CN105336840A - Method for preparing fibrous tensile thermoelectric device based on photoreduction graphene - Google Patents
Method for preparing fibrous tensile thermoelectric device based on photoreduction graphene Download PDFInfo
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- CN105336840A CN105336840A CN201510906902.6A CN201510906902A CN105336840A CN 105336840 A CN105336840 A CN 105336840A CN 201510906902 A CN201510906902 A CN 201510906902A CN 105336840 A CN105336840 A CN 105336840A
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Abstract
The invention relates to a method for preparing a fibrous tensile thermoelectric device based on photoreduction graphene. Graphite oxide is dispersed in deionized water, graphite oxide gel is obtained through mechanical stirring, water bath ultrasound and probe ultrasound, blade coating is performed on a substrate, drying is performed, refrigeration is performed through liquid nitrogen, freeze drying and stripping are performed, one side of an obtained self-supported three-dimensional graphene film undergoes photoreduction, the other side of the film is not reduced, the film is cut into strips, the strips are wound spirally around and fixed to elastic polymer fibers, conductive silver paste is adopted to connect the tail ends of the film strips, series connection is achieved, and the fibrous tensile thermoelectric device is obtained. According to the method, an isolating film is not needed in the assembly process, a process is simple, the cost is low, and the prepared fibrous tensile thermoelectric conversion device has excellent stretchability and flexibility and can be applied to the field of portable detection and energy supply of future smart clothing.
Description
Technical field
The invention belongs to the preparation field of thermoelectric device, particularly a kind of threadiness based on photo-reduction Graphene can stretch the preparation method of thermoelectric device.
Background technology
Traditional film-form detects with oneself and energy capture device is difficult to owing to not possessing tensility adapt to human body daily exercise on the one hand, greatly reduces the comfortableness of human clothing's dress on the other hand because it is airtight.Fibrous sensing and energy capture device are except having good integration with human clothing, the distortion such as bending, the stretching caused by human motion, distortion can also be met, more because fibrous device can be good at for the network after weaving the exchange ensureing inside and outside air-flow, heat and moisture in clothes wearing process, thus ensure that the comfortableness that clothes are worn.
The two-dimensional material that Graphene is formed as a kind of monolayer carbon atom sp2 hydridization, has the carrier mobility (200000cm of superelevation
2v
-1s
-1) and carrier concentration (2 × 10
11cm
-1) (K.S.Novoselov, etal.Nature.2012,490 (7419): 192-200), thus huge application potential is had in sensing and energy conversion.The graphene oxide prepared based on chemical method provides possibility because macroscopical grapheme material is assembled in the existence of surface oxygen functional group.Research in recent years for macroscopical graphene oxide film and graphene film gets more and more, but employing photoreduction met hod carries out controlled one side reduction to graphene oxide film and the preparation for thermoelectricity energy conversion devices have not been reported.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of threadiness based on photo-reduction Graphene and can stretches the preparation method of thermoelectric device, assembling process of the present invention is without the need to barrier film, technique is simple, with low cost, prepared can have excellent draftability and pliability by drawing of fiber shape thermoelectric conversion element, can be applicable to the energy resource supply of carry-on detection field and following intelligent clothing.
A kind of threadiness based on photo-reduction Graphene of the present invention can stretch the preparation method of thermoelectric device, comprising:
(1) 1 weight portion graphite oxide is dispersed in the deionized water of 10-30 weight portion, mechanical agitation, water bath sonicator, Probe Ultrasonic Searching, obtain finely dispersed graphene oxide gel, then adopt automatic sweep-out mechanism blade coating in substrate, obtain graphene oxide film;
(2) above-mentioned graphene oxide film is carried out drying, with liquid nitrogen frozen, freeze drying, peel off from base, obtain the three-dimensional graphene oxide film of self-supporting;
(3) photo-reduction is carried out in the one side A face (end face) of the three-dimensional graphene oxide film of above-mentioned self-supporting, carry out the reduction that the longitudinal degree of depth of film is controlled, another side B face (bottom surface) is not reduced, and is then cut to band shape, obtains film strip;
(4) above-mentioned film strip spiral wound is fixed on eiastomeric polymer fibers, adopts conductive silver paste to be connected by film strip end, realize series connection, obtain flexible fiber shape thermoelectric conversion element.
