CN105491695A - Two-dimensional nano carbon heating body, and flexible electric heating module and preparation method therefor - Google Patents
Two-dimensional nano carbon heating body, and flexible electric heating module and preparation method therefor Download PDFInfo
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- CN105491695A CN105491695A CN201511029718.4A CN201511029718A CN105491695A CN 105491695 A CN105491695 A CN 105491695A CN 201511029718 A CN201511029718 A CN 201511029718A CN 105491695 A CN105491695 A CN 105491695A
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- 238000010438 heat treatment Methods 0.000 title claims abstract description 113
- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 53
- 238000005485 electric heating Methods 0.000 title abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 24
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 24
- 239000010410 layer Substances 0.000 claims description 51
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- 229910052751 metal Inorganic materials 0.000 claims description 13
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- 239000011248 coating agent Substances 0.000 description 1
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- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
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- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
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- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
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- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
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Classifications
-
- 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
- H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
- H05B3/34—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater flexible, e.g. heating nets or webs
-
- 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—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
-
- 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
- H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
- H05B2203/013—Heaters using resistive films or coatings
Landscapes
- Resistance Heating (AREA)
- Surface Heating Bodies (AREA)
Abstract
The invention discloses a two-dimensional nano carbon heating body, and a flexible electric heating module and a preparation method therefor. The two-dimensional nano carbon heating body comprises at least a membrane-shaped electric heating structure, and at least two flexible electrodes, wherein the membrane-shaped electric heating structure comprises a porous structure mainly formed by multiple layers of two-dimensional carbon nanotube networks, and the porous structure is positioned in a plane corresponding to the membrane-shaped electric heating structure; the conductivity of the membrane-shaped electric heating structure in a chosen direction is higher than the conductivity of the membrane-shaped electric heating structure in other directions different from the chosen direction; the at least two flexible electrodes are arranged at intervals in a set direction, and electrically connected with the membrane-shaped electric heating structure. The two-dimensional nano carbon heating body does not need to be combined with a substrate, so that the two-dimensional nano carbon heating body has the characteristics of lightness, thinness, ventilation and the like, and large-area preparation can be realized; therefore, when the two-dimensional nano carbon heating body is used for preparing the flexible electric heating module, characteristics of convenient cutting and processing, still high electric/thermal conversion efficiency, rapid temperature rise, uniform heating, high radiating efficiency, excellent electric heating stability and the like are achieved; and therefore, the two-dimensional nano carbon heating body is applicable to manufacturing of wearable products.
Description
Technical field
The present invention relates to a kind of electric heating goods, be specifically related to a kind of two-dimensional nano carbon heating body, flexible electrical heating module and preparation method thereof.
Background technology
Electric heating material is the material utilizing heating effect of current and produce heat energy, civilian and to be industrially widely used.Common thermo electric material can be divided into metal electric heating material and non-metal electrothermal material two class.Metal species thermo electric material mainly comprises noble metal (Pt), high temperature melting point metals (W, Mo, Ta, Nb) and alloy, nickel-base alloy and iron aluminum series alloy.Non-metal electrothermal material mainly contains carbon fiber, carborundum, Lanthanum Chromite, zirconia, molybdenum disilicide etc.All there are some problems in simple metal electric hot body and non-metal electrothermal material, such as, high-temperature creep resistance and Toughness lower, bend resistance, the anti-Flexible Ability such as to rub are all undesirable, especially metal species thermo electric material has corrosion resistance difference, and circuit Integrated manufacture process depends on strong acid etching and there is the shortcomings such as potential safety hazard.
