CN109228578A - A kind of graphene carbon nanometer tube composite materials and preparation method thereof - Google Patents
A kind of graphene carbon nanometer tube composite materials and preparation method thereof Download PDFInfo
- Publication number
- CN109228578A CN109228578A CN201810672474.9A CN201810672474A CN109228578A CN 109228578 A CN109228578 A CN 109228578A CN 201810672474 A CN201810672474 A CN 201810672474A CN 109228578 A CN109228578 A CN 109228578A
- Authority
- CN
- China
- Prior art keywords
- layer
- graphene
- carbon nanotube
- polyaniline
- carbon
- 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.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
- B32B2037/243—Coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/24—Organic non-macromolecular coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/28—Multiple coating on one surface
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/212—Electromagnetic interference shielding
Abstract
The invention discloses a kind of graphene carbon nanometer tube composite materials and preparation method thereof; including the first resin protective layer, the first polyaniline, the first carbon nanotube layer, graphene layer, the second carbon nanotube layer, the second polyaniline and the second resin protective layer; the graphene layer has been sequentially arranged above the first carbon nanotube layer, the first polyaniline and the first resin protective layer, and is disposed with the second carbon nanotube layer, the second polyaniline and the second resin protective layer below graphene layer.The graphene carbon nanometer tube composite materials are as electromagnetic shielding material, folding, and flexibility is good; waterproof, anti-certain temperature; moreover, the material is disposed with carbon nanotube layer, polyaniline and resin protective layer using graphene layer as center line, to two sides; so that front and back sides shield effectiveness is equal; it can be in protective garment, mask, protective plate; shield, a variety of applications such as protection curtain.
Description
Technical field
The present invention relates to graphene correlative technology field, specially a kind of graphene carbon nanometer tube composite materials and its preparation
Method.
Background technique
With the high speed development of modern electronics industry, electronic apparatus and radio communication are generally used, and electromagnetic wave draws
Rise electromagnetic interference problem get worse, Contamination of Electromagnetic Wave oneself become after noise pollution, atmosphere pollution, water pollution, solid waste
Another big public hazards after pollution.Electromagnetic wave can not only interfere the normal operation of various electronic equipments, threaten communication equipment
Information security, but also greatly harm can be generated to the health of the mankind.The main method of electromagnetic wave harm is eliminated at present
It is to be shielded using electromagnetic shielding material to it.Efficient electromagnetic shielding material is explored, prevents Contamination of Electromagnetic Wave with protection ring
The health in border and human body prevents electromagnetic-wave leakage to ensure information safety, and has become that today's society is in the urgent need to address to ask
Topic.
Many electromagnetic shielding materials are splashed, are coated by material surface metal-plated, pasted or by mixed currently on the market
The modes such as conductive fiber are spun, many problems are easy to appear during making and using, if metal and material binding ability are poor, are held
It is easy to fall off, coating is easy to be scratched and lose shielding properties, and preparation process is seriously polluted etc., and material is more thick and stiff, flexibility
Difference, it is airtight, handling property is poor, it is not wearable, and it is difficult needed for meeting modern electromagnetic shielding material " thin, light, wide, strong "
Characteristic, therefore, there is an urgent need to research and develop a kind of durable, good electromagnetism that can be used for clothes, outer packing, shielded layer etc. of performance
Shielding material.
If only carbon nanotube layer, graphene layer, if be not durable, it is easy to fracture, scratch, but appearance setting protection
Layer, basal layer, common method are bondings, and this mode firmness is very problematic.If between the multilayer of composite layer all
Bonding, then by falling off by external force, fold, internal form cavity etc., it is easy to lose shielding action.For
Multilayer materials, between combination it is very problematic.
Summary of the invention
The purpose of the present invention is to provide a kind of graphene carbon nanometer tube composite materials and preparation method thereof, to solve background
It can not combine closely mutually when the multilayer materials shielding proposed in technology, disengaging or empty, empty can be generated because of many reasons
The problem of gap.
