CN112234136A - High-efficiency fiber-based thermoelectric energy supply material and preparation method thereof - Google Patents
High-efficiency fiber-based thermoelectric energy supply material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a high-efficiency fiber-based thermoelectric energy supply material and a preparation method thereof. The efficient fiber-based thermoelectric energy supply material comprises a fiber-based self-generating layer and a photo-thermal film arranged on the upper surface of the fiber-based self-generating layer. The fiber-based self-generating layer is prepared by dipping a fiber base material into a thermoelectric solution and arranging electrodes on the upper surface and the lower surface of the dipped and dried fiber base material; and coating the colloidal photo-thermal material formed by mixing the photo-thermal nano particles and the viscose solution on the upper surface of the fiber-based self-generating layer to form the photo-thermal film. Through the mode, the fiber-based self-generating layer can utilize molecular thermal motion generated after the photo-thermal film absorbs solar rays and infrared rays emitted by a human body, so that the temperature of the upper surface of the fiber-based self-generating layer is increased, and the temperature difference is formed between the upper surface and the lower surface of the fiber-based self-generating layer, so that a thermoelectric material is driven to generate voltage, and the self-generating function is realized; and the high-efficiency fiber-based thermoelectric energy supply material has excellent thermoelectric performance, high power generation efficiency, good flexibility and higher application value.
Description
Technical Field
The invention relates to the technical field of thermoelectric energy supply materials, in particular to a high-efficiency fiber-based thermoelectric energy supply material and a preparation method thereof.
Background
The thermoelectric material is a functional material capable of realizing the interconversion of electric energy and heat energy by utilizing the Seebeck effect, has no noise and pollution in the using process, stable performance and long service life, and has wide application prospect. In recent years, with the acceleration of global industrialization progress, the consumption of energy is increasing, the energy shortage crisis and the environmental pollution problem are becoming more severe, and the thermoelectric material has attracted much attention as a renewable green energy. How to use thermoelectric materials for high-efficiency energy supply is the focus of current research.
However, the conventional thermoelectric material is mainly in a block shape, and has the disadvantages of high rigidity, easy breaking, portability and the like, which limits the application of the thermoelectric material to a certain extent, and also promotes the development of the thermoelectric material from a rigid material to a flexible material. The appearance of the flexible thermoelectric material not only provides a new direction for the research of the thermoelectric material, but also expands the application of the thermoelectric material in the field of wearable electronic devices. Therefore, the research on the flexible thermoelectric material and the energy supply mode thereof is of great significance.
Patent publication No. CN110736559A provides a flexible temperature-pressure sensor, and a preparation method and application thereof. This patent prepares a flexible temperature-pressure sensor by attaching PEDOT: PSS having excellent conductivity and pyroelectricity to a flexible three-dimensional fiber substrate by means of dip-adsorption, and preparing upper and lower electrodes on the upper and lower surfaces thereof. The flexible temperature-pressure sensor can form temperature difference self-generation by utilizing the temperature difference between the upper surface and the lower surface, but the temperature difference between the upper surface and the lower surface is realized by arranging the sensor on the heating plate, and the heating plate needs to consume electric energy in use and is not easy to carry about, so that the application of the flexible temperature-pressure sensor is limited. In order to enable the flexible thermoelectric material to be used for energy supply, it is necessary to enable the upper surface and the lower surface of the flexible thermoelectric material to be capable of automatically generating temperature difference, in the prior art, the temperature difference between body temperature and environment temperature is generally used for self-generating electricity, but the temperature difference is too small, the generating efficiency is low, and the requirements of practical application are difficult to meet. Therefore, how to form a large temperature difference on the upper and lower surfaces of the flexible fiber substrate is a problem to be solved.
