CN111691061B - Photo-thermal and piezoelectric heating dual-mechanism heating film, preparation method thereof and heating garment - Google Patents
Photo-thermal and piezoelectric heating dual-mechanism heating film, preparation method thereof and heating garment Download PDFInfo
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- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
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- A41D13/002—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches with controlled internal environment
- A41D13/005—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches with controlled internal environment with controlled temperature
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
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- D—TEXTILES; PAPER
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
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Abstract
The invention provides a preparation method of a photo-thermal and piezoelectric heating dual-mechanism heating film, which comprises the following steps: preparing a mixture of the tellurite and the graphene oxide, preparing a tellurite/graphene oxide mixed dispersion liquid, spinning, preparing a tellurite/graphene hybrid fiber membrane and preparing a photo-thermal and piezoelectric heating dual-mechanism heating membrane. The preparation method of the photo-thermal and piezoelectric heating dual-mechanism heating film overcomes the defects that mutual stacking of telluroene is easy to occur, the dispersibility in water is poor, and the telluroene dispersion liquid does not have spinnability and the like through the functions of graphene oxide auxiliary dispersion and auxiliary spinning. The photothermal and piezoelectric heating dual-mechanism heating film comprises a tellurium/graphene hybrid fiber film with a photo-thermal effect and an ink/PVDF nano-fiber film with a piezoelectric thermal effect, and can generate heat through physical bending or deformation and also generate heat through electricity under the illumination condition. The invention also provides a photo-thermal and piezoelectric heating dual-mechanism heating film and application thereof.
Description
Technical Field
The invention relates to the technical field of nano semiconductor materials, in particular to a heating film with a photo-thermal and piezoelectric-thermal double heat production mechanism, a preparation method of the photo-thermal and piezoelectric-thermal double heat production heating film, and a heating garment with the photo-thermal and piezoelectric-thermal double heat production mechanism.
Background
The self-heating clothes have the main functions of preventing the heat loss of a human body, ensuring the normal life and work of the human body under the condition of a cold environment and preventing the human body from being injured by the cold. The current self-heating clothes mostly adopt an electric heating mode. For example, the self-heating clothes are powered and heated by a power supply, are mostly limited by the heavy weight, inconvenient carrying and the like of the power supply, can only be applied to the field of special clothes, and are difficult to effectively popularize. When the clothes are worn, various folds, transverse and longitudinal pulls or other changes can occur to cause the physical shape change of the clothes, and a raw material and the clothes which can convert the energy of the physical shape change into electric energy and further be used for electric heating are developed, thereby becoming a great hotspot in the textile field.
The PVDF piezoelectric film, namely the polyvinylidene fluoride piezoelectric film, is a novel high-molecular piezoelectric material which is produced in Japan in the 70 th century. The PVDF piezoelectric film has unique dielectric effect, piezoelectric effect and thermoelectric effect. Compared with the traditional piezoelectric material, the material has the characteristics of wide frequency response, large dynamic range, high power-electricity conversion sensitivity, high mechanical property strength, easy matching of acoustic impedance and the like, and is mainly applied to piezoelectric sensors. In the piezoelectric film preparation method in the 'preparation, performance and application research of polyvinylidene fluoride electrostatic spinning nano generator' in the doctor of Huangtao, the PVDF piezoelectric film and the graphene film are not combined and applied to heating clothes, and the polyvinylidene fluoride electrostatic spinning nano generator only has a piezoelectric mechanism, can form current and cannot efficiently generate heat.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a photothermal and piezoelectric heating dual-mechanism heating film, and also provides a photothermal and piezoelectric heating dual-mechanism heating film prepared by the method for preparing a photothermal and piezoelectric heating dual-mechanism heating film, and applications of the photothermal and piezoelectric heating dual-mechanism heating film in the technical field of self-heating clothes. The preparation method of the photothermal and piezoelectric heating dual-mechanism heating film provided by the invention can effectively solve the problems that in the prior art, the tellurium and graphene are not uniformly dispersed, the ratio of the tellurium and the graphene is difficult to regulate and control, the spinnability is poor, the content selection of additives and additives has relatively small flexibility, and the like, and the prepared photothermal and piezoelectric heating dual-mechanism heating film has the advantages of easy control of flexibility, size and the like, excellent physical properties, remarkable photothermal effect and piezoelectric heat effect, and can be widely applied to the field of self-produced heating clothes.
