阅读说明：本技术 一种卷筒式横向热电器件及其制造方法 (Reel type transverse thermoelectric device and manufacturing method thereof ) 是由 周洪宇 钱国平 于华南 龚湘兵 李希 蔡军 祝轩 于 2020-05-25 设计创作，主要内容包括：本发明公开了一种卷筒式横向热电器件及其制造方法,其由横向热电器件和导线组成,所述横向热电器件由两种异质材料倾斜交替排列形成的异质膜和柔性基板组合而成,横向热电器件卷曲形成卷筒式结构,其始、末两端设有导线。卷筒式横向热电器件经搅拌、超声、3D打印或丝网印刷、烧结、卷曲而成。本发明可以在设置的路径下实现任意几何构造的横向热电器件的制造,且卷筒式横向热电器件具有大长厚比,可实现小温差下高输出电压,特别适合小温差下电能高效收集。(The invention discloses a reel type transverse thermoelectric device and a manufacturing method thereof, wherein the reel type transverse thermoelectric device consists of a transverse thermoelectric device and a lead, the transverse thermoelectric device is formed by combining a heterogeneous film and a flexible substrate which are formed by obliquely and alternately arranging two heterogeneous materials, the transverse thermoelectric device is coiled into a reel type structure, and the two ends of the transverse thermoelectric device are provided with the lead. The reel type transverse thermoelectric device is formed by stirring, ultrasonic printing, 3D printing or silk-screen printing, sintering and curling. The invention can realize the manufacture of the transverse thermoelectric device with any geometric structure under the arranged path, and the winding drum type transverse thermoelectric device has large length-thickness ratio, can realize high output voltage under small temperature difference, and is particularly suitable for efficiently collecting electric energy under small temperature difference.)

1. A reel-type transverse thermoelectric device, characterized in that: the transverse thermoelectric device is formed by combining a heterogeneous film and a flexible substrate which are formed by obliquely and alternately arranging two heterogeneous materials, the transverse thermoelectric device is curled into a barrel-shaped structure, and the two ends of the transverse thermoelectric device are provided with the leads.

2. The reel-type transverse thermoelectric device as claimed in claim 1, wherein: the radius of the central hole of the reel type transverse thermoelectric device is 2-10 mm.

3. The reel-type transverse thermoelectric device as claimed in claim 1, wherein: the inclined included angle between the interface of the two heterogeneous materials and the lower end face of the curled transverse thermoelectric device is 1-89 degrees.

4. The reel-type transverse thermoelectric device as claimed in claim 1, wherein: the thickness of the heterogeneous film of the reel type transverse thermoelectric device is 0.1-3 mm; the flexible substrate is made of polyimide and has a thickness of 0.1-0.5 mm; the conducting wire is a Cu wire.

5. The method for manufacturing a rolled transverse thermoelectric device as claimed in any one of claims 1 to 4, comprising the steps of:

1) preparing heterogeneous slurry: stirring and ultrasonically treating the heterogeneous material A and the heterogeneous material B with an adhesive, a modifier, a curing agent and a diluent respectively to obtain heterogeneous material A slurry and heterogeneous material B slurry; in the slurry of the heterogeneous material A, the mass percent of the heterogeneous material A is 60-80%, the mass percent of the adhesive is 3-10%, the mass percent of the modifier is 0-5%, the mass percent of the curing agent is 2-8%, and the mass percent of the diluent is 10-30%; in the slurry of the heterogeneous material B, the mass percent of the heterogeneous material B is 60-80%, the mass percent of the adhesive is 3-10%, the mass percent of the modifier is 0-5%, the mass percent of the curing agent is 2-8%, and the mass percent of the diluent is 10-30%;

2) assembling a transverse thermoelectric device: according to a preset geometric pattern, adopting 3D printing or silk screen printing to alternately form heterogeneous material A slurry and heterogeneous material B slurry on a flexible substrate in sequence to form a heterogeneous film and flexible substrate combined transverse thermoelectric device formed by continuously obliquely and alternately stacking the heterogeneous material A film and the heterogeneous material B film in an alternating mode;

3) sintering of the transverse thermoelectric device: sintering and molding the transverse thermoelectric device;

4) reel type transverse thermoelectric device integration: and welding wires at the beginning and the end of the sintered and molded transverse thermoelectric device, and curling to obtain the reel-type transverse thermoelectric device with high integration level.

