CN109851312A - Graphene thermal isolation film and preparation method thereof - Google Patents
Graphene thermal isolation film and preparation method thereof Download PDFInfo
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- CN109851312A CN109851312A CN201811603259.XA CN201811603259A CN109851312A CN 109851312 A CN109851312 A CN 109851312A CN 201811603259 A CN201811603259 A CN 201811603259A CN 109851312 A CN109851312 A CN 109851312A
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- cenosphere
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- aeroge
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of preparation method of graphene heat-barrier material, comprising: mixes graphene carbon materials dispersion with cenosphere and/or aeroge dispersion liquid liquid, obtains composite mortar；The composite mortar passes through deaeration, coating, drying, forms composite membrane；It is heat-treated with to the composite membrane, decomposes the functional group in graphene carbon materials, ultimately form graphene thermal isolation film.Graphene thermal isolation film provided by the invention, using graphene/graphene oxide composite aerogel or cenosphere, form graphene face interior orientation arrangement (piece interlayer minimum energy assembling, hydrogen bond and capillary pressure assembling), aeroge nano particle and/or cenosphere are between graphene sheet layer.Graphene has as many as tens of thousands of layers to form effective reflection partition, and the aeroge or cenosphere of interlayer play the contact for reducing graphene film, increase thermal resistance.The gap very little formed between graphene layer with aeroge or cenosphere, barrier gas is in internal convection current.
Description
Technical field
The present invention relates to a kind of heat-barrier materials and preparation method thereof, and in particular to a kind of heat-insulated carbon material and its preparation side
Method.
Background technique
Electric car uses lithium ion battery to drive as energy, and lithium ion battery has some potential safety problems now,
The report of annual electric car kindling is commonplace.To solve or delaying electric car thermal runaway, or even kindling, engineering occur
Teacher has made various effort, wherein separating battery core using thermal isolation film between every battery core, avoids a wherein battery core heat mistake
Control, causes moment to catch fire.
Oxidization fiber aerogel blanket, thermal coefficient < 0.018W/m K, possesses excellent heat-proof quality, has been supplied in power electric
In the packet of pond, the time of the precarious positions such as out of control, kindling of delay battery pack.But cost is too high；When processing, dust pollution is big.
A kind of preparation method of closed pore graphite oxide alkenyl heat-barrier material of patent CN201710384128.6, by graphite oxide
It is made into lotion, using freeze-drying 5~7 days.It is long using freeze-drying manufacturing cost height, production cycle.
The content of background technology part is only the technology that inventor is known, not the existing skill of natural representative this field
Art.
Summary of the invention
In order to overcome the problems, such as that the prior art exists, the present invention provides a kind of good heat-insulation effect, density
Low graphene heat-barrier material；
It is a further object of the present invention to provide the preparation methods of above-mentioned graphene heat-barrier material.
Above-mentioned purpose is achieved through the following technical solutions.
A kind of preparation method of graphene heat-barrier material, comprising:
Graphene carbon materials dispersion is mixed with cenosphere and/or aeroge dispersion liquid liquid, obtains composite pulp
Material；
The composite mortar passes through deaeration, coating, drying, forms composite membrane；With
The composite membrane is heat-treated, the functional group in graphene carbon materials is decomposed, it is heat-insulated to ultimately form graphene
Film.
According to an aspect of the present invention, the graphene carbon materials are graphene oxide and/or graphene.
According to an aspect of the present invention, 48~60wt% of the graphene oxide carbon content, 41~53wt% of oxygen content.
According to an aspect of the present invention, the graphene is the graphene of oxidation-reduction method preparation.
According to an aspect of the present invention, the graphene carbon materials are graphene oxide, or in graphene oxide
Mixed with the mixing of a small amount of graphene, and the incorporation of graphene is according to mass ratio >=5 of graphene oxide and graphene.
It is further preferred that the graphene carbon materials are graphene oxide.
According to an aspect of the present invention, graphene carbon materials described in the graphene carbon materials dispersion and first molten
Agent, the content of the graphene carbon materials are 3-10wt%, preferably 8wt%.
Preferably, first solvent is selected from water and/or NMP；It is further preferred that first solvent is water and NMP
According to (3-5): 1 mass ratio is configured to mixed solvent, further preferential, and first solvent is the matter of water and NMP according to 4:1
Amount ratio is configured to mixed solvent.
According to an aspect of the present invention, the graphene carbon materials system is prepared by the following method:
Graphene carbon materials are added in the first solvent, using planetary stirring machine, 300-2200 turn/min under stir to
Uniformly.
Preferably, it stirs to 20 μm of slurry fineness <, 20000~40000mPa.s of viscosity.
It is preferred that 60 ± 30min of stirring.
According to an aspect of the present invention, the heat-barrier material is cenosphere and/aeroge.
According to an aspect of the present invention, the heat-barrier material is cenosphere, or to be mixed with gas in cenosphere
The mixing material of gel, and the mixed volume of aeroge presses cenosphere: mass ratio >=0.5 of aeroge.
