CN105336840B - A kind of preparation method of the fibrous stretchable thermo-electric device based on photo-reduction graphene - Google Patents
A kind of preparation method of the fibrous stretchable thermo-electric device based on photo-reduction graphene Download PDFInfo
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- CN105336840B CN105336840B CN201510906902.6A CN201510906902A CN105336840B CN 105336840 B CN105336840 B CN 105336840B CN 201510906902 A CN201510906902 A CN 201510906902A CN 105336840 B CN105336840 B CN 105336840B
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- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
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Abstract
The present invention relates to a kind of preparation method of the fibrous stretchable thermo-electric device based on photo-reduction graphene, graphite oxide is disperseed in deionized water, mechanical agitation, water bath sonicator, Probe Ultrasonic Searching, obtain graphene oxide gel, then scratched in substrate, it is dry, with liquid nitrogen frozen, freeze-drying, peel off, the one side of the three-dimensional graphene oxide film of obtained self-supporting carries out photo-reduction, another side does not reduce, then it is cut to banding, spiral wound is simultaneously fixed on eiastomeric polymer fibers, film end of tape is connected using conductive silver paste, realize series connection, to obtain the final product.Assembling process of the present invention is without isolation film, and technique is simple, of low cost, and prepared stretchable fibrous thermoelectric conversion element has excellent draftability and pliability, can be applied to the energy resource supply of carry-on detection field and following intelligent clothing.
Description
Technical field
The invention belongs to the preparation field of thermo-electric device, more particularly to a kind of threadiness based on photo-reduction graphene can be drawn
Stretch the preparation method of thermo-electric device.
Background technology
On the one hand the detection with oneself of traditional film-form and energy capture device are difficult in adapt to due to not possessing tensility
Human body daily exercise, on the other hand greatly reduces the comfort of human clothing's dress since its is airtight.The biography of threadiness
Sense and energy capture device with human clothing except having good integration, additionally it is possible to meet bending caused by human motion,
The deformations such as stretching, distortion, the network being more used for due to fibrous device after weaving can be good at ensureing that clothes were worn
The exchange of inside and outside air-flow, heat and moisture in journey, so as to ensure that the comfort of clothes dress.
The two-dimensional material that graphene is formed as a kind of single layer of carbon atom sp2 hydridization, has the carrier mobility of superelevation
(200000cm2V-1s-1) and carrier concentration (2 × 1011cm-1)(K.S.Novoselov,et al.Nature.2012,490
(7419):192-200), so as to there is huge application potential in terms of sensing and energy conversion.The oxidation prepared based on chemical method
Graphene provides possibility due to the macroscopical grapheme material of presence assembling of surface oxygen functional group.In recent years for macroscopic view oxidation
The research of graphene film and graphene film is more and more, but controllable to graphene oxide film progress using photoreduction met hod
Single side is reduced and had not been reported for the preparation of thermoelectricity energy conversion devices.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of fibrous stretchable thermoelectricity based on photo-reduction graphene
The preparation method of device, assembling process of the invention is without isolation film, and technique is simple, of low cost, prepared stretchable fibre
Dimension shape thermoelectric conversion element has excellent draftability and pliability, can be applied to carry-on detection field and following intelligent clothing
Energy resource supply.
A kind of preparation method of fibrous stretchable thermo-electric device based on photo-reduction graphene of the present invention, including：
(1) 1 parts by weight graphite oxide is dispersed in the deionized water of 10-30 parts by weight, mechanical agitation, water bath sonicator,
Probe Ultrasonic Searching, obtains finely dispersed graphene oxide gel, is then scratched, is aoxidized in substrate using automatic sweep-out mechanism
Graphene film；
(2) above-mentioned graphene oxide film is dried, with liquid nitrogen frozen, freeze-drying, is peeled off from base, is obtained certainly
The three-dimensional graphene oxide film of support；
(3) the one side A faces (top surface) of the three-dimensional graphene oxide film of above-mentioned self-supporting are subjected to photo-reduction, carry out film
The controllable reduction of longitudinal depth, another side B faces (bottom surface) do not reduce, are then cut to banding, obtain film band；
(4) above-mentioned film band and is fixed on eiastomeric polymer fibers spiral wound, using conductive silver paste by film
End of tape connects, and series connection is realized, up to flexible fiber shape thermoelectric conversion element.
Mechanical agitation 5-30min, water bath sonicator 10-120min, Probe Ultrasonic Searching 10-180min in the step (1).
Substrate is one kind in copper foil, aluminium foil, sand paper, PET in the step (1)；Blade coating speed is 0.5-20cm/s, is scraped
It is 100-500 μm to apply thickness.
It is dry for dry 1-24h under room temperature in the step (2)；The liquid nitrogen frozen time is 30-300s；Freeze-drying
Time is 5-48h.