In recent years, the nano-carbon material such as carbon nano-tube, Graphene, because all showing excellent performance in mechanics, electricity, calorifics, chemical stability etc., is also applied to preparing electric heating material and element gradually, and is more and more subject to the favor of researcher.Such as, the existing more report about the plane heat source, line heat source, electric heating fabrics etc. based on carbon nano-tube film, carbon nano-tube fibre etc. at present, these reports can consult CN101090586A, CN101400198A, CN101090586A, CN101192490A etc.But all more or less there are some defects in the application in these electrical heating elements existing etc.For the flexible electric heating material of nanometer disclosed in CN101090586A, wherein carbon nano-tube is dispersed in flexible substrate, if content of carbon nanotubes is high, then can there is serious agglomeration, cause the heating property of each local of this thermo electric material uneven, if content of carbon nanotubes is low, then the thermal response speed of this thermo electric material and electric conversion efficiency will be lower, heating temp is not high, and these flexible substrates can only selective polymer material, and temperature capacity is poor.Again for a kind of plane heat source that the researchers such as Fan Shoushan propose, it comprises a heating element, this heating element comprises the carbon nano tube structure of the self-supporting of matrix and one, described carbon nano tube structure comprises at least one deck carbon nano-tube laminate, the mutual part of carbon nano-tube adjacent in every one deck carbon nano-tube laminate is overlapping, and attracted each other by Van der Waals force, combine closely; At least two electrode gap arrange and are electrically connected with this heating element.In this plane heat source, carbon nano-tube need be joined integrally with certain thickness matrix, therefore light, thin, ventilative requirement may more difficultly be met on the one hand, another aspect is also more difficult realizes large-area plane heat source, also substantially cannot cut randomly according to the demand of practical application in use, well can not build softness, frivolous wearable heating product.
Summary of the invention
Main purpose of the present invention is to provide a kind of two-dimensional nano carbon heating body, flexible electrical to heat module and preparation method thereof, to overcome deficiency of the prior art.
For realizing aforementioned invention object, the technical solution used in the present invention comprises:
The embodiment provides a kind of two-dimensional nano carbon heating body, it comprises:
At least one membranaceous electrothermal structure, described membranaceous electrothermal structure comprises the loose structure formed primarily of multilayer two-dimension carbon nano tube network, the aperture of described membranaceous electrothermal structure contained hole is 1 ~ 100nm, porosity is more than 30%, and in the plane corresponding with described membranaceous electrothermal structure, described membranaceous electrothermal structure conductivity is in a selected direction greater than the conductivity of described membranaceous electrothermal structure on all the other directions being different from described preferential direction;
At least two flexible electrodes, these at least two flexible electrodes are arranged along described direction initialization interval, and are all electrically connected with described membranaceous electrothermal structure.
The embodiment of the present invention additionally provides a kind of flexible electrical heating module, and it comprises:
Nanometer heating layer, comprises described two-dimensional nano carbon heating body,
And, be directly incorporated into two flexible surface layer of the opposing both side surface of described nanometer heating layer;
Wherein at least one flexible surface layer be heat carrier and can make described two-dimensional nano carbon heating body in work time produce thermal radiation through, and when the temperature that these two flexible surface layer can tolerate all work with maximum service rating higher than described two-dimensional nano carbon heating body generation temperature.
The embodiment of the present invention additionally provides a kind of method preparing described flexible electrical heating module, and it comprises:
At least one described membranaceous electrothermal structure is provided, and this at least one membranaceous electrothermal structure is cut to required form;
Flexible electrode described at least two is provided, and these at least two flexible electrodes are arranged along described direction initialization interval, and these at least two flexible electrodes are all electrically connected with described membranaceous electrothermal structure, thus the two-dimensional nano carbon heating body described in forming;
Using described two-dimensional nano carbon heating body as nanometer heating layer, and described two flexible surface layer are directly fitted in the opposing both side surface of described nanometer heating layer.
Preferably, described preparation method also can comprise and suppresses by described nanometer heating layer and described two sandwich structures that flexible surface layer is formed and this triplicity all-in-one-piece is operated.
