CN105657877A - Super-stretchable graphene electro-thermal film and preparation method thereof - Google Patents
Super-stretchable graphene electro-thermal film and preparation method thereof Download PDFInfo
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- CN105657877A CN105657877A CN201610049453.2A CN201610049453A CN105657877A CN 105657877 A CN105657877 A CN 105657877A CN 201610049453 A CN201610049453 A CN 201610049453A CN 105657877 A CN105657877 A CN 105657877A
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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
- H05B3/20—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
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
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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
Abstract
The invention discloses a super-stretchable graphene electro-thermal film and a preparation method thereof. The electro-thermal film is formed through knitting graphene fibers with a spiral structure; the fibers not only have ultrahigh elongation at break, and can realize rapid response on a high temperature of 30-420 DEG C under safety voltage of 0.5-5V. The preparation method is simple and specifically comprises the following steps: after chemically reducing graphene oxide, carrying out heat treatment in a high-temperature furnace at 500-3000 DEG C to obtain a graphene film; after uniformly winding, obtaining graphene fibers; and knitting the graphene fibers to obtain the graphene electro-thermal film. The graphene electro-thermal film has ultrahigh heating speed and cooling speed, and ultrahigh temperature response; the working voltage is relatively low so that the graphene electro-thermal film can be used for human bodies and is used as human body heating cloth; and the graphene electro-thermal film has a stretchable property so that the graphene electro-thermal film can be adaptive to the movement of the human bodies, such as muscle stretching, in a utilization process, and furthermore, the graphene electro-thermal film can be widely applied as an intelligent electro-thermal material.
Description
Technical field
The present invention relates to a kind of super stretchable Graphene Electric radiant Heating Film and preparation method thereof.
Background technology
Grapheme material causes whole world scientists to study widely, and within 2004, Univ Manchester UK's peace moral is strong. and Jim and Constantine. Nuo Woxiao love professor are because the initiative experiment on two-dimensional graphene material obtains the Nobel Prize in physics of 2010. Graphene shows abundant chemical property, it is possible to carry out finishing by different chemical reactions, obtains a series of chemical derivative. Graphene has high fracture strength and Young's modulus, and electric property is excellent. Grapheme material is also excellent heat conduction and thermo electric material. Tradition thermo electric material such as nichrome, there is cost height, density is big, quality weight and the shortcoming such as processing technique is complicated, use procedure can not stretch, and graphene fiber pliability is good, the rate of heat addition is fast, and thermal response temperature is high, may be used for variously-shaped substrate, and super stretchable, it is possible to adapt to physical activity such as muscle stretch etc., it is hopeful to substitute tradition thermo electric material extensive use.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of super stretchable Graphene Electric radiant Heating Film and preparation method thereof.
It is an object of the invention to be achieved through the following technical solutions: a kind of super stretchable Graphene Electric radiant Heating Film, described Electric radiant Heating Film is formed by the braiding of Graphene fibre electroheating, described Graphene fibre electroheating has the double; two Archimedian screw structures being made up of graphene nanometer sheet, sheet interlayer spacing is 0.3��0.35nm, the carbon-to-oxygen ratio of fiber is 52.66��98, and conductivity is 0.8-2.36 �� 106S/m, elongation at break is 30%-220%.
A kind of preparation method of super stretchable Graphene Electric radiant Heating Film, its step is as follows:
(1) graphene oxide membrane that thickness is 0.8��50 ��m is prepared;
(2) with the ramp of 0.1-1 DEG C/min to 500-800 DEG C, it is incubated 0.5-2h then the ramp to 1000-1300 DEG C with 1-3 DEG C/min, is incubated 0.5-3h, then with the ramp of 5-8 DEG C/min to 2000-3000 DEG C, be incubated 0.5-4h;
(3) graphene film after step 3 heat treatment is cut into graphene strips, graphene strips one end is fixed, the other end and rotating speed be 250-300 turn/rotor of min is connected, and after radially winding 1��5min, obtains the graphene fiber of quickly response;
(4) graphene fiber of ultrafast electro-thermal response step 3 obtained is woven into Electric radiant Heating Film.
Further, the graphene oxide membrane in described step (1) is by the aqueous solution of graphene oxide by vacuum filtration method, and spin-coating method, the one in the method such as spraying process prepares.
Further, described graphene oxide is obtained by native graphite chemical oxidation stripping method.
The present invention compared with prior art has advantageous effect in that:
1. the raw material of Graphene is extensively easy to get, with low cost.
2. preparation technology is simple, and size is controlled.
