Integrated thermoelectric device intelligent temperature controller with cooling alarm function and preparation method

Abstract

The invention discloses an integrated thermoelectric device intelligent temperature controller with a cooling alarm function and a preparation method thereof, the temperature controller is coated with a substrate, the top and two sides of the temperature controller are exposed to form a double-sided part thermoelectric device, a plurality of double-sided part thermoelectric devices are assembled through a copper strip, and then the thermoelectric devices are connected in series to form the integrated thermoelectric device intelligent temperature controller with the cooling alarm function. An intelligent temperature controller is formed; the temperature controller is manufactured through the following process that a plurality of thermoelectric devices and temperature sensors are assembled into the intelligent temperature controller. Contact resistance and contact thermal resistance caused by connection nodes are eliminated, the internal resistance of the thermoelectric device is reduced, and the temperature difference between the two ends of the thermoelectric leg is improved. Wherein the P-type and N-type thermoelectric legs are provided with heat rectification structures with asymmetric cold and hot end shapes, and the temperature difference and the output power / power density of the two ends of the thermoelectric device are improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of temperature control of thermoelectric devices, and in particular relates to an integrated thermoelectric device intelligent temperature controller with cooling alarm function and a preparation method thereof. Background Art

[0002] The gradual miniaturization and sophistication of electronic devices has brought about the problem of heat dissipation. Temperature has a great impact on the working performance of electronic devices. For an electronic chip that works stably and continuously, the maximum temperature is required not to exceed 85°C. For every 10°C increase in the temperature of a semiconductor component, the reliability of the system will decrease by 50%. According to statistics, more than 55% of electronic equipment fails due to excessive temperature. In traditional electronic chips, 98% of the volume is used for cooling, and only 2% is used for computing and operation, but it is still difficult to solve the existing heat dissipation problem. High temperature can have a harmful effect on the performance of electronic equipment, and those traditional heat dissipation methods have certain limitations. Therefore, in order to ensure the service life and efficient performance of electronic equipment, it is urgent to explore and develop better heat dissipation methods for electronic equipment.

[0003] Thermoelectric power generation technology can effectively dissipate the waste heat generated by electronic components. It uses the thermoelectric effect of two different metal or semiconductor materials to directly convert thermal energy into electrical energy. It has the characteristics of no need for external energy, small size, long life, and environmental friendliness. It can meet the needs of long-term continuous use of electronic components.

[0004] Connect two metal wires of different materials together to form a closed loop. When one of the nodes at the connection of the wires is heated, a current will be generated in the loop. If one end of any two metals or semiconductors is combined together and the other end is kept open, when there is a temperature difference between the two ends, an electromotive force will be generated at the open end. This effect is called the Seebeck effect. Thermoelectric power generation is based on the Seebeck effect of thermoelectric power generation materials to achieve direct conversion of thermal energy into electrical energy. Thermoelectric power generation relies on the Peltier effect, which is commonly used in semiconductor cooling chips in CPU heat sinks and pocket refrigerators. Usually, when a current is applied to the cooling chip, one side will become hot and the other side will become cold. But this effect can also be reversed: as long as there is a temperature difference between the two ends of the cooling chip, a voltage will be generated.

[0005] The traditional thermoelectric fan includes a heat conducting sheet, a Peltier heat sink, and a fan (propeller and motor). The bottom of the thermoelectric sheet is fixedly connected to a heat conducting copper sheet, and the upper end of the thermoelectric sheet is fixedly connected to the bottom of the fan. The thermoelectric sheet and the fan motor are electrically connected through wires. The thermoelectric module absorbs a large amount of heat from the CPU to generate electricity, and drives the small fan to rotate to achieve heat dissipation. As long as a thermoelectric device is placed on a high-temperature electronic component, it will absorb heat energy to drive the fan to rotate, and supply energy to the fan through thermoelectric power generation, thereby achieving the purpose of heat dissipation. This structure has a relatively simple temperature control for the system. Therefore, it is necessary to further optimize the material and structural assembly of the radiator and prepare a new type of intelligent temperature controller. Summary of the invention

[0006] In order to overcome the problem of poor heat dissipation effect of the radiator in the prior art, the purpose of the present invention is to provide an integrated thermoelectric device intelligent temperature controller with cooling alarm function and a preparation method, which can achieve heat dissipation and self-powered alarm.

