CN114601210B - Flexible wearable thermoelectric cooling device and its preparation method - Google Patents

Abstract

The invention discloses a wearable flexible thermoelectric refrigeration device, comprising: an energy storage and heat conduction substrate, a plurality of flexible heat dissipation fins, a heat insulation layer, a plurality of semiconductor refrigeration sheets and a heat conduction fiber fabric; the flexible heat dissipation fins are formed on the energy storage heat conduction On one side of the substrate, a heat insulation layer is formed on the other side of the energy storage and heat conduction substrate; semiconductor refrigeration chips are packaged in the heat insulation layer at intervals in a series manner, and their hot surfaces are closely attached to the energy storage and heat conduction substrate ; The thermally conductive fiber fabric is attached to the surface of the heat insulation layer and is in contact with the cold surface of the semiconductor refrigeration sheet; wherein, the energy storage conductor matrix is made of flexible matrix materials, thermally conductive fillers, metal foam materials and organic phase change materials. , the flexible heat dissipation fins are made of flexible base material and thermal conductive filler, and the heat insulation layer is made of flexible base material. The wearable flexible thermoelectric refrigeration device of the present invention has high thermal conductivity while ensuring flexibility.

Description

Flexible wearable thermoelectric cooling device and its preparation method

technical field

The invention relates to the technical field of refrigeration devices, in particular to a flexible wearable thermoelectric refrigeration device and a preparation method thereof.

Background technique

Wearable cooling devices not only play a vital role in human comfort and health, but also can effectively reduce energy consumption. On the one hand, in the hot outdoor environment, it can directly and effectively reduce the body surface temperature of the individual, and relieve the heat stress response at high temperature; The device can quickly and efficiently achieve high-efficiency cooling under low power supply.

Wearable cooling devices based on thermoelectric devices, because they do not involve chemical reactions, have no moving parts, do not use working fluids, do not produce emissions that cause global warming, and have efficient and reliable cooling effects, have great potential in the field of personal wearable cooling devices. Great potential for development. Semiconductor refrigeration chip is a typical refrigeration product based on thermoelectric effect. Due to its mature preparation process, various shapes and specifications can be customized in the market, and it has a wide range of application fields. Therefore, the development of flexible wearable devices using semiconductor refrigeration chips has great market potential.

However, when the semiconductor cooling sheet is working, if there is no additional heat dissipation device on the hot surface, the temperature will rise rapidly by more than 100°C, which will damage the device and also pose a safety hazard. Therefore, when the semiconductor cooling sheet is used, it usually adds a lot of weight Large, hard radiators, but this greatly limits the application of semiconductor cooling chips in the flexible and wearable field.

The Chinese patent with the publication number CN205424859U (the date of publication is August 3, 2016) discloses an LED cooling device using semiconductor cooling sheets and phase change materials, including LED devices, heat-conducting substrates, cooling fins, and semiconductor cooling sheets, phase change materials and cooling fans. By combining the advantages of the powerful cooling capacity of the semiconductor cooling sheet and the great phase change latent heat of the phase change material, and introducing closed-loop feedback control, efficient heat dissipation and reliable thermal control of LED devices can be achieved. However, this type of semiconductor refrigeration device still has the following disadvantages: 1. The fan is built into the radiator, which increases the volume and weight, and also makes the entire radiator hard and not flexible, so it cannot be used in the flexible and wearable field; 2. The fan of the radiator requires additional energy consumption; 3. The use of copper or aluminum heat-conducting substrates increases the rigidity of the entire structure; 4. The phase change materials are reunited inside the heat dissipation structure, and the non-dispersed phase reduces the heat dissipation of the radiator. Thermal conductivity is not conducive to the transmission and dissipation of heat, and it is prone to high temperature leakage; 5. It cannot be combined with fabrics and worn on the human body.

Therefore, inventing a flexible structure that can efficiently dissipate heat for semiconductor refrigeration sheets is a key problem in solving the application of thermoelectric devices in personal refrigeration clothing.

Contents of the invention

The purpose of the present invention is to provide a flexible and wearable thermoelectric refrigeration device, which has high thermal conductivity while ensuring flexibility.

