CN113725348A - Flexible thermoelectric and electromagnetic energy conversion film with enhanced refrigeration performance and preparation method thereof - Google Patents
Flexible thermoelectric and electromagnetic energy conversion film with enhanced refrigeration performance and preparation method thereof Download PDFInfo
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- H10N10/851—Thermoelectric active materials comprising inorganic compositions
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Abstract
The invention relates to a flexible thermoelectric magnetic energy conversion film with enhanced refrigeration performance and a preparation method thereof. Firstly, ball-milling and uniformly mixing thermoelectric material powder and magnetic nanoparticles in a protective atmosphere to obtain thermoelectric magnetic composite powder; then adding the thermo-electromagnetic composite powder into the adhesive solution and uniformly mixing to obtain thermo-electromagnetic ink; and finally, printing a thermal electromagnetic wet film on the substrate by using the thermal electromagnetic ink, and drying and hot-pressing sintering to obtain the flexible thermal electromagnetic energy conversion film. The invention induces the new effect of thermo-electric magnetic coupling by introducing the magnetic nano particles into the thermoelectric film, not only endows the film with certain magnetic performance, but also obviously improves the thermoelectric performance and the refrigerating capacity near room temperature. The technology provided by the invention is expected to promote the development and application of the active heat dissipation technology in the all-solid-state refrigeration surface based on thermoelectric magnetic energy conversion.
Description
Technical Field
The invention relates to the technical field of functional materials, in particular to a flexible thermoelectric and electromagnetic energy conversion film with enhanced refrigeration performance and a preparation method thereof.
Background
The thermoelectric material is a new energy material which can realize the direct conversion of heat energy and electric energy. Thermoelectric conversion devices made of thermoelectric materials can be classified into two types according to the difference in the direction of heat flow: out-of-plane type thermoelectric devices and in-plane type thermoelectric devices. The heat flow direction of the out-of-plane type thermoelectric device is vertical to the substrate surface, has the advantages of large heat absorption area, high heat utilization rate and the like, and is applied to the fields of automobile exhaust waste heat power generation, solar full-spectrum efficient power generation, deep space power supplies, thermoelectric refrigerators and the like. However, out-of-plane type thermoelectric devices also have some disadvantages, such as poor flexibility, large volume, low power density, and difficulty in application in shaped, narrow, and high heat flux density spaces. The heat flow direction of the in-plane thermoelectric device is parallel to the substrate surface, and the in-plane thermoelectric device has the advantages of good flexibility, small size and the like, and is expected to be applied to the fields of efficient heat dissipation in a mobile phone chip plane, a self-powered bidirectional temperature control sensor, a low-power-consumption self-powered Internet of things node, self-powered flexible wearable equipment and the like. At present, no commercial products exist for the internal type thermoelectric devices, and one of the main reasons is that high-performance thermoelectric films which completely meet the application requirements are not prepared.
At present, the thermoelectric film can be prepared by evaporation coating, magnetron sputtering, pulsed laser deposition, chemical vapor deposition and other technologies, the thermoelectric performance of the thermoelectric film is usually high, and some thermoelectric materials are even close to block thermoelectric materials with the same composition, but the cost of the deposition preparation technology is high and the consistency of the film is poor. In addition, the slurry or ink can be used for preparing a high-flexibility thermoelectric thin film in a controllable manner at low cost through wet film forming modes such as brushing, spin coating, ink-jet printing and screen printing, but the thermoelectric conversion performance, particularly the electrotransport performance, of the thermoelectric thin film is seriously deteriorated. Although researchers have explored various solutions to this problem, they still cannot fully meet the practical application requirements.
