CN106255238B - A kind of graphene thermo electric material and its application - Google Patents
A kind of graphene thermo electric material and its application Download PDFInfo
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- CN106255238B CN106255238B CN201610079331.8A CN201610079331A CN106255238B CN 106255238 B CN106255238 B CN 106255238B CN 201610079331 A CN201610079331 A CN 201610079331A CN 106255238 B CN106255238 B CN 106255238B
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
- H05B3/146—Conductive polymers, e.g. polyethylene, thermoplastics
Abstract
The present invention provides a kind of graphene thermo electric material and its applications.A kind of graphene thermo electric material, mainly it is made of graphene, other carbon materials and solvent, wherein the weight ratio of graphene and other carbon materials is 0.5-10:1, it is preferred that 2-10:1, preferably 5-10:1, other carbon materials include one or more of combinations of carbon fiber, graphite, carbon nanotube, the preferred carbon fiber of other carbon materials.Graphene thermo electric material of the invention have many advantages, such as energy saving, light, flexibility is good, can large area use, not oxidizable, electrical and thermal conductivity performance is high, applied widely, can be used for manufacturing the multiple fields such as clothes, personal care, air equipment, Medical Devices, domestic heating equipment, automobile.
Description
Technical field
The present invention relates to thermo electric material fields, in particular to a kind of graphene thermo electric material and its application.
Background technique
With the continuous exhaustion of the non-renewable resources such as coal, petroleum, natural gas and getting worse for environmental pollution, grind
Studying carefully and developing renewable, green clean energy resource and its matched industrial goods, daily necessities seems especially urgent and important.Too
Positive energy, nuclear power, water power and wind-powered electricity generation substitution non-renewable resources are come under the overall background for power generation of generating heat, numerous industrial goods and daily necessities
Increasingly focus on energy-saving and emission-reduction.In addition, the demand with people's performance portable to product and wearable is promoted, it is low energy consumption, light
Integrated product has shown huge market potential.
Graphene is as emerging carbon material, while having electric-conductivity heat-conductivity high performance, with light, flexibility is good, can
The advantages that large area uses, is not oxidizable has far-infrared radiated property more outstanding than other carbon materials, manufactured heating
Component has the characteristics that sendible temperature is high, thermal comfort is good, therefore graphene has the characteristics of excellent thermo electric material.But city
It with the energy saving of thermo electric material made of graphene is not fine on face.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of graphene thermo electric material, and the graphene thermo electric material has light
Just, flexibility it is good, can large area use, the advantages that not oxidizable, electrical and thermal conductivity performance is high, applied widely, can be used for manufacturing
The multiple fields such as clothes, personal care, air equipment, Medical Devices, household electronic products, heating equipment, automobile.
The second object of the present invention be to provide the graphene thermo electric material as matrix surface electro-thermal coatings
Using the application improves the synthesis electric heating property of current material.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of graphene thermo electric material is mainly made of graphene, other carbon materials and solvent, wherein graphene and other
The weight ratio of carbon material is 0.5-10:1, preferably 2-10:1, preferably 5-10:1, other carbon materials include carbon fiber, graphite, carbon
One or more of combinations of nanotube, the preferred carbon fiber of other carbon materials.
By taking carbon fiber as an example, carbon fiber and graphene belong to carbon-based material, and the compatibility and associativity of the two are good, are not easy oxygen
Change, stability is good.For graphene/carbon fiber-incorporated slurry, carbon fiber has soft machinability, therefore with suitable
Ratio, which is mixed into carbon fiber, can improve the machinability of graphene, can be easy to process, be easily formed membrane structure, while again
The thermal conductivity of graphene will not be reduced, the two can cooperate with enhancing thermal conductivity instead, this is and existing graphene electricity
One of important difference of hot material, meanwhile, the introducing of carbon fiber can also reduce the cost of graphene thermo electric material, can promote
Using；Solvent can, reagent that compatibility good good, safe and harmless with optional dissolved degree, dosage according to actual needs depending on.In addition,
When carbon fiber carries out with matrix compound in advance, graphene, can be to attachment one stable conduction of offer of slurry as slurry
Supporter.
Similarly, other carbon materials such as graphene and graphite, carbon nanotube are mixed and made into thermo electric material also and can achieve and is above-mentioned
Technical effect.
Through examining, graphene conductive heat-conducting layer thermal conductivity of the invention can reach 1000W/m ﹒ k or more, and resistivity is 0.5
Ω/sq~5 Ω/sq (1-5V) can work in lower voltage range, compared with market Electric radiant Heating Film energy conservation 50%-70%.
Thermo electric material of the invention be mainly used under the heating under lower pressure, especially 1-5V high-temperature (room temperature~
130 DEG C) it works, certainly, if the modifying agent of addition is rationally, it can be used for hyperbaric heating.There are many its application methods, both may be used
With by printing, blade coating, spraying, dipping, pressing etc. process combinings play effect on the surface of other materials, can also with it is other
Material, which mixes together, is made Electric radiant Heating Film, such as paper pulp.