The present invention provides a wearable flexible thermoelectric cooling device, including:

Energy storage heat conduction matrix;

A plurality of flexible heat dissipation fins formed on one side surface of the energy storage and heat conduction base;

a heat insulation layer formed on the other surface of the energy storage and heat conduction substrate;

A plurality of semiconductor refrigeration chips are packaged in the heat insulation layer at intervals in a series manner, and their hot surfaces are closely attached to the energy storage and heat conduction substrate; and

The thermally conductive fiber fabric is attached to the surface of the heat insulation layer and is in contact with the cold surface of the semiconductor refrigeration sheet;

Wherein, the energy storage conductor matrix is prepared from a flexible matrix material, thermally conductive filler, metal foam material and organic phase change material, and the flexible heat dissipation fin is prepared from a flexible matrix material and thermally conductive filler, so The heat insulation layer is made of flexible matrix material.

Preferably, the refrigeration device has a block structure as a whole, and can be conveniently worn on different parts of the human body.

Further, the flexible base material is two-component silicone rubber or polybutylene terephthalate-adipate.

Further, the metal foam material is one or more of copper foam, nickel foam, zinc foam, titanium foam, the porosity is preferably 95%-99%, and the thickness is preferably 1mm-2mm.

Further, the thermally conductive filler includes one or more of carbon fibers, carbon nanotubes, graphite, graphene, aluminum oxide, aluminum nitride, and boron nitride, and the particle size is preferably 1 μm-100 μm. Preferably, the thermally conductive filler is selected from block, sheet or spherical thermally conductive fillers.

Further, the organic phase change material is one or more of aliphatic hydrocarbons, fatty acids, alcohols and polyenols. Preferably, the organic phase change material is polyethylene glycol, and its molecular weight is preferably 2000.

Further, in the flexible heat dissipation fins, the mass fraction of the flexible base material is 30%-70% by weight, and the mass fraction of the thermally conductive filler is 70%-30%.

Further, in the energy storage and heat conducting matrix, the mass fraction of the flexible matrix material is 40wt%-65wt%, the mass fraction of the metal foam is 20wt%-30wt%, and the mass fraction of polyethylene glycol is 1wt%-15wt%, The mass fraction of the thermally conductive filler is 15wt%-80wt%.

Further, the structure of the flexible cooling fins is cylindrical or strip-shaped, and its height is 3mm-4mm.

Further, the thermally conductive fiber fabric is silver fiber fabric.

The present invention also provides a preparation method of the wearable flexible thermoelectric refrigeration device, comprising the following steps:

S1. The flexible base material, curing agent and thermally conductive filler are evenly mixed, poured into a mold and cured at a first temperature to obtain a flexible heat dissipation fin preform; the first temperature is 60°C-70°C;

S2. Place the metal foam on the surface of the cured flexible heat dissipation fin pre-product, mix the flexible matrix material, curing agent and thermal conductive filler evenly, then add polyethylene glycol at the second temperature, heat and stir in a water bath to obtain Continue to pour the slurry into the above-mentioned mold, and after the metal foam is completely impregnated, vacuum defoaming; the second temperature is 55°C-60°C;

S3. curing the mold at a third temperature to obtain a heat sink preform; the third temperature is 130°C-150°C;

S4. Place the semiconducting cooling chips evenly on the surface of the cured radiator preform in a series manner, mix the flexible base material and the curing agent evenly, and then pour them into the above mold. After the semiconducting cooling chips are packaged, place them in the The uncured surface is covered with a heat-conducting fiber fabric, and then heat-pressed and solidified at the first temperature to obtain the wearable flexible thermoelectric cooling device.

The above technical solution of the present invention has the following advantages compared with the prior art:

1. The present invention uses a semiconductor refrigeration chip for wearable refrigeration design. The overall device is compact in size, without any moving parts, and there is no liquid flow. It can effectively perform personal refrigeration, reduce the energy consumption of the centralized refrigeration system for the overall space, and save energy Environmental friendly.

2. The flexible and wearable thermoelectric refrigeration device of the present invention does not have any additional rigid materials and devices, and the entire heat dissipation device is flexible and bendable, small and light, and can be flexibly designed to be wearable, which promotes the use of thermoelectric effect-based semiconductor refrigeration chips in refrigeration. The field of application on the device.

3. In the flexible and wearable thermoelectric cooling device of the present invention, the heat dissipation structure integrates a fin-type heat dissipation structure and an energy storage heat conduction sheet. On the one hand, the shape of the fin increases heat dissipation; on the other hand, in the heat storage heat conduction sheet, the The flexible matrix, phase change heat storage, heat conduction filler and heat conduction metal foam skeleton are effectively combined to give full play to the collaborative heat dissipation operation of heat storage and heat conduction, and can effectively control the temperature of the hot surface of the semiconductor refrigeration sheet.

4. The flexible and wearable thermoelectric refrigeration device of the present invention does not need to use any organic solvent during the preparation process, which meets the requirements of green and environmental protection.

