CN105732036A - Method for preparing three-dimensional graphene/carbon nanotube composite material - Google Patents
Method for preparing three-dimensional graphene/carbon nanotube composite material Download PDFInfo
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
Abstract
The invention relates to a method for preparing a three-dimensional graphene/carbon nanotube composite material. The method comprises the following steps: (1) preparing graphene oxide suspension; (2) preparing carbon nanotube suspension; (3) preparing polystyrene resin microspheres; (4) preparing graphene/carbon nanotube gel; (5) preparing a three-dimensional graphene/carbon nanotube compound. The three-dimensional graphene/carbon nanotube compound prepared by using the method is rich in graded porous structure, the advantage of structural complementation of graphene and carbon nanotubes is achieved, and thus the composite material is relatively good in electric and heat conduction property. The composite material has wide application in fields such as traffic transportation, electronic industry, civil construction, buildings and chemical engineering. The method provided by the invention is low in equipment requirement, simple in process and easy in large-scale production.
Description
Technical field
The invention belongs to material with carbon element preparation field, the preparation method particularly relating to a kind of three-dimensional grapheme/carbon nano tube compound material.
Background technology
Since Iijima in 1991 finds that CNT and AndreGeim and KostyaNovoselov in 2004 prepare Graphene first, both carbon nanomaterials are just paid attention to widely, because both of which has very prominent physical property, it is expected to by polymer modification, giving polymer better performance.But the application of CNT exists two important problems to be not solved by always, one is the dispersion of CNT, because it is very easy to reunite, another problem is that high cost.The appearance of Graphene seems to be a solution the two difficult problem and provides answer.Graphene is similar to the chemical constitution of CNT, but Graphene is the planar structure of two dimension, and CNT is one-dimensional linear structure, and the difference of both form result in the character of both uniquenesses just.A large amount of storages of native graphite so that the preparation of substantial amounts of cheap Graphene is possibly realized.
Graphene is the material of the thinnest, maximum intensity known today, has excellent conductive capability, it is possible to bear the electric current density of high six orders of magnitude than copper, has the record-breaking capacity of heat transmission, and have high rigidity and good ductility simultaneously.Graphene is the novel nano-material piled up with hexagon by carbon atom, and it has much excellent performance, such as bigger serface, high heat conductance, rapid electric charge transfer rate etc., is widely used at numerous areas such as materials chemistry, Optical Electro-Chemistry, catalyst.But Graphene also has two big weak points, first Graphene itself does not have band gap, which greatly limits Graphene application on electricity device.Secondly, the surface of Graphene does not have activating functional group, is unfavorable for and the compound of other materials (such as metallic and the little molecule of organic functions), and this also have impact on the Graphene research and extension in a lot of applications.
Polymer matrix composites are one of Graphene and the most important application of CNT.Apply CNT in composite, Graphene technology starting point is generally: promote electric conductivity or the heat conductivity of composite as functive, the high conductivity of using mineral carbon alkene and high electron mobility speed；Two is as structure reinforcement, the superhigh intensity of using mineral carbon alkene, high-modulus and dimensional properties to carrying out composite enhancing, toughness reinforcing.Obtained lightweight, high structure/function integration polymer matrix composites tough, conduction have high using value at national economy key areas such as space flight, aviation, electronics, automobile, Structural Engineerings and are widely applied prospect.
But up to now, major part experimental studies results all shows, in composite, the Strengthening and Toughening effect of Graphene and CNT reaches all far away ideal.CNT, Graphene lack effectively dispersion, fail to form the active path that can provide load transmission and carrier transport between isolated aggregate, are the mechanical property of its composite and bottleneck place that the unrealized expection of electric conductivity promotes.Graphene and CNT are made an addition in phenolic resin cladding polystyrene microsphere by the present invention jointly, form three-dimensional grapheme/CNT gel, heat conduction and the good three-dimensional grapheme/carbon mano-tube composite of electric conductivity is obtained after drying sintering, it has abundant hierarchical porous structure, achieve the complementary advantage on Graphene and carbon nano tube structure, it is possible to have a wide range of applications in fields such as transportation, electronics industry, civilian construction, building and chemical industry.