In addition, above-mentioned thermo electric material can be used for multiple fields, medical treatment, the heating of daily household goods folder both can be applied to
Layer, it can also be used to build warm, greenhouse of floor heating wall etc., can also be applied to the naval vessels to work under low temperature environment, vehicle, aircraft
Deng pipeline, instrument, components deicing.
Above-mentioned graphene thermo electric material can also be further improved:
Preferably, the concentration of the graphene is 2mg/mL~200mg/mL.
It is that such concentration has enough viscosityes first, solid difficulty is low, secondly in cost of material and conductive and heat-conductive
Higher cost performance, more preferably 50mg/mL~200mg/mL, 100mg/mL~150mg/mL can be obtained between property.
Preferably, the solvent is one of water, hydrophilic solvent or a variety of mixing.The cost of both solvents is low,
It is safe and harmless, it is suitable for a variety of matrixes, the hydrophilic solvent includes alcohols solvent, it is preferred that the alcohol is ethyl alcohol.
Preferably, the graphene thermo electric material further includes dispersing agent, and dispersing agent can improve graphene in the solution
Dispersion degree guarantees that cured structure has uniform physicochemical property；Preferably, the dispersing agent is total for phenylethylene-maleic anhydride
Polyester, polyvinylpyrrolidone, polyethenoxy ether metacrylic acid ester, polyoxyethylene ether acrylate, polyethenoxy ether propylene
One of acid esters, polyoxypropylene ether metacrylic acid ester or a variety of mixing.The above dispersing agent, which can achieve, makes slurry in water system
Solvent middle and high concentration and evenly dispersed effect.
Preferably, the graphene thermo electric material further includes modifying agent, to meet different demands, such as improves conductive, machine
The performances such as tool.
Preferably, the modifying agent is selected from one of far-infrared finishing agent, defoaming agent, adhesion promoter or a variety of；
The far-infrared finishing agent is selected from one of titanium oxide, zirconium oxide, yttrium oxide, zinc oxide, aluminium oxide or a variety of.
The normal emittance of the above far-infrared finishing agent reaches 0.85 or more, and product is made to have superior far infrared performance；
The defoaming agent is selected from one of silicone oil, tallow amide, aluminum stearate or a variety of.The above defoaming agent can increase
Add the mobility of slurry, coat the uniformity on carrier and improves the heating uniformity of electro-thermal coatings.
The adhesion promoter is selected from aminopropyl trimethoxysilane, dimethyl silicone polymer, acrylic acid bicyclic penta 2
One of allyl ester monomer is a variety of.The above adhesion promoter can be such that slurry is more firmly adhered on carrier.
Preferably, the graphene is biomass graphene.The biomass graphene is prepared by biomass；It is preferred that
The biomass graphene is prepared by the cellulose that biomass obtains.
The number of plies is more than 10 layers, the hexatomic ring honeycomb lamellar structure of thickness carbon within 100nm, referred to as graphene nanometer sheet
Layer；The number of plies prepared using biomass as carbon source is more than 10 layers, the hexatomic ring honeycomb lamellar structure of thickness carbon within 100nm,
Referred to as biomass graphene nano lamella；The number of plies is the hexatomic ring honeycomb lamellar structure of 1~10 layer of carbon, referred to as graphene；With
Biomass is that the number of plies of carbon source preparation is the hexatomic ring honeycomb lamellar structure of 1~10 layer of carbon, referred to as biomass graphene.
Graphene of the present invention includes graphene nano lamella and graphene, further comprises biomass graphene nano
Lamella and biomass graphene.
Graphene of the present invention can be obtained by different preparation methods, such as mechanical stripping method, epitaxial growth method, change
Vapor deposition method is learned, graphite oxidation reduction method can also be by biomass resource hydrothermal carbonization method, and in the prior art
The graphene of other method preparations.But no matter which kind of method large scale preparation all difficult to realize obtains stricti jurise theoretically
Graphene, such as to have certain impurity elements, other homoatomics of carbon in the obtained graphene of prior art preparation different
Body or the non-single layer of the number of plies even graphene-structured (such as 3 layers, 5 layers, 10 layers, 20 layers etc.) of multilayer, what the present invention was utilized
Graphene also includes the graphene on above-mentioned non-critical theory of meaning.
Preferably, any a kind or at least two kinds of of combination of the biomass in agriculture and forestry organic waste material and/or plant.
Preferably, the plant is any a kind or at least two kinds of of combination in needlebush and/or leaf wood.
Preferably, the agriculture and forestry organic waste material is cornstalk, corncob, kaoliang stalk, megasse, bagasse, furfural dregs, xylose
Any a kind or at least two kinds of of combination in slag, sawdust, cotton stalk, shell and reed.
Preferably, the agriculture and forestry organic waste material is corncob.
In addition to it is above-mentioned to the enumerating of biomass other than, biomass of the present invention can be those skilled in the art and can obtain
Any biomass resource known, the present invention do not continue to repeat.