Preferably, when the heat-barrier material is to be mixed with the mixing material of aeroge in cenosphere, aeroge is mixed
Enter amount by cenosphere: the mass ratio of aeroge is preferably >=1；Most preferably cenosphere: the mass ratio of aeroge is 3:2.
It according to an aspect of the present invention, include heat-barrier material and the second solvent, institute in the heat-barrier material dispersion
The content for stating heat-barrier material is 3-15wt%, preferably 5wt%.
Preferably, second solvent is selected from water and/or NMP；It is further preferred that second solvent is water and NMP
According to (3-5): 1 mass ratio is configured to mixed solvent, further preferential, and second solvent is the matter of water and NMP according to 4:1
Amount ratio is configured to mixed solvent.
According to an aspect of the present invention, the heat-barrier material is prepared by the following method:
Heat-barrier material is added in the second solvent, stirs evenly to form the stable liquid that poises, not settle.
According to an aspect of the present invention, the partial size of the cenosphere is 1-50 μm, preferably 5 μm.
According to an aspect of the present invention, the wall thickness of the air microballon is 0.2-2.0 μm, preferably 1.0 μm.
According to an aspect of the present invention, the cenosphere is selected from hollow glass bead, ceramic hollow microballon.
According to an aspect of the present invention, the partial size of the aeroge is 20-100nm, preferably 50nm.
According to an aspect of the present invention, the aeroge is selected from aerosil.
According to an aspect of the present invention, the liquid liquid mixes method particularly includes: accounts for graphene carbon according to heat-barrier material
Air bound hot material dispersion is added in graphene carbon materials dispersion by the proportionate relationship of material 0.5-10wt%, and dispersion is equal
It is even.
Preferably, the heat-barrier material accounts for graphene carbon materials 1wt%.
Preferably, described be uniformly dispersed is completed using under the mixing speed of 300-1000rpmg.
According to an aspect of the present invention, the method for the deaeration are as follows: continuous film deaeration is stirred under vacuum deaeration.According to
Slurry blade coating or squash type are coated in base band by one aspect of the present invention by base band as supporting.
According to an aspect of the present invention, the coating thickness of the composite mortar is 2-3mm.
According to an aspect of the present invention, the temperature of the drying is -90 DEG C of room temperature, dry 1-3h；
According to an aspect of the present invention, the drying temperature is 50~90 DEG C, dry 2h.
According to an aspect of the present invention, the composite membrane formed after the drying with a thickness of 80-150 μm.
According to an aspect of the present invention, the temperature of the heat treatment is 100-300 DEG C, constant temperature 2- under heat treatment temperature
12h。
Preferably, the temperature of the heat treatment is 200 DEG C, constant temperature 3h.
According to an aspect of the present invention, constant temperature to composite membrane is expanded to a thickness of 300-1000 μm under heat treatment temperature；
According to an aspect of the present invention, the heat treatment uses the heating rate of 0.01~2 DEG C/min, and temperature is risen to
The temperature of heat treatment, then constant temperature.
According to an aspect of the present invention, the equipment used that is heat-treated can be baking oven, heating furnace, continuous tunnel furnace etc..
A kind of graphene thermal isolation film, including graphene and cenosphere and/or aeroge, the cenosphere and/or gas
Gel is distributed in the interlayer of the graphene, is packaged in the network formed between graphene film.
According to an aspect of the present invention, the thermal coefficient of the graphene thermal isolation film is in 0.018W/m*K or less.
According to an aspect of the present invention, the density of the graphene thermal isolation film is in 0.15g/cm3Below.
According to an aspect of the present invention, the compression strength of the graphene thermal isolation film is greater than 10MPa.
According to an aspect of the present invention, the oxygen content of the graphene is 10~30wt%.The present invention make graphene every
Graphene oxygen content in hotting mask is finally controlled in 10~30wt%, when graphene oxygen content is less than 10wt%, thermal isolation film
Heat-proof quality decline can decreased significantly, and when graphene oxygen content is greater than 30wt%, the heat resistance of thermal isolation film is decreased obviously,
The oxygen content for guaranteeing thermal isolation film graphene is the best performance that 10~30wt% makes product of the present invention graphene thermal isolation film.
Graphene thermal isolation film provided by the invention, using graphene/graphene oxide composite aerogel or cenosphere, shape
At graphene face interior orientation arrangement (piece interlayer minimum energy assembling, hydrogen bond and capillary pressure assembling), aeroge nano particle and/
Or cenosphere is between graphene sheet layer.Graphene has as many as tens of thousands of layers to form effective reflection partition, the airsetting of interlayer
Glue or cenosphere play the contact for reducing graphene film, increase thermal resistance.It is formed between graphene layer with aeroge or cenosphere
Gap very little, barrier gas is in internal convection current.The present invention realizes low thermally conductive, inhibition air thermal convection, infrared external reflection, system
For thermal isolation film excellent out.And aeroge nano particle and/or cenosphere are packaged between graphene layer, product is asked without picking
Topic.