To achieve the above object, the invention provides the following technical scheme: a kind of graphene carbon nanometer tube composite materials, including
Graphene layer and two carbon nanotube layers, it is characterised in that: from outside to inside successively by the first resin protective layer, the first polyaniline
Layer, the first carbon nanotube layer, graphene layer, the second carbon nanotube layer, the second polyaniline and the second resin protective layer overlapping group
At.
The graphene layer has been sequentially arranged above the first carbon nanotube layer, the first polyaniline and the protection of the first resin
Layer, and the second carbon nanotube layer, the second polyaniline and the second resin protective layer are disposed with below graphene layer.
First carbon nanotube layer and the second carbon nanotube layer are porous materials made of carbon nanotube debris accumulation,
Accumulation carbon nanotube average diameter used is between 5-60nm, first carbon nanotube layer and the second carbon nanotube layer thickness
Between 5-40um, the porosity of first carbon nanotube layer and the second carbon nanotube layer is described between 45-80%
The fragment of carbon nanotube fragment selection double-walled carbon nano-tube.
The graphene layer be using rich in single-layer graphene fragment suspension carbon nano-tube film surface repeatedly
Spin coating-drying forms, and the suspension is that graphene fragment is mixed in basal liquid, and the basal liquid is distilled water and nothing
The weight proportion of the mixed liquor of water-ethanol, distilled water and dehydrated alcohol is 50%-10%:50-90%.
Dimethyl silicone polymer is also uniformly mixed in the suspension.
The present invention also provides a kind of preparation method of graphene carbon nanometer tube composite materials, it is used to be made foregoing
Graphene carbon nanometer tube composite materials, include the following steps.
Step 1: carbon nanotube the preparation of two carbon nanotube layers/polyaniline two-layer composite: being made by ultrasound
Dispersion liquid, the ultrasound parameter frequency >=25KHz, power density=transmission power (W)/emission area (cm2) >=0.4W/cm2,
Duration is not less than 3min；The filter membrane for preparing even compact on suction funnel, is filtered with excessive foregoing carbon nanotubes dispersion liquid, is made
The carbon nanotube fragment obtained in the carbon nano tube dispersion liquid is deposited on filter membrane, uses the sulfuric acid or KOH aqueous solution of 0.2M
Embathed repeatedly as removing liquid filter membrane and carbon nano-tube film combination 10-20 time, each 3-12h, use polyaniline as
The combination of filter membrane and carbon nano-tube film is inverted compacting in substrate, ethyl alcohol or isopropanol is placed in together with substrate by substrate
Low-temperature reduced-pressure steam at least 2-4h to remove filter membrane, vacuum drying 24-72h receives under room temperature to get to polyaniline and carbon
The composite construction of mitron layer, respectively as the first polyaniline 2 and the first carbon nanotube layer and the second carbon nanotube layer and
Two polyanilines.
Step 2: resin protective layer forming step: by protectiveness resin such as layer of polyurethane even application in the first polyaniline
With outside the second polyaniline, the protective layer of 0.2-1mm is formed, under 50-70 DEG C of environment temperature, nitrogen protection solidifies 2-4
Hour, form the first resin protective layer and the second resin protective layer.
Step 3: graphene layer preliminarily forms step: the graphene suspension of 5-15mg/ml is added drop-wise to the first carbon nanometer
The inner surface of tube layer and the second carbon nanotube layer forms film layer with the mode of spin coating, the rotation recycled by least 15-20
Painting-drying process forms two graphene spin coating inner surfaces.
Step 4: shielded layer forming step: configuring the graphene suspension of a large amount of 5-30mg/ml, and add 5- wherein
The PMDS polydimethylsiloxane liquid of 10% mass percentage concentration and the curing agent of the mass percentage concentration less than 1%, in step
On rapid 3 two graphene spin coating inner surfaces after spin coating, under uniformly alignment stress condition, takes advantage of not dry inversion and be incorporated in one
It rises, after drying solidification, the graphene layer containing PMDS and curing agent and both of the aforesaid graphene spin coating inner surface are collectively formed
Graphene layer.