In view of the above, there is a need to design an improved high-efficiency fiber-based thermoelectric energy supply material and a preparation method thereof to solve the above problems.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention provides a high-efficiency fiber-based thermoelectric energy supply material and a method for preparing the same. The upper surface of the fiber-based self-generating layer is provided with the photo-thermal film to prepare the high-efficiency fiber-based thermoelectric energy supply material; the molecular heat movement generated after the photo-thermal film absorbs infrared rays emitted by the sun or a human body raises the temperature of the upper surface of the fiber-based self-generating layer, so that a temperature difference is formed between the fiber-based self-generating layer and the lower surface of the fiber-based self-generating layer, a thermoelectric channel is formed in the vertical direction, and the function of self-generation is realized.
In order to achieve the aim, the invention provides a preparation method of a high-efficiency fiber-based thermoelectric energy supply material, which comprises the following steps:
s1, preparing a thermoelectric solution containing thermoelectric materials;
s2, soaking the fiber base material in the thermoelectric solution prepared in the step S1, taking out and drying to obtain the fiber base material with the thermoelectric material adsorption capacity of 10% -40%; then arranging electrodes on the upper surface and the lower surface of the fiber base material to obtain a fiber-based self-generating layer;
s3, adding the photo-thermal nano particles into a viscose solution containing a bonding material, and uniformly mixing to obtain a colloidal photo-thermal material; and then uniformly coating the colloidal photo-thermal material on the upper surface of the fiber-based self-power generation layer obtained in the step S2, and after drying treatment, forming a photo-thermal film on the upper surface to obtain the high-efficiency fiber-based thermoelectric energy supply material.
As a further improvement of the present invention, in step S2, the fiber base material immersed in the thermoelectric solution is taken out and dried, and then the fiber base material is immersed in an ethylene glycol solution for 2 to 5 hours, and is taken out and dried again.
As a further improvement of the present invention, in step S3, after the photo-thermal film is formed by the baking process, the fiber-based self-power generation layer and the photo-thermal film are perforated.
As a further improvement of the present invention, in step S3, the content of the photothermal nanoparticles in the colloidal photothermal material is 0.1% to 3%; the drying temperature of the colloidal photo-thermal material is 60-80 ℃.
As a further improvement of the present invention, in step S1, the thermoelectric material is an organic thermoelectric material or a mixture thereof with an inorganic thermoelectric material; the thermoelectric solution is one of an organic thermoelectric solution formed by an organic thermoelectric material, a thermoelectric mixed solution formed by mixing the organic thermoelectric solution and an organic solvent, and a thermoelectric composite solution formed by blending the thermoelectric mixed solution and the inorganic thermoelectric material; in the thermoelectric mixed solution, the addition amount of the organic solvent is 1-5%; in the thermoelectric composite solution, the addition amount of the inorganic thermoelectric material is 0.5-5%.
As a further improvement of the invention, the organic thermoelectric material is one of PEDOT, PSS, polyaniline and polypyrrole; the inorganic thermoelectric material is one of bismuth telluride, lead telluride, carbon nano tubes and graphene; the organic solvent is one or more of glycol, polyethylene glycol, glycerol and dimethyl sulfoxide.
In order to achieve the purpose, the invention also provides a high-efficiency fiber-based thermoelectric energy supply material, which is prepared according to any one of the technical schemes and comprises a fiber-based self-generating layer and a photo-thermal film arranged on the upper surface of the fiber-based self-generating layer; the fiber-based self-generating layer comprises a fiber base material adsorbed with thermoelectric materials and electrodes arranged on the upper surface and the lower surface of the fiber base material; the photo-thermal film contains photo-thermal nano particles and a binding material.
As a further improvement of the invention, the thickness of the photo-thermal film is 100-300 μm; the photo-thermal nano particles are one or a mixture of ZrC, SiC, TiC and far infrared ceramic powder; the bonding material is one of epoxy resin, polydimethylsiloxane, polyurethane and polyethylene terephthalate.
As a further improvement of the invention, the thickness of the fiber base material is 1-10 mm, and the fiber base material contains a heat insulation layer with a hollow structure; the fiber base material is one of woven fabric, knitted fabric, three-dimensional fabric and non-woven fabric.