The preparation method of graphene thermal isolation film provided by the invention, simple production process, manufacturing cycle are short.Nanometer or micron
Particle is prevented from losing powder by fixation between graphene layer, solves the defect of above-mentioned heat-barrier material.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Fig. 1 is graphene thermal isolation film according to the present invention section microstructure schematic diagram；
Wherein, 1-graphene, 2-aeroges, 3-cenospheres.
Specific embodiment
Hereinafter, certain exemplary embodiments are simply just described.As one skilled in the art will recognize that
Like that, without departing from the spirit or scope of the present invention, described embodiment can be modified by various different modes.
Therefore, attached drawing and description are considered essentially illustrative rather than restrictive.
In the description of the present invention, term " first ", " second " are used for description purposes only, and should not be understood as instruction or dark
Show relative importance or implicitly indicates the quantity of indicated technical characteristic.The feature of " first ", " second " is defined as a result,
It can explicitly or implicitly include one or more feature.
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings, it should be understood that preferred reality described herein
Apply example only for the purpose of illustrating and explaining the present invention and is not intended to limit the present invention.
In an embodiment of the invention, a kind of preparation method of graphene heat-barrier material is provided, comprising:
Graphene carbon materials dispersion is mixed with cenosphere and/or aeroge dispersion liquid liquid, obtains composite pulp
Material；
The composite mortar passes through deaeration, coating, drying, forms composite membrane；With
The composite membrane is heat-treated, the functional group in graphene carbon materials is decomposed, it is heat-insulated to ultimately form graphene
Film.
The graphene carbon materials are graphene oxide and/or graphene.48~60wt% of the graphene oxide carbon content,
41~53wt% of oxygen content.The graphene is the graphene of oxidation-reduction method preparation.Present embodiment graphene carbon materials are preferred
For graphene oxide.Or mixed with the mixing of a small amount of graphene in graphene oxide, and the incorporation of graphene according to
Mass ratio >=5 of graphene oxide and graphene.Graphene carbon materials described in the graphene carbon materials dispersion and first molten
Agent, the content of the graphene carbon materials are 3-10wt%, such as: 3-2wt%, 3-5wt%, 5-6wt%, 5-8wt%, 6-
9wt%, 6-10wt%, 7-9wt%, 7.5-9wt%, 6-8.5wt%, 7-10wt%, 8.5-10wt%, etc.；It is preferred that 8wt%.
First solvent is selected from water and/or NMP.As a kind of selection of the first solvent preferred embodiment, first solvent be water and
NMP is according to (3-5): 1 mass ratio is configured to mixed solvent, such as: 3:1,3.5:1,4:1,4.2:1,4.5:1,5:1, etc.；Make
For a kind of selection of the first solvent preferred plan, first solvent is water and NMP be configured to mix according to the mass ratio of 4:1 it is molten
Agent.
The graphene carbon materials system is prepared by the following method:
Graphene carbon materials are added in the first solvent, using planetary stirring machine, 300-2200 turn/min under stir to
Uniformly.The uniform index are as follows: stirring to 20 μm of slurry fineness <, 20000~40000mPa.s of viscosity.Under normal circumstances,
These parameters can be realized in 60 ± 30min of stirring.
The heat-barrier material is cenosphere, or to be mixed with the mixing material of aeroge, and airsetting in cenosphere
The mixed volume of glue press cenosphere: mass ratio >=0.5 of aeroge, such as: cenosphere: the mass ratio of aeroge be 0.5,
0.6,0.8,1,1.5,2,3,5,6,8,10,15,20,30,50,70,90,100, etc..A kind of preferred side as heat-barrier material
The selection of case, heat-barrier material are by cenosphere: the mixing material of mass ratio >=1 of aeroge, such as: cenosphere: airsetting
The mass ratio of glue is 1,1.2,1.5,1.7,2,3,4,5,8,10,12,14,18,20,50,70,100,200,300,500, etc.；
A kind of selection of preferred plan as heat-barrier material, heat-barrier material are by cenosphere: the mass ratio of aeroge is the mixed of 3:2
Condensation material.It include heat-barrier material and the second solvent in the heat-barrier material dispersion, the content of the heat-barrier material is 3-
15wt%, such as: 3-5wt%, 3-8wt%, 3-10wt%, 3.5-6wt%, 4-5wt%, 4.5-6.5wt%, 4-6wt%,
3.5-5.5wt%, 4-6.5wt%, 5-7wt%, 6-10wt%, 8-9wt%, etc.；It is preferred that 5wt%.Second solvent is selected from
Water and/or NMP；As a kind of preferred embodiment of the second solvent, second solvent is water and NMP according to (3-5): 1 quality
Than being configured to mixed solvent, such as: 3:1,3.2:1,3.5:1,3.8:1,4:1,4.3:1,4.5:1,4.9:1,5:1, etc.；As
A kind of preferred plan of second solvent, second solvent are configured to mixed solvent according to the mass ratio of 4:1 for water and NMP.