6. The method for manufacturing a reel-type transverse thermoelectric device according to claim 5, wherein: in the step 1), the heterogeneous material A and the heterogeneous material B are selected from Al, Cu, Bi, Fe, Co and CoSb₃、Bi_0.5Sb_1.5Te₃、Bi₂Te_2.7Se_0.3、Mg₂Si、Cu₂Se、SnSe and YbAl₃Any two of them in combination.

7. The method for manufacturing a reel-type transverse thermoelectric device according to claim 5, wherein: in the step 1), the adhesive is bisphenol F type epoxy resin; the modifier is one or more of furfural resin, acetaldehyde resin and polyester resin; the curing agent is one or more of aliphatic amine, arylamine addition compound, phthalic anhydride and acid anhydride; the diluent is one or more of toluene, dibutyl phthalate, propenyl glycidyl ether, butyl glycidyl ether and phenyl glycidyl ether.

8. The method for manufacturing a reel-type transverse thermoelectric device according to claim 5, wherein: in the step 1), the viscosities of the heterogeneous material A slurry and the heterogeneous material B slurry are both 1000-3000 cps at 25 ℃.

9. The method for manufacturing a reel-type transverse thermoelectric device according to claim 5, wherein: in the step 3), the sintering temperature is 300-350 ℃, and the sintering time is 2-20 hours.

10. The method for manufacturing a reel-type transverse thermoelectric device according to claim 5, wherein: in the step 4), the welding mode is soldering.

Technical Field

The invention belongs to the field of new energy of thermoelectric conversion, and particularly relates to a reel type transverse thermoelectric device and a manufacturing method thereof.

Background

With the rapid development of information technology, various miniature electronic devices from network nodes of the internet of things to intelligent wireless sensors of roads and the like have been integrated into the aspects of life of people, but the miniature devices often have the problems of limited battery life, difficulty in replacement and the like. How to develop a sustainable power supply scheme has become a concern in the microelectronics integration industry. In fact, the natural world has temperature difference heat energy all the time, and the temperature difference heat energy can be directly converted into clean electric energy by utilizing a thermoelectric device. It has the advantages of all weather, sustainability, no noise, no pollution, high reliability, long service life and the like. A typical microelectronic thermoelectric self-powered unit consists of a pi-type thermoelectric device, a low-power-consumption boosting chip and an electricity utilization unit. However, such a unit faces two major difficulties: 1) the pi-type thermoelectric device is composed of a p-type material, an n-type material and an electrode, has a complex structure and is difficult to miniaturize; 2) under natural conditions, the temperature difference is large in floating, the temperature difference at night is often small, and stable voltage is difficult to acquire even if the low-power-consumption boost chip is used for processing.