3. Graphene Electric radiant Heating Film has the rate of heat addition and the rate of temperature fall of superelevation, the temperature-responsive of superelevation, and running voltage is relatively low, may be used for human body, use as human body electrothermal cloth, and owing to performance (single elongation at break reaches 150%) can be drawn high, in use adapt to physical activity, such as muscle stretch etc., therefore can as Intelligent electric-heating material extensive use.
Accompanying drawing explanation
Fig. 1 is the schematic diagram radially wound.
Fig. 2 is that Graphene Electric radiant Heating Film produces fast electric heating response gray-scale map;
Fig. 3 be 4.1V unstretched 1. with the infrared imaging gray-scale map stretching fiber in various degree.
Fig. 4 is the sectional view of fiber, and what lower right embedded is double; two Archimedian screw structural representations.
Detailed description of the invention
As shown in Figure 4, a kind of super stretchable Graphene Electric radiant Heating Film of the present invention, described Electric radiant Heating Film is formed by the braiding of Graphene fibre electroheating, described Graphene fibre electroheating has the double; two Archimedian screw structures (structure is referred to document BiscrollingNanotubeSheetsandFunctionalGuestsintoYarns) being made up of graphene nanometer sheet, sheet interlayer spacing is 0.3��0.34nm, the carbon-to-oxygen ratio of fiber is 52.66��98, and conductivity is 0.8-2.36 �� 106S/m, elongation at break is 30%-220%. Fig. 2 is the Graphene electrothermal membrane infrared image that the present invention prepares, as can be seen from the figure, Electric radiant Heating Film uniformity of temperature profile, and electric heating speed is fast, Fig. 3 is after the fiber in Electric radiant Heating Film is extracted out, the infrared imaging figure after stretching under 4.1V, as can be seen from the figure, graphene fiber after stretching still has the electric heating property of excellence, uniformity of temperature profile.
Graphene fiber of a kind of super stretchable high connductivity of the present invention and preparation method thereof, step is as follows:
(1) obtain graphene oxide by native graphite chemical oxidation stripping method, be configured to graphene oxide water solution, prepare the graphene oxide membrane that thickness is 0.5��50 ��m;
(2) with the ramp of 0.1-1 DEG C/min to 500-800 DEG C, it is incubated 0.5-2h then the ramp to 1000-1300 DEG C with 1-3 DEG C/min, is incubated 0.5-3h, then with the ramp of 5-8 DEG C/min to 2000-3000 DEG C, be incubated 0.5-4h;
(3) graphene film after step 3 heat treatment is cut into graphene strips, graphene strips one end is fixed, the other end and rotating speed be 250-300 turn/rotor of min is connected, and (one end is fixed, the other end constantly rotates under rotor drives, it is similar to and makes cord, as shown in Figure 1), after radially winding 1��5min, obtain the graphene fiber (realizing the quick response to high temperature 30 DEG C-420 DEG C under safe voltage 0.5V-5V) of quickly response.
(4) graphene fiber of ultrafast electro-thermal response step 3 obtained is woven into Electric radiant Heating Film.
Compared with traditional heating element heater nichrome etc., graphene fiber can realize the quick response to high temperature within a short period of time, the thermal capacitance that reason is Graphene is only small, and thermal mass is also only small, the heat produced can not be assembled in a large number and be produced the dissipation of heat, and after high-temperature process, substantial amounts of oxygen-containing functional group is removed, conjugated structure is restored, and electric conductivity is greatly improved. Further by winding so that the internal voids of graphene fiber is extruded gradually, and graphene fiber has close winding-structure, and therefore resistance diminishes, so that graphene fiber has better electrocaloric effect. Under identical voltage, heating rate and saturation temperature are all significantly increased.
On the other hand, winding also makes the graphene film of strip constitute helical structure, causes that graphene fiber has super tensility. In drawing process, the multilayered fold that graphene film produces in the process of mechanical compaction after high-temperature process is stretched out gradually, and when pulling force continues to increase, serpentine graphene fiber structure is opened gradually. When the fault of construction introduced in wound membrane process ruptures under stress concentration effect, serpentine graphene fiber starts progressively to rupture, under a stretching force, the graphene film of different layers is progressively hauled out, flake graphite alkene in graphene film is also successively hauled out, so the graphene fiber of this winding-structure layer by layer has super stretchable character. Therefore, the Graphene Electric radiant Heating Film obtained by the braiding of above-mentioned graphene fiber has the rate of heat addition and the rate of temperature fall of superelevation, the temperature-responsive of superelevation, and running voltage is relatively low, it is possible to for human body, use as human body electrothermal cloth, and owing to performance (single elongation at break reaches 150%) can be drawn high, under drawing high state, good electric heating property still can be kept, it is suitable for physical activity, such as muscle stretch etc.