[0007] To achieve the above object, the technical solution adopted by the present invention is:

[0008] A method for preparing an integrated thermoelectric device intelligent temperature controller with a cooling alarm function comprises the following steps:

[0009] The substrate is wrapped around the temperature controller, and the top and both sides of the temperature controller are exposed to form a double-sided partial thermoelectric device, and a plurality of double-sided partial thermoelectric devices are assembled through copper tape, and then the thermoelectric devices are connected in series to form an intelligent temperature controller;

[0010] The temperature controller is prepared by the following process:

[0011] Several thermoelectric devices and temperature sensors are assembled into an intelligent temperature controller.

[0012] Further, the thermoelectric device is prepared by the following process:

[0013] 1) cutting the flexible thermoelectric film and sealing it with a polyethylene terephthalate film having a pattern structure;

[0014] 2) depositing P-type dopant molecules on the flexible thermoelectric film treated in step 1) by steam doping to obtain P-type thermoelectric legs;

[0015] Depositing N-type dopant molecules on the flexible thermoelectric film treated in step 1) by steam doping to obtain N-type thermoelectric legs;

[0016] Connect the P-type and N-type thermoelectric legs in series to obtain a thermoelectric device;

[0017] Furthermore, the flexible thermoelectric material includes organic thermoelectric materials and inorganic thermoelectric materials.

[0018] Furthermore, the organic thermoelectric material is one or more of carbon nanotubes, graphene, poly (3,4-ethylenedioxythiophene), 3-hexyl-substituted polythiophene, polypyrrole and polyaniline film.

[0019] Furthermore, inorganic thermoelectric materials such as one or more of bismuth telluride, antimony telluride, MXene, silver selenide and tin selenide.

[0020] Furthermore, the temperature of steam doping is 25° C.-300° C., the time of steam doping is 0.5-10 h, and the steam doping is performed in a closed container.

[0021] Furthermore, the temperature of steam doping is 25° C.-300° C., and the time of steam doping is 0.5-10 h.

[0022] Further, the P-type dopant is 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone, 2-fluoro-7,7,8,8-tetracyanoquinodimethane, ferric chloride, iodine or hexameric trimethylcyclopropane;

[0023] Furthermore, the N-type dopant is polyethyleneimine, diethylenetriamine, ethylenediamine, 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzimidazole, triphenyl phosphate, 1,3-bis(diphenylphosphino)propane, ethylenediaminetetraacetic acid, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5,7-triazidobicyclo(4.4.0)dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene or tetramethylguanidine.

[0024] Furthermore, the temperature sensor is composed of a pn thermoelectric leg.

[0025] The invention discloses an integrated thermoelectric device intelligent temperature controller with cooling alarm function.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] The structure of a thermoelectric device (SP-TEG) ​​intelligent temperature controller of the present invention is simple and easy to install; the temperature controller can work in three modes: low temperature, high temperature and over-high temperature: at low temperature, heat can be directly dissipated through the thermoelectric device of ITC, at high temperature, a large temperature difference is formed between the upper end and the lower end of the thermoelectric device, and the generated output voltage exceeds the critical voltage of the relay, the relay is closed to form a path, and the current is then transmitted to the circuit of the fan motor through the wire, so that the fan motor can start to work, thereby reducing the system temperature. Since thermoelectric materials can realize direct conversion between heat and electricity, they have great application potential in waste heat recovery and solid-state cooling. For waste heat recovery, thermoelectric devices can overcome the technical problem of contact resistance (contact thermal resistance) caused by electrode connection nodes, increase the temperature difference between the two ends of the thermoelectric device, and reduce the internal resistance of the thermoelectric device. Compared with traditional π-type thermoelectric devices, they have better thermoelectric device output performance. The P-type thermoelectric legs, N-type thermoelectric legs and electrodes in the thermoelectric device are completely made of the same flexible thermoelectric material. The alternating connection between the P-type thermoelectric legs, N-type thermoelectric legs and electrodes is continuous and uninterrupted, avoiding the use of metal electrodes in traditional thermoelectric devices, eliminating the connection nodes between the thermoelectric legs and the metal connection electrodes in traditional thermoelectric devices, thereby eliminating the contact resistance and contact thermal resistance caused by the connection nodes, reducing the internal resistance of the thermoelectric device, and improving the temperature difference between the two ends of the thermoelectric legs. The P-type and N-type thermoelectric legs have a thermal rectification structure with asymmetric shapes of the cold and hot ends, which improves the temperature difference and output power / power density at both ends of the thermoelectric device. The present invention assembles the thermoelectric device into an intelligent temperature controller (ITC), and uses LED alarm as a concept of potential application, integrating cooling and alarm functions into one device. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 It is a circuit diagram of the intelligent temperature controller of the present invention;