The heat-barrier material is prepared by the following method:
Heat-barrier material is added in the second solvent, stirs evenly to form the stable liquid that poises, not settle.
The partial size of the cenosphere is 1-50 μm, such as: 1-10 μm, 1-20 μm, 1-30 μm, 1-5 μm, 1-8 μm, 2-6 μ
m、2-8μm、2-10μm、2-20μm、2-40μm、2-50μm、3-7μm、3-6μm、3-15μm、3-30μm、3.5-5.5μm、3.5-9
μm、3.5-45μm、4-6μm、4-8μm、4-7μm、4-9μm、4-50μm、4-25μm、4.5-6μm、4.5-8.5μm、4.5-22μm、
5-10μm、5-50μm、5-45μm、5-30μm、5-25μm、6-15μm、8-10μm、8-33μm、10-20μm、20-30μm、15-20
μm, 18-36 μm, 30-50 μm, 35-45 μm, 40-50 μm, 45-50 μm, etc.；It is preferred that 5 μm.The wall thickness of the air microballon is
0.2-2.0 μm, such as: 0.2-1.5 μm, 0.2-0.5 μm, 0.5-1.2 μm, 0.5-1.5 μm, 0.5-2 μm, 0.6-1.5 μm, 0.6-
1.2μm、0.8-1.2μm、0.8-2μm、0.8-1.5μm、0.9-1.1μm、0.9-1.5μm、0.9-2μm、1μm、1-2μm、1.2-2
μm, 0.2-1.5 μm, etc.；It is preferred that 1.0 μm.In present embodiment, cenosphere is selected from hollow glass bead, ceramic hollow microballon.
It can also be replaced with other air microballons.The partial size of the aeroge is 20-100nm, such as: 20-50nm, 20-30nm, 20-
25nm、22-28nm、25-55nm、25-60nm、20-80nm、30-60nm、30-55nm、30-90nm、30-75nm、35-55nm、
35-60nm、35-70nm、35-80nm、35-85nm、40-60nm、40-55nm、40-52nm、40-70nm、40-95nm、45-
55nm、45-60nm、45-65nm、45-85nm、48-52nm、50-60nm、50-70nm、50-80nm、50-100nm、65-
80nm, 70-90nm, 75-86nm, 80-100nm, 85-90nm, 90-100nm, etc.；It is preferred that 50nm.It is described in present embodiment
Aeroge is selected from aerosil.It can also be replaced with the aeroge of other types.
The liquid liquid mixing method particularly includes: closed according to the ratio that heat-barrier material accounts for graphene carbon materials 0.5-10wt%
System, air bound hot material dispersion is added in graphene carbon materials dispersion, is uniformly dispersed.
Heat-barrier material accounts for the proportionate relationship of graphene carbon materials 0.5-10wt%, such as: 0.5-9wt%, 0.5-8wt%,
0.5-7wt%, 0.5-6wt%, 0.5-5wt%, 0.5-4wt%, 0.5-2.5wt%, 0.5-2wt%, 0.5-1.5wt%,
0.5-1.2wt%, 0.6-1.2wt%, 0.6-6wt%, 0.6-4.5wt%, 0.8-1.2wt%, 0.8-1.5wt%, 0.8-
2.5wt%, 0.8-3wt%, 0.8-8wt%, 0.9-1.5wt%, 0.9-2wt0.9-7wt%, 0.9-9wt%, 1-10wt%,
1-5wt%, 1-2wt%, 1-3wt%, 1.5-2.5wt%, 2-4wt%, 2-9wt%, 3-5wt%, 3.5-7wt%, 4-
9wt%, 4.5-10wt%, 4.8-6wt%, 5-10wt%, 5-8wt%, 6-9wt%, 6-10wt%, 8-10wt%, etc.；As
Preferred embodiment, the heat-barrier material account for graphene carbon materials 1wt%.The mixing speed being uniformly dispersed using 300-1000rpm
Lower completion, such as: 300rpm, 400rpm, 450rpm, 350rpm, 500rpm, 550rpm, 600rpm, 650rpm, 700rpm,
750rpm, 800rpm, 850rpm, 900rpm, 1000rpm, etc..
The method of the deaeration are as follows: continuous film deaeration is stirred under vacuum deaeration.Line continuous film deaeration
Slurry blade coating or squash type are coated in base band by the coating by base band as supporting.The composite pulp
The coating thickness of material is 2-3mm, such as: 2-2.5mm, 2-2.2mm, 2-2.8mm, 2.2-2.5mm, 2.2-2.7mm, 2.4-
2.5mm, 2.4-2.7mm, 2.6-3mm, 2.5-3mm, 2.5-2.8mm, 2.8-3mm, etc..