In step 1, ultrasound parameter frequency 30KHz, power density=transmission power (W)/emission area (cm2)=0.5W/
Cm2, duration 5min；Use 0.2M sulfuric acid or KOH aqueous solution as removing liquid embathe filter membrane and carbon nano-tube film repeatedly
Combination 18 times, each 8h；At least 4h in the low-temperature reduced-pressure steam of ethyl alcohol or isopropanol is placed in together with substrate to filter to remove
Film is dried in vacuo 48h under room temperature；In step 2, the protective layer of 0.6-0.8mm is formed, under 60 DEG C of environment temperature, nitrogen is protected
Shield solidification 3 hours；In step 4, the graphene suspension of a large amount of 20-30mg/ml is configured, and adds 8-10% mass wherein
The curing agent of the mass percentage concentration of the PMDS polydimethylsiloxane liquid and 0.6-0.9% of percentage concentration.
Compared with prior art, the beneficial effects of the present invention are: the graphene carbon nanometer tube composite materials are as electromagnetic screen
Material is covered, folding, flexibility is good, waterproof, anti-certain temperature, moreover, material layer centered on graphene layer, successively to two sides
Be provided with carbon nanotube layer, polyaniline and resin protective layer so that front and back sides shield effectiveness is equal, can in protective garment, mask,
Protective plate, shield, a variety of applications such as protection curtain.In existing shielding material layer, generally seldom with such interlayer
Structure, because being difficult preferably to be attached together, but the present processes make this combination very firm, general rubbing
Folding will not influence structure substantially, will not simply damage.Especially intermediate polyaniline-carbon nanotube layer-graphene layer-carbon is received
The combination of mitron layer-polyaniline is very secured, and polyaniline is combined as basal layer and carbon nanotube layer, dexterously solves
Carbon nanotube layer take off after in conjunction with firmness deficiency problem, intermediate graphene layer had both been utilized spin coating and solves to be received with carbon
The combination problem of mitron layer, and solve the problems, such as composite material combination in opposite side under the intervention of PDMS under not dry state, it is real
Survey functional, processing method intention is full, has embodied unexpected technical effect.
Detailed description of the invention
Fig. 1 is vertical cross-section structural schematic diagram of the present invention.
In figure: 1, first resin protective layer, the 2, first polyaniline, the 3, first carbon nanotube layer, 4, graphene layer, 5,
Two carbon nanotube layers, the 6, second polyaniline, the 7, second resin protective layer.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.It is original that the application belongs to the mode of several layers of composite materials combinations, and effect
Very well, it does not enlighten in the prior art.
Referring to Fig. 1, the present invention provides a kind of technical solution: a kind of graphene carbon nanometer tube composite materials, including graphite
Alkene layer 4 and two carbon nanotube layers, it is characterised in that: from outside to inside successively by the first resin protective layer 1, the first polyaniline 2,
First carbon nanotube layer 3, graphene layer 4, the second carbon nanotube layer 5, the second polyaniline 6 and the second resin protective layer 7 overlapping
Composition.
The graphene layer 4 has been sequentially arranged above the first carbon nanotube layer 3, the first polyaniline 2 and the first resin and has protected
Sheath 1, and the second carbon nanotube layer 5, the second polyaniline 6 and the second resin protective layer are disposed with below graphene layer 4
7。
First carbon nanotube layer 3 and the second carbon nanotube layer 5 are porous materials made of carbon nanotube debris accumulation
Material accumulates carbon nanotube average diameter used between 5-60nm, first carbon nanotube layer 3 and the second carbon nanotube layer
5 thickness between 5-40um, the porosity of first carbon nanotube layer 3 and the second carbon nanotube layer 5 between 45-80% it
Between, the fragment of the carbon nanotube fragment selection double-walled carbon nano-tube.