Photo-reduction is using Xenon light shining in the step (3), carries out film and longitudinally reduces.
It is specially using Xenon light shining：Xenon lamp is xenon long-arc lamp or xenon short-act lamp, power 100W-1000W, irradiation distance
For 5cm-30cm, exposure time 1min-600min.
The draw ratio 20-100 of film band in the step (3).
Eiastomeric polymer fibers are in the step (4)：Polyurethane fiber, dimethyl silicone polymer fiber, IR fiber,
One kind in latex fiber.
The quantity of film band selects the different numbers of plies according to the requirement of required fiber device diameters in step (4).
The form that the laminated layer sequence of film band is according to ABABAB in step (4) ....
The present invention prepares macroscopical graphene oxide film material, and graphene film material is prepared using the method for photo-reduction,
And further this thin-film material is assembled on eiastomeric polymer fibers, the stretchable thermoelectric conversion element of threadiness is made.This
Method assembling process is without isolation film, and technique is simple, of low cost, and prepared stretchable fibrous thermoelectric conversion element has
Excellent draftability and pliability, can be applied to the energy resource supply of carry-on detection field and following intelligent clothing.
Beneficial effect
(1) fibrous thermoelectric conversion element of the invention have excellent pliability, light weight, stretchable, stitchability,
Snugness of fit after highly integrated property and integration；
(2) assembling process of the present invention is simple, of low cost without isolation film, technique；
(3) present invention prepares graphene film material using high-throughout knife coating, and preparation speed is fast, is more conducive to industrial
Production is promoted.
Brief description of the drawings
Fig. 1 is three-dimensional grapheme film scanning electron microscope (SEM) photo in embodiment 1.
Embodiment
With reference to specific embodiment, the present invention is further explained.It is to be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Scope.
Embodiment 1
(i) 0.5g graphite oxides are dispersed in the deionized water of 50mL, mechanical agitation 15min, water bath sonicator 60min,
Probe Ultrasonic Searching 30min, obtains finely dispersed graphene oxide gel；
(ii) graphene oxide film is prepared using automatic sweep-out mechanism blade coating in 1000 mesh sand paper substrates, it is thick adjusts blade coating
100 μm of degree, the dry 6h under room temperature environment, with liquid nitrogen frozen 120s, is freeze-dried 24h, is peeled off from substrate, obtain self-supporting
Three-dimensional graphene oxide film；
(iii) gained top surface (A faces) in (ii) is reduced into 60min, irradiation distance 20cm under 500W xenon long-arc lamps,
And film is cut into 150mm long, the banding of 2mm wide；
(iv) gained film band in 5 (iii) is selected, is fastened according to the laminated layer sequence of ABABA a diameter of
On the dimethyl silicone polymer fiber of 1mm, end silver paste connects fixation with conductive tape.
It is uniformly dispersed through graphene oxide gel made from above-mentioned steps, gained film pliability is good, and has porous knot
Structure.The stretching of gained threadiness thermoelectric conversion element is up to 36.5%, and open circuit voltage signal is 2.5mV under 30 DEG C of temperature difference, 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 oxides are dispersed in the deionized water of 50mL, mechanical agitation 30min, water bath sonicator 60min,
Probe Ultrasonic Searching 45min, obtains finely dispersed graphene oxide gel；
(ii) graphene oxide film is prepared using automatic sweep-out mechanism blade coating in 1000 mesh sand paper substrates, it is thick adjusts blade coating
80 μm of degree, the dry 5h under room temperature environment, with liquid nitrogen frozen 120s, is freeze-dried 24h, is peeled off from substrate, obtain self-supporting
Three-dimensional graphene oxide film；
(iii) gained top surface (A faces) in (ii) is reduced into 30min, irradiation distance 20cm under 800W xenon long-arc lamps,
And film is cut into 150mm long, the banding of 3mm wide；
(iv) gained film band, the laminated layer sequence according to ABABA ... in 8 (iii) is selected to be fastened straight
Footpath is that end silver paste connects fixation with conductive tape on the polyurethane fiber of 1mm.
It is uniformly dispersed through graphene oxide gel made from above-mentioned steps, gained film pliability is good, and has porous knot
Structure.The stretching of gained threadiness thermoelectric conversion element is up to 40.0%, and open circuit voltage signal is 1.7mV under 30 DEG C of temperature difference, short circuit
Current signal is 4.1 μ A.