The new mechanism for enhancing thermoelectric conversion performance by the thermo-electric magnetic coupling effect discovered in the research of bulk thermoelectric materials by the group of the inventors of the present application is expected to provide a new idea for the research of thermoelectric thin films. Earlier we found the use of BaFe12O19The new thermo-electric magnetic coupling effect generated by the ferromagnetic-paramagnetic transition of the magnetic nano particles can effectively inhibit the medium-temperature thermoelectric material filled CoSb3The performance deterioration caused by intrinsic excitation, and the electron multiple scattering effect generated by the superparamagnetic Co nano particles3Cooperative regulation and control of transport of mesophonon and electron, and utilization of Fe in super paramagnetic state3O4P-type Bi of thermoelectric material with magnetic nanoparticles at room temperature2Te3The generated superparamagnetic reinforced thermoelectric potential effect obviously improves the electric heat transport performance of the composite material.
The introduction of the magnetic nanoparticles is an effective way to improve the thermoelectric performance of the bulk thermoelectric material, but the bulk thermoelectric material and the flexible thermoelectric film have great differences in composition, structure, preparation method and the like, and whether the method can be used for the flexible thermoelectric film and improve the thermoelectric performance of the flexible thermoelectric film needs to be further explored and verified, and no relevant report is found at present.
Disclosure of Invention
The invention aims to provide a preparation method of a flexible thermoelectric magnetic energy conversion film with enhanced refrigerating performance, which comprises the following steps: (a) mixing thermoelectric material powder and magnetic nanoparticles to obtain thermoelectric magnetic composite powder; (b) mixing the thermo-electromagnetic composite powder with a binder solution to obtain thermo-electromagnetic ink; (c) preparing a thermo-electromagnetic wet film on a substrate by using thermo-electromagnetic ink, and then drying and hot-pressing sintering.
Further, the thermoelectric material powder in the step (a) is p-type or n-type, and is specifically selected from Bi2Te3Base thermoelectric material, Sb2Te3Based on one of the thermoelectric materials. The particle size of the thermoelectric material powder is not more than 120 μm.
Further, the magnetic nanoparticles in step (a) are specifically magnetic nanomaterials of ferromagnetic metals of Fe, Co or Ni.
Further, the mixing mode of the thermoelectric material powder and the magnetic nanoparticles in the step (a) is ball milling, the ball milling medium is an alcohol solvent (such as absolute ethyl alcohol), during ball milling, vacuum pumping is performed, protective gas (such as Ar) is introduced, the ball milling rotating speed is 100-400r/min, and the ball milling time is 0.5-12 h. Compared with mixing modes such as ultrasonic dispersion, mechanical stirring, manual grinding and the like, the ball milling mixing is easier to realize the dispersion uniformity of the composite powder, and the powder can be refined. The introduction of the alcohol solvent and the protective atmosphere can prevent the thermoelectric powder and the magnetic particles from being oxidized in the ball milling process.
Further, the mass of the magnetic nanoparticles in the thermal-electromagnetic composite powder in the step (a) is not more than 10%.
Further, the raw materials for preparing the adhesive solution in the step (b) comprise an adhesive and a solvent, and a curing agent, a catalyst or other surface aids can also be added. The adhesive is at least one selected from acrylic resin, polyurethane resin, epoxy resin and cellulose resin, the solvent is at least one selected from N-methyl pyrrolidone, ethanol, butyl glycidyl ether, terpineol and dimethyl ester, the curing agent is at least one selected from methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride and pyromellitic dianhydride, and the catalyst is at least one selected from 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole. Adding a curing agent and a catalyst to ensure that the epoxy resin is cured; other additives are added to make the ink or paste more suitable for printing.
Furthermore, the concentration of the adhesive in the adhesive solution is 1-400g/L, the concentration of the curing agent is not more than 400g/L, and the concentration of the catalyst is not more than 100 g/L.
Further, the mass ratio of the thermal-electromagnetic composite powder and the adhesive solution in the step (b) is 1:0.2-0.6, the mixing method is that the thermo-electromagnetic composite powder is added into the adhesive solution, and then the thermo-electromagnetic composite powder is mechanically stirred and ultrasonically mixed evenly.
Further, in the step (c), the thermoelectric magnetic wet film is prepared on the substrate by adopting any one of screen printing, 3D printing, gravure printing, ink-jet printing or dispensing printing, and the material of the substrate is selected from any one of polyimide, polyethylene terephthalate, polyethylene naphthalate and glass cloth.