Biomass graphene of the present invention refers to the graphene being prepared using biomass as carbon source, specifically with biology
Matter is that carbon source prepares process this field of graphene it has been reported that typical but non-limiting includes CN104724699A, this hair
It is bright to repeat no more.
Preferably, the graphene thermo electric material is plate, column or fabric shape.
The shape of graphene thermo electric material mainly determines by its purposes, for example, when for when making functional fabric, generally
For fabric shape；When being used for family or industrial heating, generally column, and generally plate when being used for the deicing of mechanical equipment.
It is of course also possible to be designed to arbitrary shape according to actual techniques demand or aesthetic.
The preparation method that sheet film shape is made in the above graphene thermo electric material, which may is that, mixes all raw materials according to formula
It is slurried, is then attached on carrier according to preset shape and technique, final curing or dry.It is also possible to: first by carbon
Fiber and matrix slurry (referring mainly to paper pulp) carry out composite papermaking, then the slurry that graphene is mixed into other auxiliary agents is according to pre-
If technique is attached on matrix, final curing or drying.
The application of graphene thermo electric material described above as matrix surface electro-thermal coatings is mainly used to improve material
Comprehensive electric heating property, makes material on the basis of having many advantages, such as that electrical and thermal conductivity performance is high, applied widely, also have it is light,
Flexibility is good, can large area the advantages that using, is not oxidizable.
Specific application method can improve as follows:
Preferably, the electro-thermal coatings further include the circuit layer of its surface printing.
The compatible materials of this structure are produced in enormous quantities, i.e., print multiple sons on the graphene conductive heat-conducting layer of large area
Circuit, then small element is cut into, and be easier to realize quality control.In addition, in order to improve circuit layer leading on graphene layer
Dispersion degree or viscosity that modifying agent improves graphene can also be added in electrical property when making graphene layer.
Preferably, phase-change material layers are adhered on the electro-thermal coatings surface, first by graphene thermo electric material and phase-change material
The advantages of combining, maximize favourable factors and minimize unfavourable ones, making full use of the two, the thermo electric material of composition had both had the excellent electric heating of graphene
Can, but also with good heat storage performance.Secondly, avoiding the performance interference between material using the tectonic relationship being layering.
When electro-thermal coatings surface printing circuit layer, layer printed circuit board can be directly and phase change material contacts, it can also be with
It is graphene layer and phase change material contacts, actual conditions adjustment can be regarded.
Preferably, the phase-change material layers are made of inorganic phase-changing material, organic phase change material goods polymeric phase change material；
Preferably, the inorganic phase-changing material is selected from one of sodium sulphate class, sodium acetate class, calcium chloride, phosphoric acid salt or a variety of,
The organic phase change material be selected from paraffin class, fatty acid or its lipid, higher aliphatic hydro carbons, alcohols, arene, amides and
One of polyhydroxy carbonic acid class is a variety of, and the polymeric phase change material polyolefins, polyene alcohols, is gathered polymeric polyalcohols
One of olefin(e) acid class, polyamide-based are a variety of.
In the above material, the solid-solid phase transition material layer scope of application is wider, avoids solid-liquid phase change material and is flowed by liquid
Limitation, and with polyalcohols solid-solid phase transition material layer be it is optimal, cost is relatively low.
Preferably, it is encapsulated between the electro-thermal coatings and the phase-change material layers with insulating materials, the phase-change material layers
Surface encapsulated with insulating materials, adding insulating protective layer is the safety in order to improve thermo electric material, to be directly used in people
Body.Plastics or resinous material can be used in insulating protective layer, according to application field difference, can add 1 ‰-in the insulating materials
3 ‰ oxytolerant heat-resistant agent, it is preferable that the oxytolerant heat-resistant agent be selected from diphenyl acrylate, 2,5- ditert-butylhydro quinone,
One of distearyl pentaerythritol diphosphite is a variety of.
Preferably, described matrix surface is welded with circuit layer.The setting position of circuit is generally depending on application field.
Preferably, described matrix includes needing to play the solid encasement of thermal effect, it is preferred that described matrix includes knitting
Object, building, Plastic, naval vessels, aircraft, deicing vehicle；Matrix is also depending on material applications, and the compound of interlayer can lead to
The techniques such as printing, blade coating, spraying, dipping and pressing are crossed to realize.
In addition, the application field of graphene thermo electric material is different according to the present invention, compound method has with other materials
Institute is different, generally uses following two method:
Method one is printed on the graphene layer surface mainly for circuit layer, including the following steps:
Step A: according to the formula of the graphene conductive heat-conducting layer, all raw materials are mixed to prepare graphene slurry；
Step B: by the graphene impregnating slurry, printing, the surface for spraying or pressing to the base layer, shape after drying
At graphene layer；
Step C: in the surface printing circuit of the graphene layer, circuit layer is formed；
Step D: dipping, printing, spraying or pressing phase-change material on the surface of the circuit layer obtain product.
It preferably, further include the surface encapsulation in phase-change material after dipping, printing, spraying or pressing phase-change material
Thermal insulation layer.
