CN116033816A - Flexible stretchable thermoelectric refrigerator and preparation method thereof - Google Patents
Flexible stretchable thermoelectric refrigerator and preparation method thereof Download PDFInfo
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- CN116033816A CN116033816A CN202211521876.1A CN202211521876A CN116033816A CN 116033816 A CN116033816 A CN 116033816A CN 202211521876 A CN202211521876 A CN 202211521876A CN 116033816 A CN116033816 A CN 116033816A
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Abstract
The invention relates to a flexible stretchable thermoelectric refrigerator and a preparation method thereof. The device structure of the invention ensures that the thermoelectric refrigeration device has high flexibility and stretchability, and has important scientific value and wide application prospect in the thermoelectric refrigeration field.
Description
Technical Field
The invention belongs to the technical field of thermoelectric refrigeration, and particularly relates to a flexible stretchable thermoelectric refrigerator and a preparation method thereof.
Background
The human body can cause heat stress effect under high temperature environment, so that the physical energy consumption is too fast, and the human body health can be endangered in serious cases. In order to ensure the health of the high temperature environment operators and improve the working efficiency, effective heat protection measures are required to be adopted for the high temperature operators.
Thermoelectric materials have seebeck effect and peltier effect, and thus can be applied to thermoelectric generation and solid-state refrigeration. The thermoelectric power generation device and the solid-state refrigeration device have the advantages of small volume, no noise, stable operation and the like, and are widely applied to the fields of chip refrigeration, portable refrigerators, red wine cabinets, automobile tail gas thermal power generation and the like. The wearable refrigeration equipment based on the thermoelectric device has the characteristics of high efficiency and reliability in refrigeration effect, no movable parts, no chemical reaction and the like, and has great development potential in the field of personal wearable refrigeration devices. Flexible self-supporting thermoelectric generation structures such as disclosed in CN104410331a have been provided with flexible wearable properties, but their conductive electrodes do not have flexibility, resulting in very easy wire breakage when bent, which limits the application of thermoelectric devices in the wearable field.
Disclosure of Invention
The invention aims to provide a flexible stretchable thermoelectric refrigerator and a preparation method thereof, so that the thermoelectric refrigerator has flexible stretchable characteristics under the condition of ensuring the refrigerating effect of the thermoelectric refrigerator.
The invention provides a flexible stretchable thermoelectric refrigerator, wherein a hollowed stretchable silica gel insulating layer is arranged at the bottom of the thermoelectric refrigerator, and a block thermoelectric material is embedded into the insulating layer and is conducted by taking composite liquid metal as a conductive electrode.
The hollow stretchable silica gel insulating layer is made of copolyester or polydimethylsiloxane, the size of the hollow stretchable silica gel insulating layer is 2-10 cm X0.1-1 cm, the number of hollows is even-numbered pairs of 10-32X 10-32, and the size of each hollow is 1.4-5 mm X1.4-5 mm.
The block thermoelectric material is semiconductor thermoelectric particles of P type and N type, and the size is 1.4-5 mm X1.6-10 mm.
The semiconductor thermoelectric particles include, but are not limited to, bi 2 Te or Bi 2 Te 3 Is a solid solution alloy material based on PbTe or a solid solution alloy material based on PbTe, and is alternately embedded in the insulating layer.
The composite liquid metal is a composite of liquid metal and nickel powder in a mass ratio of 9:1-1:1.
The liquid metal is gallium-based liquid metal and comprises but is not limited to gallium-indium alloy or gallium-indium-tin alloy, wherein the mass ratio of gallium to indium of the gallium-indium alloy is 80:20-70:30, and the mass ratio of gallium to indium to tin of the gallium-indium-tin alloy is 68.5:21.5:10.
The invention also provides a preparation method of the flexible stretchable thermoelectric refrigerator, which comprises the following steps:
(1) Printing a mould through a three-dimensional printer, pouring copolyester or polydimethylsiloxane into the mould, casting a hollowed-out stretchable silica gel insulating layer or casting a whole silica gel insulating layer, and then hollowing out the hollowed-out stretchable silica gel insulating layer;
(2) Stirring the liquid metal and the nickel powder by a refiner, and fully mixing the liquid metal and the nickel powder to prepare the flexible stretchable conductive electrode;
(3) Alternately embedding P-type and N-type semiconductor thermoelectric particles into the hollowed stretchable silica gel insulating layer;
(4) The flexible stretchable conductive electrode connects the P-type semiconductor thermoelectric particles and the N-type semiconductor thermoelectric particles in series in a brushing or spraying mode;
(5) And packaging one surface coated with the conductive electrode by using silica gel, and then coating the other surface with the conductive electrode, and packaging in the same way to conduct the whole device circuit.