Compared with prior art, advantage of the present invention comprises: described two-dimensional nano carbon heating body, without the need to being combined with matrix, has the features such as light, thin, large area preparation can be realized, when making flexible electrical heating module, can cut randomly according to actual needs, being convenient to processing, and can still keep electricity/thermal conversion efficiency high, heat up rapidly, evenly, radiation efficiency is high in heating, the features such as electric stability is excellent, are particularly suited for preparing wearable heating health care product.
Accompanying drawing explanation
Fig. 1 is the SEM figure of a kind of carbon nano-tube film in the better embodiment of the present invention one;
Fig. 2 is the structural representation of a kind of two-dimensional nano carbon heating body in the better embodiment of the present invention one;
Fig. 3 is the structural representation of a kind of flexible electrical heating module in the comparatively typical embodiment of the present invention one;
Fig. 4 is the structural representation of another kind of flexible electrical heating module in the comparatively typical embodiment of the present invention one.
Embodiment
The exemplary embodiments embodying feature & benefits of the present invention will describe in detail in the following description.Be understood that the present invention can have various changes in different embodiments, it neither departs from the scope of the present invention, and explanation wherein and to be shown in be use when explain in essence, and be not used to limit the present invention.
Unless otherwise defined, all technology used herein and scientific terminology are identical with belonging to the implication that those skilled in the art of the present invention understand usually.The object of term used in the description of the invention herein just in order to describe specific embodiment, is not intended to be restriction the present invention.
A kind of two-dimensional nano carbon heating body provided in the first embodiment of the present invention comprises:
At least one membranaceous electrothermal structure, described membranaceous electrothermal structure comprises the loose structure formed primarily of multilayer two-dimension carbon nano tube network, the aperture of described membranaceous electrothermal structure contained hole is 1 ~ 100nm, porosity is more than 30%, and in the plane corresponding with described membranaceous electrothermal structure, described membranaceous electrothermal structure conductivity is in a selected direction greater than the conductivity of described membranaceous electrothermal structure on all the other directions being different from described preferential direction;
At least two flexible electrodes, these at least two flexible electrodes are arranged along described direction initialization interval, and are all electrically connected with described membranaceous electrothermal structure.
Described " two dimension " is the structure referring to and extend along two-dimensional directional, but it is not only confined to plane completely, and can be have certain thickness film, laminar structured etc.
Such as, in one specific embodiment, refer to Fig. 2, this two-dimensional nano carbon heating body can comprise membranaceous electrothermal structure 100 described in one and two flexible electrodes 200,300, these two flexible electrodes are arranged along described direction initialization (as indicated by the arrow) interval, and are electrically connected with described membranaceous electrothermal structure.
Wherein, after being connected with low-tension supply by these two flexible electrodes, electric current can pass through rapidly along these two flexible electrodes in described membranaceous electrothermal structure, thus orders about rapidly described membranaceous electrothermal structure generation heat and thermal radiation.
Wherein, the loose structure that should form primarily of multilayer two-dimension carbon nano tube network preferably can have the carbon nano-tube film of self supporting structure, and it is when without support body supports, still can keep self intrinsic form.The three-dimensional pore space structure of a large amount of aforementioned aperture scope that this carbon nano-tube film has, this carbon nano-tube film can be made under the prerequisite of maintenance higher force intensity (such as tensile strength is at more than 80MPa, resistance to rub) and better gas permeability to have less surface density (about 3 ~ 15g/m
2), more frivolous softness, also make this carbon nano-tube film keep lower surface resistance (on described preferential direction, conductance is 1.0 × 10 simultaneously
4more than s/m) and larger current current capacity (about 10 ~ 50A/mm
2), that is, ensure that it has comparatively high connductivity ability.
Further, the carbon nano-tube in this carbon nano-tube film comprise in Single Walled Carbon Nanotube, double-walled carbon nano-tube and multi-walled carbon nano-tubes one or more.