In a first aspect, the invention provides a method for preparing a photothermal and piezoelectric heating dual-mechanism heating film, comprising the following steps:
preparing a mixture of tellurium and graphene oxide: providing a tellurium alkene pre-stripping dispersion liquid, adding graphene oxide into the tellurium alkene pre-stripping dispersion liquid, carrying out constant-temperature water bath ultrasonic treatment, centrifuging, collecting a bottom layer mixture, dispersing the bottom layer mixture into water, washing, concentrating and drying to obtain a mixture of tellurium alkene and graphene oxide;
preparing a tellurium alkene/graphene oxide mixed dispersion liquid: adding water into a mixture of the tellurium and the graphene, stirring to obtain a mixed solution, performing ultrasonic treatment on the mixed solution in a pulse type tip ultrasonic mode, and concentrating the mixed solution after the ultrasonic treatment is finished to obtain a tellurium/graphene oxide mixed dispersion solution;
spinning: taking the tellurium alkene/graphene oxide mixed dispersion liquid as a spinning stock solution, taking glacial acetic acid as a coagulating bath, and carrying out wet spinning by adopting a rotating table, wherein the linear speed of a spinning needle relative to the coagulating bath of the rotating table is greater than the maximum linear speed capable of continuously forming fibers, so as to prepare tellurium alkene/graphene oxide hybrid short fibers;
preparing a tellurium alkene/graphene hybrid fiber membrane: after collecting the tellurium alkene/graphene oxide hybrid short fiber, carrying out suction filtration and reduction on a coagulating bath containing the tellurium alkene/graphene oxide hybrid short fiber to obtain a tellurium alkene/graphene hybrid fiber membrane;
preparing a photo-thermal and piezoelectric heating dual-mechanism heating film: and (3) performing electrostatic spinning by taking the tellurium/graphene hybrid fiber membrane as a receiving plate and taking the mixed solution of graphene/PVDF as a spinning solution to form a double-layer fiber membrane of the tellurium/graphene hybrid fiber membrane and the graphene/PVDF nanofiber membrane, so as to prepare the photothermal and piezoelectric heating dual-mechanism heating membrane.
The preparation method of the photo-thermal and piezoelectric heating dual-mechanism heating film overcomes the defects that mutual stacking of telluroene is easy to occur, the dispersibility in water is poor, and the telluroene dispersion liquid does not have spinnability and the like through the functions of graphene oxide auxiliary dispersion and auxiliary spinning. In the existing method, the mixing mode of the additive and the graphene oxide is too simple, and for two-dimensional crystals such as tellurium and the like which are easy to stack mutually and have poor dispersibility in water, the two-dimensional crystals and the graphene oxide are difficult to form a structure with mutually staggered lamellae, so that the phenomenon that the local concentration of the tellurium and the like is too high or the tellurium and the like are stacked easily occurs, and the problem that fibers cannot be spun is caused. By adding the graphene oxide in the process of stripping the tellurium, the uniform mixing of the graphene oxide and the tellurium and the stable dispersion of the whole system can be realized, the stripped tellurium can be effectively prevented from being piled together again to be settled, and the stable dispersion of high-concentration tellurium and the continuous spinning of the tellurium/graphene oxide with high tellurium ratio are realized.
The photothermal and piezoelectric heating dual-mechanism heating film comprises a tellurium/graphene hybrid fiber film with a photothermal effect and an ink/PVDF nano-fiber film with a piezoelectric effect, can generate heat through physical bending or deformation and also generate electricity and heat under the illumination condition, can effectively improve the heat generation quantity of the photothermal and piezoelectric heating dual-mechanism heating film by combining various heat generation modes, and can also widen the use scene of the photothermal and piezoelectric heating dual-mechanism heating film.
In a specific embodiment of the invention, in the step of preparing the photothermal and piezoelectric heating dual-machine heating film, one surface of the graphene/PVDF nanofiber film, which is opposite to the tellurium/graphene hybrid fiber film, is connected to another tellurium/graphene hybrid fiber film to form a sandwich structure of the tellurium/graphene hybrid fiber film-graphene/PVDF nanofiber film-tellurium/graphene hybrid fiber film, so as to prepare the photothermal and piezoelectric heating dual-machine heating film. By preparing the sandwich structure of the tellurium-graphene/graphene hybrid fiber membrane-graphene/PVDF nanofiber membrane-tellurium-graphene/graphene hybrid fiber membrane, the exterior of the photo-thermal and piezoelectric heating dual-mechanism heating membrane is surrounded by the tellurium-graphene/graphene hybrid fiber membrane with photo-thermal effect, so that the maximum photo-thermal effect of the photo-thermal and piezoelectric heating dual-mechanism heating membrane is realized, and the piezoelectric thermal effect of the graphene/PVDF nanofiber membrane is not influenced.
Preferably, the sandwich structure of the tellurium-graphene/graphene hybrid fiber membrane-graphene/PVDF nanofiber membrane-tellurium-graphene/graphene hybrid fiber membrane is packaged by a PET membrane. The PET film has good flexibility and light passing effect, protects the sandwich structure of the tellurium/graphene hybrid fiber film-graphene/PVDF nano fiber film-tellurium/graphene hybrid fiber film, and simultaneously does not influence the photo-thermal and piezoelectric heating effects of the photo-thermal and piezoelectric heating dual-mechanism heating film.
Preferably, in the step of preparing the photothermal and piezoelectric heating dual-mechanism heating film, the graphene/PVDF mixed solution includes a solute: PVDF and graphene, wherein the mass fraction of the PVDF is 10%, and the mass fraction of the graphene is 1% -5%; also comprises a solvent: the mixed solution of DMF and acetone, wherein the mass ratio of DMF to acetone is 6: 4.
More preferably, the mass fraction of the graphene is 3%.
In a specific embodiment of the present invention, in the step of preparing the mixture of the tellurium alkene and the graphene oxide, the solvent of the tellurium alkene pre-stripping dispersion liquid is N-methyl pyrrolidone. The N-methyl pyrrolidone solvent dissolves the tellurium, so that the graphene oxide and the tellurium can be uniformly mixed conveniently, the subsequent ultrasonic dispersion process is facilitated, and the ultrasonic dispersion efficiency is improved.