The graphene layer 4 be using rich in single-layer graphene fragment suspension carbon nano-tube film surface repeatedly
Spin coating-drying forms, and the suspension is that graphene fragment is mixed in basal liquid, and the basal liquid is distilled water and nothing
The weight proportion of the mixed liquor of water-ethanol, distilled water and dehydrated alcohol is 50%-10%:50-90%.
Dimethyl silicone polymer is also uniformly mixed in the suspension.
The present invention also provides a kind of preparation method of graphene carbon nanometer tube composite materials, it is used to be made foregoing
Graphene carbon nanometer tube composite materials, include the following steps.
Step 1: carbon nanotube the preparation of two carbon nanotube layers/polyaniline two-layer composite: being made by ultrasound
Dispersion liquid, the ultrasound parameter frequency >=25KHz, power density=transmission power (W)/emission area (cm2) >=0.4W/cm2,
Duration is not less than 3min；The filter membrane for preparing even compact on suction funnel, is filtered with excessive foregoing carbon nanotubes dispersion liquid, is made
The carbon nanotube fragment obtained in the carbon nano tube dispersion liquid is deposited on filter membrane, uses the sulfuric acid or KOH aqueous solution of 0.2M
Embathed repeatedly as removing liquid filter membrane and carbon nano-tube film combination 10-20 time, each 3-12h, use polyaniline as
The combination of filter membrane and carbon nano-tube film is inverted compacting in substrate, ethyl alcohol or isopropanol is placed in together with substrate by substrate
Low-temperature reduced-pressure steam at least 2-4h to remove filter membrane, vacuum drying 24-72h receives under room temperature to get to polyaniline and carbon
The composite construction of mitron layer, respectively as 5 He of the first polyaniline 2 and the first carbon nanotube layer 3 and the second carbon nanotube layer
Second polyaniline 6.
Experiments verify that polyaniline and carbon nanotube layer binding force are enough under the conditions of such, bend test is done, is passed through
Through Electronic Speculum observation, there is no obviously removing phenomenon after 30 ° of bendings.The splicing face of doing shear strength test, fixed wherein one layer, will
Another layer is pulled away along the direction of parallel two interface layer, needs biggish power that could laterally pull polyaniline.
Step 2: resin protective layer forming step: by protectiveness resin such as layer of polyurethane even application in the first polyaniline
2 and the outside of the second polyaniline 6, the protective layer of 0.2-1mm is formed, under 50-70 DEG C of environment temperature, nitrogen protection solidifies 2-
4 hours, form the first resin protective layer 1 and the second resin protective layer 7.After actual measurement, first pass through uniform coating, room temperature 2h it
Afterwards, the case where solidification effect is preferable, and heated under nitrogen solidifies just is carried out, attachment degree, which has, to be obviously improved.
Step 3: graphene layer preliminarily forms step: the graphene suspension of 5-15mg/ml is added drop-wise to the first carbon nanometer
The inner surface of tube layer 3 and the second carbon nanotube layer 5 forms film layer with the mode of spin coating, the rotation recycled by least 15-20
Painting-drying process forms two graphene spin coating inner surfaces.This, which accelerates drying process, can use quickening indoor air convection
Mode, it is noted that wind-force blow-through spin coating surface cannot be used.
Step 4: shielded layer forming step: configuring the graphene suspension of a large amount of 5-30mg/ml, and add 5- wherein
The PMDS polydimethylsiloxane liquid of 10% mass percentage concentration and the curing agent of the mass percentage concentration less than 1%, in step
On rapid 3 two graphene spin coating inner surfaces after spin coating, under uniformly alignment stress condition, takes advantage of not dry inversion and be incorporated in one
It rises, after drying solidification, the graphene layer containing PMDS and curing agent and both of the aforesaid graphene spin coating inner surface are collectively formed
Graphene layer 4.Drying solidification and can be carried out under room temperature under ultraviolet light irradiation, under nitrogen protection herein.