Preferably, method dry in step B are as follows: drying or vacuum drying.
Method two is welded on matrix mainly for circuit layer, including the following steps:
Step I: according to the formula of the graphene conductive heat-conducting layer, all raw materials are mixed to prepare graphene slurry；
Step II: in the surface printing circuit of matrix, circuit layer is formed；
Step III: by the graphene impregnating slurry, printing, the surface for spraying or pressing to described matrix, shape after drying
At graphene layer；
Step IV: dipping, printing, spraying or pressing phase-change material on the surface of the graphene layer obtain product.
Preferably, after the step of forming graphene layer and dipping, printing, spraying or pressing phase-change material the step of it
Before further include: in the surface encapsulation insulating protective layer of the graphene layer.
Above two method can be achieved by conventional mechanical equipment, and process is simple, therefore easy to accomplish extensive
Production.
It in addition is to be blended in the slurry of graphene thermo electric material and matrix slurry (referring mainly to paper pulp) there are also a kind of situation
Together, it is then cured into integral structure, forms Electric radiant Heating Film；Or carbon fiber is individually mixed with matrix slurry (referring mainly to paper pulp)
Solidification is used as carrier together, and graphene thermo electric material slurry is then formed Electric radiant Heating Film by being impregnated into matrix and drying.
The preparation method of graphene thermo electric material spin-off, material impossible to exhaust therefore of the invention are only listed above
Material is not to be limited within the scope of use above.
Compared with prior art, the invention has the benefit that
(1) it is strong that type can be processed in material softness；
(2) thermal conductivity of material is excellent；
(3) material has good heat storage performance；
(4) material energy conservation and environmental protection；
(5) material has a wide range of application；
(6) light portable；
(7) material preparation method is simple, is suitable for industrialized production.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the structure for the thermo electric material that the embodiment of the present invention 3 provides；
Fig. 2 is a kind of structure of thermo electric material provided by the invention；
Fig. 3 is a kind of structure of thermo electric material provided by the invention；
Fig. 4 is the structure for the thermo electric material that the embodiment of the present invention 4 provides；
Appended drawing reference:
1- base layer；2- electrode；The thermally conductive layer of 3- containing graphene
4- thermal insulation layer 5- phase-change material layers 6- insulating protective layer
7- circuit layer.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
The percentage of added various modifying agent is referred both to relative to slurry total amount in Examples below.
Prepare graphene A:
First prepare cellulose:
(1) dense for the formic acid of 80wt% and the organic acid solution pair of acetic acid using total acid by after wheat straw comminution pretreatment
Treated, and wheat straw carries out boiling, and the mass ratio of acetic acid and formic acid is 1:12 in the organic acid solution of the present embodiment, and is being added
Hydrogen peroxide (the H for accounting for wheat straw raw material 1wt% is added before entering raw material2O2) it is used as catalyst, 120 DEG C of reaction temperature are controlled, instead
30min, solid-liquid mass ratio 1:10 are answered, and obtained reaction solution is subjected to first time separation of solid and liquid；
(2) being separated by solid-liquid separation obtained solid for the first time, that total acid is added is dense for the formic acid of 75wt% and the organic acid solution of acetic acid
Acid elution is carried out, wherein joined the peroxide for accounting for wheat straw raw material 8wt% in the dense organic acid solution for 75wt% of above-mentioned total acid
Change hydrogen (H2O2) it as the mass ratio of catalyst and acetic acid and formic acid is 1:12, controlled at 90 DEG C, wash time 1h, solid-liquid
Mass ratio is 1:9, and reaction solution is carried out second and is separated by solid-liquid separation；
(3) it collects for the first time and is separated by solid-liquid separation obtained liquid for the second time, high temperature and pressure is carried out under 120 DEG C, 301kPa
Obtained formic acid and acetic acid vapor are condensed back into the reaction kettle of step (1) as cooking liquor, use until being evaporated by evaporation
Boiling in step (1)；
(4) it collects and is separated by solid-liquid separation obtained solid for the second time, and washed, control washing temperature is 80 DEG C, washing slurry
Dense is 6wt%, and obtained washing slurry is carried out third time separation of solid and liquid；
(5) it collects and is separated by solid-liquid separation obtained liquid for the third time, carry out water, sour rectifying, obtained mix acid liquor is back to step
Suddenly the boiling of step (1) is used in the reaction kettle of (1) as cooking liquor, obtained water to be back to step (5) and water is washed with water；
(6) it collects and is separated by solid-liquid separation obtained solid for the third time and is screened to obtain required screened stock cellulose.
Then graphene is prepared as raw material using the cellulose being prepared as above:
(1) 1:1 cellulose mixture and frerrous chloride in mass ratio, stirring carries out catalytic treatment 4h at 150 DEG C, it is dry extremely
Presoma moisture content 10wt%, obtains presoma；
(2)N2In atmosphere, presoma is warming up to 170 DEG C with 3 DEG C/min rate, keeps the temperature 2h, temperature programming later to 400
DEG C, 3h is kept the temperature, is warming up to 1200 DEG C later, obtains crude product after keeping the temperature 3h；The heating rate of described program heating is 15 DEG C/min；
At (3) 55~65 DEG C, by crude product through over-richness be 10% sodium hydroxide solution, 4wt% chlorohydric acid pickling after, water
It washes to obtain biomass graphene, is denoted as graphene A.