As a further improvement of the invention, the thickness of the electrode is 30-50 μm, and the material of the electrode is one or a mixture of more of silver, gold, aluminum and nickel.
The invention has the beneficial effects that:
(1) the high-efficiency fiber-based thermoelectric energy supply material provided by the invention comprises a fiber-based self-generating layer and a photo-thermal film attached to the upper surface of the fiber-based self-generating layer. The photothermal nanoparticles contained in the photothermal film can absorb infrared rays in solar rays or infrared rays emitted by a human body and generate molecular thermal motion, so that the temperature of the upper surface of the fiber-based self-power generation layer attached to the photothermal film is increased, and the obvious temperature difference is generated on the upper surface and the lower surface of the fiber-based self-power generation layer. Meanwhile, the thermoelectric material adsorbed in the fiber-based self-generating layer can form a thermoelectric channel in the vertical direction by utilizing the temperature difference generated by the upper surface and the lower surface, so that thermoelectric potential is generated, and the self-generating function is realized by utilizing the synergistic effect between the thermoelectric film and the fiber-based self-generating layer.
(2) According to the preparation method of the high-efficiency fiber-based thermoelectric energy supply material, the photo-thermal nanoparticles and the bonding material are mixed to form the colloidal photo-thermal material, the colloidal photo-thermal material is coated on the upper surface of the fiber-based self-generating layer, and the photo-thermal film is formed after drying. In the process, the preferred bonding materials such as epoxy resin, polyethylene glycol terephthalate and the like can not only have the function of adhering photo-thermal nanoparticles to the upper surface of the fiber-based self-generating layer, but also ensure that the adhered fiber-based self-generating layer has a good carrier passage due to good insulating property; meanwhile, the excellent flexibility of the bonding materials can also enable the bonding materials to be always tightly bonded with the fiber-based self-generating layer in the states of stretching or bending and the like, so that the photo-thermal nano particles are not easy to fall off in the actual use process, and the service life is longer. In addition, the nano-scale photothermal particles are selected for preparing the photothermal film, so that the photothermal film can be fully absorbed by utilizing the larger specific surface area of the photothermal film, the photothermal conversion efficiency is improved, the photothermal film and a bonding material can form the photothermal film with higher flexibility by utilizing the smaller particle size of the photothermal film, the photothermal film can be fully attached to the fiber-based self-generating layer with the same flexibility, the heat transfer efficiency is improved, the efficient conversion and conduction of energy are realized, the photothermal film can be suitable for various environments such as indoor environment, outdoor environment, light and dark environment, and the application range is wider.
(3) According to the invention, the holes penetrating through the fiber-based self-generating layer and the photo-thermal film are formed in the prepared high-efficiency fiber-based thermoelectric energy supply material, so that the air permeability of the thermoelectric energy supply material can be effectively improved while high-efficiency energy supply is ensured, and the thermoelectric energy supply material has better wearability, and is convenient to apply to the field of wearable electronic devices.
(4) The preparation method of the high-efficiency fiber-based thermoelectric energy supply material provided by the invention is simple and feasible, and can meet the requirements of industrial large-scale production; the prepared high-efficiency fiber-based thermoelectric energy supply material is excellent in thermoelectric performance and good in flexibility, can independently generate large temperature difference under sunlight, achieves full utilization of solar energy, has high energy conversion and conduction efficiency, and has good application prospects in the fields of solar power generation and wearable electronic devices.
Drawings
FIG. 1 is a schematic diagram of a high efficiency fiber-based thermoelectric energy supply material provided by the present invention.
Fig. 2 is a graph showing temperature change curves under light irradiation of the photothermal film prepared in example 4 and the general film prepared in comparative example 1.
Fig. 3 is a graph comparing the voltage generated by the high-efficiency fiber-based thermoelectric energy supply material prepared in example 4 and the fiber-based thermoelectric energy supply material prepared in comparative example 3 under different illumination intensities.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the aspects of the present invention are shown in the drawings, and other details not closely related to the present invention are omitted.