In step 1, ultrasound parameter frequency 30KHz, power density=transmission power (W)/emission area (cm2)=0.5W/
Cm2, duration 5min；Use 0.2M sulfuric acid or KOH aqueous solution as removing liquid embathe filter membrane and carbon nano-tube film repeatedly
Combination 18 times, each 8h；At least 4h in the low-temperature reduced-pressure steam of ethyl alcohol or isopropanol is placed in together with substrate to filter to remove
Film is dried in vacuo 48h under room temperature；In step 2, the protective layer of 0.6-0.8mm is formed, under 60 DEG C of environment temperature, nitrogen is protected
Shield solidification 3 hours；In step 4, the graphene suspension of a large amount of 20-30mg/ml is configured, and adds 8-10% mass wherein
The curing agent of the mass percentage concentration of the PMDS polydimethylsiloxane liquid and 0.6-0.9% of percentage concentration.
Embodiment 2
In step 1, ultrasound parameter frequency 25KHz, power density=transmission power (W)/emission area (cm2)=0.45W/
Cm2, duration 4min；Use 0.3M sulfuric acid or KOH aqueous solution as removing liquid embathe filter membrane and carbon nano-tube film repeatedly
Combination 20 times, each 7h；At least 3h in the low-temperature reduced-pressure steam of ethyl alcohol or isopropanol is placed in together with substrate to filter to remove
Film is dried in vacuo 60h under room temperature；In step 2, the protective layer of 0.7-0.9mm is formed, under 60 DEG C of environment temperature, nitrogen is protected
Shield solidification 2.5 hours；In step 4, the graphene suspension of a large amount of 22-30mg/ml is configured, and adds 10% mass wherein
The curing agent of the mass percentage concentration of the PMDS polydimethylsiloxane liquid and 0.8-0.9% of percentage concentration.Other conditions are same
Embodiment 1.
The microstructure of graphene layer 4 is only illustrative nature in Fig. 1, due to being single-layer graphene fragment multiple spin coating and
At actual microstructure is more complicated.
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art,
It is still possible to modify the technical solutions described in the foregoing embodiments, or part of technical characteristic is carried out etc.
With replacement, all within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in this
Within the protection scope of invention.
Claims (5)
1. a kind of graphene carbon nanometer tube composite materials, including graphene layer (4) and two carbon nanotube layers, it is characterised in that:
From outside to inside successively by the first resin protective layer (1), the first polyaniline (2), the first carbon nanotube layer (3), graphene layer
(4), the second carbon nanotube layer (5), the second polyaniline (6) and the second resin protective layer (7) overlapping composition；
The graphene layer (4) has been sequentially arranged above the first carbon nanotube layer (3), the first polyaniline (2) and the first resin
Protective layer (1), and the second carbon nanotube layer (5), the second polyaniline (6) and second are disposed with below graphene layer (4)
Resin protective layer (7).
2. a kind of graphene carbon nanometer tube composite materials as described in claim 1, it is characterised in that: first carbon nanotube
Layer (3) and the second carbon nanotube layer (5) are porous materials made of carbon nanotube debris accumulation, accumulate carbon nanotube used
Average diameter between 5-60nm, first carbon nanotube layer (3) and the second carbon nanotube layer (5) thickness 5-40um it
Between, the porosity of first carbon nanotube layer (3) and the second carbon nanotube layer (5) is between 45-80%, the carbon nanometer
The fragment of pipe fragment selection double-walled carbon nano-tube；
The graphene layer (4) is repeatedly to be revolved using the suspension rich in single-layer graphene fragment on carbon nano-tube film surface
Painting-drying forms, and the suspension is that graphene fragment is mixed in basal liquid, the basal liquid be distilled water with it is anhydrous
The weight proportion of the mixed liquor of ethyl alcohol, distilled water and dehydrated alcohol is 50%-10%:50-90%.