Prepare biomass graphene B:
Using the method for embodiment 10 in the patent of Publication No. CN104724696A, specifically: stalk is collected, processing is dry
Small pieces are shredded into after net, is immersed in ethanol solution, is at the uniform velocity stirred 5 hours with the revolving speed of 100r/min；Then solution is shifted
Into supercentrifuge, revolving speed is set as 3000r/min, and centrifugation time is 20 minutes, after take the broken sample of lower layer.Normal temperature and pressure
Under, broken sample is fitted into the Tissue Culture Dish that diameter is 15cm, is placed in air inlet, adjust flow parameter, setting wind speed is 6m/
S, air quantity 1400m3/ h is kept for ventilation state 12 hours；Tube furnace is warming up to 1300 DEG C, is passed through inert gas shielding, keeps
30 minutes；Broken sample after drying is placed in tube furnace, heats 5 hours, after being cooled to room temperature, it is obvious to obtain overburden ratio
Biomass graphene is denoted as graphene B.
Prepare graphene C:
Using the method for embodiment 1 in the patent of Publication No. CN105217621A, specifically:
(1) by the mixing of 2g graphite powder and 3g potassium dithionate, 3g phosphorus pentoxide and the 12mL concentrated sulfuric acid in reactor
It reacts in system, is stirred 4 hours under 80 DEG C of water bath conditions, until forming dark blue solution, obtain pre- oxygen after cooling, suction filtration, drying
The graphite of change；
(2) take graphite oxide 2g obtained by step (1) in three-neck flask, it is dense with 150mL under conditions of ice-water bath
Sulfuric acid solution is gradually added into the potassium permanganate of 25g, stirs 2 hours；
(3) three-neck flask of above-mentioned steps (2) is transferred to oil bath, is warming up to 35 DEG C, stirred 2 hours, continue stirring and by
The mixed solution of 30wt% hydrogen peroxide and deionized water is added according to the amount that volume ratio is 1:15；It filters, respectively with 4mL mass point
Number cleans 1 time for 10% dilute hydrochloric acid and deionized water, and centrifugation obtains the graphene oxide aoxidized for the first time after dry；
(4) the graphene oxide 2g prepared in step (3) is molten with the concentrated sulfuric acid of 50mL under conditions of ice-water bath again
Liquid is mixed in three-neck flask, is gradually added into the KMnO of 8g4, stir 1 hour；
(5) three-neck flask of above-mentioned steps (4) is transferred to oil bath, is warming up to 40 DEG C, stirred 1 hour, then proceed to heat up
To 90 DEG C, after stirring 1 hour, continues stirring and 30wt% hydrogen peroxide and deionized water is added according to the amount that volume ratio is 1:7
Mixed solution, it is cooling after continuing stirring 6 hours, filter, respectively with 4mL mass fraction be 10% dilute hydrochloric acid and deionized water
Cleaning 2 times, centrifugation obtain the graphene oxide of size uniformity after dry, are denoted as graphene C.
Embodiment 1:
(1) graphene A and carbon fiber are equipped with the styrene-of a certain amount of dispersing agent 1wt% according to the ratio of 0.5:1
Maleic anhydride ester, 0.1wt% silicone oil and 2wt% aminopropyl trimethoxysilane and be dissolved in ethyl alcohol, obtain concentration be
The graphene composite material slurry of 2mg/mL.
(2) above-mentioned slurry is sprayed at naval vessels ship pipeline, satellite antenna, the surfaces such as aircraft, automobile component are sufficiently done
It is dry.
(3) heating film for finishing above-mentioned drying accesses low-voltage circuit.
(4) Yu Jiare film surface sprays one layer of thermally conductive protective layer.
The present embodiment can be applied to the pipeline, instrument, components of the naval vessels to work under low temperature environment, vehicle, aircraft etc.
Deicing.(1~5V) purpose that surface is quickly heated can be realized under the conditions of small voltage.
Embodiment 2:
(1) graphene A is mixed with carbon fiber with the ratio uniform of 2:1, is equipped with the benzene second of a certain amount of dispersing agent 1wt%
Alkene-maleic anhydride ester, 0.1wt% silicone oil and 2wt% aminopropyl trimethoxysilane and be dissolved in ethyl alcohol, obtain concentration
For the graphene composite material slurry of 10mg/mL.
(2) above-mentioned slurry is sprayed at naval vessels ship pipeline, satellite antenna, the surfaces such as aircraft, automobile component are sufficiently done
It is dry.
(3) heating film for finishing above-mentioned drying accesses low-voltage circuit.
(4) Yu Jiare film surface sprays one layer of thermally conductive protective layer.