In recent years, lateral thermoelectric devices based on the lateral thermoelectric effect have been receiving increasing attention. Lateral thermoelectric effects (CN103344328A, CN107634138A, US9012848B2, etc.) can be constructed using the intrinsic anisotropy of crystalline materials, and also can be obtained by artificially constructing an inclined structure (US20150325768, US7560639B2, etc.). The transverse thermoelectric device has the advantages of no need of electrodes, easy miniaturization and the like, and can realize thermoelectric power generation by welding wires at two ends of the transverse thermoelectric device. In addition, the temperature difference voltage V of the device is changed from V to S_zx× Δ T × l/d, wherein S is_zxIs the Seebeck coefficient value of the transverse thermoelectric device, Delta T is the temperature difference in the thickness direction, and l and d are the length and the thickness of the transverse thermoelectric device respectively. Therefore, by increasing the length l of the transverse thermoelectric device and reducing the thickness d of the transverse thermoelectric device, high-V acquisition can be realized at a small time delta T, even a low-power-consumption boost chip is not needed, and the transverse thermoelectric device is particularly suitable for self-powering of miniature electronic equipment. But of the prior art intrinsic lateral thermoelectric device_zxThe value is small and the manufacturing cost is high. The artificial transverse thermoelectric device has higher performance and can be manufactured by adopting sintering and wire cutting methods, but the following methods exist: (1) the wire-electrode cutting wire is manufactured by adopting sintering and wire-electrode cutting, has complicated process and needs to be subjected to wire-electrode cutting twiceThe inclined structure can be obtained; (2) in order to obtain the optimal performance, the inclination angle needs to be controlled with high precision, but the machining and forming are difficult due to the limitation of linear cutting precision, and especially the cutting is carried out at the inclination angle below 10 degrees; (3) in order to ensure that a high V is obtained, the length of the transverse thermoelectric device needs to be increased, but the conventional transverse thermoelectric device is made of inorganic materials and cannot be bent, so that the V is increased, and the material space occupation ratio is increased. This greatly limits the application of lateral thermoelectric devices.

Disclosure of Invention

The invention aims to provide a simple, high-controllability, small-space-occupation and large-scale winding drum type transverse thermoelectric device and a manufacturing method thereof, which can realize the manufacturing of the transverse thermoelectric device with any geometric structure under a set path, have a large length-thickness ratio, can realize high output voltage under small temperature difference and are particularly suitable for efficiently collecting electric energy under small temperature difference.

In order to achieve the technical purpose, the invention adopts the following technical scheme:

the reel type transverse thermoelectric device consists of a transverse thermoelectric device and a wire, wherein the transverse thermoelectric device is formed by combining a heterogeneous film and a flexible substrate which are formed by obliquely and alternately arranging two heterogeneous materials, the transverse thermoelectric device is coiled into a reel type structure, and the wire is arranged at the beginning end and the end of the transverse thermoelectric device.

In the preferable scheme, the radius of a central hole of the winding drum type transverse thermoelectric device is 2-10 mm.

In the preferable scheme, the inclined included angle between the interface of the two heterogeneous materials and the lower end face of the curled transverse thermoelectric device is 1-89 degrees.

Preferably, the heterogeneous material is selected from Al, Cu, Bi, Fe, Co and CoSb₃、Bi_0.5Sb_1.5Te₃、Bi₂Te_2.7Se_0.3、Mg₂Si、Cu₂Se, SnSe and YbAl₃Any two of them in combination.

In the preferable scheme, the thickness of the heterogeneous film of the winding drum type transverse thermoelectric device is 0.1-3 mm.

In a preferable scheme, the flexible substrate is polyimide, and the thickness of the flexible substrate is 0.1-0.5 mm.

Preferably, the conducting wire is a Cu wire.

The invention also provides a manufacturing method of the reel type transverse thermoelectric device, which comprises the following steps:

1) preparing heterogeneous slurry: stirring and ultrasonically treating the heterogeneous material A and the heterogeneous material B with an adhesive, a modifier, a curing agent and a diluent respectively to obtain heterogeneous material A slurry and heterogeneous material B slurry; in the slurry of the heterogeneous material A, the mass percent of the heterogeneous material A is 60-80%, the mass percent of the adhesive is 3-10%, the mass percent of the modifier is 0-5%, the mass percent of the curing agent is 2-8%, and the mass percent of the diluent is 10-30%; in the slurry of the heterogeneous material B, the mass percent of the heterogeneous material B is 60-80%, the mass percent of the adhesive is 3-10%, the mass percent of the modifier is 0-5%, the mass percent of the curing agent is 2-8%, and the mass percent of the diluent is 10-30%;

2) assembling a transverse thermoelectric device: according to a preset geometric pattern, adopting 3D printing or silk screen printing to alternately form heterogeneous material A slurry and heterogeneous material B slurry on a flexible substrate in sequence to form a heterogeneous film and flexible substrate combined transverse thermoelectric device formed by continuously obliquely and alternately stacking the heterogeneous material A film and the heterogeneous material B film in an alternating mode;

3) sintering of the transverse thermoelectric device: sintering and molding the transverse thermoelectric device;

4) reel type transverse thermoelectric device integration: and welding wires at the beginning and the end of the sintered and molded transverse thermoelectric device, and curling to obtain the reel-type transverse thermoelectric device with high integration level.

