again and join ultrasound procedure (the employing 800W power that carried out in the 15ml ethyl acetate solution 1.0 hours; ultrasonic 1min; the mode of 5s intermittently); mix with the ethyl acetate solution of polystyrene then; and under argon shield; stirring at room is even; the cast film forming; room temperature is dried; behind the vacuum drying; it is 160 ℃ in temperature again; pressure is to place moulding in 20 minutes in the environment of 12.5MPa, at last at normal temperature; place typing in 20 minutes in the non-pressurized environment, promptly obtain the matrix material (being designated as 0.06MWCNT@PPy/PS) of modified carbon nano-tube/polystyrene high energy storage density.
Embodiment 3
Take by weighing 1 gram polystyrene, under the agitation condition it is dissolved in the 10ml ethyl acetate solution.Take by weighing the modified carbon nano-tube described in the 0.08 gram above-mentioned steps (1) again and join ultrasound procedure (the employing 800W power that carried out in the 20ml ethyl acetate solution 1.5 hours; ultrasonic 1min; the mode of 5s intermittently); mix with the ethyl acetate solution of polystyrene then; and under argon shield; stirring at room is even; the cast film forming; room temperature is dried; behind the vacuum drying; it is 170 ℃ in temperature again; pressure is to place moulding in 20 minutes in the environment of 15MPa, at last at normal temperature; place typing in 20 minutes in the non-pressurized environment, promptly obtain the matrix material (being designated as 0.08MWCNT@PPy/PS) of modified carbon nano-tube/polystyrene high energy storage density.
Take by weighing 1 gram polystyrene, under the agitation condition it is dissolved in the 10ml ethyl acetate solution.Take by weighing the modified carbon nano-tube described in the 0.1 gram above-mentioned steps (1) again and join ultrasound procedure (the employing 800W power that carried out in the 25ml ethyl acetate solution 2.0 hours; ultrasonic 1min; the mode of 5s intermittently); mix with the ethyl acetate solution of polystyrene then; and under argon shield; stirring at room is even; the cast film forming; room temperature is dried; behind the vacuum drying; it is 180 ℃ in temperature again; pressure is to place moulding in 20 minutes in the environment of 20MPa, at last at normal temperature; place typing in 20 minutes in the non-pressurized environment, promptly obtain the matrix material (being designated as 0.1MWCNT@PPy/PS) of modified carbon nano-tube/polystyrene high energy storage density.
The embodiment test result is:
Matrix material to gained among embodiment 1, embodiment 2, embodiment 3 and the embodiment 4 carries out the dielectric properties test respectively.
Fig. 3 is the variation relation figure (0.03,0.06,0.08,0.1MWCNT@PPy/PS matrix material) of the specific inductivity of matrix material with frequency.As seen, the specific inductivity of matrix material increases along with the increase of MWCNT@PPy addition, and remains stable in wide frequency range, is up to 44.
Fig. 4 is the variation relation figure (0.03,0.06,0.08,0.1MWCNT@PPy/PS matrix material) of the dielectric loss of matrix material with frequency.As can be seen, the dielectric loss of matrix material is lower, less than 0.07.Matrix material to gained among the embodiment 4 carries out following test.
Fig. 5 is the variation relation figure (0.1MWCNT@PPy/PS matrix material) of the dielectric constant with temperature of matrix material.Change in dielectric constant is less in-60 ℃ to 60 ℃ scopes, only is 2.
Fig. 6 is the variation relation figure (0.1MWCNT@PPy/PS matrix material) of the leakage current density of matrix material with breaking down field strength.Show less leakage current density, be lower than 1.0 * 10-7A/cm
2
Fig. 7 is the ferroelectric hysteresis loop figure (electricdisplacement-breaking down field strength figure) (0.1MWCNT@PPy/PS matrix material) of matrix material.As seen the breaking down field strength of 0.1MWCNT@PPy/PS matrix material is up to 226MV/m.
Above-described embodiment is several typical embodiment of the present invention, and those skilled in the art can make various modifications within the scope of the appended claims.
Claims (8)
1. a polymer-based high energy storage density material is characterized in that, described polymer-based high energy storage density material is by being that body material is formed in the ratio of 3～10wt% with organism modified carbon nanotube material and fragrant olefin polymer.
2. the preparation method of a polymer-based high energy storage density material, it is characterized in that, with modified carbon nano-tube and body material by the mixed of 3～10wt%, stir after, carry out solution casting, the normal temperature film forming, again at 150～180 ℃, hot pressing moulding in 20 minutes under the condition of 10～20MPa, colding pressing at last typing prepares the high energy storage density dielectric composite material.
3. according to the preparation method of the described polymer-based high energy storage density material of claim 2, it is characterized in that, the preparation of described modified carbon nanotube material is to utilize the method for in-situ polymerization to coat an organic charge on the carbon nanotube wall to intercept nanometer layer, formation is nuclear with the carbon nanotube, organic layer is the core/shell structure material of shell, concrete grammar is that 0.5～3 milligram of carbon nanotube is added 1～5ml organic modifiers, 0.1 the dispersion agent or the emulsifying agent of the initiator of～3 grams and 4～8 grams, and in 1～2 liter/minute inert atmosphere, at room temperature ultrasonic or stir, reacted 0.5～10 hour down at-5～5 ℃, forming after drying with the carbon nanotube is nuclear, and organic layer is the modified carbon nano tube tube material of the nucleocapsid structure of shell.
4. according to the preparation method of the described polymer-based high energy storage density material of claim 2, it is characterized in that described body material is that polystyrene is dissolved in fully and stirs into homogeneous solution in the ethyl acetate solution.
5. according to the preparation method of the described polymer-based high energy storage density material of claim 2, it is characterized in that described organic modifiers is the pyrroles.
6. according to the preparation method of the described polymer-based high energy storage density material of claim 2, it is characterized in that described initiator is an ammonium persulphate.
7. according to the preparation method of the described polymer-based high energy storage density material of claim 2, it is characterized in that described emulsifying agent is the hexadecyl benzene sulfonic acid sodium salt.
8. according to the preparation method of the described polymer-based high energy storage density material of claim 2, it is characterized in that described inert atmosphere is an argon gas.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504449A (en) * | 2011-11-01 | 2012-06-20 | 清华大学 | Polymer matrix composite membrane with high energy density and preparation method thereof |
| CN107245152A (en) * | 2017-05-15 | 2017-10-13 | 浙江大学 | A kind of preparation method of magnesia/polystyrene composite dielectric material |
| CN109535581A (en) * | 2018-11-28 | 2019-03-29 | 长春工业大学 | Carbon nano tube-doped polystyrene-based composite material and preparation method with core-shell structure |
-
2008
- 2008-07-04 CN CNA200810116165XA patent/CN101323692A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504449A (en) * | 2011-11-01 | 2012-06-20 | 清华大学 | Polymer matrix composite membrane with high energy density and preparation method thereof |
| CN102504449B (en) * | 2011-11-01 | 2014-04-23 | 清华大学 | Polymer matrix composite membrane with high energy density and preparation method thereof |
| CN107245152A (en) * | 2017-05-15 | 2017-10-13 | 浙江大学 | A kind of preparation method of magnesia/polystyrene composite dielectric material |
| CN109535581A (en) * | 2018-11-28 | 2019-03-29 | 长春工业大学 | Carbon nano tube-doped polystyrene-based composite material and preparation method with core-shell structure |
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Open date: 20081217 |