[0029] Figure 2 The implementation process of temperature control and alarm work of intelligent temperature controller (ITC). Among them, (a) is a schematic diagram of double-sided thermoelectric device, (b) is an image of ITC placed on the electric heating table, (c) is an alarm image of ITC under over-temperature, (d) is the temperature change of heating plate under 4.5V voltage with and without ITC, (e) is the temperature change of heating plate under 6V voltage with and without ITC, (f) is an infrared image of heating plate without ITC, (g) is an infrared image of heating plate with ITC, (h) is an infrared image of heating plate with ITC after forced heat dissipation by fan, (i) is the temperature change of heating plate with and without ITC under 22V voltage;

[0030] Figure 3 It is a schematic diagram of the structure of a thermoelectric device (SP-TEG / w-hr) with a rectangular planar shape;

[0031] Figure 4 It is a schematic diagram of the structure of a folded three-dimensional thermoelectric device (SP-TEG / w-hr). DETAILED DESCRIPTION

[0032] In order to facilitate the understanding of the present invention, the present invention will be described more fully below with reference to the relevant drawings. The preferred embodiments of the present invention are given in the drawings. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thoroughly and comprehensively understood.

[0033] The method for preparing the integrated thermoelectric device intelligent temperature controller with cooling alarm function in the present invention comprises the following steps:

[0034] 1. Preparation of thermoelectric devices

[0035] The thermoelectric device in the present invention is an "integrated" flexible organic thermoelectric device with a thermal rectification structure, including a P-type thermoelectric leg and an N-type thermoelectric leg.

[0036] Thermoelectric device with a length of 94mm and a width of 51mm (see Figure 2 (a) is obtained by doping and cutting in an aligned carbon nanotube film, wherein the length direction of the thermoelectric device is perpendicular to the orientation direction of the carbon nanotubes. The thermoelectric device contains 22 pairs of pn thermoelectric legs with a length of 25 mm and a width of 2 mm.

[0037] In the process of preparing the thermoelectric device, a carbon nanotube film with a length of 94 mm and a width of 51 mm is first encapsulated in a polyethylene terephthalate (PET) film with a pattern structure, and then the carbon nanotube film is doped with dopant vapor.

[0038] Specifically, the method for preparing a thermoelectric device comprises the following steps:

[0039] 1) The flexible thermoelectric film was manually made into a thermoelectric device with a length of 94 mm and a width of 51 mm by cutting, knife engraving, wire cutting and laser engraving. It had 11 pairs of pn legs, a length of 25 mm and a width of 2 mm.

[0040] The flexible thermoelectric film having a length of 94 mm and a width of 51 mm was sealed with a polyethylene terephthalate (PET) film having a pattern structure, and then the flexible thermoelectric film was treated with a dopant gas.

[0041] Among them, the flexible thermoelectric film includes organic thermoelectric materials and inorganic thermoelectric materials, organic thermoelectric materials such as carbon nanotubes (MWCNT), graphene, poly 3,4-ethylenedioxythiophene (PEDOT), 3-hexyl substituted polythiophene (P3HT), polypyrrole and polyaniline film, etc., one or more; inorganic thermoelectric materials such as bismuth telluride (Bi2Te3), antimony telluride (Sb2Te3), MXene, silver selenide (Ag2Se) and tin selenide (SnSe), etc., one or more.

[0042] 2) Then, the dopant is added to the same flexible thermoelectric film by steam doping (fixing the flexible thermoelectric film on the top of the glass sublimation chamber and placing a certain amount of dopant at the bottom. Heating causes the dopant molecules to deposit on the surface of the flexible thermoelectric film) to prepare P-type or N-type thermoelectric legs, respectively, and the P-type and N-type thermoelectric legs are connected in series to obtain a thermoelectric device with a narrow PN interface with a thermal rectification structure.

[0043] The mass of the dopant is 0.0001 g-10 g, the temperature of steam doping is 25° C.-300° C., the time of steam doping is 0.5-10 h, and the environment of steam doping is in a closed container.