Preferably, in the step of preparing the mixture of the tellurium alkene and the graphene oxide, the tellurium alkene pre-stripping dispersion liquid is prepared by the following method: providing tellurium powder, adding the tellurium powder into N-methyl pyrrolidone, and carrying out constant-temperature water bath ultrasound on an N-methyl pyrrolidone solution of the tellurium powder for 24-120 h, wherein the temperature of the constant-temperature water bath ultrasound is less than or equal to 10 ℃;
and centrifuging the mixed solution after the ultrasonic treatment is finished, and collecting supernatant, namely the tellurium alkene pre-stripping dispersion liquid.
More preferably, in the step of preparing the mixture of the tellurium and the graphene, the N-methylpyrrolidone solution of the tellurium powder is subjected to constant-temperature water bath ultrasound for 72 hours, wherein the temperature of the constant-temperature water bath ultrasound is 10 ℃.
More preferably, the mixed solution is centrifuged after the ultrasound is finished, the centrifugation speed is 5000rpm, and the centrifugation time is 60 min.
Preferably, in the step of preparing the mixture of the tellurium and the graphene oxide, the mass ratio of the tellurium to the graphene oxide is 0.1-7: 3. More preferably, the mass ratio of the tellurite to the graphene oxide is 1: 1. The tellurium alkene/graphene hybrid fiber within the proportion range has better physical property and better photoelectric response.
Preferably, in the step of preparing the mixture of the telluroene and the graphene oxide, the temperature of the constant-temperature water bath ultrasound is less than or equal to 10 ℃, and the time of the constant-temperature water bath ultrasound is 4-36 hours. More preferably, the temperature of the constant-temperature water bath ultrasound is 10 ℃, and the time of the constant-temperature water bath ultrasound is 12 h. Can promote the better homodisperse of the mixture of tellurium alkene and oxidation graphite alkene under this constant temperature water bath supersound condition, prevent that tellurium alkene from piling up each other.
Preferably, in the step of preparing the mixture of the telluroene and the graphene oxide, the centrifugal speed is 8000-15000 rpm, and the centrifugal time is 20-200 min. More preferably, the centrifugation speed is 10000rpm, and the centrifugation time is 60 min. The centrifugal condition can ensure that the mixture of the tellurite alkene and the graphene oxide is fully separated from the solvent, the mixture of the tellurite alkene and the graphene oxide can be fully collected while the solvent water is removed, and the subsequent concentration and drying processes are facilitated.
Preferably, after centrifugation, the supernatant is poured off, and the mixture of the telluroene and the graphene oxide attached to the wall of the centrifuge tube is scraped.
Preferably, in the step of preparing the tellurium alkene/graphene oxide mixed dispersion liquid, the mixture of the tellurium alkene and the graphene oxide is dispersed in water, and the mixture of the tellurium alkene and the graphene oxide is washed and dried by a method of removing the solvent through rotary evaporation.
Preferably, in the step of preparing the tellurium alkene/graphene oxide mixed dispersion liquid, the prepared mixed liquid is 5-20 mg/ml in concentration, and then pulse type tip ultrasound is carried out on the mixed liquid of 5-20 mg/ml. More preferably, the concentration of the resulting mixture is adjusted to 10 mg/ml.
Preferably, the ultrasound interval time of the pulsed tip ultrasound is: and 5s of ultrasound, 5s of interval and 4h of total ultrasound time.
Preferably, in the step of preparing the tellurium alkene/graphene oxide mixed dispersion liquid, after the ultrasonic treatment is finished, the mixed liquid is concentrated by heating until the solid content concentration is 15-25 mg/ml, and the tellurium alkene/graphene oxide mixed dispersion liquid is obtained. More preferably, after the completion of the sonication, the mixture is concentrated by heating to a solid content of 20 mg/ml.
Preferably, in the spinning step, the rotating speed of the spinning needle relative to the coagulating bath of the rotating table is 30rpm, and the distance between the spinning needle and the center of the rotating table is 20 mm.
Preferably, in the step of preparing the tellurium alkene/graphene oxide hybrid fiber membrane, after the coagulating bath containing the tellurium alkene/graphene oxide hybrid short fiber is filtered, the unreduced tellurium alkene/graphene oxide hybrid fiber membrane is obtained.
Preferably, in the step of preparing the tellurium/graphene hybrid fiber membrane, the tellurium/graphene oxide hybrid fiber membrane is immersed in any one of HI, NaBH4, hydrazine hydrate and ascorbic acid for chemical reduction, so as to obtain the tellurium/graphene hybrid fiber membrane.
More preferably, in the step of preparing the tellurium alkene/graphene hybrid fiber membrane, the tellurium alkene/graphene oxide hybrid fiber membrane is soaked in HI for chemical reduction, so as to obtain the tellurium alkene/graphene hybrid fiber membrane.
In a second aspect, the invention provides a photothermal and piezoelectric heating dual-mechanism heating film, which is prepared by the preparation method of the photothermal and piezoelectric heating dual-mechanism heating film provided in the first aspect.