In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a preparation method of a high-efficiency fiber-based thermoelectric energy supply material, which comprises the following steps:
s1, preparing a thermoelectric solution containing thermoelectric materials;
s2, soaking the fiber base material in the thermoelectric solution prepared in the step S1, taking out and drying to obtain the fiber base material with the thermoelectric material adsorption capacity of 10% -40%; then arranging electrodes on the upper surface and the lower surface of the fiber base material to obtain a fiber-based self-generating layer;
s3, adding the photo-thermal nano particles into a viscose solution containing a bonding material, and uniformly mixing to obtain a colloidal photo-thermal material; and then uniformly coating the colloidal photo-thermal material on the upper surface of the fiber-based self-power generation layer obtained in the step S2, and after drying treatment, forming a photo-thermal film on the upper surface to obtain the high-efficiency fiber-based thermoelectric energy supply material.
In step S1, the thermoelectric material is an organic thermoelectric material or a mixture thereof with an inorganic thermoelectric material; the thermoelectric solution is one of an organic thermoelectric solution formed by an organic thermoelectric material, a thermoelectric mixed solution formed by mixing the organic thermoelectric solution and an organic solvent, and a thermoelectric composite solution formed by blending the thermoelectric mixed solution and the inorganic thermoelectric material; in the thermoelectric mixed solution, the addition amount of the organic solvent is 1-5%; in the thermoelectric composite solution, the addition amount of the inorganic thermoelectric material is 0.5-5%.
The organic thermoelectric material is one of PEDOT, PSS, polyaniline and polypyrrole; the inorganic thermoelectric material is one of bismuth telluride, lead telluride, carbon nano tubes and graphene; the organic solvent is one or more of glycol, polyethylene glycol, glycerol and dimethyl sulfoxide.
In step S2, the fiber base material immersed in the thermoelectric solution is taken out and dried, and then the fiber base material is immersed in an ethylene glycol solution for 2 to 5 hours, and is taken out and dried again.
In step S3, after the photo-thermal film is formed by the baking process, the fiber-based self-power generation layer and the photo-thermal film are perforated; the content of photo-thermal nano particles in the colloidal photo-thermal material is 0.1-3%; the drying temperature of the colloidal photo-thermal material is 60-80 ℃.
The invention also provides a high-efficiency fiber-based thermoelectric energy supply material, which is prepared according to the technical scheme, and the physical diagram of the high-efficiency fiber-based thermoelectric energy supply material is shown in figure 1. The high-efficiency fiber-based thermoelectric energy supply material comprises a fiber-based self-generating layer and a photo-thermal film arranged on the upper surface of the fiber-based self-generating layer; the fiber-based self-generating layer comprises a fiber base material adsorbed with thermoelectric materials and electrodes arranged on the upper surface and the lower surface of the fiber base material; the photo-thermal film contains photo-thermal nano particles and a binding material.
The thickness of the photo-thermal film is 100-300 mu m; the photo-thermal nano particles are one or a mixture of ZrC, SiC, TiC and far infrared ceramic powder; the bonding material is one of epoxy resin, polydimethylsiloxane, polyurethane and polyethylene terephthalate.
The thickness of the fiber base material is 1-10 mm, and the fiber base material contains a heat insulation layer with a hollow structure; the fiber base material is one of woven fabric, knitted fabric, three-dimensional fabric and non-woven fabric.
The thickness of the electrode is 30-50 mu m, and the material of the electrode is one or a mixture of silver, gold, aluminum and nickel.
The high-efficiency fiber-based thermoelectric energy supply material and the preparation method thereof provided by the invention are explained below with reference to specific examples.
Example 1
The embodiment provides a preparation method of a high-efficiency fiber-based thermoelectric energy supply material, which comprises the following steps:
and S1, adding dimethyl sulfoxide and carbon nano tubes into the aqueous solution of PEDOT (PSS), and carrying out ultrasonic treatment for 1h to uniformly mix the dimethyl sulfoxide and the carbon nano tubes to obtain the thermoelectric composite solution. In the thermoelectric composite solution, the volume fraction of dimethyl sulfoxide is 5%, and the mass fraction of carbon nano tubes is 2%.