Further, in the step (c), the prepared thermoelectric magnetic wet film is heated to 50-150 ℃ for drying, and then heated and hot pressed for sintering, wherein the sintering temperature does not exceed the tolerance temperature of the substrate, and the hot pressing pressure is 1-20 MPa.
The invention also provides a flexible thermoelectric magnetic energy conversion film material with enhanced refrigerating performance.
The mechanism of the invention is as follows: the electric charge transfer, the magnetic resistance effect, the defect reaction and the interface bridging effect exist between the ferromagnetic metal nano particles and the thermoelectric material matrix component, so that the coordinated regulation and control of the electric transport performance and the thermal transport performance of the thermoelectric magnetic energy conversion film are realized, and further the thermoelectric performance and the refrigerating capacity near the room temperature of the flexible thermoelectric magnetic energy conversion film are obviously improved.
Compared with the prior art, the invention has the advantages that: (1) by introducing the magnetic nanoparticles into the thermoelectric thin film, the induced thermoelectric magnetic coupling new effect remarkably improves the thermoelectric performance and the refrigerating capacity near room temperature while endowing the flexible thermal electromagnetic composite thin film with certain magnetic performance; (2) after the magnetic nano particles are introduced, the performance parameters of the thermoelectric and electromagnetic energy conversion film and the single-arm device formed by assembly, such as the electrical conductivity, the power factor, the refrigeration temperature difference and the like, are greatly improved; (3) the whole preparation method is simple and controllable, and is expected to promote the development of the active heat dissipation technology in the all-solid-state refrigeration surface based on the thermoelectric energy conversion.
Drawings
FIG. 1(a-c) shows Fe/Bi0.5Sb1.5Te3Thermal electromagnetic fieldEnergy conversion film (Fe02) and Bi0.5Sb1.5Te3The relationship among the electrical conductivity, the seebeck coefficient, the power factor and the test temperature of the thermoelectric thin film (Fe00) is shown in fig. 1(d), which is a relationship graph between the temperature of the cold end and the temperature of the hot end of the one-armed device obtained by assembling the two thin films and the test time.
FIG. 2 shows Co/Bi0.5Sb1.5Te3Thermo-electromagnetic energy conversion film (Co02) and Bi0.5Sb1.5Te3The electrical conductivity, seebeck coefficient and power factor of the thermoelectric film (Co00) are plotted against the test temperature, and fig. 2(d) is a plot of the temperature of both the cold and hot ends of the one-armed device assembled based on the two films against the test time.
FIG. 3 shows Ni/Bi0.5Sb1.5Te3Thermo-electromagnetic energy conversion film (Ni01) and Bi0.5Sb1.5Te3The electrical conductivity, seebeck coefficient and power factor of the thermoelectric thin film (Ni00) are plotted against the test temperature, and fig. 3(d) is a plot of the temperature of both the cold and hot ends of the one-armed device assembled based on the two thin films against the test time.
Detailed Description
In order to make those skilled in the art fully understand the technical solutions and advantages of the present invention, the following description is further provided with reference to the specific embodiments and the accompanying drawings.
Example 1
Preparation of Fe/Bi by adding 0.2 wt% of Fe magnetic nanoparticles0.5Sb1.5Te3The process of thermoelectric magnetic energy conversion film is as follows:
p-type bismuth telluride (Bi)0.5Sb1.5Te3BST) crystal bar is crushed and screened by a screen to obtain BST thermoelectric powder with the grain diameter less than 120 mu m. Accurately weighing 9.98g of BST powder and 0.02g of Fe magnetic nanoparticles, adding the BST powder and the Fe magnetic nanoparticles into a high-energy ball milling tank, adding 50g of absolute ethyl alcohol as a ball milling medium, vacuumizing, and introducing Ar gas for protection, wherein the ball milling process parameters are as follows: the rotating speed is 200r/min, and the ball milling time is 2 h. Centrifuging and drying the mixture after ball milling to obtain Fe/Bi0.5Sb1.5Te3A thermo-electromagnetic composite powder.