[0044] The dopant includes a P-type dopant and an N-type dopant, wherein the P-type dopant is 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone (F4TCNQ), 2-fluoro-7,7,8,8-tetracyanoquinodimethane (FTCNQ), ferric chloride (FeCl 3 ), iodine (I 2 ) or hexameric trimethylcyclopropane (CN6-CP), etc. The N-type dopant is polyethyleneimine (PEI), diethylenetriamine (DETA), ethylenediamine, 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzimidazole (N-DMBI), triphenyl phosphate (TPP), 1,3-bis(diphenylphosphino)propane (d-TPP), ethylenediaminetetraacetic acid (EDTA), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5,7-triazidobicyclo(4.4.0)dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (Me-TBD) or tetramethylguanidine (TMG), etc.

[0045] When the dopant is PEI, the specific doping process is: after doping with 0.2g PEI at 120°C for 0.5h, the exposed part changes from p-type to n-type.

[0046] The preparation of thermoelectric devices without connection nodes (SP-TEG) ​​is an effective strategy to avoid contact resistance (contact thermal resistance) at the electrode connection nodes. Compared with the traditional π-leg structure TEG, the "integrated" flexible thermoelectric device without connection nodes has better flexibility and durability. In addition, the introduction of the thermal rectification structure can effectively increase the temperature difference between the two ends of the thermoelectric device. The "integrated" structure prepared by the present invention reduces the internal resistance of the thermoelectric device and improves the output power / output power density of the thermoelectric device. The interface of the P and N thermoelectric legs prepared by the steam doping method improves the integration of the thermoelectric device and further optimizes and improves the output performance of the thermoelectric device.

[0047] 2. Assembly of intelligent temperature controller

[0048] Use 16 tablets Figure 2 The thermoelectric device shown in (a) and a temperature sensor consisting of a pair of pn thermoelectric legs are assembled into an intelligent temperature controller (ITC).

[0049] Specifically, Figure 2 The thermoelectric device shown in (a) is pasted to both sides of a PET film substrate (0.5×25×90 mm), that is, the PET film substrate is wrapped around the thermoelectric device, and the two sides and the top of the thermoelectric device are exposed, so as to obtain the following Figure 2 The flexible thermoelectric device shown in (b).

[0050] 16 flexible thermoelectric devices and 1 temperature sensor were assembled using copper blocks of 3×5×12 mm in a Lego-like way. The copper blocks were interlocked with each other using polyimide tape, that is, adjacent flexible thermoelectric devices were connected through copper blocks, and polyimide tape was set between the copper blocks. Insulating paper or thermal conductive silicone grease was used to isolate the copper blocks from the thermoelectric devices to prevent short circuits. After assembly, the thermoelectric devices were connected in series using conductive silver glue to obtain the following: Figure 2 (b) The intelligent temperature controller shown.

[0051] 3. Intelligent Temperature Controller (ITC) Operation

[0052] The present invention assembles high-performance thermoelectric devices into an intelligent temperature controller (ITC) and uses LED alarm as a potential application, integrating cooling and alarm functions into one device.

[0053] like Figure 2As shown in (c), the entire test system includes a fan, a power supply and a temperature monitor. One end of the power supply is connected to the fan, the fan is connected to one end of the temperature control relay, the other end of the temperature control relay is connected to the voltage, and the temperature sensor (TES) of the ITC is connected in parallel at both ends of the temperature control relay. The ITC is placed on the heating plate. The ITC can operate in three modes: low temperature, high temperature and over-high temperature. At low temperatures, heat can be dissipated through the ITC. For example, when the heating plate is heated at a voltage of 4.5V, its temperature is ~46°C. After placing the ITC on the heating plate, due to the good thermal conductivity of the carbon nanotube module, the heat is dissipated through the ITC, and the temperature drops and stabilizes at ~37°C (see Figure 2 (d)). When the heating plate is heated at 6V at high temperature, the temperature of the heating plate is ~61℃ without ITC. After placing the ITC on the heating table, although the temperature drops to ~48℃, it is still 36℃ higher than the set temperature ( Figure 2 (e)). Then, the temperature sensor in the ITC provides a voltage signal that closes the relay controller and turns on the fan to force heat dissipation at a flow rate of 2m / s. As a result, the temperature drops to ~35°C. Figure 2 Middle (f), Figure 2 Medium (g), Figure 2 (h) in the middle shows the infrared images without ITC cooling, with ITC cooling, and with ITC cooling and fan forced cooling. Figure 2 In (i), when the temperature is too high, 22V is supplied to the heating plate, and the temperature rises to 260°C. The ITC temperature is still as high as 145°C, which is higher than the alarm temperature (120°C). Then, the thermoelectric device (TEG) in the ITC turns on the LED.