Description of drawings

Fig. 1 is a schematic structural diagram of a flexible wearable thermoelectric cooling device of the present invention;

Fig. 2 is the physical figure of the flexible wearable thermoelectric refrigeration device of embodiment 1;

3 is a schematic diagram of the flexible wearable thermoelectric cooling device of Embodiment 1 in a wearing state;

Fig. 4 is the physical figure of the flexible wearable thermoelectric refrigeration device of embodiment 2;

Fig. 5 is the physical figure of the flexible wearable thermoelectric refrigeration device of comparative example 1;

Fig. 6 is a schematic diagram of the temperature change of the flexible wearable thermoelectric refrigeration device of embodiment 1;

Fig. 7 is a comparison diagram of the temperature change of the flexible wearable thermoelectric refrigeration device and a separate semiconductor refrigeration sheet in Example 1 and Comparative Example 1;

Among them: 1. Flexible heat dissipation fins; 2. Heat storage and heat conduction substrate; 3. Heat insulation layer; 4. Semiconductor refrigeration sheet; 5. Thermally conductive fiber fabric; 6. Flexible matrix material; 7. Metal foam; 8. Organic phase change Material; 9. Thermally conductive filler.

Detailed ways

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field of the invention. The terms used in the description of the present invention are only for the purpose of describing specific embodiments, and are not intended to limit the present invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

As shown in Figure 1, the present invention provides a flexible and wearable thermoelectric refrigeration device, including: energy storage and heat conduction substrate 2, multiple flexible heat dissipation fins 1, heat insulation layer 3, multiple semiconductor refrigeration sheets 4 and thermally conductive fiber fabrics 5. Wherein, the flexible cooling fins 1 are formed on one side surface of the energy storage and heat conduction base 2 , and the heat insulation layer 3 is formed on the other side surface of the energy storage heat conduction base 2 . The semiconductor cooling chips 4 are packaged in the heat insulation layer 3 at intervals, and their hot surfaces are closely attached to the energy storage and heat conduction base 2 . The thermally conductive fiber fabric 5 is pasted on the surface of the heat insulation layer 3 and is in contact with the cold surface of the semiconductor cooling sheet 4 .

In the present invention, the energy storage conductor matrix 2 is prepared from a flexible base material 6, a thermally conductive filler 9, a metal foam 7 and an organic phase change material 8, and the flexible heat dissipation fin 1 is prepared from a flexible base material and a thermally conductive filler Yes, the heat insulation layer 3 is made of a flexible base material.

The flexible and wearable thermoelectric refrigeration device of the present invention includes a skin-adhering fabric layer, a heat insulation layer in the middle and a flexible heat storage and heat conduction radiator at the outer end, which has high thermal conductivity while ensuring flexibility. The heat conduction skeleton established by metal foam and high thermal conductivity filler effectively improves the heat conductivity of the heat sink; at the same time, adding organic phase change materials makes the heat sink have the function of storing heat, which can further control the temperature of the hot end. On the other hand, the entire radiator is small in size, light in weight, flexible and bendable, and the radiator can be compounded on the fabric for wearable design.

The present invention will be further described below in conjunction with specific examples, so that those skilled in the art can better understand the present invention and implement it, but the given examples are not intended to limit the present invention.

Example 1

This embodiment provides a method for preparing the above-mentioned flexible wearable thermoelectric cooling device, including the following steps:

1) Provide raw materials: 4 semiconductor refrigeration sheets, silver fiber fabric, flexible matrix material polydimethylsiloxane A, B component (curing agent Dao Kang-184), 2mm thick metal foam 47mm×47mm, polyethylene glycol Alcohol, thermally conductive filler;

2) Mix 3g of component A, 0.3g of component B and 1.1g of thermally conductive filler in the flexible matrix material evenly at room temperature, then pour it into a cylindrical fin mold and cure it in vacuum at the first temperature for 2 hours to obtain flexible heat dissipation fins Preform, placing the metal foam on the surface of the cured flexible heat dissipation fin preform; the first temperature is 60°C-70°C;

3) Mix 5g of component A of the flexible base material, 0.5g of component B curing agent, and 2.75g of thermally conductive filler at room temperature, then add 1.5g of polyethylene glycol at the second temperature, heat and stir in a water bath to obtain a slurry continue Pour into the above mold, completely impregnate the metal foam, and vacuum defoam for 1 hour; the second temperature is 55°C-60°C;

4) Place the mold in an oven at a third temperature and solidify for 2 hours to obtain a preform of the heat sink, and place 4 semiconducting cooling fins in series on the surface of the preform of the heat sink after being evenly spaced; The third temperature is 130°C-150°C;

5) Mix the 3gA component of the flexible base material and the 0.3gB component curing agent evenly at room temperature, then pour it into the above-mentioned mold, and after the semiconductor refrigeration chip is completely packaged, spread the silver fiber fabric on the uncured surface evenly, and then Place it under a hot press at the first temperature and cure for 2 hours to obtain a preform of a flexible thermoelectric cooling device.