Mechanical agitation 5-30min, water bath sonicator 10-120min, Probe Ultrasonic Searching 10-180min in described step (1).
In described step (1), substrate is the one in Copper Foil, aluminium foil, sand paper, PET; Blade coating speed is 0.5-20cm/s, and blade coating thickness is 100-500 μm.
In described step (2), drying is dry 1-24h under room temperature condition; The liquid nitrogen frozen time is 30-300s; Sublimation drying is 5-48h.
In described step (3), photo-reduction is for adopting Xenon light shining, carries out film longitudinally reduction.
Employing Xenon light shining is specially: xenon lamp is xenon long-arc lamp or xenon short-act lamp, and power is 100W-1000W, and irradiation distance is 5cm-30cm, and exposure time is 1min-600min.
The draw ratio 20-100 of film strip in described step (3).
Described step (4) Elastic polymer fiber is: the one in polyurethane fiber, dimethyl silicone polymer fiber, IR fiber, latex fiber.
In step (4), the quantity of film strip selects the different number of plies according to the requirement of required fiber device diameters.
In step (4), the laminated layer sequence of film strip is according to ABABAB ... form.
The present invention prepares macroscopical graphene oxide film material, adopts the method for photo-reduction to prepare graphene film material, and is assembled on eiastomeric polymer fibers by this thin-film material further, and obtained threadiness can stretch thermoelectric conversion element.This method assembling process is without the need to barrier film, and technique is simple, with low cost, and prepared can have excellent draftability and pliability by drawing of fiber shape thermoelectric conversion element, can be applicable to the energy resource supply of carry-on detection field and following intelligent clothing.
beneficial effect
(1) fibrous thermoelectric conversion element of the present invention there is excellent pliability, light weight, can stretch, stitchability, high integration and the snugness of fit after integrating;
(2) assembling process of the present invention is without the need to barrier film, and technique is simple, with low cost;
(3) the present invention adopts high-throughout knife coating to prepare graphene film material, and preparation speed is fast, is more conducive to industrial production and promotes.
Accompanying drawing explanation
Fig. 1 is three-dimensional grapheme film scanning electron microscope (SEM) photo in embodiment 1.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
I 0.5g graphite oxide is dispersed in the deionized water of 50mL by (), mechanical agitation 15min, water bath sonicator 60min, and Probe Ultrasonic Searching 30min obtains finely dispersed graphene oxide gel;
(ii) adopt automatic sweep-out mechanism blade coating in 1000 order sand paper substrates to prepare graphene oxide film, regulate blade coating thickness 100 μm, dry 6h under room temperature environment, use liquid nitrogen frozen 120s, freeze drying 24h, peels off from substrate, obtains the three-dimensional graphene oxide film of self-supporting;
(iii) gained top surface (A face) in (ii) is reduced under 500W xenon long-arc lamp 60min, irradiation distance 20cm, and it is long film to be cut into 150mm, the band shape that 2mm is wide;
(iv) select gained film strip in 5 (iii), be fastened on the dimethyl silicone polymer fiber that diameter is 1mm according to the laminated layer sequence of ABABA, end silver slurry and conductive tape are connected and fixed.
The graphene oxide gel obtained through above-mentioned steps is uniformly dispersed, and gained film pliability is good, and has loose structure.Gained threadiness thermoelectric conversion element stretches and can reach 36.5%, and under 30 DEG C of temperature difference, open circuit voltage signal is 2.5mV, and short circuit current signal is 5 μ A.