Graphene oxide membrane in described step (1) can pass through vacuum filtration method, and the one in the method such as spin-coating method or spraying process prepares.
Below in conjunction with embodiment, present aspect is described further.
Embodiment 1: the preparation method of the graphene fiber of a kind of super stretchable high connductivity of the present invention, step is as follows:
(1) obtain graphene oxide by native graphite chemical oxidation stripping method, prepare the graphene oxide membrane that thickness is 0.8��50 ��m;
(2) thickness prepared by step 1 is the graphene oxide membrane of 0.8��50 ��m, and the mode shown in table 1��table 3 carries out heat treatment, obtains graphene film.
(3) graphene film after step 2 being processed is cut into graphene strips, graphene strips one end is fixed, the other end is connected with the rotor that rotating speed is 260 turns/min, radially after winding 3min, (one end is fixed, the other end constantly rotates under rotor drives, being similar to and make cord, as shown in Figure 2), the electric property of each product that different heat treatment mode obtains is in Table 1��table 3.
Wherein the graphene oxide membrane in step (1) can pass through vacuum filtration method, and the one in the method such as spin-coating method or spraying process prepares.
Table 1
Table 2
Table 3
It can be seen that the stretching electric heating property of this material is mainly by internal oxidation graphene film structure repair situation from table 1��table 3, namely functional group come off and under high temperature, the reparation of carbon conjugated structure determines.
In table 1, by compare A1 B1 C1 D1 the temperature of E1, A1 too low, be not enough to remove the functional group that major part is degradable, cause that in second step pyroprocess, gas quickly produces in a large number, at high temperature tearing sheet Rotating fields;E1 temperature is too high, produces gas too fast, can tear material internal structure in a large number, and material mechanical performance and electric property both can be made to be deteriorated. Having only at B1, C1, D1 temperature, functional group can slowly and thoroughly remove, to ensure that material has efficient stretching electro-thermal response performance. By compare C1 F1 G1 H1, F1 heating rate too low, gas release excessively slow; H1 temperature-rise period is too fast, and gas release is too fast, tears material internal structure, is unfavorable for forming transmission channel. Too short by comparing C1 I1 J1 K1 L1 M1, I1 temperature retention time, it is impossible to ensure the degraded of major part functional group so that materials conductive performance is deteriorated; M1 insulating process is long, can absorb the tar inside stove, is unfavorable for the lifting of performance. J1, K1, L1, M1 are owing to avoiding with middle adverse conditions, and performance is greatly improved.
In table 2, by compare A2 B2 C2 D2 E2, A2 heating rate too low, have a strong impact on elongation at break and electric heating property. E2 programming rate is too high, can tear Graphene interlayer structure so that degradation. Have only under the programming rate of B2, C2, D2, just capable not only can ensure structure but also ensure the electric conductivity of Graphene. By compare C2 F2 G2 H2, F2 temperature too low so that stable functional group can not be sufficiently disengaged from, in follow-up graphited process easy transition release gas, destroy internal structure; By compare C2 I2 J2 K2 L2 M2, I2 temperature retention time too short, stable functional group can not fully come off; M2 overlong time, the easy tar adsorption of graphene film, it is unfavorable for the lifting of graphene film performance; And when C2, J2, K2, M2, both can ensure that fully coming off of stabilising functional group, it is avoided that again the puzzlement of tar.
In table 3, by compare A3 B3 C3 D3 E3, A3 heating rate too low, it is excessively slow that most stabilising functional group comes off, and is unfavorable for the formation of conductive network, thus affecting the electric heating property of grapheme material; E3 temperature-rise period is too fast, and gas release and high-temperature expansion are too fast, it is easy to destroy structure. Only when B3, C3, D3, the formation that the graphene film of conductive network could be stable, the structure on Graphene could be repaired slowly. By compare C3 F3 G3 H3 I3, F3 outlet temperature too low, graphene-structured reparation is perfect not, so mechanics and electric property are all very poor; I3 outlet temperature is too high, and Graphene can be vaporized; Could both ensure the reparation of graphene-structured at the temperature of C3, G3, H3, will not be vaporized again. By compare C3 J3 K3 L3 M3, J3 temperature retention time too low, graphene-structured can not fully be repaired, and M3 temperature retention time is long, also can make absorption body of heater in tar, affect the performance of grapheme material.