S2, taking a three-dimensional fabric (10mm multiplied by 3mm) with a hollow heat insulation layer inside as a fiber base material, soaking the three-dimensional fabric into the thermoelectric composite solution prepared in the step S1, performing ultrasonic treatment for 2 hours, taking out the three-dimensional fabric, drying the three-dimensional fabric at 130 ℃ for 15 minutes, soaking the three-dimensional fabric into an ethylene glycol solution for 2 hours, taking out the three-dimensional fabric, and drying the three-dimensional fabric at 130 ℃ in vacuum for 5 minutes to obtain the fiber base material with the thermoelectric material adsorption capacity of 30%. And then, respectively coating silver paste with the thickness of 40 mu m on the upper surface and the lower surface of the fiber base material to serve as electrodes, and drying for 5min at the temperature of 80 ℃ to obtain the fiber-based self-generating layer.
S3, adding ZrC particles with the particle size of 50-500 nm into an epoxy resin solution, and uniformly mixing to obtain a colloidal photo-thermal material with the ZrC nanoparticles content of 0.1%; and uniformly coating the colloidal photo-thermal material on the upper surface of the fiber-based self-generating layer obtained in the step S2, and drying the colloidal photo-thermal material at 70 ℃ to form a 120-micrometer photo-thermal film on the upper surface of the fiber-based self-generating layer. And perforating the fiber-based self-generating layer and the photo-thermal film by using a puncher to ensure that the fiber-based self-generating layer and the photo-thermal film have the air permeability function, so that the high-efficiency fiber-based thermoelectric energy supply material is obtained.
Examples 2 to 7 and comparative examples 1 to 2
Comparative examples 1 to 2 each provide a fiber-based thermoelectric energy supply material, and are different from example 1 in that photothermal nanoparticles are not added in step S3 of comparative example 1; whereas in step S3 of comparative example 2, photo-thermal nanoparticles were added in a mass fraction of 3.5%, and a photo-thermal film having a thickness of 200 μm was formed; the remaining steps of comparative examples 1-2 are the same as example 1 and are not repeated herein.
TABLE 1 content of photothermal nanoparticles and photothermal film thickness in examples 2-7 and comparative examples 1-2
| Examples/comparative examples | Photothermal nanoparticle content (%) | Photothermal film thickness (μm) |
| Example 2 | 0.5 | 130 |
| Example 3 | 1 | 160 |
| Example 4 | 1.5 | 200 |
| Example 5 | 2 | 240 |
| Example 6 | 2.5 | 270 |
| Example 7 | 3 | 300 |
| Comparative example 1 | 0 | 200 |
| Comparative example 2 | 3.5 | 200 |
In order to study the energy supply condition of the high-efficiency fiber-based thermoelectric energy supply materials prepared in the examples, the fiber-based thermoelectric energy supply materials prepared in the examples 1 to 7 and the comparative examples 1 to 2 were placed at a strength of 100mw/cm2The temperature difference between the upper surface and the lower surface of each fiber-based thermoelectric energy supply material and the heating efficiency are tested and calculated after the fiber-based thermoelectric energy supply material is irradiated for 300s under the illumination, and the results are shown in table 2.
TABLE 2 Properties of fiber-based thermoelectric energy supply materials prepared in examples 1 to 6 and comparative examples 1 to 2
As can be seen from table 2, the fiber-based thermoelectric energy supply materials of examples 1 to 7 containing photothermal nanoparticles have significantly higher power generation efficiency than comparative example 1 containing no photothermal nanoparticles. And with the increase of the addition amount of the photothermal nanoparticles and the thickness of the photothermal film, the heating capacity of the photothermal film is increased, and the temperature difference between the upper surface and the lower surface and the power generation efficiency are increased, which shows that the heating capacity of the photothermal film is increased due to the increase of the addition amount of the photothermal nanoparticles, so that the temperature difference between the upper surface and the lower surface of the fiber base is increased, and the optimization of the power generation efficiency is facilitated.