The photo-thermal and piezoelectric heating dual-mechanism heating film has good flexibility, uniform strand silk and excellent tensile strength, elongation at break and fiber conductivity, and when simulated sunlight irradiation is applied after shading treatment, the fiber generates photocurrent, thereby showing a remarkable photoelectric effect. The photo-thermal and piezoelectric heating dual-mechanism heating film also has excellent photo-thermal effect and piezoelectric thermal effect, can convert mechanical energy or optical energy of physical deformation into heat energy, and plays a role in self-heating.
In a third aspect, the present invention provides a heating suit, which is made of the photothermal and piezoelectric heating dual-mechanism heating film described in the second aspect.
The heating suit has excellent flexibility and obvious photo-thermal and piezoelectric thermal effects, can convert light energy irradiated by light and mechanical energy generated by physical deformation of the heating film into heat energy, plays a role in self-heating, improves heat production through the synergistic effect of multiple self-heat production modes, and widens the application scene of the heating suit.
Advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of embodiments of the invention.
Drawings
In order to more clearly illustrate the contents of the present invention, a detailed description thereof will be given below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is a flow chart of preparation of a tellurium/graphene hybrid fiber membrane provided by the present invention;
FIG. 2 is a flow chart of a process for preparing a photothermal and piezoelectric heating film according to the present invention;
fig. 3 is an SEM image of the graphene/PVDF nanofiber membrane prepared in example 1 of the present invention.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
The invention provides a preparation method of a tellurium alkene/graphene hybrid fiber membrane with photoelectric effect, which comprises the following steps:
preparing a mixture of tellurium and graphene oxide: providing a tellurium alkene pre-stripping dispersion liquid, adding graphene oxide into the tellurium alkene pre-stripping dispersion liquid, carrying out constant-temperature water bath ultrasonic treatment, centrifuging, collecting a bottom layer mixture, dispersing the bottom layer mixture into water, washing, concentrating and drying to obtain a mixture of tellurium alkene and graphene oxide;
preparing a tellurium alkene/graphene oxide mixed dispersion liquid: adding water into a mixture of the tellurium and the graphene, stirring to obtain a mixed solution, performing ultrasonic treatment on the mixed solution in a pulse type tip ultrasonic mode, and concentrating the mixed solution after the ultrasonic treatment is finished to obtain a tellurium/graphene oxide mixed dispersion solution;
spinning: taking the tellurium alkene/graphene oxide mixed dispersion liquid as a spinning stock solution, taking glacial acetic acid as a coagulating bath, and carrying out wet spinning by adopting a rotating table, wherein the linear speed of a spinning needle relative to the coagulating bath of the rotating table is greater than the maximum linear speed capable of continuously forming fibers, so as to prepare tellurium alkene/graphene oxide hybrid short fibers;
preparing a tellurium alkene/graphene hybrid fiber membrane: after collecting the tellurium alkene/graphene oxide hybrid short fiber, carrying out suction filtration and reduction on a coagulating bath containing the tellurium alkene/graphene oxide hybrid short fiber to obtain a tellurium alkene/graphene hybrid fiber membrane;
preparing a photo-thermal and piezoelectric heating dual-mechanism heating film: and (3) performing electrostatic spinning by taking the tellurium/graphene hybrid fiber membrane as a receiving plate and taking the mixed solution of graphene/PVDF as a spinning solution to form a double-layer fiber membrane of the tellurium/graphene hybrid fiber membrane and the graphene/PVDF nanofiber membrane, so as to prepare the photothermal and piezoelectric heating dual-mechanism heating membrane.
In a specific embodiment of the invention, in the step of preparing the photothermal and piezoelectric heating dual-machine heating film, one surface of the graphene/PVDF nanofiber film, which is opposite to the tellurium/graphene hybrid fiber film, is connected to another tellurium/graphene hybrid fiber film to form a sandwich structure of the tellurium/graphene hybrid fiber film-graphene/PVDF nanofiber film-tellurium/graphene hybrid fiber film, so as to prepare the photothermal and piezoelectric heating dual-machine heating film.
Preferably, the sandwich structure of the tellurium-graphene/graphene hybrid fiber membrane-graphene/PVDF nanofiber membrane-tellurium-graphene/graphene hybrid fiber membrane is packaged by a PET membrane.
Preferably, in the step of preparing the photothermal and piezoelectric heating dual-mechanism heating film, the graphene/PVDF mixed solution includes a solute: PVDF and graphene, wherein the mass fraction of the PVDF is 10%, and the mass fraction of the graphene is 1% -5%; also comprises a solvent: the mixed solution of DMF and acetone, wherein the mass ratio of DMF to acetone is 6: 4.
More preferably, the mass fraction of the graphene is 3%.
In a specific embodiment of the present invention, in the step of preparing the mixture of the tellurium alkene and the graphene oxide, the solvent of the tellurium alkene pre-stripping dispersion liquid is N-methyl pyrrolidone.
Preferably, in the step of preparing the mixture of the tellurium alkene and the graphene oxide, the tellurium alkene pre-stripping dispersion liquid is prepared by the following method: providing tellurium powder, adding the tellurium powder into N-methyl pyrrolidone, and carrying out constant-temperature water bath ultrasound on an N-methyl pyrrolidone solution of the tellurium powder for 24-120 h, wherein the temperature of the constant-temperature water bath ultrasound is less than or equal to 10 ℃;
and centrifuging the mixed solution after the ultrasonic treatment is finished, and collecting supernatant, namely the tellurium alkene pre-stripping dispersion liquid.