3. a kind of graphene carbon nanometer tube composite materials as claimed in claim 2, it is characterised in that:
Dimethyl silicone polymer is also uniformly mixed in the suspension.
4. a kind of preparation method of graphene carbon nanometer tube composite materials, is used to be made graphene as claimed in claim 3
Carbon nano tube compound material, comprising:
1) carbon nano tube dispersion liquid, institute two carbon nanotube layers/polyaniline two-layer composite preparation: are made by ultrasound
State ultrasound parameter frequency >=25KHz, power density=transmission power (W)/emission area (cm2) >=0.4W/cm2, duration is low
In 3min；The filter membrane for preparing even compact on suction funnel, is filtered with excessive foregoing carbon nanotubes dispersion liquid, so that the carbon
Carbon nanotube fragment in nanotube dispersion liquid is deposited on filter membrane, use 0.2M sulfuric acid or KOH aqueous solution as removing
Liquid embathes combination 10-20 times of filter membrane and carbon nano-tube film repeatedly, and each 3-12h uses polyaniline as substrate, will filter
The combination of film and carbon nano-tube film is inverted compacting in substrate, and the low-temperature reduced-pressure of ethyl alcohol or isopropanol is placed in together with substrate
At least 2-4h to be in steam to remove filter membrane, and vacuum drying 24-72h is under room temperature to get answering to polyaniline and carbon nanotube layer
Structure is closed, respectively as the first polyaniline (2) and the first carbon nanotube layer (3) and the second carbon nanotube layer (5) and second
Polyaniline (6)；
2) resin protective layer forming step: by protectiveness resin (such as layer of polyurethane) even application in the first polyaniline (2) and
Outside second polyaniline (6), the protective layer of 0.2-1mm is formed, under 50-70 DEG C of environment temperature, nitrogen protection solidifies 2-4
Hour, form the first resin protective layer (1) and the second resin protective layer (7)；
3) graphene layer preliminarily forms step: by the graphene suspension of 5-15mg/ml be added drop-wise to the first carbon nanotube layer (3) with
And second carbon nanotube layer (5) inner surface, form film layer with the mode of spin coating, the spin coating-recycled by least 15-20 is dry
Dry process forms two graphene spin coating inner surfaces；
4) shielded layer forming step: configuring the graphene suspension of a large amount of 5-30mg/ml, and adds 5-10% mass wherein
The curing agent of PMDS (dimethyl silicone polymer) liquid and the mass percentage concentration less than 1% of percentage concentration, in step (3)
On two graphene spin coating inner surfaces after spin coating, under uniformly alignment stress condition, takes advantage of not dry inversion and be combined together, drying in the air
After solidization, the graphene layer containing PMDS and curing agent and both of the aforesaid graphene spin coating inner surface together form graphene
Layer (4).