Wherein, Fig. 1 is three-dimensional grapheme film scanning electron microscope (SEM) photo in the present embodiment;
Embodiment 2
I 0.75g graphite oxide is dispersed in the deionized water of 50mL by (), mechanical agitation 30min, water bath sonicator 60min, and Probe Ultrasonic Searching 45min obtains finely dispersed graphene oxide gel;
(ii) adopt automatic sweep-out mechanism blade coating in 1000 order sand paper substrates to prepare graphene oxide film, regulate blade coating thickness 80 μm, dry 5h under room temperature environment, use liquid nitrogen frozen 120s, freeze drying 24h, peels off from substrate, obtains the three-dimensional graphene oxide film of self-supporting;
(iii) gained top surface (A face) in (ii) is reduced under 800W xenon long-arc lamp 30min, irradiation distance 20cm, and it is long film to be cut into 150mm, the band shape that 3mm is wide;
(iv) gained film strip in 8 (iii) is selected, according to ABABA ... laminated layer sequence be fastened on the polyurethane fiber that diameter is 1mm, end silver slurry and conductive tape be connected and fixed.
The graphene oxide gel obtained through above-mentioned steps is uniformly dispersed, and gained film pliability is good, and has loose structure.Gained threadiness thermoelectric conversion element stretches and can reach 40.0%, and under 30 DEG C of temperature difference, open circuit voltage signal is 1.7mV, and short circuit current signal is 4.1 μ A.
Embodiment 3
I 1.0g graphite oxide is dispersed in the deionized water of 50mL by (), mechanical agitation 30min, water bath sonicator 120min, and Probe Ultrasonic Searching 30min obtains finely dispersed graphene oxide gel;
(ii) adopt automatic sweep-out mechanism blade coating in Copper Foil substrate to prepare graphene oxide film, regulate blade coating thickness 50 μm, dry 6h under room temperature environment, use liquid nitrogen frozen 60s, freeze drying 15h, peels off from substrate, obtains the three-dimensional graphene oxide film of self-supporting;
(iii) by gained top surface (A face) reductase 12 0min under 1000W xenon long-arc lamp, irradiation distance 20cm in (ii), and it is long film to be cut into 100mm, the band shape that 1mm is wide;
(iv) gained film strip in 10 (iii) is selected, according to ABABAB ... laminated layer sequence be fastened on the latex fiber that diameter is 1mm, end silver slurry and conductive tape be connected and fixed.
The graphene oxide gel obtained through above-mentioned steps is uniformly dispersed, and gained film pliability is good, and has loose structure.Gained threadiness thermoelectric conversion element stretches and can reach 48.5%, and under 30 DEG C of temperature difference, open circuit voltage signal is 2.1mV, and short circuit current signal is 3.7 μ A.
Claims (10)
1. can stretch based on the threadiness of photo-reduction Graphene the preparation method of thermoelectric device, comprising:
(1) be dispersed in the deionized water of 10-30 weight portion by 1 weight portion graphite oxide, mechanical agitation, water bath sonicator, Probe Ultrasonic Searching, obtains graphene oxide gel, and then blade coating in substrate, obtains graphene oxide film;
(2) above-mentioned graphene oxide film is carried out drying, with liquid nitrogen frozen, freeze drying, peel off, obtain the three-dimensional graphene oxide film of self-supporting;
(3) photo-reduction is carried out in the one side A face of the three-dimensional graphene oxide film of above-mentioned self-supporting, another side B does not reduce in face, is then cut to band shape, obtains film strip;
(4) above-mentioned film strip spiral wound is fixed on eiastomeric polymer fibers, adopts conductive silver paste to be connected by film strip end, realize series connection, obtain flexible fiber shape thermoelectric conversion element.
2. a kind of threadiness based on photo-reduction Graphene according to claim 1 can stretch the preparation method of thermoelectric device, it is characterized in that: mechanical agitation 5-30min in described step (1), water bath sonicator 10-120min, Probe Ultrasonic Searching 10-180min.
3. a kind of threadiness based on photo-reduction Graphene according to claim 1 can stretch the preparation method of thermoelectric device, it is characterized in that: in described step (1), substrate is the one in Copper Foil, aluminium foil, sand paper, PET; Blade coating speed is 0.5-20cm/s, and blade coating thickness is 100-500 μm.