Summary of the invention
The preparation method that the invention provides a kind of three-dimensional grapheme/carbon nano tube compound material, specifically includes following steps:
(1) graphene oxide suspension is prepared: add in deionized water by graphene oxide and surfactant, the mass ratio of graphene oxide and surfactant is (1～10): 1, ultrasonic disperse mix homogeneously, obtains the graphene oxide solution that concentration is (5～30) g/L；
(2) preparing carbon nano tube suspension: joined by CNT in deionized water, forming concentration after ultrasonic disperse is the carbon nano tube suspension of 0.5～1g/L；
(3) polystyrene resin microsphere is prepared: joined by polystyrene microsphere in deionized water, concentration is 5～10%, then be sequentially added into the alcoholic solution of the aldehydes matter that concentration is 1mol/L, concentration is the aqueous solution of 2mol/L aldehyde material, and the mol ratio of its aldehyde material and aldehydes matter is 1: 1；The mass ratio (1～5) of described aldehyde material and polystyrene microsphere: 1, carries out hydro-thermal reaction, it is thus achieved that phenolic resin cladding polystyrene microsphere；
(4) graphene/carbon nano-tube gel is prepared: by the described graphene oxide suspension obtained and described carbon nano tube suspension by volume for 1:(0.5 ~ 2) mixing, the phenolic resin cladding polystyrene microsphere that step (3) obtains is added after ultrasonic disperse, stirring mixing, adding concentration is the reducing agent of 0.5～2%, carry out hydro-thermal reaction, obtain three-dimensional grapheme/CNT gel；
(5) after three-dimensional grapheme/CNT gel drying that step (4) is obtained, in temperature T=600～1200 DEG C, the lower sintering of nitrogen atmosphere protection, obtain three-dimensional grapheme/carbon mano-tube composite.
In above-mentioned preparation method, the surfactant described in step (1) is one or more in dodecylbenzene sodium sulfonate, dodecyl sodium sulfate, sodium lauryl sulphate or sodium stearyl sulfate.
In above-mentioned preparation method, the particle diameter of the polystyrene microsphere described in step (3) is 250～1000nm.
In above-mentioned preparation method, the aldehydes matter described in step (3) includes one or more in phenol, cresol, resorcinol, catechol；Described aldehyde material includes one or more in formaldehyde, furfural, paraformaldehyde.
In above-mentioned preparation method, the described reducing agent described in step (4) includes one or more in ascorbic acid, ammonia, hydrazine hydrate, oxalic acid, boric acid.
The method have the advantages that (1) due to the fact that the addition of phenolic resin cladding polystyrene microsphere, it is to avoid the reunion of Graphene and CNT, Graphene and CNT are uniformly dispersed in system；(2) composite prepared by the present invention has abundant hierarchical porous structure, it is achieved that Graphene and the complementary advantage on carbon nano tube structure；(3) present invention can have a wide range of applications in fields such as transportation, electronics industry, civilian construction, building and chemical industry.(4) preparation method of the present invention is low for equipment requirements, technique simply, easily realizes large-scale production.
Detailed description of the invention
Embodiment 1
(1) graphene oxide suspension is prepared: add in deionized water by graphene oxide and dodecylbenzene sodium sulfonate, the mass ratio of graphene oxide and dodecylbenzene sodium sulfonate is 1:1, ultrasonic disperse mix homogeneously, obtains the graphene oxide solution that concentration is 5g/L；
(2) preparing carbon nano tube suspension: joined by CNT in deionized water, forming concentration after ultrasonic disperse is the carbon nano tube suspension of 0.5g/L；
(3) polystyrene resin microsphere is prepared: joined in deionized water by the polystyrene microsphere that particle diameter is 300nm, preparation concentration is the polystyrene microsphere solution of 5%, then be sequentially added into the alcoholic solution of the phenol that concentration is 1mol/L, concentration is the aqueous solution of 2mol/L formaldehyde, and the mol ratio of its formaldehyde and phenol is 1: 1；Described formaldehyde and the mass ratio 1: 1 of polystyrene microsphere, carry out hydro-thermal reaction, it is thus achieved that the polystyrene microsphere of phenolic resin cladding；
(4) graphene/carbon nano-tube gel is prepared: the described graphene oxide suspension obtained and described carbon nano tube suspension are mixed for 1:0.5 by volume, the phenolic resin cladding polystyrene microsphere that step (3) obtains is added after ultrasonic disperse, stirring mixing, adding concentration is the ascorbic acid of 0.5%, at temperature T=60 DEG C, carry out hydro-thermal reaction, obtain three-dimensional grapheme/CNT gel；
(5) after three-dimensional grapheme/CNT gel drying that step (4) is obtained, at temperature T=800 DEG C, the lower sintering of nitrogen atmosphere protection, obtain three-dimensional grapheme/carbon mano-tube composite.