More preferably, in the step of preparing the mixture of the tellurium and the graphene, the N-methylpyrrolidone solution of the tellurium powder is subjected to constant-temperature water bath ultrasound for 72 hours, wherein the temperature of the constant-temperature water bath ultrasound is 10 ℃.
More preferably, the mixed solution is centrifuged after the ultrasound is finished, the centrifugation speed is 5000rpm, and the centrifugation time is 60 min.
Preferably, in the step of preparing the mixture of the tellurium and the graphene oxide, the mass ratio of the tellurium to the graphene oxide is 0.1-15: 10.
More preferably, the mass ratio of the tellurite to the graphene oxide is 1: 1.
Preferably, in the step of preparing the mixture of the telluroene and the graphene oxide, the temperature of the constant-temperature water bath ultrasound is less than or equal to 10 ℃, and the time of the constant-temperature water bath ultrasound is 4-36 hours.
More preferably, the temperature of the constant-temperature water bath ultrasound is 10 ℃, and the time of the constant-temperature water bath ultrasound is 12 h.
Preferably, in the step of preparing the mixture of the telluroene and the graphene oxide, the centrifugal speed is 8000-15000 rpm, and the centrifugal time is 20-200 min.
More preferably, the centrifugation speed is 10000rpm, and the centrifugation time is 60 min.
Preferably, after centrifugation, the supernatant is poured off, and the mixture of the telluroene and the graphene oxide attached to the wall of the centrifuge tube is scraped.
Preferably, in the step of preparing the tellurium alkene/graphene oxide mixed dispersion liquid, the mixture of the tellurium alkene and the graphene oxide is dispersed in water, and the mixture of the tellurium alkene and the graphene oxide is washed and dried by a method of removing the solvent through rotary evaporation.
Preferably, in the step of preparing the tellurium alkene/graphene oxide mixed dispersion liquid, the prepared mixed liquid is 5-20 mg/ml in concentration, and then pulse type tip ultrasound is carried out on the mixed liquid of 5-20 mg/ml.
More preferably, the concentration of the resulting mixture is adjusted to 10 mg/ml.
Preferably, the ultrasound interval time of the pulsed tip ultrasound is: and 5s of ultrasound, 5s of interval and 4h of total ultrasound time.
Preferably, in the step of preparing the tellurium alkene/graphene oxide mixed dispersion liquid, after the ultrasonic treatment is finished, the mixed liquid is concentrated by heating until the solid content concentration is 15-25 mg/ml, and the tellurium alkene/graphene oxide mixed dispersion liquid is obtained.
More preferably, after the completion of the sonication, the mixture is concentrated by heating to a solid content of 20 mg/ml.
Preferably, in the spinning step, the rotating speed of the spinning needle relative to the coagulating bath of the rotating table is 30rpm, and the spinning needle is 20mm away from the center of the rotating table.
Preferably, in the step of preparing the tellurium alkene/graphene oxide hybrid fiber membrane, after the coagulating bath containing the tellurium alkene/graphene oxide hybrid short fiber is filtered, the unreduced tellurium alkene/graphene oxide hybrid fiber membrane is obtained.
Preferably, in the step of preparing the tellurium/graphene hybrid fiber membrane, the tellurium/graphene oxide hybrid fiber membrane is immersed in any one of HI, NaBH4, hydrazine hydrate and ascorbic acid for chemical reduction, so as to obtain the tellurium/graphene hybrid fiber membrane.
More preferably, in the step of preparing the tellurium alkene/graphene hybrid fiber membrane, the tellurium alkene/graphene oxide hybrid fiber membrane is soaked in HI for chemical reduction, so as to obtain the tellurium alkene/graphene hybrid fiber membrane.
The tellurium alkene/graphene hybrid fiber membrane with photoelectric effect prepared by the invention has the following advantages:
(1) the tellurium alkene/graphene oxide dispersion liquid is uniformly and stably dispersed;
(2) the preparation process of the tellurium alkene/graphene oxide fiber membrane is simple, and the bonding force between fibers is strong;
(3) the ratio of the tellurite to the graphene oxide in the tellurite/graphene hybrid fiber is adjustable in a large range (0: 100-70: 30), so that the conductivity and the photoelectric property of the fiber can be adjusted;
(4) the length of the short fiber in the tellurium alkene/graphene hybrid fiber membrane is uniform and adjustable
(5) The tellurium alkene/graphene hybrid fiber has excellent conductivity, and also has photoelectric and photo-thermal characteristics; the graphene/PVDF nanofiber membrane has the piezoelectric effect, good flexibility and high physical strength. The tellurium alkene/graphite alkene hybridization fibrous membrane combines with graphite alkene/PVDF nanofiber membrane, makes the light and heat, piezoelectricity heat double-system heating membrane of the invention can both produce a large amount of heats under illumination and bending, can be used as the surface fabric that generates heat in clothing, home textile field and carry out the application.