Claims (4)
1. a super stretchable Graphene Electric radiant Heating Film, it is characterized in that, described Electric radiant Heating Film is formed by the braiding of Graphene fibre electroheating, described Graphene fibre electroheating has the double; two Archimedian screw structures being made up of graphene nanometer sheet, sheet interlayer spacing is 0.3��0.35nm, the carbon-to-oxygen ratio of fiber is 52.66��98, and conductivity is 0.8-2.36 �� 106S/m, elongation at break is 30%-220%.
2. the preparation method of a super stretchable Graphene Electric radiant Heating Film, it is characterised in that its step is as follows:
(1) graphene oxide membrane that thickness is 0.8��50 ��m is prepared;
(2) with the ramp of 0.1-1 DEG C/min to 500-800 DEG C, it is incubated 0.5-2h then the ramp to 1000-1300 DEG C with 1-3 DEG C/min, is incubated 0.5-3h, then with the ramp of 5-8 DEG C/min to 2000-3000 DEG C, be incubated 0.5-4h;
(3) graphene film after step 3 heat treatment is cut into graphene strips, graphene strips one end is fixed, the other end and rotating speed be 250-300 turn/rotor of min is connected, and after radially winding 1��5min, obtains the graphene fiber of quickly response;
(4) graphene fiber of ultrafast electro-thermal response step 3 obtained is woven into Electric radiant Heating Film.
3. method according to claim 2, it is characterised in that the one in the methods such as the graphene oxide membrane in described step (1) is vacuum filtration method of being passed through by the aqueous solution of graphene oxide, spin-coating method, spraying process prepares.
4. method according to claim 3, it is characterised in that described graphene oxide is obtained by native graphite chemical oxidation stripping method.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108892133A (en) * | 2018-07-10 | 2018-11-27 | 浙江大学 | A kind of nanoscale sound generating membranes and nanoscale sonic generator |
| CN110483099A (en) * | 2019-08-23 | 2019-11-22 | 山东大学 | A method of improve continuous zirconia fiber intensity and can prehensile |
| CN112291868A (en) * | 2020-09-14 | 2021-01-29 | 兰州大学 | Self-annealing graphene self-supporting high-temperature electrothermal film and preparation method thereof |
| CN113340110A (en) * | 2021-06-03 | 2021-09-03 | 合肥工业大学 | Novel resistance type ultrafast temperature-changing heating furnace and use method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103449423A (en) * | 2013-08-27 | 2013-12-18 | 常州第六元素材料科技股份有限公司 | Graphene heat conducting membrane and preparation method thereof |
| CN104085143A (en) * | 2014-05-29 | 2014-10-08 | 深圳市铭晶科技有限公司 | Preparation method of composite heat conduction graphene film and composite heat conduction graphene film |
| CN105603581A (en) * | 2016-01-25 | 2016-05-25 | 浙江大学 | Graphene fiber capable of achieving raid response and preparation method thereof |
-
2016
- 2016-01-25 CN CN201610049453.2A patent/CN105657877B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103449423A (en) * | 2013-08-27 | 2013-12-18 | 常州第六元素材料科技股份有限公司 | Graphene heat conducting membrane and preparation method thereof |
| CN104085143A (en) * | 2014-05-29 | 2014-10-08 | 深圳市铭晶科技有限公司 | Preparation method of composite heat conduction graphene film and composite heat conduction graphene film |
| CN105603581A (en) * | 2016-01-25 | 2016-05-25 | 浙江大学 | Graphene fiber capable of achieving raid response and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| RODOLFO CRUZ-SILVA ET AL: "Super-stretchable Graphene Oxide Macroscopic Fibers with Outstanding Knotability Fabricated by Dry Film Scrolling", 《ACSNANO》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108892133A (en) * | 2018-07-10 | 2018-11-27 | 浙江大学 | A kind of nanoscale sound generating membranes and nanoscale sonic generator |
| CN108892133B (en) * | 2018-07-10 | 2020-08-14 | 浙江大学 | Nanoscale sound wave generating film and nanoscale sound wave generator |
| CN110483099A (en) * | 2019-08-23 | 2019-11-22 | 山东大学 | A method of improve continuous zirconia fiber intensity and can prehensile |
| CN112291868A (en) * | 2020-09-14 | 2021-01-29 | 兰州大学 | Self-annealing graphene self-supporting high-temperature electrothermal film and preparation method thereof |
| CN112291868B (en) * | 2020-09-14 | 2021-12-14 | 兰州大学 | Self-annealing graphene self-supporting high-temperature electrothermal film and preparation method thereof |
| CN113340110A (en) * | 2021-06-03 | 2021-09-03 | 合肥工业大学 | Novel resistance type ultrafast temperature-changing heating furnace and use method thereof |
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