Embodiment 2
(1) graphene oxide suspension is prepared: add in deionized water by graphene oxide and dodecylbenzene sodium sulfonate, the mass ratio of graphene oxide and dodecylbenzene sodium sulfonate is 2:1, ultrasonic disperse mix homogeneously, obtains the graphene oxide solution that concentration is 10g/L；
(2) preparing carbon nano tube suspension: joined by CNT in deionized water, forming concentration after ultrasonic disperse is the carbon nano tube suspension of 0.5g/L；
(3) polystyrene resin microsphere is prepared: joined in deionized water by the polystyrene microsphere that particle diameter is 500nm, preparation concentration is the polystyrene microsphere solution of 5%, then be sequentially added into the alcoholic solution of the phenol that concentration is 1mol/L, concentration is the aqueous solution of 2mol/L formaldehyde, and the mol ratio of its formaldehyde and phenol is 1: 1；Described formaldehyde and the mass ratio 1: 1 of polystyrene microsphere, carry out hydro-thermal reaction, it is thus achieved that the polystyrene microsphere of phenolic resin cladding；
(4) graphene/carbon nano-tube gel is prepared: the described graphene oxide suspension obtained and described carbon nano tube suspension are mixed for 1:0.5 by volume, the phenolic resin cladding polystyrene microsphere that step (3) obtains is added after ultrasonic disperse, stirring mixing, adding concentration is the ascorbic acid of 0.5%, at temperature T=60 DEG C, carry out hydro-thermal reaction, obtain three-dimensional grapheme/CNT gel；
(5) after three-dimensional grapheme/CNT gel drying that step (4) is obtained, at temperature T=800 DEG C, the lower sintering of nitrogen atmosphere protection, obtain three-dimensional grapheme/carbon mano-tube composite.
Embodiment 3
(1) graphene oxide suspension is prepared: adding in deionized water by graphene oxide and sodium stearyl sulfate, the mass ratio of graphene oxide and sodium stearyl sulfate is 2:1, and ultrasonic disperse mix homogeneously obtains the graphene oxide solution that concentration is 10g/L；
(2) preparing carbon nano tube suspension: joined by CNT in deionized water, forming concentration after ultrasonic disperse is the carbon nano tube suspension of 1g/L；
(3) polystyrene resin microsphere is prepared: joined in deionized water by the polystyrene microsphere that particle diameter is 500nm, preparation concentration is the polystyrene microsphere solution of 5%, then be sequentially added into the alcoholic solution of the phenol that concentration is 1mol/L, concentration is the aqueous solution of 2mol/L formaldehyde, and the mol ratio of its formaldehyde and phenol is 1: 1；Described formaldehyde and the mass ratio 2: 1 of polystyrene microsphere, carry out hydro-thermal reaction, it is thus achieved that the polystyrene microsphere of phenolic resin cladding；
(4) graphene/carbon nano-tube gel is prepared: the described graphene oxide suspension obtained and described carbon nano tube suspension are mixed for 1:1 by volume, the phenolic resin cladding polystyrene microsphere that step (3) obtains is added after ultrasonic disperse, stirring mixing, adding concentration is the ascorbic acid of 0.5%, at temperature T=60 DEG C, carry out hydro-thermal reaction, obtain three-dimensional grapheme/CNT gel；
(5) after three-dimensional grapheme/CNT gel drying that step (4) is obtained, at temperature T=800 DEG C, the lower sintering of nitrogen atmosphere protection, obtain three-dimensional grapheme/carbon mano-tube composite.