Comparatively preferred, this carbon nano-tube film can be adopt the large area carbon nano-tube film directly prepared by chemical vapour deposition technique, and this film can bending fold and cutting arbitrarily, and thickness can preferably be controlled in 3 ~ 50 μm, and surface density preferably can be controlled in 3 ~ 15g/m
2, there is light weight, softness, ventilative, the feature such as high conductivity, big current bearing capacity.Such as, the conductivity on described preferential direction about 1.0 × 10
4~ 1.0 × 10
6s/m, tensile strength is 80 ~ 200MPa about, refers to Fig. 1.
Such as, in an embodiment of the present invention, a kind of technique preparing described large area carbon nano-tube film with floating catalytic chemical vapour deposition technique can comprise:
1) carbon raw material, metallic catalyst and reaction promoter reactant are input in reactor by injection device.
2) in reaction vessel, carbon nano-tube is formed in the gas phase by catalytic pyrolysis.
3) by step 2) in the carbon nano-tube that formed spin mechanically, be wrapped on roller.
4) by step 3) in be wrapped in carbon nano-tube on cylinder through rolling in various degree, the carbon nano-tube film with different densities structure can be formed.
In above-mentioned steps, described injection device can adopt syringe pump, liquid ejector or ultrasonic atomizatio injection device, and injection mode can adopt single hole or porous series connection side-by-side configuration.
Described carbon raw material is hydrocarbon gas, carbonaceous organic material and mixed carbon source.Hydrocarbon gas comprises methane, ethene or acetylene etc.; Hydrocarbon organic substance comprises ethanol, acetone, ethylene glycol, ether, benzene or n-hexane and mixing etc.; Mixed carbon source comprises methane and methyl alcohol, ethene and methyl alcohol etc.
Described catalyst is ferrocene, iron chloride, iron sulfide, ferric sulfate, nickel oxalate etc., and the best is ferrocene or cobalt acetate.Described catalyst accounts for reactant mass percent 0.01 ~ 15%.
Described promoter is water, thiophene, acetic acid molybdenum etc.The consumption of promoter is the 0.01-10% of reactant quality.
Described reaction gas flow is 2000 ~ 8000 milliliters per minute.
Described temperature of reactor is 1000 ~ 1700 DEG C.
10 ~ 100 milliliters per hour of described hydrocarbon thing charge velocity.
In some embodiments, described membranaceous electrothermal structure also can comprise at least one layer graphene or the coat of metal of at least part of carbon nano tube surface being incorporated into the described loose structure of composition.By at carbon nano tube surface composite graphite alkene or metal, the conductivity of described membranaceous electrothermal structure also can be promoted further.
Wherein, described Graphene the mode of chemical bonding or physical absorption can be incorporated into described carbon nano tube surface, and can be single or multiple lift.Described chemical bonding mode can be realized by the method such as plasma treatment or high-temperature heat treatment.Described physical absorption can be realized by methods such as immersion, spraying or brushings.
The described coat of metal can be incorporated into described carbon nano tube surface by modes such as plating, chemical platings.
Described Graphene can be the graphene microchip etc. of graphene oxide, redox graphene, individual layer or few layer, and thickness is preferably 1 μm-3 μm.
The material of the described coat of metal can be nickel, nichrome etc., and thickness is preferably 0.1 μm ~ 5 μm.
In the present invention, the Infrared wavelength given off under "on" position based on the membranaceous electrothermal structure of previous designs is 3 μm ~ 25 μm, and wherein the ultrared wavelength of more than 90% is 3 μm ~ 16 μm, belong to the light region of the life that human body easily absorbs, as desirable IR emitting heating element, therefore can there is better health care.Further, described membranaceous electrothermal structure can tolerate the high temperature of 500 DEG C, and fire resistance can reach UL-94 standard V-0 rank.
In the present invention, based on the design temperature (design temperature is relevant with heating area) reaching rapidly less than 100 DEG C under the safety low-voltage driving that the membranaceous electrothermal structure of previous designs can be below 25V at voltage, and its programming rate is exceedingly fast, design temperature can be reached at 1 ~ 2 second; In the temperature range of 100 DEG C, along with the increase of heating time, the resistance value of described membranaceous electrothermal structure remains unchanged, and has excellent electric stability.