Preferably, in step 1), the heterogeneous material A and the heterogeneous material B are selected from Al, Cu, Bi, Fe, Co and CoSb₃、Bi_0.5Sb_1.5Te₃、Bi₂Te_2.7Se_0.3、Mg₂Si、Cu₂Se, SnSe and YbAl₃Any two of them in combination.

Preferably, in step 1), the adhesive is bisphenol F epoxy resin.

In a preferable scheme, in the step 1), the modifier is one or more of furfural resin, acetaldehyde resin and polyester resin.

In a preferable scheme, in the step 1), the curing agent is one or more of aliphatic amine, arylamine adduct, phthalic anhydride and acid anhydride.

In a preferable scheme, in the step 1), the diluent is one or more of toluene, dibutyl phthalate, propenyl glycidyl ether, butyl glycidyl ether and phenyl glycidyl ether.

Preferably, in the step 1), the flexible substrate is polyimide and has a thickness of 0.1-0.5 mm.

In the preferable scheme, in the step 1), the viscosities of the heterogeneous material A slurry and the heterogeneous material B slurry are both 1000-3000 cps at 25 ℃.

In a preferable scheme, in the step 3), the sintering temperature is 300-350 ℃, and the sintering time is 2-20 hours.

Preferably, in the step 4), the welding mode is soldering.

Compared with the prior art, the invention has the beneficial effects that:

1. the invention provides a simple, highly controllable, small-space-occupation and large-scale manufacturing method of a reel-type transverse thermoelectric device, which can realize the manufacturing of the transverse thermoelectric device with any geometric structure under a preset geometric pattern.

2. The prepared reel type transverse thermoelectric device has a large length-thickness ratio, can realize high output voltage under small temperature difference, and is particularly suitable for efficiently collecting electric energy under small temperature difference.

Drawings

FIG. 1 is a schematic perspective view of a roll-type transverse thermoelectric device according to the present invention; wherein: 1 is a heterogeneous material A film, 2 is a heterogeneous material B film, 3 is a lead, and 4 is a flexible substrate.

Fig. 2 is a schematic diagram of a 3D printing process of the roll type transverse thermoelectric device of the present invention, wherein: 1 is heterogeneous material A membrane, 2 is heterogeneous material B membrane, 4 is the flexible substrate, and 5 is the 3D printer.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

As shown in figure 1, the reel type transverse thermoelectric device of the invention is composed of a transverse thermoelectric device and a lead 3, wherein the transverse thermoelectric device is formed by combining a heterogeneous film and a flexible substrate 4, the heterogeneous film is formed by obliquely and alternately arranging heterogeneous material A films 1 and heterogeneous material B films 2, the heterogeneous film is positioned on the flexible substrate 4, the transverse thermoelectric device is wound into a reel type structure, and the lead 3 is arranged at the beginning and the end of the reel type structure. In the reel-type transverse thermoelectric device shown in fig. 1, when a temperature difference is given to the upper end surface and the lower end surface, a potential difference is generated between the first position and the last position of the reel-type transverse thermoelectric device, and the upper end surface (the lower end surface) of the reel-type transverse thermoelectric device can be used as a cold (hot) end or a hot (cold) end.

As shown in fig. 2, which is a schematic view of the 3D printing process of the roll type transverse thermoelectric device of the present invention,

the 3D printer 5 firstly forms the heterogeneous material A slurry on the flexible substrate 4 to obtain a heterogeneous material A film 1, then forms the heterogeneous material B slurry on the flexible substrate 4 through the 3D printer 5 to obtain a heterogeneous material B film 2, and finally forms the heterogeneous film and flexible substrate 4 combined transverse thermoelectric device formed by combining the heterogeneous material A films 1 and the heterogeneous material B films 2 which are obliquely, alternately and continuously arranged. In the invention, the thickness, the inclination angle, the printed pattern, the height, the length and the like of the heterogeneous material A film 1 and the heterogeneous material B film 2 can be flexibly adjusted according to actual requirements.