[0054] The results show that high-performance thermoelectric devices have potential application prospects in intelligent temperature control and alarm of electronic devices.

[0055] The application principle of the temperature controller TEG in the present invention can be found in Figure 1 In (a), the fan is connected to one end of the temperature control relay, the other end of the temperature control relay is connected to the positive pole of the power supply, the negative pole of the voltage is connected to the fan, and TES is connected in parallel at both ends of the temperature control relay. Figure 1 In (b), one end of the TES is connected to one end of the boost module, and the other end of the boost module is connected to the other end of the TES. LED lights are arranged in parallel at both ends of the boost module.

[0056] Comparative Example 1

[0057] Conventional thermoelectric devices (Con-TEG) ​​for comparison; similar size ( Figure 2(a) shows that 11 pairs of rectangular thermoelectric legs with a width of 0.15 cm and a length of 1.8 cm are connected in series by copper foil with a length of 0.94 cm and a width of 0.15 cm and silver paste, and then PET is used to shield the thermoelectric legs. In a sealed glass container, 0.1 g of P-type dopant F4TCNQ is used to dope for 30 minutes at 120°C to obtain a P-type thermoelectric leg; the PET center is rotated 22.5° to shield the P-type doped P-type thermoelectric leg, and in a sealed glass container, 0.2 g of N-type dopant PEI is used to dope for 30 minutes at 120°C to obtain an N-type thermoelectric leg; the device is taken out and placed in a vacuum oven at 50°C for drying for 2 hours to obtain a traditional thermoelectric device consisting of P-type and N-type thermoelectric legs alternately connected in series.

[0058] Con-TEG has a distinct connection node between the metal electrode and the thermoelectric leg.

[0059] The connection nodes in the integrated thermoelectric device of the present invention make the electrical resistance and thermal resistance of the device lower, thereby having a higher output power density and a better heat dissipation effect.

[0060] The present invention uses a high-performance carbon nanotube film with anisotropy to obtain a high power density rollable TEG, and the TEG has a high output power density of 110W m-2 (560.2μW m-1K-2). The present invention provides an intelligent temperature controller integrating temperature control and alarm, which realizes automatic temperature control.

[0061] Example 1

[0062] (1) Using a multi-walled carbon nanotube film prepared by chemical vapor deposition as a raw material, the multi-walled carbon nanotube film is cut into 11 pairs of thermoelectric leg patterns (shaped as Figure 2 (a)

[0063] (2) The 11 pairs of thermoelectric legs in the hollow circular pattern obtained in step (1) are shielded with polyethylene terephthalate (PET) at intervals, and 0.1 g of a P-type dopant F4TCNQ is used for doping for 30 min at 120° C. in a sealed glass container to obtain a P-type thermoelectric leg; in a sealed glass container, the center of the PET is rotated 22.5° to shield the P-type thermoelectric leg, and 0.2 g of an N-type dopant PEI is used for doping for 30 min at 120° C. to obtain an N-type thermoelectric leg; the device is taken out and placed in a vacuum oven at 50° C. for drying for 2 h to obtain an "integrated" flexible thermoelectric device (SP-TEG / w-hr, such as Figure 2 (as shown in (a)).

[0064] from Figure 2As can be seen in (a), SP-TEG / w-hr is completely composed of the same material, carbon nanotube film, which avoids the existence of metal electrode connection nodes and eliminates contact resistance (contact thermal resistance). The "integrated" structure design allows the cold end to have a larger heat dissipation area.

[0065] Example 2

[0066] (1) Graphene was deposited into a 6.9 cm long and 3 cm wide hollow rectangular film by electrochemical deposition, specifically, three pairs of isosceles trapezoidal thermoelectric legs with an upper base (hot end) width of 0.3 cm, a lower base (cold end) width of 0.9 cm, and a height (thermoelectric leg length) of 3 cm, and five isosceles trapezoidal electrodes (three of which were isosceles trapezoids with an upper base of 0.84 cm, a lower base of 0.9 cm, and a height of 0.3 cm, and the other two were isosceles trapezoids with an upper base of 0.3 cm, a lower base of 0.36 cm, and a height of 0.3 cm) connected in series alternately to form a rectangular plane (the thermoelectric legs were arranged in parallel, and the electrodes connected the upper and lower bases of adjacent thermoelectric legs in series in sequence, and the overall shape was a hollow rectangle, as shown in FIG. Figure 3 The "integrated" device pattern of all-graphene with a thermal rectification structure (shaped as shown) Figure 3 shown).