The temperature of the drying is -90 DEG C of room temperature, such as: 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 50 DEG C, 52 DEG C, 55 DEG C, 60
DEG C, 63 DEG C, 65 DEG C, 68 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 86 DEG C, 90 DEG C, etc.；Dry 1-3h, such as: 1h, 1.2h, 1.5h, 2h,
2.3h, 2.5h, 2.7h, 3h, etc..In present embodiment, as a kind of preferred embodiment of drying process condition, the drying temperature
It is 50~90 DEG C, such as: 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, etc.；Dry 2h.After drying
The composite membrane of formation with a thickness of 80-150 μm.
The temperature of the heat treatment is 100-300 DEG C, such as: 100-150 DEG C, 100-200 DEG C, 100-250 DEG C, 150-
200℃、150-250℃、150-300℃、120-180℃、180-250℃、180-220℃、200-230℃、200-300℃、
250-280 DEG C, 250-300 DEG C, etc.；Constant temperature 2-12h under heat treatment temperature, such as: 2-10h, 2-8h, 2-5h, 2-4h, 2.5-
3.5h、2.5-4h、2.5-5h、2.5-12h、3-5h、3-4h、3-8h、3-10h、3-12h、5-10h、5-8h、5-7h、4.5-9h、
4.5-6.5h, 6-9h, 6-7.5h, 8-12h, 6-12h, 6.5-11h, 8-10.5h, 9-12h, 10-12h, etc..As heat treatment work
A kind of preferred embodiment of skill parameter, the temperature of the heat treatment are 200 DEG C, constant temperature 3h.Constant temperature is to composite membrane under heat treatment temperature
It is expanded to a thickness of 300-1000 μm, such as: 300-500 μm, 300-700 μm, 400-800 μm, 450-750 μm, 500-800 μ
m、500-900μm、600-800μm、650-750μm、700-900μm、700-750μm、700-1000μm、400-1000μm、
800-1000 μm, etc..The heat treatment uses the heating rate of 0.01~2 DEG C/min, and temperature is risen to the temperature of heat treatment, then
Heng Chu.Heating rate can for 0.01 DEG C/min, 0.02 DEG C/min, 0.03 DEG C/min, 0.04 DEG C/min, 0.05 DEG C/min,
0.08℃/min、0.1℃/min、0.12℃/min、0.13℃/min、0.15℃/min、0.16℃/min、0.17℃/min、
0.18℃/min、0.2℃/min、0.3℃/min、0.4℃/min、0.5℃/min、0.6℃/min、0.7℃/min、0.8℃/
Min, 1.0 DEG C/min, 1.2 DEG C/min, 1.5 DEG C/min, 1.7 DEG C/min, 1.9 DEG C/min, 2 DEG C/min, etc..The heat treatment is adopted
Equipment can be baking oven, heating furnace, continuous tunnel furnace etc..
Another embodiment of the invention provides a kind of graphene thermal isolation film, as shown in Figure 1, including 1 He of graphene
Cenosphere 3 and/or aeroge 2, the cenosphere 3 and/or aeroge 2 are distributed in the interlayer of the graphene 1, are packaged in
In the network formed between graphene 1.The thermal coefficient of the graphene thermal isolation film is in 0.018W/m*K or less.The graphene
The density of thermal isolation film is in 0.15g/cm3Below.The compression strength of the graphene thermal isolation film is greater than 10MPa.The graphene
Oxygen content be 10~30wt%, such as: 10-25wt%, 10-20wt%, 10-15wt%, 10-12wt%, 12-15wt%,
12-18wt%, 12-25wt%, 15-20wt%, 15-30wt%, 15-18wt%, 15-15.5wt%, 17-20wt%, 17-
26wt%, 17-30wt%, 17.5-19wt%, 18-30wt%, 18.5-20wt%, 19-26wt%, 19-20wt%, 19-
30wt%, 20-25wt%, 20-22.5wt%, 20-30wt%, 20-28wt%, 27-30wt%, 27-28wt%, 28-
30wt%, etc..The present invention controls the graphene oxygen content in graphene thermal isolation film finally in 10~30wt%, when graphene contains
When oxygen amount is less than 10wt%, the heat-proof quality decline of thermal isolation film can be decreased significantly, when graphene oxygen content is greater than 30wt%,
The heat resistance of thermal isolation film is decreased obviously, and guarantees that the oxygen content of thermal isolation film graphene is that 10~30wt% makes product of the present invention graphite
The best performance of alkene thermal isolation film.
Graphene thermal isolation film provided by the invention, using graphene/graphene oxide composite aerogel or cenosphere, shape
At graphene face interior orientation arrangement (piece interlayer minimum energy assembling, hydrogen bond and capillary pressure assembling), aeroge nano particle and/
Or cenosphere is between graphene sheet layer.Graphene has as many as tens of thousands of layers to form effective reflection partition, the airsetting of interlayer
Glue or cenosphere play the contact for reducing graphene film, increase thermal resistance.It is formed between graphene layer with aeroge or cenosphere
Gap very little, barrier gas is in internal convection current.The present invention realizes low thermally conductive, inhibition air thermal convection, infrared external reflection, system
For thermal isolation film excellent out.And aeroge nano particle and/or cenosphere are packaged between graphene layer, product is asked without picking
Topic.