Accurately weighing 0.612g of bisphenol F diglycidyl ether epoxy resin, 0.521g of methylhexahydrophthalic anhydride, 0.123g of 2-ethyl-4-methylimidazole and 1.8g of butyl glycidyl ether, and uniformly mixing to obtain the epoxy resin adhesive solution.
10g of Fe/Bi0.5Sb1.5Te3Adding the thermal electromagnetic composite powder into 3.056g of epoxy resin adhesive solution for mixing, firstly mechanically stirring and then ultrasonically dispersing to obtain uniform and stable Fe/Bi0.5Sb1.5Te3Thermo-electromagnetic ink.
Placing the polyimide substrate in absolute ethyl alcohol, ultrasonically cleaning for 15min, then airing, and then adopting a screen printer to carry out Fe/Bi treatment0.5Sb1.5Te3Printing the thermo-electromagnetic ink on a substrate, drying the obtained wet film at 80 ℃ in vacuum, transferring the film into a hot press, and hot-pressing the film for 4 hours under 10MPa and 543K to obtain Fe/Bi0.5Sb1.5Te3A thin film of thermo-electromagnetic energy conversion (Fe 02).
Bi without Fe magnetic nano-particles is prepared under the same process conditions0.5Sb1.5Te3Thermoelectric thin film (Fe 00).
Respectively test Fe/Bi0.5Sb1.5Te3Thermo-electromagnetic energy conversion film and Bi0.5Sb1.5Te3The electrotransport performance and the near room temperature refrigeration performance of the thermoelectric film are shown in fig. 1.
As can be seen from FIGS. 1(a-c), Fe/Bi0.5Sb1.5Te3The electric conductivity of the thermoelectric magnetic energy conversion film is more Bi than that of the thermoelectric magnetic energy conversion film0.5Sb1.5Te3The thermoelectric film is obviously improved, meanwhile, the Seebeck coefficient is slightly reduced, but the final power factor is obviously improved; by using Fe/Bi0.5Sb1.5Te3The refrigeration temperature difference of the single-arm device prepared by the thermoelectric and electromagnetic energy conversion film is more than that of Bi0.5Sb1.5Te3The single-arm device prepared by the thermoelectric film is improved by 1.7 times, and the improvement effect is obvious.
Example 2
AddingCo/Bi prepared from 0.2 wt% Co magnetic nanoparticles0.5Sb1.5Te3The process of thermoelectric magnetic energy conversion film is as follows:
p-type bismuth telluride (Bi)0.5Sb1.5Te3BST) crystal bar is crushed and screened by a screen to obtain BST thermoelectric powder with the grain diameter less than 120 mu m. Accurately weighing 9.98g of BST powder and 0.02g of Co magnetic nanoparticles, adding the BST powder and the Co magnetic nanoparticles into a high-energy ball milling tank, adding 50g of absolute ethyl alcohol as a ball milling medium, vacuumizing, and introducing Ar gas for protection, wherein the ball milling process parameters are as follows: the rotating speed is 200r/min, and the ball milling time is 2 h. Centrifuging and drying the mixture after ball milling to obtain Co/Bi0.5Sb1.5Te3A thermo-electromagnetic composite powder.
Accurately weighing 0.2g of bisphenol F diglycidyl ether epoxy resin, 0.17g of methylhexahydrophthalic anhydride, 0.04g of 2-ethyl-4-methylimidazole and 0.9g of butyl glycidyl ether, and uniformly mixing to obtain the epoxy resin adhesive solution.
4g of Co/Bi0.5Sb1.5Te3Adding the thermal electromagnetic composite powder into 1.31g of epoxy resin adhesive solution for mixing, firstly mechanically stirring and then ultrasonically dispersing to obtain uniform and stable Co/Bi0.5Sb1.5Te3Thermo-electromagnetic ink.