Figure 2-3 is the physical picture of the prepared flexible wearable thermoelectric cooling device and the schematic diagram in the wearing state.

Fig. 6 is a schematic diagram of the temperature change of the flexible and wearable thermoelectric cooling device of Example 1,

It can be seen from the figure that the flexible wearable thermoelectric cooling device can greatly reduce the temperature. Low temperatures as low as 10°C below ambient temperature can be achieved and maintained at 8°C below room temperature for more than five hours.

Example 2

This embodiment provides a method for preparing the above-mentioned flexible wearable thermoelectric cooling device, including the following steps:

1) Provide raw materials: 4 semiconductor refrigeration sheets, silver fiber fabric, flexible base material polybutylene terephthalate adipate A, B component, flexible base material polydimethylsiloxane A, B Components (curing agent Daokang-184), 2mm thick metal foam 47mm×47mm, polyethylene glycol, thermally conductive filler;

2) Evenly mix 2gA component, 2gB component and 0.9g thermal conductive filler of the flexible base material at room temperature, then pour it into a cylindrical fin mold and cure it in vacuum at the first temperature for 2 hours to obtain a flexible heat dissipation fin preform. A product, placing the metal foam on the surface of the cured flexible heat dissipation fin pre-product; the first temperature is 60°C-70°C;

3) Mix 5g of polydimethylsiloxane, a flexible matrix material, component A, 0.5g of component B (curing agent Daokang-184), and 2.75g of thermally conductive filler at room temperature, and then add 1.5g of polydimethylsiloxane at the second temperature. Ethylene glycol, heated in a water bath and stirred evenly, and the obtained slurry was continuously poured into the above-mentioned mold, and after the metal foam was completely impregnated, vacuum defoamed for 1 hour; the second temperature was 55°C-60°C;

4) Place the mold in an oven at a third temperature and solidify for 2 hours to obtain a preform of the heat sink, and place 4 semiconducting cooling fins in series on the surface of the preform of the heat sink after being evenly spaced; The third temperature is 130°C-150°C;

5) Mix the 3gA component and 0.3gB component of the flexible matrix material polydimethylsiloxane evenly at room temperature, then pour it into the above mold, and after the semiconductor refrigeration chip is completely packaged, spread it evenly on the uncured surface The silver fiber fabric is then placed under a hot press at the first temperature and cured for 2 hours to obtain a preform of a flexible thermoelectric cooling device.

Fig. 4 is a physical diagram of the flexible and wearable thermoelectric cooling device of embodiment 2.

After testing, the flexible and wearable thermoelectric cooling device prepared in this example can reach a minimum temperature of 11°C lower than the ambient temperature, and keep it 7°C lower than the room temperature for more than five hours.

Comparative example 1

This comparative example provides a preparation method of a flexible wearable thermoelectric refrigeration device, comprising the following steps:

1) Provide raw materials: 4 semiconductor refrigeration chips, silver fiber fabric, flexible matrix material polydimethylsiloxane A, B component (curing agent Dao Kang-184), polyethylene glycol, thermal conductivity filler;

2) Mix 5g of component A of the flexible base material, 0.5g of component B curing agent, and 2.75g of thermally conductive filler at room temperature, then add 1.5g of polyethylene glycol at the second temperature, heat and stir in a water bath to obtain a slurry; The second temperature is 55°C-60°C;

3) Pour the slurry into the mold. After vacuum defoaming at the second temperature for 1 hour, place it in an oven at the third temperature and cure it for 2 hours. Put 4 semiconductor refrigeration chips in series and evenly place them for curing on the surface of the preformed heat sink; the third temperature is 130°C-150°C;

4) Evenly mix 3gA component of the flexible base material and 0.3gB component curing agent at room temperature, then pour it into the above-mentioned mold, after the semiconductor refrigeration chip is completely packaged, spread the silver fiber fabric on the uncured surface, and then Place it under a hot press at the first temperature and cure for 2 hours to obtain a preform of a flexible thermoelectric cooling device.