Embodiment 4
(1) graphene oxide suspension is prepared: adding in deionized water by graphene oxide and sodium stearyl sulfate, the mass ratio of graphene oxide and sodium stearyl sulfate is 2:1, and ultrasonic disperse mix homogeneously obtains the graphene oxide solution that concentration is 10g/L；
(2) preparing carbon nano tube suspension: joined by CNT in deionized water, forming concentration after ultrasonic disperse is the carbon nano tube suspension of 1g/L；
(3) polystyrene resin microsphere is prepared: joined in deionized water by the polystyrene microsphere that particle diameter is 500nm, preparation concentration is the polystyrene microsphere solution of 10%, then be sequentially added into the alcoholic solution of the resorcinol that concentration is 1mol/L, concentration is the aqueous solution of 2mol/L formaldehyde, and the mol ratio of its formaldehyde and resorcinol is 1: 1；Described formaldehyde and the mass ratio 2: 1 of polystyrene microsphere, carry out hydro-thermal reaction, it is thus achieved that the polystyrene microsphere of phenolic resin cladding；
(4) graphene/carbon nano-tube gel is prepared: the described graphene oxide suspension obtained and described carbon nano tube suspension are mixed for 1:1 by volume, the phenolic resin cladding polystyrene microsphere that step (3) obtains is added after ultrasonic disperse, stirring mixing, adding concentration is the ascorbic acid of 0.5%, at temperature T=60 DEG C, carry out hydro-thermal reaction, obtain three-dimensional grapheme/CNT gel；
(5) after three-dimensional grapheme/CNT gel drying that step (4) is obtained, at temperature T=800 DEG C, the lower sintering of nitrogen atmosphere protection, obtain three-dimensional grapheme/carbon mano-tube composite.
Embodiment 4
(1) graphene oxide suspension is prepared: adding in deionized water by graphene oxide and sodium stearyl sulfate, the mass ratio of graphene oxide and sodium stearyl sulfate is 2:1, and ultrasonic disperse mix homogeneously obtains the graphene oxide solution that concentration is 10g/L；
(2) preparing carbon nano tube suspension: joined by CNT in deionized water, forming concentration after ultrasonic disperse is the carbon nano tube suspension of 1g/L；
(3) polystyrene resin microsphere is prepared: joined in deionized water by the polystyrene microsphere that particle diameter is 500nm, preparation concentration is the polystyrene microsphere solution of 10%, then be sequentially added into the alcoholic solution of the resorcinol that concentration is 1mol/L, concentration is the aqueous solution of 2mol/L formaldehyde, and the mol ratio of its formaldehyde and resorcinol is 1: 1；Described formaldehyde and the mass ratio 2: 1 of polystyrene microsphere, carry out hydro-thermal reaction, it is thus achieved that the polystyrene microsphere of phenolic resin cladding；
(4) graphene/carbon nano-tube gel is prepared: the described graphene oxide suspension obtained and described carbon nano tube suspension are mixed for 1:1 by volume, the phenolic resin cladding polystyrene microsphere that step (3) obtains is added after ultrasonic disperse, stirring mixing, adding concentration is the hydrazine hydrate of 1%, at temperature T=60 DEG C, carry out hydro-thermal reaction, obtain three-dimensional grapheme/CNT gel；
(5) after three-dimensional grapheme/CNT gel drying that step (4) is obtained, at temperature T=1000 DEG C, the lower sintering of nitrogen atmosphere protection, obtain three-dimensional grapheme/carbon mano-tube composite.
With the above-mentioned desirable embodiment according to the present invention for enlightenment, by above-mentioned description, relevant staff in the scope not necessarily departing from this invention technological thought, can carry out various change and amendment completely.The technical scope of this invention is not limited to the content in description, it is necessary to determine its technical scope according to right.