Placing the polyimide substrate in absolute ethyl alcohol, ultrasonically cleaning for 5min, then drying, and then adopting a screen printer to carry out Co/Bi treatment0.5Sb1.5Te3Printing the thermo-electromagnetic ink on a substrate, drying the obtained wet film in vacuum at 90 ℃, putting the wet film in a hot press, and hot-pressing the wet film for 4 hours under the conditions of 8MPa and 573K to obtain Co/Bi0.5Sb1.5Te3A thin film of thermo-electromagnetic energy conversion (Co 02).
Bi without Co magnetic nano-particles is prepared under the same process conditions0.5Sb1.5Te3Thermoelectric thin film (Co 00).
Respectively test Co/Bi0.5Sb1.5Te3Thermo-electromagnetic energy conversion film and Bi0.5Sb1.5Te3The electrotransport performance and the near room temperature refrigeration performance of the thermoelectric film are shown in fig. 2.
As can be seen from FIGS. 2(a-c), Co/Bi0.5Sb1.5Te3The electric conductivity of the thermoelectric magnetic energy conversion film is more Bi than that of the thermoelectric magnetic energy conversion film0.5Sb1.5Te3The thermoelectric film is obviously improved, meanwhile, the Seebeck coefficient is slightly reduced, but the final power factor is obviously improved; by using Co/Bi0.5Sb1.5Te3The refrigeration temperature difference of the single-arm device prepared by the thermoelectric and electromagnetic energy conversion film is more than that of Bi0.5Sb1.5Te3The single-arm device prepared by the thermoelectric film is improved by 1.5 times, and the improvement effect is also obvious.
Example 3
Ni/Bi prepared by adding 0.1 wt% of Ni magnetic nanoparticles0.5Sb1.5Te3The process of the thermal electromagnetic film is as follows:
p-type bismuth telluride (Bi)0.5Sb1.5Te3BST) crystal bar is crushed and screened by a screen to obtain BST thermoelectric powder with the grain diameter less than 120 mu m. Accurately weighing 9.98g of BST powder and 0.01g of Ni magnetic nanoparticles, adding the BST powder and the Ni magnetic nanoparticles into a high-energy ball milling tank, adding 50g of absolute ethyl alcohol as a ball milling medium, vacuumizing, and introducing Ar gas for protection, wherein the ball milling process parameters are as follows: the rotating speed is 200r/min, and the ball milling time is 2 h. Centrifuging and drying the mixture after ball milling to obtain Ni/Bi0.5Sb1.5Te3A thermo-electromagnetic composite powder.
Accurately weighing 0.2g of bisphenol F diglycidyl ether epoxy resin, 0.17g of methylhexahydrophthalic anhydride, 0.04g of 2-ethyl-4-methylimidazole and 0.9g of butyl glycidyl ether, and uniformly mixing to obtain the epoxy resin adhesive solution.
4g of Ni/Bi0.5Sb1.5Te3Adding the thermal electromagnetic composite powder into 1.31g of epoxy resin adhesive solution for mixing, firstly mechanically stirring and then ultrasonically dispersing to obtain uniform and stable Ni/Bi0.5Sb1.5Te3Thermo-electromagnetic ink.
Placing the polyimide substrate in absolute ethyl alcohol, ultrasonically cleaning for 5min, drying, and then adopting a screen printer to carry out Ni/Bi treatment0.5Sb1.5Te3Printing the thermo-electromagnetic ink on a substrate, and vacuum drying the obtained wet film at 120 deg.CThen placing the mixture into a hot press, and hot-pressing the mixture for 5 hours under the pressure of 8MPa and the pressure of 573K to obtain Ni/Bi0.5Sb1.5Te3A thermo-electromagnetic energy conversion film (Ni 01).
Bi without Ni magnetic nano-particles is prepared under the same process conditions0.5Sb1.5Te3Thermoelectric thin film (Ni 00).
Respectively test Ni/Bi0.5Sb1.5Te3Thermo-electromagnetic energy conversion film and Bi0.5Sb1.5Te3The electrotransport performance and the near room temperature refrigeration performance of the thermoelectric film are shown in fig. 3.