5 is a physical diagram of the flexible wearable thermoelectric cooling device of Comparative Example 1.

The final flexible and wearable thermoelectric cooling device can reach a minimum temperature of 7°C below the ambient temperature, and keep it below room temperature at 5°C for 2 hours. The subsequent temperature rises slowly, and after four hours, the temperature rises above room temperature.

Apparently, the above-mentioned embodiments are only examples for clear description, and are not intended to limit the implementation. For those of ordinary skill in the art, on the basis of the above description, other changes or changes in various forms can also be made. It is not necessary and impossible to exhaustively list all the implementation manners here. And the obvious changes or changes derived therefrom are still within the scope of protection of the present invention.

Claims (7)

1. A wearable flexible thermoelectric cooling device, comprising:

an energy storage and heat conduction substrate;

the flexible heat dissipation fins are formed on one side surface of the energy storage and heat conduction substrate;

the heat insulation layer is formed on the other side surface of the energy storage and heat conduction substrate;

the semiconductor refrigeration pieces are packaged in the heat insulation layer at intervals in a series connection mode, and the hot surfaces of the semiconductor refrigeration pieces are tightly attached to the energy storage heat conduction substrate; and

the heat-conducting fiber fabric is attached to the surface of the heat insulation layer and is in contact with the cold surface of the semiconductor refrigeration piece;

the energy storage heat conduction substrate is prepared from a flexible substrate material, a heat conduction filler, a metal foam material and an organic phase change material, the flexible heat dissipation fins are prepared from a flexible substrate material and a heat conduction filler, and the heat insulation layer is prepared from a flexible substrate material; the organic phase change material is one or more of aliphatic hydrocarbon, aliphatic acid, alcohol and polyvinyl alcohol; in the flexible radiating fin, the mass fraction of the flexible base material is 30-70 wt%, and the mass fraction of the heat-conducting filler is 30-70%; in the energy storage heat conduction matrix, the mass fraction of the flexible matrix material is 40-65 wt%, the mass fraction of the metal foam is 20-30 wt%, the mass fraction of the polyethylene glycol is 1-15 wt%, and the mass fraction of the heat conduction filler is 15-80 wt%;

the preparation method of the wearable flexible thermoelectric refrigerating device comprises the following steps:

s1, uniformly mixing a flexible matrix material, a curing agent and a heat-conducting filler, pouring the mixture into a mold, and curing at a first temperature to obtain a flexible radiating fin prefabricated product; the first temperature is 60-70 ℃;

s2, placing metal foam on the surface of the cured flexible radiating fin prefabricated product, uniformly mixing the flexible base material, the curing agent and the heat conducting filler, then adding polyethylene glycol at a second temperature, heating in a water bath, uniformly stirring, continuously pouring the obtained slurry into the mold, and defoaming in vacuum after completely soaking the metal foam; the second temperature is 55-60 ℃;

s3, curing the die at a third temperature to obtain a prefabricated product of the radiator; the third temperature is 130-150 ℃;

and S4, placing the semiconductor refrigeration sheets on the surface of the solidified radiator prefabricated product at intervals and uniformly in a series connection mode, uniformly mixing the flexible base material and the curing agent, pouring the mixture into the mold, laying a heat-conducting fiber fabric on the uncured surface after the semiconductor refrigeration sheets are packaged, and performing hot-pressing solidification at a first temperature to obtain the wearable flexible thermoelectric refrigeration device.

2. A wearable flexible thermoelectric cooling device as recited in claim 1 wherein said flexible base material is bicomponent silicone rubber or polybutylene terephthalate-adipate.

3. A wearable flexible thermoelectric cooling device according to claim 1, wherein the organic phase change material is polyethylene glycol with a molecular weight of 2000.

4. A wearable flexible thermoelectric cooling device according to claim 1, characterized in that the metal foam material is one or more of copper foam, nickel foam, zinc foam, titanium foam, with a porosity of 95-99% and a thickness of 1-2 mm.

5. A wearable flexible thermoelectric cooling device according to claim 1, wherein the heat conducting filler comprises one or more of carbon fiber, carbon nanotube, graphite, graphene, alumina, aluminum nitride, boron nitride, with a particle size of 1 μm to 100 μm.

6. A wearable flexible thermoelectric cooling device according to claim 1, wherein the structure of the flexible heat dissipation fin is cylindrical or long and the height thereof is 3mm-4mm.

7. A wearable flexible thermoelectric cooling device as recited in claim 1 wherein said thermally conductive fiber fabric is silver fiber fabric.

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