[0067] (2) The thermoelectric legs of the "integrated" device pattern (shape) obtained in step (1) are shielded with polyPET, and 0.15 g of P-type dopant FTCNQ is used for doping for 50 min at 180° C. in a sealed glass container to obtain P-type thermoelectric legs; the PET is removed and the FTCNQ-doped P-type thermoelectric legs are shielded again, and 0.05 g of N-type dopant N-DMBI is used for doping for 45 min at 190° C. in a sealed glass container to obtain N-type thermoelectric legs; the device is taken out and placed in a vacuum oven at 50° C. for drying for 6 h to obtain a rectangular planar "integrated" flexible thermoelectric device with a thermal rectification structure consisting of P-type and N-type thermoelectric legs alternately connected in series.

[0068] Example 3

[0069] (1) CNT / PEODT slurry was printed on a polytetrafluoroethylene substrate by 3D printing to form a zigzag thin film thermoelectric material with a thickness of 10 μm and a length of 10 cm, wherein along the length direction of the film, 10 trapezoids with an upper base (hot end) width of 0.25 cm, a lower base (cold end) width of 0.6 cm, and a height (thermoelectric leg length) of 1 cm were continuously formed in a manner such that the upper bases of adjacent isosceles trapezoids were connected to each other and the lower bases were connected to each other (e.g. Figure 4 shown).

[0070] (2) The 10 isosceles trapezoids of the zigzag thin-film thermoelectric material obtained in step (1) are alternately shielded with PET, and then 0.3 g of a P-type dopant C6CP is doped for 20 min in a sealed glass container under heating conditions at 90° C. to obtain a P-type thermoelectric leg; the PET is removed and the P-type thermoelectric leg obtained by C6CP doping is shielded again, and 0.25 g of an N-type dopant DBU is doped for 40 min in a sealed glass container under heating conditions at 90° C. to obtain an N-type thermoelectric leg; and then the thermoelectric leg is placed in a vacuum oven at 50° C. and dried for 4 h, and the trapezoidal thermoelectric legs are rotated (folded) into an angle of 60° (such as 1 / 40°) with the upper base or the lower base as the axis. Figure 4 As shown), a folded three-dimensional "integrated" flexible thermoelectric device with a thermal rectification structure is obtained, in which P-type and N-type thermoelectric legs are alternately connected in series.

[0071] Example 4

[0072] (1) CNT / P3HT slurry was printed on a polytetrafluoroethylene substrate by 3D printing to form a zigzag thin film thermoelectric material with a thickness of 10 μm and a length of 10 cm, wherein along the length direction of the film, 10 trapezoids with an upper base (hot end) width of 0.25 cm, a lower base (cold end) width of 0.6 cm, and a height (thermoelectric leg length) of 1 cm were continuously formed in a manner such that the upper bases of adjacent isosceles trapezoids were connected to each other and the lower bases were connected to each other (e.g. Figure 4 shown).

[0073] (2) The 10 isosceles trapezoids of the zigzag thin-film thermoelectric material obtained in step (1) were alternately covered with PET, and then 0.15 g of a P-type dopant FTCNQ was used for doping for 50 min in a sealed glass container under heating conditions at 180°C to obtain a P-type thermoelectric leg; the PET was removed and the FTCNQ-doped P-type thermoelectric leg was covered again, and 0.05 g of an N-type dopant N-DMBI was used for doping for 45 min in a sealed glass container under heating conditions at 190°C to obtain an N-type thermoelectric leg; and then the thermoelectric leg was placed in a vacuum oven at 50°C and dried for 4 h, and the trapezoidal thermoelectric legs were rotated (folded) into an angle of 60° (such as 1 / 40°C) with the upper base or the lower base as the axis. Figure 4 As shown), a folded three-dimensional "integrated" flexible thermoelectric device with a thermal rectification structure is obtained, in which P-type and N-type thermoelectric legs are alternately connected in series.