However, when the amount of the photothermal nanoparticles added is increased to 3%, the amount of the photothermal nanoparticles added and the photothermal film thickness thereof are continuously increased, and the heating power of the photothermal film is substantially maintained and is not significantly increased, so that the amount of the photothermal nanoparticles added is preferably 0.1% to 3% by mass in consideration of the production cost and the flexibility of the photothermal film.
In order to further compare the temperature change of the photothermal film containing photothermal nanoparticles and the common film containing no photothermal nanoparticles under light irradiation, the photothermal film containing 1.5 wt% photothermal nanoparticles prepared in example 4 and the common film containing no photothermal nanoparticles in comparative example 1 were exposed to the same light irradiation, and the temperature change curves thereof were measured as shown in fig. 2. As can be seen from FIG. 2, under the illumination condition of 0-1000 s, the temperature of the photo-thermal film is rapidly increased and is obviously higher than that of a common film; when the light is removed, the temperature of the photothermal film and the ordinary film both fall back to the normal temperature state. Therefore, the invention can greatly increase the temperature difference of the upper surface and the lower surface of the fiber-based spontaneous electric layer by preparing the photo-thermal film on the surface of the fiber-based spontaneous electric layer, thereby achieving higher generating efficiency.
Examples 8 to 14
Examples 8 to 14 each provide a method for preparing a high-efficiency fiber-based thermoelectric energy supply material, which is different from example 4 in that the types of the photo-thermal nanoparticles and the binding material used in step S3 are changed, and the remaining steps are the same as those in example 4, and are not repeated herein. The kinds of photo-thermal nanoparticles and the binding material corresponding to each example are shown in table 3.
TABLE 3 kinds of photothermal nanoparticles and binder in examples 8 to 14
In order to study the thermoelectric performance and energy supply condition of the high-efficiency fiber-based thermoelectric energy supply materials prepared in the examples, the high-efficiency fiber-based thermoelectric energy supply materials prepared in the examples 8 to 14 were tested, and the results are shown in table 4.
TABLE 4 Properties of high-efficiency fiber-based thermoelectric energy supply materials prepared in examples 8 to 14
| Examples | Temperature difference between upper and lower surfaces (. degree. C.) | Efficiency of Power Generation (%) |
| Example 8 | 63 | 0.014 |
| Example 9 | 65 | 0.0146 |
| Example 10 | 45 | 0.01 |
| Example 11 | 68 | 0.0153 |
| Example 12 | 70 | 0.0157 |
| Example 13 | 65 | 0.0146 |
| Example 14 | 75 | 0.0169 |
As can be seen from table 4, the change of the type of the photo-thermal nanoparticles or the change of the type of the binding material affects the temperature change condition, so that the power generation efficiency of the prepared high-efficiency fiber-based thermoelectric energy supply material is affected, and the preferred photo-thermal nanoparticles and binding materials of the present invention can achieve higher power generation efficiency. The photothermal nanoparticles used in example 14 are formed by blending ZrC particles and far infrared ceramic powder in a mass ratio of 1:1, and can absorb near infrared rays and far infrared rays emitted from sunlight at the same time, so that the photothermal capability is improved, and the power generation efficiency is significantly improved.
Comparative example 3
Comparative example 3 provides a fiber-based thermoelectric energy supply material, which is different from example 4 in that the photothermal material is not coated on the surface of the fiber-based self-power generation layer, and a thermoelectric energy supply material without a photothermal film is prepared. The rest steps are the same as those in embodiment 4, and are not described herein again.