In order to which more deep illustrates essence of the invention, the preparation method of some graphene thermal isolation films is as follows
Specific embodiment.
In the method that following embodiment provides, graphene oxide and graphene used are purchased from the hexa-atomic element in Changzhou.Aoxidize stone
The technical requirements index of black alkene are as follows: graphene oxide carbon content within the scope of 48-60wt%, graphene oxide oxygen content 41~
Within the scope of 53wt%.Graphene is the graphene of oxidation-reduction method preparation.
Embodiment 1:
A kind of preparation of graphene thermal isolation film:
The graphene oxide of 5.40kg is added into 174.6kg water, using planetary stirring machine, 1000 turns/min, divides
30min is dissipated, at this time slurry fineness < 20μM, 20000~40000mPa.s of viscosity；
By 0.11kg hollow glass bead (partial size 1μM, wall thickness 0.2μM) it is added into 2.2kg water, stirs evenly, until
Gained suspension does not settle substantially.
By in hollow glass bead suspension in addition graphene oxide slurry, using 300 turns/min, disperses 1h, answered
Close slurry；
Above-mentioned composite mortar is subjected to continuous film deaeration, by base band as supporting, by the composite mortar after deaeration
In base band, coating thickness 2.0mm.Continuous film deaeration
Base band drives composite mortar to be dried into drying tunnel, and the drying temperature of drying tunnel is set as 75 DEG C, and drying time is
80 are obtained after 3h is dryμThe graphene oxide composite membrane of m thickness, graphene oxide composite membrane is separated from base band；It will be above-mentioned
Graphene oxide composite membrane is placed in heating device, is warming up to 160 DEG C with 0.01 DEG C/min, 160 DEG C at a temperature of handle
10h obtains the graphene thermal isolation film of 500 μ m-thicks, thermal coefficient 0.018W/m K, density 0.13g/cm3, resistance to compression 15MPa.
Embodiment 2:
A kind of preparation of graphene thermal isolation film:
The graphene oxide of 9.00kg is added into 171kgNMP, using planetary stirring machine, 800 turns/min, disperses
30min, at this time slurry fineness < 20μM, 20000~40000mPa.s of viscosity；
By 0.45kg aeroge (aerosil, it is also possible to which other aeroges replace, and the partial size of aeroge is
It 20nm) is added into 3.00kgNMP, stirs evenly, until gained suspension does not settle substantially；
By in gel suspension in addition above-mentioned graphene oxide slurry, using 500 turns/min, disperses 1h, obtain composite pulp
Material；
Above-mentioned composite mortar is subjected to continuous film deaeration, by base band as supporting, by the composite mortar after deaeration
In base band, coating 2.5mm is thick；
Base band drives composite mortar to be dried into drying tunnel, 90 DEG C, drying time 1h of the drying temperature of drying tunnel, dry
After obtain 100μThe graphene oxide composite membrane of m thickness, graphene oxide composite membrane is separated from base band；
Above-mentioned graphene oxide composite membrane is placed in heating device, 300 DEG C are warming up to 2 DEG C/min, in 300 DEG C of temperature
Degree is lower to handle 12h, obtains the graphene thermal isolation film of 800 μ m-thicks, thermal coefficient 0.016W/m K, density 0.10g/cm3, resistance to compression
11MPa。
Embodiment 3:
A kind of preparation of graphene thermal isolation film:
Water and NMP are configured to mixed solvent using the mass ratio of 80:20；
The graphene oxide of 14.4kg is added to 165.6kg in the mixed solvent, using planetary stirring machine, 1000 turns/
Min disperses 30min, at this time slurry fineness < 20μM, 20000~40000mPa.s of viscosity；
By 0.15kg hollow glass bead and aerosil (hollow glass bead: the matter of aerosil
Amount is than being 60:40, and hollow glass bead partial size is 5 μm, wall thickness is 1 μm, and the partial size of aerosil is 50nm) mixing
Object is added to 2.85kg in the mixed solvent, stirs evenly, until gained suspension does not settle substantially；
The suspension that upper cenosphere and aeroge are mixed is in addition in above-mentioned graphene oxide slurry, using 350 turns/
Min disperses 1h, obtains composite mortar；
Above-mentioned composite mortar is subjected to continuous film deaeration, by base band as supporting, by the composite mortar after deaeration
In base band, coating 3.0mm is thick；
Base band drives composite mortar to be dried into drying tunnel, 60 DEG C, drying time 2h of the drying temperature of drying tunnel, dry
After obtain 125μThe graphene oxide composite membrane of m thickness, graphene oxide composite membrane is separated from base band；
Above-mentioned graphene oxide composite membrane is placed in heating device, 200 DEG C are warming up to 1 DEG C/min, in 200 DEG C of temperature
Degree is lower to handle 3h, obtains the graphene thermal isolation film of 1000 μ m-thicks, thermal coefficient 0.015W/m K, density 0.15g/cm3, resistance to compression
20MPa.Its microstructure schematic diagram is referring to Fig. 1, including graphene 1, cenosphere 3 and aeroge 2,3 He of cenosphere
Aeroge 2 is distributed in the interlayer of the graphene 1 of the sheet, in the network formed between being packaged in graphene 1.