The present embodiment can be applied to the pipeline, instrument, components of the naval vessels to work under low temperature environment, vehicle, aircraft etc.
Deicing.(1~5V) purpose that surface is quickly heated can be realized under the conditions of small voltage.
Embodiment 3
(1) graphene A and carbon fiber is compound with the ratio uniform of 3:1, the far-infrared finishing agent (oxygen of 0.5wt% is added
Change titanium), and be added 1wt% styrene-maleic anhydride copolymer ester, the silicone oil of 0.1wt% and 2% aminopropyl trimethoxy silicon
Alkane is well-dispersed in water, obtains the slurry of 100mg/mL.
(2) welding copper chaff is pressed as electrode at fabric lining both ends.
(3) slurry is coated uniformly on the formation of fabric lining surface with a thickness of the film of 0.1mm, dries or forms stone after drying
Black alkene radiates heating film.
(4) degasification is then once encapsulated using conductive plastic material.
(5) it cuts, mill target, obtain wiring solder joint, close contact using insulating materials after wiring.
(6) after stacking is with a thickness of phase-change material (sodium acetate) film of 0.5mm outside the heat-conducting plastic, using insulating layer into
Row entirety secondary encapsulation.
The present embodiment, which obtains, has excellent far-infrared functional, the Electric radiant Heating Film that heat storage capacity is good, energy saving, resistance value is stable, favorably
It is comfortable in human health.It can be applied to the heating interlayer of medical treatment, daily household goods.
The product structure that the embodiment obtains is as shown in Figure 1, include base layer 1 (i.e. fabric lining), electrode 2, graphitiferous
The thermally conductive layer 3 of alkene, thermal insulation layer 4, phase-change material layers 5, insulating protective layer 6.
On this basis, it can also be symmetrical arranged thermal insulation layer 4 in the lower surface of base layer 1, as shown in Figure 2；Or
The lower surface of base layer 1 be symmetrical arranged thermal insulation layer 4, phase-change material layers 5, as shown in Figure 3.
Embodiment 4:
(1) graphene A is mixed with carbon fiber with the ratio uniform of 5:1, is equipped with the polyvinyl pyrrole of a certain amount of 2wt%
Alkanone, the tallow amide of 0.05wt% and 1wt% dimethyl silicone polymer and be dissolved in ethyl alcohol, acquisition concentration be 150mg/
The graphene composite material slurry of mL.
(2) ratio of heat-resisting paper pulp and above-mentioned biomass graphene slurry 1:1 is combined heat-resisting conductive paper, thickness can
Regulated and controled according to actual needs.
(3) go out electrode and route in heat-resisting conductive paper surface printing using copper slurry (silver paste).Film production is then heated to finish.
(4) the polyalcohols solid-solid phase transition material film (pentaerythrite PE) of suitable phase transition temperature is selected to be fitted in heating
Film surface.
(5) degasification, then using insulating layer carry out overall package.
The heating film that the present embodiment obtains is light, and flexibility is good, is suitable for small work voltage power supply, operating temperature is suitable for people
Body is born.It can be widely applied to clothes, personal care's wearable items.
The product structure that the embodiment obtains is as shown in figure 4, include the thermally conductive layer 3 of containing graphene, circuit layer 7, phase
Change material layer 5, insulating protective layer 6.
Embodiment 5:
(1) by graphene A and carbon fiber according to the ratio of 10:1, be equipped with 0.5wt% polyethenoxy ether acrylate,
The silicone oil of 0.1wt% and the aminopropyl trimethoxysilane of 2wt% are simultaneously soluble in water, and 0.1% far-infrared finishing is then added
Agent (titanium oxide) obtains the graphene composite mortar that concentration is 100mg/mL.
(2) fabric lining, foamed material are sufficiently impregnated in above-mentioned slurry, then pass through extruding or filtering, drying etc.
Processing step.
(3) phase-change material (pentaerythrite PE) then is sprayed on the graphene layer surface of drying.
Above-mentioned fabric lining or foamed material are respectively applied to the inner surface or interlayer of clothing, filler, it can be according to reality
Border situation chooses whether external circuits.
The present embodiment applies the far-infrared radiated property and bacteriostasis property of biomass graphene itself, improve clothing,
The body-sensing comfort of the type products such as automotive seat and warming increase warm up performance.
Embodiment 6:
(1) graphene B is mixed with carbon fiber with the ratio uniform of 5:1, is equipped with the benzene second of a certain amount of dispersing agent 1wt%
Alkene-maleic anhydride ester, 0.1wt% silicone oil and 2wt% aminopropyl trimethoxysilane and be dissolved in ethyl alcohol, obtain concentration
For the graphene composite material slurry of 50mg/mL.
(2) above-mentioned slurry is sprayed at naval vessels ship pipeline, satellite antenna, the surfaces such as aircraft, automobile component are sufficiently done
It is dry.
(3) heating film for finishing above-mentioned drying accesses low-voltage circuit.
(4) Yu Jiare film surface sprays one layer of thermally conductive protective layer.