In some embodiments, described two-dimensional nano carbon heating body can comprise two or more aforementioned membranaceous electrothermal structure, according to the demand of practical application, these membranaceous electrothermal structures can be arranged side by side or stacked setting, also can be the overlapping set-up modes of part.Such as, when needing higher heating power, can by the stacked setting of multiple membranaceous electrothermal structures.Postscript, in view of aforementioned membranaceous electrothermal structure individual layer has anisotropic conductive attribute, can also by arranged in a crossed manner for these membranaceous electrothermal structures.Such as, if one of them membranaceous electrothermal structure conductivity is in a first direction greater than the conductivity of this membranaceous electrothermal structure on all the other directions being different from described first direction, another membranaceous electrothermal structure conductivity is in a second direction greater than the conductivity of this membranaceous electrothermal structure on all the other directions being different from described second direction, then these two membranaceous electrothermal structures can be crisscross arranged, make between this first direction with this second direction, to become to be greater than 0 ° and the angle being less than 180 °.
Wherein, the overlapping number of plies of aforementioned membranaceous electrothermal structure and overlapping intersecting angle will determine conductivity and the impedance of described two-dimensional nano carbon heating body, and then affect its heating power.
Postscript, described flexible electrode is the described membranaceous electrothermal structure for driving as heating layer.
Preferably, described flexible electrode is selected and is made up of electric conductivity and close one or more the flexible high conductivity material of conductive metal material, so that the connection of itself and described membranaceous electrothermal structure and power line.
Described flexible electrode can be one dimension or Two-dimensional morphology, and such as, the flexible electrode of one dimension can be flexible wire, and the flexible electrode of two dimension can be compliant conductive cloth or flexible conductive film etc., preferably adopts the latter.Such as, the compliant conductive cloth be suitable for or the thickness of flexible conductive film are preferably 10 ~ 30 μm, and square resistance is less than 20m Ω/.
For large-area described membranaceous electrothermal structure, for the benefit of it efficiently works, multiple flexible electrode can be adopted to coordinate with described membranaceous electrothermal structure, such as, plural number can be adopted flexible electrode, often pair of flexible electrode comprises one first flexible electrode and one second flexible electrode, and this first flexible electrode and this second flexible electrode are arranged along described direction initialization interval, and with described membranaceous electrothermal structure secure bond.This plural number alternate intervals can be arranged at the edge, periphery of described membranaceous electrothermal structure to flexible electrode.
Described flexible electrode can be combined with described membranaceous electrothermal structure by electrically conducting adhesive, or also can be combined by modes such as stitchings.In some embodiments, described flexible electrode also can by the regional area of described membranaceous electrothermal structure, and some regions of such as its circumference are directly formed, and in other words, described flexible electrode can be wholely set with described membranaceous electrothermal structure.
Further, for the benefit of described membranaceous electrothermal structure is connected with low-tension supply, also described flexible electrode and flexible power conductor can be connected by the mode such as fixing that bonds.The optional self-resistance value of described flexible power conductor is less than the metallization composite fibre or wire etc. of 1 Ω/m, such as silver-plated carbon nano-tube fibre, nickel-coated carbon fibers, copper carbon fiber, silver-plated carbon fiber, silver-plated aramid fiber, silver-plated polyester fiber etc., preferred nickel-coated carbon fibers.
The second embodiment of the present invention additionally provides a kind of flexible electrical heating module, and it mainly builds based on aforesaid two-dimensional nano carbon heating body.
In some embodiments, a kind of flexible electrical heating module can comprise:
Nanometer heating layer, comprises described two-dimensional nano carbon heating body,
And, be directly incorporated into two flexible surface layer of the opposing both side surface of described nanometer heating layer;
Wherein at least one flexible surface layer be heat carrier and can make described two-dimensional nano carbon heating body in work time produce thermal radiation through, and when the temperature that these two flexible surface layer can tolerate all work with maximum service rating higher than described two-dimensional nano carbon heating body generation temperature.