Embodiment 4:
A kind of preparation of graphene thermal isolation film:
Water and NMP are configured to mixed solvent using the mass ratio of 100:20；
The graphene oxide of 7.5kg and 1.5kg graphene are added to 171kg in the mixed solvent, using planetary stirring
Machine, disperses 90min, at this time slurry fineness < 20 by 300 turns/minμM, 20000~40000mPa.s of viscosity；
By 0.9kg ceramic hollow microballon and aerosil (ceramic hollow microballon: the quality of aerosil
Than for 1:1, hollow glass bead partial size is 50 μm, wall thickness is 2 μm, the partial size of aerosil is 100nm) mixing
Object is added to 29.1kg in the mixed solvent, stirs evenly, until gained suspension does not settle substantially；
By the mixing slurry of the mixing suspension of above-mentioned cenosphere and aeroge above-mentioned graphene oxide and graphene in addition
In material, using 450 turns/min, disperses 1h, obtain composite mortar；
Above-mentioned composite mortar is subjected to continuous film deaeration, by base band as supporting, by the composite mortar after deaeration
In base band, coating 2.0mm is thick；
Base band drives composite mortar to be dried into drying tunnel, 50 DEG C, drying time 2.5h of the drying temperature of drying tunnel, does
100 are obtained after dryμThe graphene oxide composite membrane of m thickness, graphene oxide composite membrane is separated from base band；
Above-mentioned graphene oxide composite membrane is placed in heating device, 300 DEG C are warming up to 0.01 DEG C/min, at 300 DEG C
At a temperature of handle 3h, obtain the graphene thermal isolation film of 300 μ m-thicks, thermal coefficient 0.016W/m K, density 0.15g/cm3 resist
Press 18.7MPa。
Embodiment 5:
A kind of preparation of graphene thermal isolation film:
Water and NMP are configured to mixed solvent using the mass ratio of 60:20；
By the graphene of the graphene oxide of 8.2kg and 0.8kg, it is added to 171kg in the mixed solvent, is stirred using planetary
Machine is mixed, 2200 turns/min, disperses 60min, at this time slurry fineness < 20μM, 20000~40000mPa.s of viscosity；
By 0.045kg hollow glass bead and aerosil (hollow glass bead: the matter of aerosil
Amount is than being 20:40, and hollow glass bead partial size is 15 μm, wall thickness is 0.5 μm, and the partial size of aerosil is 80nm)
Mixture is added to 0.255kg in the mixed solvent, stirs evenly, until gained suspension does not settle substantially；
The mixed slurry of the suspension that upper cenosphere and aeroge are mixed above-mentioned graphene oxide and graphene in addition
In, using 7000 turns/min, disperses 1h, obtain composite mortar；
Above-mentioned composite mortar is subjected to continuous film deaeration, by base band as supporting, by the composite mortar after deaeration
In base band, coating 2.5mm is thick；
Base band drives composite mortar to be dried into drying tunnel, 90 DEG C, drying time 1.5h of the drying temperature of drying tunnel, does
110 are obtained after dryμThe graphene oxide composite membrane of m thickness, graphene oxide composite membrane is separated from base band；
Above-mentioned graphene oxide composite membrane is placed in heating device, 250 DEG C are warming up to 2 DEG C/min, in 250 DEG C of temperature
Degree is lower to handle 2h, obtains the graphene thermal isolation film of 850 μ m-thicks, thermal coefficient 0.017W/m K, density 0.14g/cm3, resistance to compression
19.1MPa。
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (10)
1. a kind of preparation method of graphene thermal isolation film, which is characterized in that
Graphene carbon materials dispersion is mixed with heat-barrier material dispersion liquid liquid, obtains composite mortar；
The composite mortar passes through deaeration, coating, drying, forms composite membrane；With
The composite membrane is heat-treated, the functional group in graphene carbon materials is decomposed, ultimately forms graphene thermal isolation film.
2. the preparation method of graphene thermal isolation film according to claim 1, which is characterized in that the graphene carbon materials are oxygen
Graphite alkene and/or graphene；
Preferably, 48~60wt% of the graphene oxide carbon content, 41~53wt% of oxygen content；
It is further preferred that the graphene is the graphene of oxidation-reduction method preparation；
It it is further preferred that the graphene carbon materials are graphene oxide, or is in graphene oxide mixed with a small amount of graphite
The mixing of alkene, and the incorporation of graphene is according to mass ratio >=5 of graphene oxide and graphene；
It is further preferred that the graphene carbon materials are graphene oxide.