The following description will explain the preparation method of the photothermal and piezoelectric heating dual-mechanism heating film and the prepared photothermal and piezoelectric heating dual-mechanism heating film by specific embodiments. Tellurium powder, graphene oxide, chemical reducing agents (HI, NaBH4, hydrazine hydrate, ascorbic acid) and the like used in the examples were purchased from alatin; n-methyl pyrrolidone, glacial acetic acid and ethanol are all purchased from the national pharmaceutical group.
Example 1
As shown in fig. 1 and 2, a method for preparing a photothermal and piezoelectric heating dual-mechanism heating film includes the following steps:
preparing a mixture of tellurium and graphene oxide: to provide a telene pre-exfoliated dispersion, 10ml of the telene pre-exfoliated dispersion was taken out therefrom, weighed, and recorded as mg in mass, to obtain a concentration w of 0.1 × mg/ml (0.00394 g/ml in this example) of the telene pre-exfoliated dispersion. 0.788g of graphene oxide was added to the remaining 200ml of the tellurium-graphene pre-exfoliation dispersion at a 1:1 mass ratio of tellurium to graphene oxide to obtain a mixed solution B. And putting the mixed solution B into a constant-temperature water bath ultrasonic machine for ultrasonic treatment, wherein the water bath temperature is kept lower than 10 ℃, and the ultrasonic treatment is carried out for 12 hours. And (4) centrifuging the mixed solution after the ultrasonic treatment by using a centrifuge, wherein the centrifugation speed is 10000rpm, and the centrifugation time is 60 min. After centrifugation, the supernatant was decanted. Scraping the mixture of the tellurite and the graphene oxide attached to the wall of the centrifugal tube.
Preparing a tellurium alkene/graphene oxide mixed dispersion liquid: and (3) dispersing the mixture of the telluroene and the graphene oxide prepared in the first step into water, washing the mixture of the telluroene and the graphene oxide for three times by using a method of removing the solvent by rotary evaporation, and drying. 400mg of the mixture of the washed and dried telluroene and graphene oxide was added to 40ml of water and stirred to obtain a mixed solution C. And (3) carrying out ultrasound on the mixed solution C in a pulse type tip ultrasound mode, wherein the ultrasound interval time is as follows: and 5s of ultrasound, 5s of interval and 4h of total ultrasound time. And after the ultrasonic treatment is finished, heating the mixed solution C for concentration until the solid content concentration is 20mg/ml, and obtaining the tellurium alkene/graphene oxide mixed dispersion liquid.
Spinning: and (3) taking the tellurium alkene/graphene oxide mixed dispersion liquid obtained in the second step as spinning stock solution, taking glacial acetic acid as a coagulating bath, and performing wet spinning by adopting a rotating table coagulating bath. The rotating speed of the rotating platform is set to be 30rpm, the distance between the spinning needle head and the circle center is 20mm, the relative linear speed of the needle head in the coagulating bath of the rotating platform is greater than the maximum linear speed capable of continuously forming fibers, and the fibers can be broken at relatively stable time intervals in the coagulating bath, so that short fibers with uniform length are formed. In this example, the fibers were broken at about 1s intervals in the coagulation bath to form short fibers having a length of about 6 cm.
Preparing a tellurium alkene/graphene hybrid fiber membrane: and after collecting the tellurium alkene/graphene oxide hybrid short fiber for 10min, oscillating the coagulation bath to ensure that the tellurium alkene/graphene oxide hybrid short fiber is uniformly distributed in the coagulation bath. And (3) carrying out suction filtration on the coagulation bath containing the tellurite/graphene oxide hybrid short fiber. Thereby obtaining the fiber membrane consisting of the tellurium alkene/graphene oxide hybrid short fiber. Soaking the tellurium alkene/graphene oxide hybrid fiber membrane in HI for chemical reduction, and obtaining the final tellurium alkene/graphene oxide hybrid fiber membrane with the ratio of 1:1 of a tellurium-graphene/graphene hybrid fiber membrane.
Preparing a photo-thermal and piezoelectric heating dual-mechanism heating film: the method comprises the steps of taking a tellurium/graphene hybrid fiber membrane as a receiving plate, taking a mixed solution of graphene/PVDF as a spinning solution (wherein a solvent is a mixed solution of DMF and acetone in a mass ratio of 6:4, the mass fraction of solute PVDF is 10%, and the mass fraction of solute graphene is 3%), carrying out electrostatic spinning, and forming a double-layer fiber membrane of the tellurium/graphene hybrid fiber membrane and the graphene/PVDF nanofiber membrane, namely the photothermal and piezoelectric heating double-machine heating membrane.
Example 2
Example 2 differs from example 1 only in that: after a double-layer fiber membrane of the tellurium/graphene hybrid fiber membrane and the graphene/PVDF nanofiber membrane is prepared, a conductive adhesive is coated on the graphene/PVDF nanofiber membrane, and the other piece of tellurium/graphene hybrid fiber membrane is adhered to the graphene/PVDF nanofiber membrane to form a sandwich membrane of the tellurium/graphene hybrid fiber membrane, the graphene/PVDF nanofiber membrane and the tellurium/graphene hybrid fiber membrane. And connecting two pieces of tellurium/graphene hybrid fiber membranes by using high-conductivity graphene fibers and conductive adhesive to form a functional device. Based on the requirement of protecting the whole functional device, the functional device can be packaged by using a transparent PET film.