In some embodiments, described two-dimensional nano carbon heating body is covered completely by described two flexible surface layer, and is electrically connected with peripheral hardware low-tension supply by the flexible electrode that passes from described flexible surface layer and/or flexible power conductor.Two-dimensional nano carbon heating body so can be avoided outer and may the problems such as impaired or harm user is healthy because being exposed to, and promote the comfort of user.
Wherein, described flexible surface layer can be combined with described two-dimensional nano carbon heating body by the mode such as bonding, but the introducing of adhesives, may impact the physics of described two-dimensional nano material with carbon element, chemical property (such as affect its gas permeability, weaken its thermal radiation capability and conductance etc.), and the usual not resistant against high temperatures of these adhesivess, most probably at described two-dimensional nano carbon heating body with melting during high power work or decomposition, affect described flexible electrical heating module safety in utilization.Therefore, comparatively preferred, described membranaceous electrothermal structure and flexible surface layer directly can be fitted in the present invention, because of features such as described membranaceous electrothermal structure specific area are large, namely described membranaceous electrothermal structure and flexible surface layer the physical action such as to act on by Van der Waals force, π-π and are comparatively firmly combined.Further, after described membranaceous electrothermal structure and flexible surface layer are fitted, also can carry out pressing process to its combination, thus promote further described two-dimensional nano carbon heating body and flexible surface layer in conjunction with fastness, make it that there is ideal resistance to bending, rub resistance energy, meet the demand as Wearable device application.
In some embodiments, the capacity of heat transmission of a flexible surface layer in these two flexible surface layer is weaker than another flexible surface layer, the heat being beneficial to described two-dimensional nano carbon heating body is produced and thermal radiation are conducted to a direction initialization, and avoid heat and thermal radiation from deviating from this direction initialization, particularly run off in opposing all the other directions in this direction initialization, thus obtain better heating effect.
Such as, in some more specifically embodiment, refer to Fig. 3, in two flexible surface layer that described flexible electrical heating module comprises, a flexible surface layer comprises flexible water air-permeable layer 11 and flexible insulating layer, and another flexible surface layer comprises flexible water air-permeable layer, flexible insulating layer 13 and flexible insulating 12;
In described two flexible surface layer, described flexible water air-permeable layer is all distributed between described nanometer heating layer 10 and flexible insulating layer;
In another described flexible surface layer, described flexible insulating is distributed between described flexible water air-permeable layer and flexible insulating layer.
Or refer to Fig. 4, in other comparatively specific embodiment, described flexible insulating covers on described flexible insulating layer.
Wherein, the thickness of described nanometer heating layer is preferably 3 ~ 50 μm.
Wherein, utilize described flexible water air-permeable layer, water etc. can be intercepted and enter described two-dimensional nano carbon heating body, and ensure the normal work of described two-dimensional nano carbon heating body, and do not affect the gas permeability of described flexible electrical heating module.Described flexible water air-permeable layer can be selected from the known any suitable type of industry, can be such as in PES film, polytetrafluoroethylene film etc. any one or multiple, particularly can preferably from microporous teflon membran, its thickness is preferably 20 μm ~ 60 μm.
Wherein, utilize described flexible insulating layer, the safety in utilization of described two-dimensional nano carbon heating body can be ensured further, it can be selected from the suitable type known to industry equally, can be such as in the clothes such as nonwoven fabrics, looped fabric, woven fabric and the flexible inorganic such as silica gel, polyimide polyester or organic material any one or multiple, particularly be selected from the type wherein with fine air permeability, its thickness is preferably 0.1 ~ 0.2mm.