5. a kind of preparation method of graphene carbon nanometer tube composite materials as claimed in claim 4, it is characterised in that:
In step (1), ultrasound parameter frequency 30KHz, power density=transmission power (W)/emission area (cm2)=0.5W/
Cm2, duration 5min；Use 0.2M sulfuric acid or KOH aqueous solution as removing liquid embathe filter membrane and carbon nano-tube film repeatedly
Combination 18 times, each 8h；At least 4h in the low-temperature reduced-pressure steam of ethyl alcohol or isopropanol is placed in together with substrate to filter to remove
Film is dried in vacuo 48h under room temperature；
In step (2), the protective layer of 0.6-0.8mm is formed, under 60 DEG C of environment temperature, nitrogen protection solidifies 3 hours；
In step (4), the graphene suspension of a large amount of 20-30mg/ml is configured, and addition 8-10% mass percentage is dense wherein
The curing agent of the mass percentage concentration of PMDS (dimethyl silicone polymer) liquid and 0.6-0.9% of degree.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810672474.9A CN109228578B (en) | 2018-06-26 | 2018-06-26 | Graphene carbon nanotube composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810672474.9A CN109228578B (en) | 2018-06-26 | 2018-06-26 | Graphene carbon nanotube composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109228578A true CN109228578A (en) | 2019-01-18 |
| CN109228578B CN109228578B (en) | 2020-12-25 |
Family
ID=65071976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810672474.9A Active CN109228578B (en) | 2018-06-26 | 2018-06-26 | Graphene carbon nanotube composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109228578B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110257022A (en) * | 2019-07-18 | 2019-09-20 | 深圳前海量子翼纳米碳科技有限公司 | A kind of electromagnetic shielding thermal conductive silicon rubber mat of insulation and preparation method thereof |
| CN110421941A (en) * | 2019-08-08 | 2019-11-08 | 邦威防护科技股份有限公司 | A kind of electric heating fabric that heat preservation protection is taken |
| CN111113946A (en) * | 2019-12-17 | 2020-05-08 | 江苏理工学院 | Hybrid composite laminated board and preparation process thereof |
| CN111732743A (en) * | 2020-06-10 | 2020-10-02 | 新材料与产业技术北京研究院 | Preparation method of carbon nanotube/graphene flexible film |
| CN114430864A (en) * | 2019-09-27 | 2022-05-03 | 松下知识产权经营株式会社 | Negative electrode for lithium ion secondary battery and lithium ion secondary battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106183136A (en) * | 2016-07-08 | 2016-12-07 | 东华大学 | A kind of electromagnetic shielding composite material material and preparation thereof and application |
| CN106183211A (en) * | 2016-07-08 | 2016-12-07 | 东华大学 | A kind of electromagnetic shielding compound fabric and preparation thereof and application |
-
2018
- 2018-06-26 CN CN201810672474.9A patent/CN109228578B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106183136A (en) * | 2016-07-08 | 2016-12-07 | 东华大学 | A kind of electromagnetic shielding composite material material and preparation thereof and application |
| CN106183211A (en) * | 2016-07-08 | 2016-12-07 | 东华大学 | A kind of electromagnetic shielding compound fabric and preparation thereof and application |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110257022A (en) * | 2019-07-18 | 2019-09-20 | 深圳前海量子翼纳米碳科技有限公司 | A kind of electromagnetic shielding thermal conductive silicon rubber mat of insulation and preparation method thereof |
| CN110421941A (en) * | 2019-08-08 | 2019-11-08 | 邦威防护科技股份有限公司 | A kind of electric heating fabric that heat preservation protection is taken |
| CN110421941B (en) * | 2019-08-08 | 2021-09-10 | 邦威防护科技股份有限公司 | Electric heating fabric for thermal insulation protective clothing |
| CN114430864A (en) * | 2019-09-27 | 2022-05-03 | 松下知识产权经营株式会社 | Negative electrode for lithium ion secondary battery and lithium ion secondary battery |
| CN111113946A (en) * | 2019-12-17 | 2020-05-08 | 江苏理工学院 | Hybrid composite laminated board and preparation process thereof |
| CN111732743A (en) * | 2020-06-10 | 2020-10-02 | 新材料与产业技术北京研究院 | Preparation method of carbon nanotube/graphene flexible film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109228578B (en) | 2020-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109228578A (en) | A kind of graphene carbon nanometer tube composite materials and preparation method thereof | |