Claims (5)
1. the preparation method of three-dimensional grapheme/carbon nano tube compound material, it is characterised in that: method is specifically realized by the following steps:
(1) graphene oxide suspension is prepared: add in deionized water by graphene oxide and surfactant, the mass ratio of graphene oxide and surfactant is (1～10): 1, ultrasonic disperse mix homogeneously, obtains the graphene oxide solution that concentration is (5～30) g/L；
(2) preparing carbon nano tube suspension: joined by CNT in deionized water, forming concentration after ultrasonic disperse is the carbon nano tube suspension of 0.5～1g/L；
(3) polystyrene resin microsphere is prepared: joined by polystyrene microsphere in deionized water, concentration is 5～10%, then be sequentially added into the alcoholic solution of the aldehydes matter that concentration is 1mol/L, concentration is the aqueous solution of 2mol/L aldehyde material, and the mol ratio of its aldehyde material and aldehydes matter is 1: 1；The mass ratio (1～5) of described aldehyde material and polystyrene microsphere: 1, carries out hydro-thermal reaction, it is thus achieved that phenolic resin cladding polystyrene microsphere；
(4) graphene/carbon nano-tube gel is prepared: by the described graphene oxide suspension obtained and described carbon nano tube suspension by volume for 1:(0.5～2) mixing, the phenolic resin cladding polystyrene microsphere that step (3) obtains is added after ultrasonic disperse, stirring mixing, adding concentration is the reducing agent of 0.5～2%, carry out hydro-thermal reaction, obtain three-dimensional grapheme/CNT gel；
(5) after three-dimensional grapheme/CNT gel drying that step (4) is obtained, in temperature T=600～1200 DEG C, the lower sintering of nitrogen atmosphere protection, obtain three-dimensional grapheme/carbon mano-tube composite.
2. the preparation method of a kind of three-dimensional grapheme/carbon nano tube compound material according to claim 1, it is characterised in that the surfactant described in step (1) is one or more in dodecylbenzene sodium sulfonate, dodecyl sodium sulfate, sodium lauryl sulphate or sodium stearyl sulfate.
3. the preparation method of a kind of three-dimensional grapheme/carbon nano tube compound material according to claim 1, it is characterised in that the particle diameter of the polystyrene microsphere described in step (3) is 250～1000nm.
4. the preparation method of a kind of three-dimensional grapheme/carbon nano tube compound material according to claim 1, it is characterised in that the aldehydes matter described in step (3) includes one or more in phenol, cresol, resorcinol, catechol；Described aldehyde material includes one or more in formaldehyde, furfural, paraformaldehyde.
5. the preparation method of a kind of three-dimensional grapheme/carbon nano tube compound material according to claim 1, it is characterised in that the described reducing agent described in step (4) includes one or more in ascorbic acid, ammonia, hydrazine hydrate, oxalic acid, boric acid.
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| CN106241779A (en) * | 2016-07-19 | 2016-12-21 | 沈阳航空航天大学 | A kind of preparation method of CNT graphene oxide hybrid three-dimensional material |
| CN106433282A (en) * | 2016-09-18 | 2017-02-22 | 深圳市华星光电技术有限公司 | Heat dissipation paint and preparation method and application method thereof |
| CN106784757A (en) * | 2017-03-30 | 2017-05-31 | 青岛亨迈新能源有限公司 | A kind of preparation method of anode composite material |
| CN106832352A (en) * | 2017-01-17 | 2017-06-13 | 江苏捷峰钜容新材料有限公司 | A kind of preparation method of CNT compound resin microballoon |
| CN107325421A (en) * | 2017-06-22 | 2017-11-07 | 广州中谱检测技术服务有限公司 | A kind of preparation method of polymer/graphene/carbon nano tube compound material |
| CN108147396A (en) * | 2018-02-05 | 2018-06-12 | 山东佳星环保科技有限公司 | Controllable graphene aerogel of novel intelligent and preparation method thereof |
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| CN109173989A (en) * | 2018-09-04 | 2019-01-11 | 电子科技大学 | Three-dimensional grapheme macroscopic body loads nano zero-valence iron composite material and preparation method |
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| CN109437159A (en) * | 2018-11-07 | 2019-03-08 | 西北工业大学 | A kind of preparation method of graphene-carbon nano tube two-component suspension |
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| CN106832352A (en) * | 2017-01-17 | 2017-06-13 | 江苏捷峰钜容新材料有限公司 | A kind of preparation method of CNT compound resin microballoon |
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