3. the preparation method of graphene thermal isolation film according to claim 1 or 2, which is characterized in that the graphene carbon materials
Graphene carbon materials described in dispersion and the first solvent, the content of the graphene carbon materials are 3-10wt%, preferably 8wt%；
Preferably, first solvent is selected from water and/or NMP, it is further preferred that first solvent be water and NMP according to
(3-5): 1 mass ratio is configured to mixed solvent, further preferential, and first solvent is the mass ratio of water and NMP according to 4:1
It is configured to mixed solvent；
It is further preferred that the graphene carbon materials system is prepared by the following method:
Graphene carbon materials are added in the first solvent, using planetary stirring machine, are stirred until homogeneous under 300-2200 turns/min,
Preferably, it stirs to 20 μm of slurry fineness <, 20000~40000mPa.s of viscosity；It is preferred that 60 ± 30min of stirring.
4. the preparation method of graphene thermal isolation film according to claim 1 or 2, which is characterized in that the heat-barrier material is
Cenosphere and/aeroge；
Preferably, the heat-barrier material is cenosphere, or to be mixed with the mixing material of aeroge, and gas in cenosphere
The mixed volume of gel presses cenosphere: mass ratio >=0.5 of aeroge；
It is further preferred that when the heat-barrier material is to be mixed with the mixing material of aeroge in cenosphere, the airsetting
The mixed volume of glue presses cenosphere: the mass ratio of aeroge is preferably >=1；
Optimal, the heat-barrier material is cenosphere: the mass ratio of aeroge is the mixing material of 3:2.
5. the preparation method of graphene thermal isolation film according to claim 1 or 2, which is characterized in that the heat-barrier material point
Granular media system includes heat-barrier material and the second solvent, and the content of the heat-barrier material is 3-15wt%, preferably 5wt%；
Preferably, second solvent is selected from water and/or NMP, it is further preferred that second solvent be water and NMP according to
(3-5): 1 mass ratio is configured to mixed solvent, further preferential, and second solvent is the mass ratio of water and NMP according to 4:1
It is configured to mixed solvent；
It is further preferred that the heat-barrier material dispersion is prepared by the following method:
Heat-barrier material is added in the second solvent, is stirred evenly, it is preferable that stirring is not settled to the stable liquid that poises is formed.
6. the preparation method of graphene thermal isolation film according to claim 1 or 2, which is characterized in that the cenosphere
Partial size is 1-50 μm, preferably 5 μm；
Preferably, the wall thickness of the air microballon is 0.2-2.0 μm, preferably 1.0 μm；
It is further preferred that the cenosphere is selected from hollow glass bead, ceramic hollow microballon；
And/or the partial size of the aeroge is 20-100nm, preferably 50nm；
It is further preferred that the aeroge is selected from aerosil.
7. the preparation method of graphene thermal isolation film according to claim 1 or 2, which is characterized in that the liquid liquid mixing
Method particularly includes: the proportionate relationship that graphene carbon materials 0.5-10wt% is accounted for according to heat-barrier material adds heat-barrier material dispersion
Enter into graphene carbon materials dispersion, is uniformly dispersed；Preferably, the heat-barrier material accounts for graphene carbon materials 1wt%；
Preferably, described be uniformly dispersed is completed using under the mixing speed of 300-1000rpmg.
8. the preparation method of graphene thermal isolation film according to claim 1 or 2, which is characterized in that the method for the deaeration
Are as follows: continuous film deaeration is stirred under vacuum deaeration；And/or
And/or the method for the coating are as follows: by base band as supporting, slurry blade coating or squash type are coated in base band；
Preferably, the coating thickness of the composite mortar is 2-3mm；
And/or the temperature of the drying is -90 DEG C of room temperature, dry 1-2h；
Preferably, the drying temperature is 50~90 DEG C, dry 1h；
Preferably, the composite membrane formed after the drying with a thickness of 80-150 μm.
9. the preparation method of graphene thermal isolation film according to claim 1 or 2, which is characterized in that the temperature of the heat treatment
Degree is 100-300 DEG C, constant temperature 2-12h under heat treatment temperature；Preferably, the heat treatment temperature is 200 DEG C, constant temperature 3h；
Preferably, constant temperature to composite membrane is expanded to a thickness of 300-1000 μm under heat treatment temperature；
Preferably, the heat treatment uses the heating rate of 0.01~2 DEG C/min, temperature is risen to the temperature of heat treatment, then permanent
Temperature.
10. a kind of graphene thermal isolation film, it is characterised in that: described hollow micro- including graphene and cenosphere and/or aeroge
Pearl and/or aeroge are distributed in the interlayer of the graphene, are packaged in the network formed between graphene film；
Preferably, the thermal coefficient of the graphene thermal isolation film is in 0.018W/m*K or less；And/or the graphene thermal isolation film
Density in 0.15g/cm3Below；And/or the compression strength of the graphene thermal isolation film is greater than 10MPa；
Preferably, the oxygen content of the graphene is 10~30wt%.
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