Wherein, utilize described flexible heat-insulating thermal insulation layer, effectively can intercept heat and the insignificant loss of thermal radiation of the generation in time working of described two-dimensional nano carbon heating body, promote efficiency of energy utilization, it can be selected from the suitable type known to industry equally, but it is comparatively preferred, it can select the aerogel material with good heat preservation and insulation and fine air permeability, particularly nanoporous aerogel heat preserving and insulating material, comprise silica type, Graphene class, sulphur class or metal oxide-type any one or multiple.Described flexible heat-insulating thermal insulation layer can be the coating etc. formed by modes such as spraying, brushing or roller coating, and its thickness is preferably 0.3 ~ 1.0mm.
Among some more preferred embodiments, the thickness of described flexible electrical heating module is 0.543 ~ 1.57mm.
The third embodiment of the present invention additionally provides a kind of method preparing described flexible electrical heating module, and it can comprise the steps:
(1) provide at least one described membranaceous electrothermal structure, and this at least one membranaceous electrothermal structure is cut to required size and shape;
(2) flexible electrode described at least two is provided, and these at least two flexible electrodes are arranged along described direction initialization interval, and these at least two flexible electrodes are all electrically connected with described membranaceous electrothermal structure, thus the two-dimensional nano carbon heating body described in forming;
(3) using described two-dimensional nano carbon heating body as nanometer heating layer, and described two flexible surface layer are directly fitted in the opposing both side surface of described nanometer heating layer.
Comparatively preferred, described method also comprises being suppressed by described nanometer heating layer and described two sandwich structure that flexible surface layer is formed and this triplicity all-in-one-piece is operated.The pressure wherein adopted and pressing time are can impel this triplicity aforesaid, and do not affect the inherent structure of wherein two-dimensional nano carbon heating body and form is advisable, such as preferably being controlled in temperature is 70 ~ 85 DEG C, and pressure is 8 ~ 15MPa, and pressing time is 1 ~ 5min.
In a word, two-dimensional nano carbon heating body of the present invention and flexible electrical heating module not only have very good mechanical properties, high conduction performance, superior anti-corrosion performance, rub resistance energy and wide spectrum infrared heating performance etc., and there is stable electrical hot property and high electric conversion efficiency and low power consumption usefulness, be particularly useful for heating clothes and health care facility application as flexible wearable formula.
Should be appreciated that disclosed is one or more of preferred embodiment, the change of every local or modification and come from technological thought of the present invention and be easy to by the people that is familiar with this technology to know by inference, all do not depart from patent right scope of the present invention.
Claims (11)
1. a two-dimensional nano carbon heating body, is characterized in that comprising:
At least one membranaceous electrothermal structure, described membranaceous electrothermal structure comprises the loose structure formed primarily of multilayer two-dimension carbon nano tube network, the aperture of described membranaceous electrothermal structure contained hole is 10 ~ 100nm, porosity is more than 30%, and in the plane corresponding with described membranaceous electrothermal structure, described membranaceous electrothermal structure conductivity is in a selected direction greater than the conductivity of described membranaceous electrothermal structure on all the other directions being different from described preferential direction;
At least two flexible electrodes, these at least two flexible electrodes are arranged along described direction initialization interval, and are all electrically connected with described membranaceous electrothermal structure.
2. two-dimensional nano carbon heating body according to claim 1, is characterized in that: described membranaceous electrothermal structure also comprises at least one layer graphene or the coat of metal of at least part of carbon nano tube surface being incorporated into the described loose structure of composition;
Preferably, in described membranaceous electrothermal structure, the thickness of graphene layer or the coat of metal is 0.1 μm-5 μm, and the described coat of metal is preferably made up of nickel.
3. two-dimensional nano carbon heating body according to claim 1, is characterized in that: the conductivity of described membranaceous electrothermal structure on described preferential direction is 1.0 × 10
4more than s/m, is preferably 1.0 × 10
4~ 1.0 × 10
6s/m, tensile strength is at more than 80MPa, and be preferably 80 ~ 200MPa, surface density is 3 ~ 15g/m
2, thickness is 3 ~ 50 μm, and the Infrared wavelength given off in the energized state is 3 μm ~ 25 μm, and wherein the ultrared wavelength of more than 90% is 3 μm ~ 16 μm.