The size of the die in the step (1) is 2-10 cm X2-10 cm, and the die is made of at least one of polylactic acid, ABS plastic and PETG.
The rotating speed of the refiner in the step (2) is 1000-10000 rad/s.
The invention also provides application of the flexible stretchable thermoelectric cooler in the wearable field.
Advantageous effects
(1) The invention uses the silica gel insulating layer as a substrate, so that the whole device has high flexibility and stretchability; the liquid metal/nickel powder composite material is used as an electrode material, has good adhesion with semiconductor thermoelectric particles, and is more stable in electric connection.
(2) The preparation method is simple, low in cost and suitable for large-scale production; the prepared flexible stretchable thermoelectric refrigerator has good refrigeration effect, high refrigeration speed, good flexibility and good cooling effect, and has important scientific value and wide application prospect in the thermoelectric refrigeration field and the wearable field.
Drawings
FIG. 1 is a schematic cross-sectional view of a flexible stretchable thermoelectric cooler according to the present invention;
FIG. 2 is a schematic cross-sectional view of a flexible stretchable thermoelectric cooler of the present invention before and after stretching;
FIG. 3 is a graph showing the comparison of the cooling effect of infrared imaging when the flexible stretchable thermoelectric cooler of example 1 is stretched;
FIG. 4 is a graph showing the cooling effect of infrared imaging of the flexible stretchable thermoelectric cooler of example 2 worn on an arm;
fig. 5 is a graph showing the change of refrigeration temperature of the flexible stretchable thermoelectric refrigerator according to example 3 at different voltages.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The flexible stretchable thermoelectric refrigerator provided by the embodiment of the invention can be applied to various flexible devices and is used for cooling a structure to be cooled in flexible intelligent equipment, so that the temperature of the structure to be cooled is kept at a set temperature, and the working effect and reliability of the structure to be cooled are improved. The thermoelectric cooler in the prior art is mostly in a rigid structure, wherein the substrate and the conductive electrode are rigid, so that the substrate and the conductive electrode are changed into flexible and stretchable materials, and the obtained thermoelectric cooler can realize flexible and stretchable performances.
Example 1
Printing a polylactic acid mould by using a three-dimensional printer, wherein the mould is 5cm X5cm X0.16cm in size, the mould is provided with hollowed-out parts with 16X 16, the hollowed-out parts are 1.4mm X1.4mm X1.6mm in size, 10g of copolyester Ecoflex 00-30 (Smooth-On) A liquid and 10g of Ecoflex 00-30 (Smooth-On) B liquid are weighed and fully stirred and mixed. Casting the obtained mixed liquid into a polylactic acid mold, curing for 10 hours at room temperature, and demolding after curing to obtain the hollowed-out insulating layer. 1g of nickel powder is poured into 9g of gallium-indium-tin alloy liquid metal with the mass ratio of gallium to indium to tin of 68.5:21.5:10, and the mixture is stirred for 5 minutes by using a refiner with the ratio of 3000rad/s, so that the mixture is fully mixed, and a liquid metal/nickel powder composite material is obtained and is used as a flexible stretchable conductive electrode.
The semiconductor thermoelectric particles comprise P-type bismuth telluride particles and N-type bismuth telluride particles which are alternately placed in hollow holes of the insulating layer. The two semiconductor thermoelectric particles are connected in a brushing manner, as shown in fig. 1 and 2, the P-type bismuth telluride particles and the N-type bismuth telluride particles are sequentially and alternately connected in series and electrically connected through liquid metal/nickel powder composite materials, each liquid metal/nickel powder composite material is connected with one end of one P-type bismuth telluride particle and one end of one adjacent N-type bismuth telluride thermoelectric particle, so that the semiconductor thermoelectric particles form a structure in series electrical connection, the semiconductor thermoelectric particles have thermoelectric effect, and therefore the thermoelectric refrigerator can generate voltage by utilizing the Seebeck effect of the semiconductor thermoelectric particles under the condition of temperature difference, and the peltier effect of the semiconductor thermoelectric particles is utilized to realize the refrigeration or heating function after the thermoelectric refrigerator is electrified. After one-side electrical connection is completed, 1g of copolyester Ecoflex 00-30 (Smooth-On) A liquid and 1g of Ecoflex 00-30 (Smooth-On) B liquid are weighed, fully stirred and mixed, one-side packaging is completed, and curing is carried out at room temperature for 10 hours. And then electrically connecting the other side, and packaging in the same way to obtain the flexible stretchable thermoelectric refrigerator. Fig. 3 is a photograph of an infrared image of a refrigerator during stretching, and it can be found that the refrigerator still has a good refrigerating effect during stretching.