The present embodiment can be applied to the pipeline, instrument, components of the naval vessels to work under low temperature environment, vehicle, aircraft etc.
Deicing.(1~5V) purpose that surface is quickly heated can be realized under the conditions of small voltage.
The present embodiment has the structure of similar embodiment 4.
Embodiment 7:
(1) graphene C is mixed with carbon fiber with the ratio uniform of 5:1, is equipped with a certain amount of dispersing agent 0.5wt% polyoxy
Ethylene ether metacrylic acid ester, the aluminum stearate of 0.01wt% and 3% acrylic acid dicyclopentadiene ester monomer are simultaneously soluble in water,
Obtain the graphene composite material slurry that concentration is 100mg/mL.
(2) the far-infrared finishing agent (aluminium oxide) that 3% is added in Xiang Shangshu biomass graphene slurry, as conductive oil
Ink, by ink print on heat resistant plastice substrate.
(3) then use copper slurry or silver paste printing electrode or directly pressing copper foil as electrode.
(4) degasification is then once encapsulated using conductive plastic material.
(5) it cuts, mill target, obtain wiring solder joint, close contact using insulating materials after wiring.
(6) select the solid-solid phase transition material (pentaerythrite PE) of suitable phase transition temperature film adhered in heating film surface.
(7) degasification, then using insulating layer carry out overall package.
The present embodiment, which obtains, has excellent far-infrared functional, heat storage capacity good, energy-efficient heating Electric radiant Heating Film for building.Have
Electric conversion efficiency is high, and radiant heat accounting example is big, the feature that sendible temperature is high, thermal comfort is good.Warm suitable for building floor heating wall,
Greenhouse etc..
The present embodiment has the structure of similar embodiment 3.
Embodiment 8:
(1) graphene A is mixed with graphite with the ratio uniform of 5:1, is equipped with the polyvinylpyrrolidine of a certain amount of 2wt%
Ketone, the tallow amide of 0.05wt% and 1wt% dimethyl silicone polymer and be dissolved in ethyl alcohol, acquisition concentration be 150mg/mL
Graphene composite material slurry.
(2) ratio of heat-resisting paper pulp and above-mentioned biomass graphene slurry 1:1 is combined heat-resisting conductive paper, thickness can
Regulated and controled according to actual needs.
(3) go out electrode and route in heat-resisting conductive paper surface printing using copper slurry (silver paste).Film production is then heated to finish.
(4) the polyalcohols solid-solid phase transition material film (pentaerythrite PE) of suitable phase transition temperature is selected to be fitted in heating
Film surface.
(5) degasification, then using insulating layer carry out overall package.
The heating film that the present embodiment obtains is light, and flexibility is good, is suitable for small work voltage power supply, operating temperature is suitable for people
Body is born.It can be widely applied to clothes, personal care's wearable items.
Embodiment 9:
(1) graphene A is mixed with carbon nanotube with the ratio uniform of 5:1, is equipped with the polyethylene pyrrole of a certain amount of 2wt%
Pyrrolidone, the tallow amide of 0.05wt% and 1wt% dimethyl silicone polymer and be dissolved in ethyl alcohol, obtain concentration be
The graphene composite material slurry of 150mg/mL.
(2) ratio of heat-resisting paper pulp and above-mentioned biomass graphene slurry 1:1 is combined heat-resisting conductive paper, thickness can
Regulated and controled according to actual needs.
(3) go out electrode and route in heat-resisting conductive paper surface printing using copper slurry (silver paste).Film production is then heated to finish.
(4) the polyalcohols solid-solid phase transition material film (pentaerythrite PE) of suitable phase transition temperature is selected to be fitted in heating
Film surface.
(5) degasification, then using insulating layer carry out overall package.
The heating film that the present embodiment obtains is light, and flexibility is good, is suitable for small work voltage power supply, operating temperature is suitable for people
Body is born.It can be widely applied to clothes, personal care's wearable items.
The mainly thermo electric material of plate or fabric shape that above embodiments 1 to 9 are directed to, Coating combination is mainly using spraying
Technique can also use process for pressing when practical operation, but also thickener can be added reduce pressing difficulty, and for column
The auxiliary agent and condition that the material of (i.e. electric wire), the sequencing of technique and every step process are added are referred to above-described embodiment, but
It is that combination method between every layer more preferably uses infusion process, for example, graphene layer is impregnated into phase-change material, makes corresponding liquid
Physical efficiency is uniformly attached to graphene layer surface.
Experimental example
Test above embodiments 1-9 obtain product in graphene layer electric heating property, using heating technique index (according to
The detection of GB/T4564-2008 nonmetal basal body infrared radiation heater general technical specifications), and compared with the prior art, it is main
Comparative indices are wanted to have: electrical power density；Radiating surface electric-thermal radiates conversion ratio (it is required that being not less than 50%)；Radiating surface temperature is uneven
Even degree (highest temperature and minimum temperature difference requirement are not more than 7 DEG C), the percentage for being used herein as the highest temperature and lowest temperature difference carry out table
Show.In addition in the following table 1 also to the heating-up time (be energized to the time of the highest temperature 90%, it is desirable that be not more than 10min) and resistivity into
It has gone and has compared.