[0074] Example 5

[0075] (1) Same as Example 1;

[0076] (2) The 11 pairs of carbon nanotube thermoelectric legs in the hollow circular pattern obtained in step (1) are shielded with polyethylene terephthalate (PET) at intervals, and 0.1 g of a P-type dopant CN6-CP is used for doping for 20 min at 90°C in a sealed glass container to obtain a P-type thermoelectric leg; in a sealed glass container, the center of the PET is rotated 22.5° to shield the P-type thermoelectric leg, and 0.2 g of an N-type dopant TPP is used for doping for 2 h at 240°C to obtain an N-type thermoelectric leg; the device is taken out and placed in a vacuum oven at 50°C for drying for 2 h to obtain an "integrated" flexible thermoelectric device with a thermal rectification structure consisting of P-type thermoelectric legs and N-type thermoelectric legs alternately connected in series.

[0077] Example 6

[0078] (1) Same as Example 2;

[0079] (2) The all-graphene "integrated" device pattern with a thermal rectification structure obtained in step (1) is shielded with polyethylene terephthalate (PET) at intervals, and 0.1 g of a P-type dopant F4TCNQ is used to dope for 30 min at 120° C. in a sealed glass container to obtain a P-type thermoelectric leg; in a sealed glass container, the PET is removed and the F4TCNQ-doped P-type thermoelectric leg is shielded again, and 0.2 g of an N-type dopant PEI is used to dope for 30 min at 120° C. to obtain an N-type thermoelectric leg; the device is taken out and placed in a vacuum oven at 50° C. and dried for 2 h to obtain an "integrated" flexible thermoelectric device with a thermal rectification structure composed of P-type thermoelectric legs and N-type thermoelectric legs alternately connected in series.

[0080] Example 7

[0081] (1) Same as Example 3;

[0082] (2) The 10 isosceles trapezoids of the CNT / PEDOT zigzag thin film thermoelectric material obtained in step (1) were alternately shielded with PET, and then 0.1 g of a P-type dopant CN6-CP was used for doping for 20 min in a sealed glass container under heating conditions at 90°C to obtain a P-type thermoelectric leg; in a sealed glass container, the PET center was rotated 22.5° to shield the P-type thermoelectric leg, and 0.2 g of an N-type dopant TPP was used for doping for 2 h under heating conditions at 240°C to obtain an N-type thermoelectric leg; and then the PET was placed in a vacuum oven at 50°C and dried for 4 h, and the trapezoidal thermoelectric legs were rotated (folded) into an angle of 60° (such as 1 / 40°) with the upper base or the lower base as the axis. Figure 4 As shown), a folded three-dimensional "integrated" flexible thermoelectric device with a thermal rectification structure is obtained, in which P-type and N-type thermoelectric legs are alternately connected in series.

[0083] Example 8

[0084] (1) Same as Example 4;

[0085] (2) The 10 isosceles trapezoids of the CNT / P3HT zigzag thin film thermoelectric material obtained in step (1) were alternately shielded with PET, and then 0.1 g of a P-type dopant CN6-CP was used for doping for 20 min in a sealed glass container at 90°C to obtain a P-type thermoelectric leg; the PET was removed and the P-type thermoelectric leg obtained by CN6-CP doping was shielded again, and 0.2 g of an N-type dopant TBD was used for doping for 30 min in a sealed glass container at 120°C to obtain an N-type thermoelectric leg; and then the thermoelectric leg was placed in a vacuum oven at 50°C and dried for 4 h, and the trapezoidal thermoelectric legs were rotated (folded) into an angle of 60° (such as 1 / 40°C) with the upper base or the lower base as the axis. Figure 4 As shown), a folded three-dimensional "integrated" flexible thermoelectric device with a thermal rectification structure is obtained, in which P-type and N-type thermoelectric legs are alternately connected in series.

[0086] The P-type dopant in the present invention can also be ferric chloride (FeCl 3 ), iodine (I 2 ) or hexameric trimethylcyclopropane (CN6-CP). The N-type dopant can also be diethylenetriamine (DETA), ethylenediamine, 1,3-bis(diphenylphosphino)propane (d-TPP), ethylenediaminetetraacetic acid (EDTA), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (Me-TBD) or tetramethylguanidine (TMG).