Example 2
An ABS plastic mold was printed with a three-dimensional printer, the mold size being 3cm X3cm X0.16cm. 9g of polydimethylsiloxane elastomer liquid and 1g of curing agent are weighed, fully stirred and mixed, and the obtained mixed liquid is cast into an ABS plastic mould and cured in an oven at 60 ℃ for 30 minutes. And (3) demolding after curing to obtain an insulating layer, punching holes on the insulating layer by using a laser cutting machine, wherein the array is 10X10, and the size is 1.4mm X1.4mm X1.6mm, so that the hollowed insulating layer is obtained. 2g of nickel powder is poured into 8g of gallium-indium alloy liquid metal with the gallium-indium ratio of 65:35, and the mixture is stirred for 8 minutes by a refiner with the ratio of 5000rad/s, so that the mixture is fully mixed, and a liquid metal/nickel powder composite material is obtained and is used as a flexible stretchable conductive electrode.
The semiconductor thermoelectric particles comprise P-type bismuth telluride particles and N-type bismuth telluride particles which are alternately placed in hollow holes of the insulating layer. The two semiconductor thermoelectric particles are connected in a spraying manner, as shown in fig. 1 and 2, the P-type bismuth telluride particles and the N-type bismuth telluride thermoelectric particles are sequentially and electrically connected in series at intervals through liquid metal/nickel powder composite materials, each liquid metal/nickel powder composite material is connected with one end of one P-type bismuth telluride thermoelectric particle and one end of one adjacent N-type bismuth telluride thermoelectric particle, so that the semiconductor thermoelectric particles form a structure in series electrical connection, the semiconductor thermoelectric particles have thermoelectric effect, and therefore the thermoelectric refrigerator can generate voltage by utilizing the Seebeck effect of the semiconductor thermoelectric particles under the condition of temperature difference, and the semiconductor thermoelectric particles are utilized for peltier effect to realize refrigeration or heating after being electrified. After the electrical connection of one side was completed, 0.9g of polydimethylsiloxane elastomer liquid and 0.1g of curing agent were weighed, thoroughly stirred and mixed, and the completed side was packaged and cured in an oven at 60 ℃ for 30 minutes. And then electrically connecting the other side, and packaging in the same way to obtain the flexible stretchable thermoelectric refrigerator. Fig. 4 shows the refrigerating effect of the refrigerator on the arm under the voltage of 1.5V when the refrigerator is worn on the arm, and the refrigerating effect of the refrigerator on the human body can be found to be obvious, and the temperature can be reduced by about 3.3 ℃.
Example 3
Printing a PETG mould by a three-dimensional printer, wherein the mould is 10cm X10cm X0.16cm in size, the mould is provided with hollowed-out parts with the array of 16X 16, the hollowed-out parts are 1.4mm X1.4mm X1.6mm in size, 15g of copolyester Ecoflex 00-10 (Smooth-On) A liquid and 15g of Ecoflex 00-10 (Smooth-On) B liquid are weighed and fully stirred and mixed. Casting the obtained mixed liquid into a polylactic acid mold, curing for 10 hours at room temperature, and demolding after curing to obtain the hollowed-out insulating layer. 5g of nickel powder is poured into 15g of gallium-indium alloy liquid metal with the gallium-indium ratio of 65:35, and the mixture is stirred for 8 minutes by using a refiner with 10000rad/s, so that the mixture is fully mixed, and a liquid metal/nickel powder composite material is obtained and is used as a flexible stretchable conductive electrode.