Reference examples 1:
(1) carbon fiber and long fiber paper pulp are subjected to papermaking directly as heating film according to the ratio of 3:7.
(2) heating film for finishing above-mentioned drying accesses low-voltage circuit.
(3) Yu Jiare film surface presses one layer of thermally conductive protective layer.
1 test result of table
Wherein, embodiment 1-9 is realized at voltage 1-5V.For reference examples 1 also to measure under 1-5V, reference examples 2 are former
It is not referred in patent, reference examples 3 could then work under 220V or 380V voltage.By comparison, the control of graphene is not added
The either resistance of example 1 or non-uniform temperature degree are all significantly higher, and electric radiation transfer efficiency is relatively low；In reference examples 2
Parameter is less detailed, but can be seen that its energy saving is far below this patent；Reference examples 3 are that the product of purchase enterprise adds after actual measurement
Hot degree of irregularity is higher, and operating voltage is higher, and heating rate is also relatively slow.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (14)
1. a kind of application of graphene thermo electric material as matrix surface electro-thermal coatings, which is characterized in that the grapheme material
It is made of graphene, other carbon materials, solvent, dispersing agent and modifying agent, wherein the weight ratio of graphene and other carbon materials is
0.5-10:1, other carbon materials are one or more of combinations of carbon fiber, graphite；
The dispersing agent be styrene-maleic anhydride copolymer ester, polyvinylpyrrolidone, polyethenoxy ether metacrylic acid ester,
One of polyoxyethylene ether acrylate, polyethenoxy ether acrylate, polyoxypropylene ether metacrylic acid ester are a variety of mixed
It closes；
The concentration of the graphene is 2mg/mL~200mg/mL；
Phase-change material layers are adhered on the electro-thermal coatings surface；
The phase-change material layers are made of inorganic phase-changing material, organic phase change material or polymeric phase change material；
The inorganic phase-changing material is selected from one of sodium sulphate class, sodium acetate class, calcium chloride, phosphoric acid salt or a variety of, institute
It states organic phase change material and is selected from paraffin class, fatty acid or its lipid, higher aliphatic hydro carbons, alcohols, arene, amides and more
One of hydroxy carbonate class is a variety of, the polymeric phase change material polyolefins, polymeric polyalcohols, polyene alcohols, polyene
One of acids, polyamide-based are a variety of；
It is encapsulated between the electro-thermal coatings and the phase-change material layers with insulating materials, the surface insulation of the phase-change material layers
Material package；
Oxytolerant heat-resistant agent containing ‰ -3wt ‰ of 1wt in the insulating materials；
The oxytolerant heat-resistant agent is selected from diphenyl acrylate, 2,5- ditert-butylhydro quinone, two hard ester group pentaerythrites two
One of phosphite ester is a variety of.
2. application according to claim 1, which is characterized in that the weight ratio of graphene and other carbon materials is 2-10:1.
3. application according to claim 1, which is characterized in that the weight ratio of graphene and other carbon materials is 5-10:1.
4. application according to claim 1, which is characterized in that other carbon materials are carbon fiber.
5. application according to claim 1, which is characterized in that the concentration of the graphene is 50mg/mL~200mg/mL.
6. application according to claim 1, which is characterized in that the concentration of the graphene is 100mg/mL~150mg/
mL。
7. application according to claim 1, which is characterized in that the solvent be water, hydrophilic solvent it is one or more
Mixing, the hydrophilic solvent includes alcohols solvent.
8. application according to claim 7, which is characterized in that the alcohol is ethyl alcohol.
9. application according to claim 1, which is characterized in that the modifying agent is far-infrared finishing agent, defoaming agent, attachment
One of power promoting agent is a variety of.
10. application according to claim 9, which is characterized in that the far-infrared finishing agent be selected from titanium oxide, zirconium oxide,
One of yttrium oxide, zinc oxide, aluminium oxide are a variety of, and the defoaming agent is in silicone oil, tallow amide, aluminum stearate
One or more, the adhesion promoter is selected from aminopropyl trimethoxysilane, dimethyl silicone polymer, acrylic acid bicyclic penta
One of two allyl ester monomers are a variety of.
11. application according to claim 1, which is characterized in that the electro-thermal coatings further include the circuit of its surface printing
Layer.
12. -11 described in any item applications according to claim 1, which is characterized in that described matrix includes needing to play heating to make
Object.
13. -11 described in any item applications according to claim 1, which is characterized in that described matrix includes fabric, building, modeling
Expect class, naval vessels, aircraft, deicing vehicle.
14. -11 described in any item applications according to claim 1, which is characterized in that described matrix and the electro-thermal coatings are answered
Conjunction method is selected from printing, blade coating, spraying, dipping and pressing.
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| CN111609454B (en) * | 2020-05-08 | 2022-04-08 | 安徽宇航派蒙健康科技股份有限公司 | Electric heating picture and preparation method thereof |
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