Embodiment 3
(i) 1.0g graphite oxides are dispersed in the deionized water of 50mL, mechanical agitation 30min, water bath sonicator 120min,
Probe Ultrasonic Searching 30min, obtains finely dispersed graphene oxide gel；
(ii) graphene oxide film is prepared using automatic sweep-out mechanism blade coating in copper foil substrate, adjusts 50 μ of blade coating thickness
M, the dry 6h under room temperature environment, with liquid nitrogen frozen 60s, is freeze-dried 15h, is peeled off from substrate, obtain the three-dimensional oxygen of self-supporting
Graphite alkene film；
(iii) by gained top surface (A faces) reductase 12 0min under 1000W xenon long-arc lamps, irradiation distance in (ii)
20cm, and film is cut into 100mm long, the banding of 1mm wide；
(iv) gained film band, the laminated layer sequence according to ABABAB ... in 10 (iii) is selected to be fastened
On the latex fiber of a diameter of 1mm, end silver paste connects fixation with conductive tape.
It is uniformly dispersed through graphene oxide gel made from above-mentioned steps, gained film pliability is good, and has porous knot
Structure.The stretching of gained threadiness thermoelectric conversion element is up to 48.5%, and open circuit voltage signal is 2.1mV under 30 DEG C of temperature difference, short circuit
Current signal is 3.7 μ A.
Claims (10)
1. a kind of preparation method of the fibrous stretchable thermo-electric device based on photo-reduction graphene, including：
(1) 1 parts by weight graphite oxide is dispersed in the deionized water of 10-30 parts by weight, mechanical agitation, water bath sonicator, popped one's head in
Ultrasound, obtains graphene oxide gel, is then scratched in substrate, obtain graphene oxide film；
(2) above-mentioned graphene oxide film is dried, with liquid nitrogen frozen, is freeze-dried, peels off, obtain the three-dimensional of self-supporting
Graphene oxide film；
(3) the one side A faces of the three-dimensional graphene oxide film of above-mentioned self-supporting are subjected to photo-reduction, another side B faces do not reduce, so
After be cut to banding, obtain film band；
(4) above-mentioned film with spiral wound and is fixed on eiastomeric polymer fibers, it is using conductive silver paste that film band is last
End connection, realizes series connection, up to the stretchable thermo-electric device of threadiness.
A kind of 2. preparation side of fibrous stretchable thermo-electric device based on photo-reduction graphene according to claim 1
Method, it is characterised in that：Mechanical agitation 5-30min, water bath sonicator 10-120min, Probe Ultrasonic Searching 10- in the step (1)
180min。
A kind of 3. preparation side of fibrous stretchable thermo-electric device based on photo-reduction graphene according to claim 1
Method, it is characterised in that：Substrate is one kind in copper foil, aluminium foil, sand paper, PET in the step (1)；Blade coating speed is 0.5-
20cm/s, blade coating thickness are 100-500 μm.
A kind of 4. preparation side of fibrous stretchable thermo-electric device based on photo-reduction graphene according to claim 1
Method, it is characterised in that：It is dry for dry 1-24h under room temperature in the step (2)；The liquid nitrogen frozen time is 30-300s；It is cold
Jelly drying time is 5-48h.
A kind of 5. preparation side of fibrous stretchable thermo-electric device based on photo-reduction graphene according to claim 1
Method, it is characterised in that：Photo-reduction is using Xenon light shining in the step (3), carries out film and longitudinally reduces.
A kind of 6. preparation side of fibrous stretchable thermo-electric device based on photo-reduction graphene according to claim 5
Method, it is characterised in that：It is specially using Xenon light shining：Xenon lamp is xenon long-arc lamp or xenon short-act lamp, power 100W-1000W, spoke
Range is from for 5cm-30cm, exposure time 1min-600min.
A kind of 7. preparation side of fibrous stretchable thermo-electric device based on photo-reduction graphene according to claim 1
Method, it is characterised in that：The aspect ratio of film band is 20-100 in the step (3).
A kind of 8. preparation side of fibrous stretchable thermo-electric device based on photo-reduction graphene according to claim 1
Method, it is characterised in that：Eiastomeric polymer fibers are in the step (4)：Polyurethane fiber, dimethyl silicone polymer fiber, rubber
One kind in glue fiber, latex fiber.
A kind of 9. preparation side of fibrous stretchable thermo-electric device based on photo-reduction graphene according to claim 1
Method, it is characterised in that：The quantity of film band selects the different numbers of plies according to the requirement of required fiber device diameters in step (4).
A kind of 10. preparation side of fibrous stretchable thermo-electric device based on photo-reduction graphene according to claim 9
Method, it is characterised in that：The form that the laminated layer sequence of the film band is according to ABABAB ....
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| 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 |
| CN113380941B (en) * | 2021-06-07 | 2022-07-26 | 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 |
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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 |
|---|
| Graphene-carbon nanotube papers for energy conversion and storage under sunlight and heat;Jiuke Mu 等;《Carbon》;20150815;第95卷;150-156 * |
| Thermoelectricperformanceof p-type nanohybrids filled polymercomposites;Kun Zhang 等;《Nano Energy》;20150311;第13卷;327-335 * |
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