The semiconductor thermoelectric particles comprise P-type bismuth telluride particles and N-type bismuth telluride particles which are alternately placed in hollow holes of the insulating layer. The two semiconductor thermoelectric particles are connected in a spraying manner, as shown in fig. 1 and 2, the P-type bismuth telluride particles and the N-type bismuth telluride thermoelectric particles are sequentially and electrically connected in series at intervals through liquid metal/nickel powder composite materials, each liquid metal/nickel powder composite material is connected with one end of one P-type bismuth telluride thermoelectric particle and one end of one adjacent N-type bismuth telluride thermoelectric particle, so that the semiconductor thermoelectric particles form a structure in series electrical connection, the semiconductor thermoelectric particles have thermoelectric effect, and therefore the thermoelectric refrigerator can generate voltage by utilizing the Seebeck effect of the semiconductor thermoelectric particles under the condition of temperature difference, and the semiconductor thermoelectric particles are utilized for peltier effect to realize refrigeration or heating after being electrified. After one-side electrical connection is completed, 3g of copolyester Ecoflex 00-10 (Smooth-On) A liquid and 3g of Ecoflex 00-10 (Smooth-On) B liquid are weighed, fully stirred and mixed, one-side packaging is completed, and curing is carried out at room temperature for 10 hours. And then electrically connecting the other side, and packaging in the same way to obtain the flexible stretchable thermoelectric refrigerator. Fig. 5 is a graph showing a temperature change of the refrigerator at a voltage of 0 to 7V, and it can be found that the refrigerator has a good refrigerating effect.
Claims (10)
1. A flexible stretchable thermoelectric refrigerator, characterized by: the bottom of the thermoelectric refrigerator is provided with a hollowed stretchable silica gel insulating layer, and a block thermoelectric material is embedded into the insulating layer and is conducted by taking composite liquid metal as a conductive electrode.
2. The thermoelectric cooler of claim 1, wherein: the hollow stretchable silica gel insulating layer is made of copolyester or polydimethylsiloxane, the size of the hollow stretchable silica gel insulating layer is 2-10 cm X0.1-1 cm, the number of hollows is even-numbered pairs of 10-32X 10-32, and the size of each hollow is 1.4-5 mm X1.4-5 mm.
3. The thermoelectric cooler of claim 1, wherein: the bulk thermoelectric material is a P-type and an N-type semiconductor thermoelectric particle.
4. A thermoelectric cooler as set forth in claim 3 wherein: the semiconductor thermoelectric particles are Bi 2 Te or Bi 2 Te 3 Is a solid solution alloy material based on PbTe or a solid solution alloy material based on PbTe, and is alternately embedded in the insulating layer.
5. The thermoelectric cooler of claim 1, wherein: the composite liquid metal is a composite of liquid metal and nickel powder in a mass ratio of 9:1-1:1.
6. The thermoelectric cooler of claim 5, wherein: the liquid metal is gallium-based liquid metal.
7. A method of making a flexible stretchable thermoelectric cooler comprising:
(1) Printing a mould through a three-dimensional printer, pouring copolyester or polydimethylsiloxane into the mould, casting a hollowed-out stretchable silica gel insulating layer or casting a whole silica gel insulating layer, and then hollowing out the hollowed-out stretchable silica gel insulating layer;
(2) Stirring the liquid metal and the nickel powder by a refiner, and fully mixing the liquid metal and the nickel powder to prepare the flexible stretchable conductive electrode;
(3) Alternately embedding P-type and N-type semiconductor thermoelectric particles into the hollowed stretchable silica gel insulating layer;
(4) The flexible stretchable conductive electrode connects the P-type semiconductor thermoelectric particles and the N-type semiconductor thermoelectric particles in series in a brushing or spraying mode;
(5) And packaging one surface coated with the conductive electrode by using silica gel, and then coating the other surface with the conductive electrode, and packaging in the same way to conduct the whole device circuit.
8. The method of manufacturing according to claim 7, wherein: the size of the die in the step (1) is 2-10 cm X2-10 cm, and the die is made of at least one of polylactic acid, ABS plastic and PETG.
9. The method of manufacturing according to claim 7, wherein: the rotating speed of the refiner in the step (2) is 1000-10000 rad/s.
10. Use of the flexible stretchable thermoelectric cooler of claim 1 in the wearable domain.
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| CN116761491A (en) * | 2023-08-18 | 2023-09-15 | 武汉大学 | Flexible thermoelectric device with Kirigami structure and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116761491A (en) * | 2023-08-18 | 2023-09-15 | 武汉大学 | Flexible thermoelectric device with Kirigami structure and preparation method thereof |
| CN116761491B (en) * | 2023-08-18 | 2023-12-12 | 武汉大学 | Flexible thermoelectric device with Kirigami structure and preparation method thereof |
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