| CN106183136B (en) | A kind of electromagnetic shielding composite material material and its preparation and application | |
| Li et al. | Lightweight, flexible and superhydrophobic composite nanofiber films inspired by nacre for highly electromagnetic interference shielding | |
| Liu et al. | Well-aligned MXene/chitosan films with humidity response for high-performance electromagnetic interference shielding | |
| Zhu et al. | Ultralight, compressible, and anisotropic MXene@ Wood nanocomposite aerogel with excellent electromagnetic wave shielding and absorbing properties at different directions | |
| Cheng et al. | Recent progress of electrospun nanofibrous materials for electromagnetic interference shielding | |
| EP2687364B1 (en) | Composite conductive sheet, fabricating method and application thereof | |
| WO2016119693A1 (en) | Air filter paper and preparation method therefor | |
| KR101337958B1 (en) | Electromagnetic wave shielding composite and manufacturing method for thereof | |
| Zhang et al. | Homogeneous silver nanoparticles decorating 3D carbon nanotube sponges as flexible high-performance electromagnetic shielding composite materials | |
| CN110204898A (en) | A kind of preparation method of MXene- Kevlar fento laminated film | |
| Lan et al. | High‐loading carbon nanotube/polymer nanocomposite fabric coatings obtained by capillarity‐assisted “excess assembly” for electromagnetic interference shielding | |
| Zhang et al. | Superhydrophobic and conductive properties of carbon nanotubes/polybenzoxazine nanocomposites coated ramie fabric prepared by solution-immersion process | |
| Gao et al. | Hydrophobic, flexible electromagnetic interference shielding films derived from hydrolysate of waste leather scraps | |
| CN105504093A (en) | Method for preparing membrane electrode from chitin nano fiber/carbon nanotube composite | |
| Wu et al. | High-density grafting of carbon nanotube/carbon nanofiber hybrid on carbon fiber surface by vacuum filtration for effective interfacial reinforcement of its epoxy composites | |
| CN108611918A (en) | Nano combined conductive paper of carbon and preparation method thereof | |
| Zeng et al. | Nanocellulose‐assisted preparation of electromagnetic interference shielding materials with diversified microstructure | |
| Peng et al. | Graphitized and flexible porous textile updated from waste cotton for wearable electromagnetic interference shielding | |
| Xie et al. | Carbon nanotubes chemical bonding with cotton/spandex blended fabric via thiol-epoxy click chemistry for durable electromagnetic interference shielding | |
| CN113386412B (en) | Graphene/carbon nanotube aerogel electromagnetic shielding composite fabric and preparation method and application thereof | |
| Liu et al. | MXene-based films via scalable fabrication with improved mechanical and antioxidant properties for electromagnetic interference shielding | |
| Yun et al. | Waterproof and ultrasensitive paper-based wearable strain/pressure sensor from carbon black/multilayer graphene/carboxymethyl cellulose composite | |
| Huang et al. | Lightweight and textured Ni@ Cu-encapsulated carbon tube with outstanding electromagnetic interference shielding performance | |
| Yang et al. | Flexible and ultrathin GO@ MXene sandwich-type multilayered film toward superior electromagnetic interference shielding in a wide gigahertz range of 3.95–18.0 GHz |
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 | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20200827 Address after: 100089 building 3, 11 Changchun Road, Haidian District, Beijing 801 Applicant after: SINOHOPE GROUP Co.,Ltd. Applicant after: GUOHONG HUAYE INVESTMENT Co.,Ltd. Address before: 100081 building 4, floor 8, No. 9, Haidian District meteorological Road, Beijing City, 418 Applicant before: CISRI ENERGY SAVING TECHNOLOGY Co.,Ltd. Applicant before: GUOHONG HUAYE INVESTMENT Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211019 Address after: 1206-4, 12th floor, building 3, No. 11, Changchun Bridge Road, Haidian District, Beijing 100089 Patentee after: SINOHOPE GROUP Co.,Ltd. Address before: 100089 Building 801, No. 11 Changchun Bridge Road, Haidian District, Beijing Patentee before: SINOHOPE GROUP Co.,Ltd. Patentee before: GUOHONG HUAYE INVESTMENT Co.,Ltd. |
|
| PP01 | Preservation of patent right | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20230329 Granted publication date: 20201225 |