The fiber-based thermoelectric energy supply materials prepared in example 4 and comparative example 3 were exposed to light of different intensities, and the generated voltages thereof were measured, and the results are shown in fig. 3. In fig. 3, the high-efficiency fiber-based thermoelectric energy-supplying material prepared in example 4 is shown with a photo-thermal film, and the fiber-based thermoelectric energy-supplying material prepared in comparative example 1 is shown without a photo-thermal film. As can be seen from fig. 3, the fiber-based thermoelectric energy supply material containing the photothermal film prepared in example 4 generates a significantly higher voltage than that of comparative example 1 under the same intensity of light, and the difference between the two is larger as the intensity of light is larger. Therefore, the photo-thermal film is added on the fiber-based self-generating layer, so that the voltage for generating electricity can be obviously enhanced, and higher generating efficiency can be achieved, thereby meeting the requirements of practical application.
It should be noted that, in step S1, the fiber substrate may be one of woven fabric, knitted fabric, three-dimensional fabric and non-woven fabric, and the thickness of the fiber substrate may be adjusted between 1 mm and 10 mm. Meanwhile, the thermoelectric material may be an organic thermoelectric material or a mixture thereof with an inorganic thermoelectric material; the thermoelectric solution may be one of an organic thermoelectric solution formed of an organic thermoelectric material, a thermoelectric mixed solution formed by mixing the organic thermoelectric solution with an organic solvent, and a thermoelectric composite solution formed by blending the thermoelectric mixed solution with the inorganic thermoelectric material.
In the thermoelectric mixed solution, the addition amount of the organic solvent may be 1% to 5%; in the thermoelectric composite solution, the inorganic thermoelectric material may be added in an amount of 0.5% to 5%. The organic thermoelectric material can be one of PEDOT, PSS, polyaniline and polypyrrole; the inorganic thermoelectric material can be one of bismuth telluride, lead telluride, carbon nano tubes and graphene; the organic solvent can be one or more of ethylene glycol, polyethylene glycol, glycerol and dimethyl sulfoxide. By arranging different fiber substrates and thermoelectric materials, the adsorption amount of the thermoelectric material can be adjusted to be in the range of 10-40%. In addition, in step S2, the time for soaking in the ethylene glycol solution can be adjusted within 2-5 hours; the material of the electrode can be one or a mixture of more of silver, gold, aluminum and nickel, and the thickness of the electrode can be adjusted between 30 and 50 mu m. In step S3, the drying temperature of the gel-like photothermal material can be adjusted between 60 ℃ and 80 ℃, which all fall within the protection scope of the present invention.
In conclusion, the invention provides a high-efficiency fiber-based thermoelectric energy supply material and a preparation method thereof. The efficient fiber-based thermoelectric energy supply material comprises a fiber-based self-generating layer and a photo-thermal film arranged on the upper surface of the fiber-based self-generating layer. The fiber-based self-generating layer is prepared by dipping a fiber base material into a thermoelectric solution and arranging electrodes on the upper surface and the lower surface of the dipped and dried fiber base material; and the colloidal photo-thermal material formed by mixing the light nano-particles and the viscose solution is coated on the upper surface of the fiber-based self-generating layer to form the photo-thermal film. Through the mode, the fiber-based self-generating layer can utilize molecular thermal motion generated after the photo-thermal film absorbs infrared rays in solar rays or infrared rays emitted by a human body to increase the temperature of the upper surface of the fiber-based self-generating layer, so that temperature difference is formed between the fiber-based self-generating layer and the lower surface of the fiber-based self-generating layer, a thermoelectric material is driven to generate voltage, and the function of self-generation is realized; and the high-efficiency fiber-based thermoelectric energy supply material has excellent thermoelectric performance, high power generation efficiency, good flexibility and higher application value.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (10)
1. A preparation method of a high-efficiency fiber-based thermoelectric energy supply material is characterized by comprising the following steps:
s1, preparing a thermoelectric solution containing thermoelectric materials;
s2, soaking the fiber base material in the thermoelectric solution prepared in the step S1, taking out and drying to obtain the fiber base material with the thermoelectric material adsorption capacity of 10% -40%; then arranging electrodes on the upper surface and the lower surface of the fiber base material to obtain a fiber-based self-generating layer;
s3, adding the photo-thermal nano particles into a viscose solution containing a bonding material, and uniformly mixing to obtain a colloidal photo-thermal material; and then uniformly coating the colloidal photo-thermal material on the upper surface of the fiber-based self-power generation layer obtained in the step S2, and after drying treatment, forming a photo-thermal film on the upper surface to obtain the high-efficiency fiber-based thermoelectric energy supply material.