The invention is further illustrated by the following specific examples.

In this example, the material A is Bi_0.5Sb_1.5Te₃The material B is Co, and the specific manufacturing process is as follows:

1)Bi_0.5Sb_1.5Te₃slurry andpreparing Co slurry:

(1) commercial p-type Bi_0.5Sb_1.5Te₃Cutting and grinding the single crystal rod, and sieving the cut and ground single crystal rod by a 400-mesh sieve to obtain p-type Bi with the particle size of less than 38 mu m_0.5Sb_1.5Te₃Powder;

(2) weighing p-type Bi_0.5Sb_1.5Te₃200.00g of powder, 11.53g of bisphenol F epoxy resin, 1.52g of furfural resin, 12.78g of phthalic anhydride and 42.69g of butyl glycidyl ether are put into a beaker and mechanically stirred and ultrasonically mixed to obtain p-type Bi with the slurry viscosity of 2815cps at 25 ℃, uniform distribution and stable state_0.5Sb_1.5Te₃Slurry (heterogeneous material a slurry);

(3) 200g of n-type Co powder with the particle size of less than 38 mu m, 11.53g of bisphenol F epoxy resin, 1.52g of furfural resin, 12.78g of phthalic anhydride and 42.69g of butyl glycidyl ether are weighed and placed in a beaker, and mechanical stirring and ultrasonic mixing are carried out to obtain n-type Co slurry (heterogeneous material B slurry) which has the slurry viscosity of 2834cps at 25 ℃ and is uniformly distributed and stable in state;

2)Co/Bi_0.5Sb_1.5Te₃assembling a transverse thermoelectric device:

p-type Bi by adopting 3D printer with printing precision of 150 mu m_0.5Sb_1.5Te₃And (4) carrying out three-dimensional structure molding on the slurry and the n-type Co slurry. According to Co/Bi_0.5Sb_1.5Te₃Printing a p-type Bi with the thickness of 1mm on a polyimide substrate by using a preset geometric structural pattern of a transverse thermoelectric device_0.5Sb_1.5Te₃Printing n-type Co pattern with thickness of 1mm on the polyimide substrate by using another needle to form Co/Bi obliquely and alternately and continuously arranged_0.5Sb_1.5Te₃A lateral thermoelectric device.

3)Co/Bi_0.5Sb_1.5Te₃Sintering of the transverse thermoelectric device:

mixing the above Co/Bi_0.5Sb_1.5Te₃Placing the transverse thermoelectric device in an atmosphere high-temperature furnace, and carrying out heat treatment for 10 hours at the temperature of 350 ℃ in Ar atmosphere to obtain solidified Co/Bi_0.5Sb_1.5Te₃Transverse thermoelectric device。

4) Reel type Co/Bi_0.5Sb_1.5Te₃Transverse thermoelectric device integration:

(1) by soldering on the solidified Co/Bi_0.5Sb_1.5Te₃Plating Cu wires welded with 0.15mm on the starting and starting sides of the transverse thermoelectric device;

(2) further curling and forming to obtain a reel type Co/Bi with a wire_0.5Sb_1.5Te₃A lateral thermoelectric device.

In this example, a roll of Co/Bi of 20cm diameter and 2mm height was produced_0.5Sb_1.5Te₃The radius of a central hole of the transverse thermoelectric device is 3.5mm, and the inclined included angle between the interface of the heterogeneous material and the lower end face of the curled transverse thermoelectric device is 6 degrees. When the temperature difference between the cold end and the hot end is 1K, the manufactured Co/Bi_0.5Sb_1.5Te₃The open circuit voltage of the reel type transverse thermoelectric device is up to 0.83V.