4. two-dimensional nano carbon heating body according to claim 1, is characterized in that: described two-dimensional nano carbon heating body comprises membranaceous electrothermal structure described in two or more, and membranaceous electrothermal structure described in this two or more is arranged side by side or stacked setting.
5. two-dimensional nano carbon heating body according to claim 1, is characterized in that:
One of them membranaceous electrothermal structure conductivity is in a first direction greater than the conductivity of this membranaceous electrothermal structure on all the other directions being different from described first direction, another membranaceous electrothermal structure conductivity is in a second direction greater than the conductivity of this membranaceous electrothermal structure on all the other directions being different from described second direction, and becomes to be greater than 0 ° between this first direction with this second direction and be less than the angle of 180 °;
And/or described flexible electrode is selected from compliant conductive cloth or flexible conductive film, and thickness is 10 ~ 30 μm, and square resistance is less than 20m Ω/; And/or described flexible electrode is electrically connected with flexible power conductor, described flexible power conductor is selected from metallization composite fibre or wire, and resistance value is less than 1 Ω/m.
6. a flexible electrical heating module, is characterized in that comprising:
Nanometer heating layer, comprises the two-dimensional nano carbon heating body according to any one of claim 1-5,
And, be directly incorporated into two flexible surface layer of the opposing both side surface of described nanometer heating layer;
Wherein at least one flexible surface layer be heat carrier and can make described two-dimensional nano carbon heating body in work time produce thermal radiation through, and when the temperature that these two flexible surface layer can tolerate all work with maximum service rating higher than described two-dimensional nano carbon heating body generation temperature.
7. flexible electrical heating module according to claim 6, it is characterized in that: described two-dimensional nano carbon heating body is covered completely by described two flexible surface layer, and be electrically connected with peripheral hardware low-tension supply by the flexible electrode that passes from described flexible surface layer and/or flexible power conductor.
8. flexible electrical heating module according to claim 6, is characterized in that:
One of them flexible surface layer comprises flexible water air-permeable layer and flexible insulating layer, and another flexible surface layer comprises flexible water air-permeable layer, flexible insulating layer and flexible insulating;
In described two flexible surface layer, described flexible water air-permeable layer is all distributed between described nanometer heating layer and flexible insulating layer;
In another described flexible surface layer, described flexible insulating covers on described flexible insulating layer or is distributed between described flexible water air-permeable layer and flexible insulating layer.
9. flexible electrical heating module according to claim 8, it is characterized in that: the thickness of described flexible surface layer is 0.12mm ~ 1.26mm, and/or, the thickness of described flexible water air-permeable layer is 20 μm ~ 60 μm, and/or, the thickness of described flexible insulating layer is 0.1mm ~ 0.2mm, and/or, the thickness of described flexible insulating is 0.3mm ~ 1.0mm, and/or, the thickness of described flexible electrical heating module is 0.543 ~ 1.57mm, and/or the thickness of described nanometer heating layer is 3 ~ 50 μm.
10. prepare a method for flexible electrical heating module according to any one of claim 6-9, it is characterized in that comprising:
At least one described membranaceous electrothermal structure is provided, and this at least one membranaceous electrothermal structure is cut to required size and shape;
Flexible electrode described at least two is provided, and these at least two flexible electrodes are arranged along described direction initialization interval, and these at least two flexible electrodes are all electrically connected with described membranaceous electrothermal structure, thus the two-dimensional nano carbon heating body described in forming;
Using described two-dimensional nano carbon heating body as nanometer heating layer, and described two flexible surface layer are directly fitted in the opposing both side surface of described nanometer heating layer.
11. methods according to claim 10, characterized by further comprising and suppress by described nanometer heating layer and described two sandwich structures that flexible surface layer is formed and this triplicity all-in-one-piece is operated.
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