2. The preparation method of the high-efficiency fiber-based thermoelectric energy supply material according to claim 1, wherein the preparation method comprises the following steps: in step S2, the fiber base material immersed in the thermoelectric solution is taken out and dried, and then the fiber base material is immersed in an ethylene glycol solution for 2 to 5 hours, and is taken out and dried again.
3. The method for preparing the high-efficiency fiber-based thermoelectric energy supply material according to claim 1 or 2, wherein the method comprises the following steps: in step S3, after the photo-thermal film is formed by the baking process, the fiber-based self-power-generating layer and the photo-thermal film are perforated.
4. The preparation method of the high-efficiency fiber-based thermoelectric energy supply material according to any one of claims 1 to 3, wherein the preparation method comprises the following steps: in step S3, the content of photo-thermal nanoparticles in the colloidal photo-thermal material is 0.1% to 3%; the drying temperature of the colloidal photo-thermal material is 60-80 ℃.
5. The preparation method of the high-efficiency fiber-based thermoelectric energy supply material according to claim 1, wherein the preparation method comprises the following steps: in step S1, the thermoelectric material is an organic thermoelectric material or a mixture thereof with an inorganic thermoelectric material; the thermoelectric solution is one of an organic thermoelectric solution formed by an organic thermoelectric material, a thermoelectric mixed solution formed by mixing the organic thermoelectric solution and an organic solvent, and a thermoelectric composite solution formed by blending the thermoelectric mixed solution and the inorganic thermoelectric material; in the thermoelectric mixed solution, the addition amount of the organic solvent is 1-5%; in the thermoelectric composite solution, the addition amount of the inorganic thermoelectric material is 0.5-5%.
6. The preparation method of the high-efficiency fiber-based thermoelectric energy supply material according to claim 5, wherein the preparation method comprises the following steps: the organic thermoelectric material is one of PEDOT, PSS, polyaniline and polypyrrole; the inorganic thermoelectric material is one of bismuth telluride, lead telluride, carbon nano tubes and graphene; the organic solvent is one or more of glycol, polyethylene glycol, glycerol and dimethyl sulfoxide.
7. A high-efficiency fiber-based thermoelectric energy supply material is characterized in that: the preparation method of any one of claims 1 to 6, which comprises a fiber-based self-generating layer and a photo-thermal film arranged on the upper surface of the fiber-based self-generating layer; the fiber-based self-generating layer comprises a fiber base material adsorbed with thermoelectric materials and electrodes arranged on the upper surface and the lower surface of the fiber base material; the photo-thermal film contains photo-thermal nano particles and a binding material.
8. A high efficiency fiber based thermoelectric power generating material as defined in claim 7, wherein: the thickness of the photo-thermal film is 100-300 mu m; the photo-thermal nano particles are one or a mixture of ZrC, SiC, TiC and far infrared ceramic powder; the bonding material is one of epoxy resin, polydimethylsiloxane, polyurethane and polyethylene terephthalate.
9. A high efficiency fiber based thermoelectric power generating material as defined in claim 7, wherein: the thickness of the fiber base material is 1-10 mm, and the fiber base material contains a heat insulation layer with a hollow structure; the fiber base material is one of woven fabric, knitted fabric, three-dimensional fabric and non-woven fabric.
10. A high efficiency fiber based thermoelectric power generating material as defined in claim 7, wherein: the thickness of the electrode is 30-50 mu m, and the material of the electrode is one or a mixture of silver, gold, aluminum and nickel.
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