[0087] The present invention uses an integrated thermoelectric device with a thermal rectification structure prepared by organic and inorganic thermoelectric materials such as carbon nanotube film, graphene, CNT / PEDOT, CNT / P3HT composite materials, etc., which is an effective measure to avoid the contact resistance and contact thermal resistance caused by the electrode connection node in the traditional thermoelectric device. In traditional thermoelectric devices, due to the mismatch of the work function of the electrode material and the thermoelectric material, the transmission of current and heat flow at the heterogeneous interface of different materials is difficult, so that the contact resistance and contact thermal resistance at the electrode connection node occupy a large part of the internal resistance of the device. The structure of the integrated thermoelectric device is composed of the same thermoelectric material without interruption, eliminating the metal electrode connection node and the contact resistance and contact thermal resistance caused by the connection node, thereby reducing the internal resistance of the device, increasing the temperature difference between the two ends of the thermoelectric device, and finally increasing the output power of the device. This is also attributed to the fact that the carbon nanotubes arranged in the film have a high Seebeck coefficient, which allows the vapor of the n-type dopant to penetrate deeply into the film, thereby achieving efficient n-type doping. In addition to high thermoelectric performance, macroscopic carbon nanotube films also have excellent flexibility, high mechanical strength and good high-temperature stability (120°C), which has practical application value.

[0088] The above description is only for the best embodiment of the present invention, but it should not be understood as limiting the claims. The present invention is not limited to the above embodiments, and its specific structure is allowed to be changed. However, all changes made within the protection scope of the independent claims of the present invention are within the protection scope of the present invention.

[0089] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.

Claims

1. A method for preparing an integrated thermoelectric device intelligent temperature controller with cooling alarm function, characterized in that: The following steps are involved: The substrate is wrapped around the temperature controller, and the top and both sides of the temperature controller are exposed to form a double-sided partial thermoelectric device, and a plurality of double-sided partial thermoelectric devices are assembled through copper tape, and then the thermoelectric devices are connected in series to form an intelligent temperature controller; The temperature controller is prepared by the following process: Several thermoelectric devices and temperature sensors are assembled into an intelligent temperature controller.

2. The method for preparing the integrated thermoelectric device intelligent temperature controller with cooling alarm function according to claim 1, characterized in that: Thermoelectric devices are made through the following process: 1) cutting the flexible thermoelectric film and sealing it with a polyethylene terephthalate film having a pattern structure; 2) depositing P-type dopant molecules on the flexible thermoelectric film treated in step 1) by steam doping to obtain P-type thermoelectric legs; Depositing N-type dopant molecules on the flexible thermoelectric film treated in step 1) by steam doping to obtain N-type thermoelectric legs; The P-type and N-type thermoelectric legs are connected in series to obtain a thermoelectric device.

3. The method for preparing the integrated thermoelectric device intelligent temperature controller with cooling alarm function according to claim 2, characterized in that: Flexible thermoelectric materials include organic thermoelectric materials and inorganic thermoelectric materials.

4. The method for preparing the integrated thermoelectric device intelligent temperature controller with cooling alarm function according to claim 3, characterized in that: The organic thermoelectric material is one or more of carbon nanotubes, graphene, poly 3,4-ethylenedioxythiophene, 3-hexyl substituted polythiophene, polypyrrole and polyaniline film.

5. The method for preparing the integrated thermoelectric device intelligent temperature controller with cooling alarm function according to claim 3, characterized in that: Inorganic thermoelectric materials such as one or more of bismuth telluride, antimony telluride, MXene, silver selenide and tin selenide.

6. The method for preparing the integrated thermoelectric device intelligent temperature controller with cooling alarm function according to claim 2, characterized in that: The temperature of steam doping is 25°C-300°C, the time of steam doping is 0.5-10h, and the steam doping is carried out in a closed container.

7. The method for preparing the integrated thermoelectric device intelligent temperature controller with cooling alarm function according to claim 2, characterized in that: The P-type dopant is 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone, 2-fluoro-7,7,8,8-tetracyanoquinodimethane, ferric chloride, iodine or hexameric trimethylcyclopropane.

8. The method for preparing the integrated thermoelectric device intelligent temperature controller with cooling alarm function according to claim 2, characterized in that: The N-type dopant is polyethyleneimine, diethylenetriamine, ethylenediamine, 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzimidazole, triphenyl phosphate, 1,3-bis(diphenylphosphino)propane, ethylenediaminetetraacetic acid, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5,7-triazidobicyclo(4.4.0)dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene or tetramethylguanidine.

9. The method for preparing the integrated thermoelectric device intelligent temperature controller with cooling alarm function according to claim 3, characterized in that: The temperature sensor consists of a pn thermoelectric leg.

10. An integrated thermoelectric device intelligent temperature controller with cooling alarm function prepared according to the method according to any one of claims 1 to 9.

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