4. a kind of threadiness based on photo-reduction Graphene according to claim 1 can stretch the preparation method of thermoelectric device, it is characterized in that: dry in described step (2) is dry 1-24h under room temperature condition; The liquid nitrogen frozen time is 30-300s; Sublimation drying is 5-48h.
5. a kind of threadiness based on photo-reduction Graphene according to claim 1 can stretch the preparation method of thermoelectric device, it is characterized in that: in described step (3), photo-reduction is for adopting Xenon light shining, carries out film longitudinally reduction.
6. a kind of threadiness based on photo-reduction Graphene according to claim 5 can stretch the preparation method of thermoelectric device, it is characterized in that: adopt Xenon light shining to be specially: xenon lamp is xenon long-arc lamp or xenon short-act lamp, power is 100W-1000W, irradiation distance is 5cm-30cm, and exposure time is 1min-600min.
7. a kind of threadiness based on photo-reduction Graphene according to claim 1 can stretch the preparation method of thermoelectric device, it is characterized in that: the draw ratio 20-100 of film strip in described step (3).
8. a kind of threadiness based on photo-reduction Graphene according to claim 1 can stretch the preparation method of thermoelectric device, it is characterized in that: described step (4) Elastic polymer fiber is: the one in polyurethane fiber, dimethyl silicone polymer fiber, IR fiber, latex fiber.
9. a kind of threadiness based on photo-reduction Graphene according to claim 1 can stretch the preparation method of thermoelectric device, it is characterized in that: in step (4), the quantity of film strip selects the different number of plies according to the requirement of required fiber device diameters.
10. a kind of threadiness based on photo-reduction Graphene according to claim 1 can stretch the preparation method of thermoelectric device, it is characterized in that: in step (4), the laminated layer sequence of film strip is according to ABABAB ... form.
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| CN201510906902.6A CN105336840B (en) | 2015-12-09 | 2015-12-09 | A kind of preparation method of the fibrous stretchable thermo-electric device based on photo-reduction graphene |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108172681A (en) * | 2017-12-28 | 2018-06-15 | 浙江大学 | It is a kind of it is three-dimensionally integrated in the thermoelectric conversion system based on nano material |
| CN113380941A (en) * | 2021-06-07 | 2021-09-10 | 北京航空航天大学 | Out-of-plane thermoelectric device with stretchable porous structure |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7970242B2 (en) * | 2007-10-18 | 2011-06-28 | The Regents Of The University Of Michigan | Fiber-based electric device |
| CN103508447A (en) * | 2012-06-26 | 2014-01-15 | 海洋王照明科技股份有限公司 | Preparation method of graphene |
-
2015
- 2015-12-09 CN CN201510906902.6A patent/CN105336840B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7970242B2 (en) * | 2007-10-18 | 2011-06-28 | The Regents Of The University Of Michigan | Fiber-based electric device |
| CN103508447A (en) * | 2012-06-26 | 2014-01-15 | 海洋王照明科技股份有限公司 | Preparation method of graphene |
Non-Patent Citations (2)
| Title |
|---|
| JIUKE MU 等: "Graphene-carbon nanotube papers for energy conversion and storage under sunlight and heat", 《CARBON》 * |
| KUN ZHANG 等: "Thermoelectricperformanceof p-type nanohybrids filled polymercomposites", 《NANO ENERGY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108172681A (en) * | 2017-12-28 | 2018-06-15 | 浙江大学 | It is a kind of it is three-dimensionally integrated in the thermoelectric conversion system based on nano material |
| CN108172681B (en) * | 2017-12-28 | 2019-10-29 | 浙江大学 | It is a kind of it is three-dimensionally integrated in the thermoelectric conversion system based on nano material |
| CN113380941A (en) * | 2021-06-07 | 2021-09-10 | 北京航空航天大学 | Out-of-plane thermoelectric device with stretchable porous structure |
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