Example 3
Example 3 differs from example 1 only in that: the source of the tellurium alkene pre-exfoliation dispersion varied, and example 3 prepares the tellurium alkene pre-exfoliation dispersion by itself.
The preparation process of the tellurium alkene pre-stripping dispersion liquid is as follows:
3g of Te powder is added into 500ml of N-methyl pyrrolidone and shaken for 1min for preliminary mixing, thus obtaining mixed liquid A. And placing the prepared mixed solution A in a constant-temperature water bath ultrasonic machine to carry out ultrasonic stripping on the Te powder. The ultrasonic constant temperature should be lower than 10 ℃. Performing ultrasonic treatment for 72 hours, taking out the mixture every 6 hours in the ultrasonic treatment process, vibrating the mixture for 1min, and putting the mixture into the ultrasonic machine again to continue the ultrasonic treatment after the vibration. And after the ultrasonic treatment is finished, carrying out centrifugal treatment on the mixed solution A, wherein the centrifugal rotation speed is 5000rpm, and the centrifugal time is 60 min. And centrifuging and collecting the supernatant to obtain the tellurium alkene pre-stripping dispersion liquid.
Example 4
Example 4 differs from example 1 only in that: the mass ratio of the tellurite to the graphene oxide is 70: 30.
Effect embodiment:
the short fibers in the tellurium-graphene/graphene hybrid fiber film prepared in example 1 are observed by a scanning electron microscope, as shown in fig. 3, the tellurium-graphene/graphene hybrid fiber prepared in example 1 has good flexibility, the fiber filaments forming the film are uniform, and the diameter of the fiber filaments is about 48 μm. The conductivity of the fiber membrane is 15.8S/cm. After shading treatment, simulated sunlight is applied for irradiation, the fiber membrane generates heat, and photothermal effect is expressed.
After the photothermal and piezoelectric heating dual-mechanism heating film prepared in example 1 is further subjected to PET encapsulation, the tensile strength of the functional device encapsulated by the prepared PET film is 189.2 MPa. Under illumination or repeated bending of bending-recovery, the functional device packaged by the PET film generates obvious heating phenomenon. The maximum temperature can reach 48 ℃ only under illumination, 41 ℃ only under repeated bending and 53 ℃ when the repeated bending is carried out under illumination.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of a photo-thermal and piezoelectric heating dual-mechanism heating film is characterized by comprising the following steps:
preparing a mixture of tellurium and graphene oxide: providing a tellurium alkene pre-stripping dispersion liquid, adding graphene oxide into the tellurium alkene pre-stripping dispersion liquid, carrying out constant-temperature water bath ultrasonic treatment, centrifuging, collecting a bottom layer mixture, dispersing the bottom layer mixture into water, washing, concentrating and drying to obtain a mixture of tellurium alkene and graphene oxide;
preparing a tellurium alkene/graphene oxide mixed dispersion liquid: adding water into a mixture of the tellurite and the graphene oxide, stirring to obtain a mixed solution, performing ultrasonic treatment on the mixed solution in a pulse type tip ultrasonic mode, and concentrating the mixed solution after the ultrasonic treatment is finished to obtain a tellurite/graphene oxide mixed dispersion solution;
spinning: taking the tellurium alkene/graphene oxide mixed dispersion liquid as a spinning stock solution, taking glacial acetic acid as a coagulating bath, and carrying out wet spinning by adopting a rotating table, wherein the linear speed of a spinning needle relative to the coagulating bath of the rotating table is greater than the maximum linear speed capable of continuously forming fibers, so as to prepare tellurium alkene/graphene oxide hybrid short fibers;
preparing a tellurium alkene/graphene hybrid fiber membrane: after collecting the tellurium alkene/graphene oxide hybrid short fiber, carrying out suction filtration and reduction on a coagulating bath containing the tellurium alkene/graphene oxide hybrid short fiber to obtain a tellurium alkene/graphene hybrid fiber membrane;
preparing a photo-thermal and piezoelectric heating dual-mechanism heating film: and (3) performing electrostatic spinning by taking the tellurium/graphene hybrid fiber membrane as a receiving plate and taking the mixed solution of graphene/PVDF as a spinning solution to form a double-layer fiber membrane of the tellurium/graphene hybrid fiber membrane and the graphene/PVDF nanofiber membrane, so as to prepare the photothermal and piezoelectric heating dual-mechanism heating membrane.
2. The method for preparing a photothermal and piezoelectric heating dual-membrane as claimed in claim 1, wherein in the step of preparing the photothermal and piezoelectric heating dual-membrane, the surface of the graphene/PVDF nanofiber membrane facing away from the tellurium/graphene hybrid fiber membrane is connected to another tellurium/graphene hybrid fiber membrane to form a sandwich structure of the tellurium/graphene hybrid fiber membrane-graphene/PVDF nanofiber membrane-tellurium/graphene hybrid fiber membrane, thereby preparing the photothermal and piezoelectric heating dual-membrane.