As can be seen from FIGS. 3(a-c), Ni/Bi0.5Sb1.5Te3The thermal electromagnetic film has conductivity more than Bi0.5Sb1.5Te3The thermoelectric film is obviously improved, meanwhile, the Seebeck coefficient is slightly reduced, but the final power factor is obviously improved; using Ni/Bi0.5Sb1.5Te3The refrigeration temperature difference of the single-arm device prepared by the thermoelectric magnetic film is more than that of Bi0.5Sb1.5Te3The single-arm device prepared by the thermoelectric film is improved by 2.5 times, and the improvement effect is more prominent.
Claims (10)
1. A preparation method of a flexible thermoelectric magnetic energy conversion film with enhanced refrigeration performance is characterized by comprising the following steps:
(a) mixing thermoelectric material powder and magnetic nanoparticles to obtain thermoelectric magnetic composite powder;
(b) mixing the thermo-electromagnetic composite powder with a binder solution to obtain thermo-electromagnetic ink;
(c) preparing a thermo-electromagnetic wet film on a substrate by using thermo-electromagnetic ink, and then drying and hot-pressing sintering.
2. The method of claim 1, wherein: the thermoelectric material powder in the step (a) is p-type or n-type, and is specifically selected from Bi2Te3Base thermoelectric material, Sb2Te3Based on one of the thermoelectric materials.
3. The method of claim 1, wherein: the magnetic nanoparticles in the step (a) are magnetic nanoparticles of ferromagnetic metals Fe, Co or Ni.
4. The method of claim 1, wherein: the mixing mode of the thermoelectric material powder and the magnetic nanoparticles in the step (a) is ball milling, the ball milling medium is an alcohol solvent, during ball milling, the vacuum pumping is carried out, protective gas is introduced, the ball milling rotating speed is 100-400r/min, and the ball milling time is 0.5-12 h.
5. The method of claim 1, wherein: the mass of the magnetic nano particles in the thermal-electromagnetic composite powder in the step (a) is not more than 10%.
6. The method of claim 1, wherein: the raw materials for preparing the adhesive solution in the step (b) comprise an adhesive, a solvent, a curing agent and a catalyst, wherein the adhesive is selected from at least one of acrylic resin, polyurethane resin, epoxy resin and cellulose resin, the solvent is selected from at least one of N-methyl pyrrolidone, ethanol, butyl glycidyl ether, terpineol and dimethyl ester, the curing agent is selected from at least one of methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride and pyromellitic dianhydride, and the catalyst is selected from at least one of 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole.
7. The method of claim 6, wherein: the concentration of the adhesive in the adhesive solution is 1-400g/L, the concentration of the curing agent is not more than 400g/L, the concentration of the catalyst is not more than 100g/L, and the concentration of other surface aids is not more than 100 g/L.
8. The method of claim 1, wherein: the mass ratio of the thermo-electromagnetic composite powder to the adhesive solution in the step (b) is 1:0.2-0.6, and the thermo-electromagnetic composite powder is added into the adhesive solution, and then the thermo-electromagnetic composite powder and the adhesive solution are mechanically stirred and ultrasonically mixed uniformly.
9. The method of claim 1, wherein: preparing the thermoelectric magnetic wet film on the substrate by adopting any one of screen printing, 3D printing, gravure printing, ink-jet printing or dispensing printing in the step (c), wherein the material of the substrate is selected from any one of polyimide, polyethylene terephthalate, polyethylene naphthalate and glass cloth; the drying temperature of the thermoelectric magnetic wet film is 50-150 ℃, the sintering temperature does not exceed the tolerance temperature of the substrate, and the hot pressing pressure is 1-20 MPa.
10. A flexible thermoelectric magnetic energy conversion thin film material with enhanced refrigerating performance is characterized in that: the film material is prepared according to any one of claims 1 to 9.
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| CN115188877A (en) * | 2022-07-27 | 2022-10-14 | 武汉理工大学 | Method for preparing flexible thermoelectric film with strong texture and high thermoelectric performance |
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