3. The method for preparing a photothermal and piezoelectric heating film according to claim 1, wherein in the step of preparing the photothermal and piezoelectric heating film, the graphene/PVDF mixed solution comprises: PVDF and graphene, wherein the mass fraction of the PVDF is 10%, and the mass fraction of the graphene is 1% -5%; also comprises a solvent: the mixed solution of DMF and acetone, wherein the mass ratio of DMF to acetone is 6: 4.
4. The method for preparing a photothermal and piezoelectric heating dual-mechanism heating film according to claim 1, wherein in the step of preparing the mixture of the tellurite and the graphene oxide, the mass ratio of the tellurite to the graphene oxide is 0.1-7: 3;
the temperature of the constant-temperature water bath ultrasound is less than or equal to 10 ℃, and the time of the constant-temperature water bath ultrasound is 4-36 hours.
5. The method for preparing a photothermal and piezoelectric heating dual-mechanism heating film according to claim 1, wherein in the step of preparing the mixture of the telluroene and the graphene oxide, the centrifugation rotation speed is 8000 to 15000rpm, and the centrifugation time is 20 to 200 min;
and after centrifugation, pouring out the supernatant, wherein the precipitate is the mixture of the tellurium and the graphene oxide.
6. The method for preparing a photothermal and piezoelectric heating dual-mechanism heating film according to claim 1, wherein in the step of preparing the tellurium alkene/graphene oxide mixed dispersion liquid, the prepared mixed liquid has a modulation concentration of 5-20 mg/ml, and then pulse type tip ultrasound is performed on the mixed liquid of 5-20 mg/ml;
the ultrasonic interval time of the pulse type tip ultrasonic is as follows: and 5s of ultrasound, 5s of interval and 4h of total ultrasound time.
7. The method for preparing a photothermal and piezoelectric heating dual-machine heating film according to claim 1, wherein in the step of preparing the tellurium alkene/graphene oxide mixed dispersion liquid, after the ultrasonic treatment is finished, the mixed liquid is concentrated by heating until the solid content concentration is 15-25 mg/ml, so as to obtain the tellurium alkene/graphene oxide mixed dispersion liquid;
in the spinning step, the rotating speed of the spinning needle relative to the rotating table coagulating bath is 30rpm, and the distance between the spinning needle and the center of the rotating table is 20 mm.
8. The method for preparing a photothermal and piezoelectric heating dual-mechanism heating film according to claim 1, wherein in the step of preparing the telluriene/graphene hybrid fiber film, after the coagulation bath containing the telluriene/graphene oxide hybrid short fibers is subjected to suction filtration, an unreduced telluriene/graphene oxide hybrid fiber film is obtained;
soaking the tellurium alkene/graphene oxide hybrid fiber membrane in any one of HI, NaBH4, hydrazine hydrate and ascorbic acid for chemical reduction to obtain the tellurium alkene/graphene hybrid fiber membrane.
9. A photothermal, piezoelectric heating dual-mechanism heating film obtained by the method for preparing a photothermal, piezoelectric heating dual-mechanism heating film according to any one of claims 1 to 8.
10. A heating suit characterized by being made of the photothermal and piezoelectric heating dual-mechanism heating film according to claim 9.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101423757B1 (en) * | 2013-04-29 | 2014-08-04 | 계명대학교 산학협력단 | Manufacturing method of nanofiber-graphene membrane for water-treatment and nanofiber-graphene membrane for water-treatment thereof |
| CN108313987A (en) * | 2018-02-09 | 2018-07-24 | 深圳大学 | Two-dimentional tellurium nanometer sheet and its preparation method and application |
| CN108505213A (en) * | 2018-05-14 | 2018-09-07 | 广东石油化工学院 | A kind of preparation method of amino graphene/polyunsymfluorethylepiezoelectric piezoelectric nanometer electrospinning film |
| CN108793098A (en) * | 2018-07-16 | 2018-11-13 | 深圳大学 | Two-dimentional selenium nanometer sheet and its preparation method and application |
| CN109786619A (en) * | 2017-11-13 | 2019-05-21 | 北京碳阳科技有限公司 | A kind of battery diaphragm and preparation method thereof |
| CN109825021A (en) * | 2018-12-27 | 2019-05-31 | 张晗 | A kind of thin polymer film of the alkene containing tellurium and its preparation method and application |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101423757B1 (en) * | 2013-04-29 | 2014-08-04 | 계명대학교 산학협력단 | Manufacturing method of nanofiber-graphene membrane for water-treatment and nanofiber-graphene membrane for water-treatment thereof |
| CN109786619A (en) * | 2017-11-13 | 2019-05-21 | 北京碳阳科技有限公司 | A kind of battery diaphragm and preparation method thereof |
| CN108313987A (en) * | 2018-02-09 | 2018-07-24 | 深圳大学 | Two-dimentional tellurium nanometer sheet and its preparation method and application |
| CN108505213A (en) * | 2018-05-14 | 2018-09-07 | 广东石油化工学院 | A kind of preparation method of amino graphene/polyunsymfluorethylepiezoelectric piezoelectric nanometer electrospinning film |
| CN108793098A (en) * | 2018-07-16 | 2018-11-13 | 深圳大学 | Two-dimentional selenium nanometer sheet and its preparation method and application |
| CN109825021A (en) * | 2018-12-27 | 2019-05-31 | 张晗 | A kind of thin polymer film of the alkene containing tellurium and its preparation method and application |
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