CN108305935A - Flexible thermoelectric device and preparation method thereof - Google Patents

Abstract

The invention provides a flexible thermoelectric device and a preparation method thereof. Patterned electrodes are arranged on the first flexible substrate and the second flexible substrate respectively, and then a plurality of N-type and P-type semiconductor thermoelectric units that are staggered and arranged at intervals are arranged respectively. It is connected with the upper electrodes of the first and second flexible substrates, so that each N-type and P-type semiconductor thermoelectric units form an electrical series and thermal parallel structure and are sandwiched between the first and second flexible substrates. Furthermore, a plurality of partitions can be formed on the first flexible substrate or/and the second flexible substrate by cutting according to the electrical connection areas of N-type and P-type semiconductor thermoelectric units, so that the flexible thermoelectric device has multi-directional bendable characteristics. The thermal stress generated by the temperature change of the flexible thermoelectric device of the present invention is small, can be deformed into various shapes in real time according to the heat source, has a high degree of combination with the heat source, and has a simple structure and low cost. As the carrier of the thermoelectric element, the flexible substrate can also effectively protect the thermoelectric element and prolong the service life of the device.

Description

Flexible thermoelectric device and preparation method

technical field

The invention belongs to the technical field of thermoelectric conversion, and in particular relates to a flexible thermoelectric device and a preparation method.

Background technique

In recent years, with the continuous shortage of global resources and the increasing requirements for environmental protection, the requirements for energy utilization are also getting higher and higher. In recent years, thermoelectric conversion, as an environmentally friendly new energy technology, has received extensive attention and research at home and abroad. Thermoelectric technology based on the principle of Seebeck effect can use different forms of heat sources to convert thermal energy into electrical energy. It has the advantages of cleanness, no pollution, no mechanical vibration, and high reliability. It is used in industrial waste heat, solar infrared heat sources, and surface heat in deserts. It has very broad application prospects in fields such as waste heat utilization of automobile exhaust, and has far-reaching significance for the reuse of resources in the whole society and resource conservation.

At present, traditional thermoelectric devices mainly use non-bendable and brittle ceramic substrates as substrates, which are only suitable for the use of planar heat sources. However, at present, a large number of automobile exhaust waste heat and industrial waste heat heat sources are all cylindrical, rectangular and other complex curved surface heat sources. The inflexibility of ceramic substrates prevents traditional thermoelectric devices from being completely attached to heat sources, and the thermal contact effect is poor. It is not suitable for the utilization of various heat sources with complex shapes that currently exist.

However, most of the flexible thermoelectric devices reported at home and abroad are organic thermoelectric devices. The thermoelectric figure of merit of these organic materials is low and the material preparation process is immature. Therefore, the performance of organic flexible thermoelectric devices is poor and is not yet suitable for application. It is currently a more realistic method to use inorganic semiconductor bulk thermoelectric materials to improve the device preparation process and make them flexible. However, this method uses copper mesh and silica gel with large gaps, which greatly reduces the electrical and thermal conductivity of the device, and improves the contact resistance and contact thermal resistance. At the same time, the preparation process is cumbersome and complicated, and the manufacturing cost is high. The bonding strength is low, and the mechanical stability of the device is poor.

Therefore, there is an urgent need to develop a new flexible thermoelectric device that can utilize heat sources of different shapes, is easy to produce, and has excellent performance.

Contents of the invention

The purpose of the present invention is to overcome the shortcomings of the above-mentioned prior art. Firstly, a flexible thermoelectric device is provided, which can be deformed into various shapes according to the heat source in real time, and has a good combination with the heat source, which is convenient for the utilization of various heat sources. , and the structure is simple and the cost is low.

The flexible thermoelectric device provided by the present invention includes:

A thermoelectric element, including a plurality of N-type semiconductor thermoelectric units and P-type semiconductor thermoelectric units interlaced and arranged in intervals;

The first flexible substrate, wherein one surface has a first electrode corresponding to each of the N-type semiconductor thermoelectric units and the P-type semiconductor thermoelectric units, and the first electrode is connected to each of the N-type semiconductor thermoelectric units and the P-type semiconductor thermoelectric units. One end face of the type semiconductor thermoelectric unit is correspondingly connected;

The second flexible substrate, wherein one surface has a second electrode corresponding to each of the N-type semiconductor thermoelectric units and the P-type semiconductor thermoelectric units, and the second electrode is connected to each of the N-type semiconductor thermoelectric units and the P-type semiconductor thermoelectric units. The other end surface of the semiconductor thermoelectric unit is connected so that each of the N-type semiconductor thermoelectric unit and the P-type semiconductor thermoelectric unit is interposed between the first flexible substrate and the second flexible substrate, so that each of them is placed.

As an optional structure of the flexible thermoelectric device of the present invention, on the first flexible substrate or/and on the second flexible substrate, there is also a structure that can be electrically connected to the N-type semiconductor thermoelectric unit and the P-type semiconductor thermoelectric unit. Area, at least one partition formed by cutting.

As an optional structure of the flexible thermoelectric device of the present invention, the first flexible substrate and the second flexible substrate are made of polyimide flexible material.

As an optional structure of the flexible thermoelectric device of the present invention, the N-type semiconductor thermoelectric unit and the P-type semiconductor thermoelectric unit are made of Bi ₂ Te ₃ , MgSi ₂ , Mg ₃ Sb ₂ , GeSi, PbTe or CoSb ₃ materials; Or use half-hesuler or organic thermoelectric materials.

As an optional structure of the flexible thermoelectric device of the present invention, an isolation layer is provided on the surface of each of the N-type semiconductor thermoelectric unit and the P-type semiconductor thermoelectric unit connected to the first electrode and the second electrode.

As an optional structure of the flexible thermoelectric device of the present invention, the isolation layer is any single metal layer of Ni, Co, Fe, In, Pt, Ag, Au, Ti or Zn, or two or more of the above Metal alloy layer.

As an optional structure of the flexible thermoelectric device of the present invention, the dimensions of the N-type and the P-type semiconductor thermoelectric units are 0.1-5 mm in length, 0.1-5 mm in width, and 0.05-5 mm in height.

The flexible thermoelectric device provided by the present invention is composed of a combination of smaller thermoelectric material units. Compared with the existing thermoelectric device, the thermal stress caused by temperature change is small, and there is no complicated overall thermoelectric element processing, which simplifies the device. Advanced processing and preparation technology, and greatly improve the stability of the device work. The present invention adopts the first flexible substrate and the second flexible substrate, which can be instantly bent or deformed according to the needs of the heat source, and is well combined with the heat source, which is convenient for the utilization of heat sources of various forms and complex shapes, so it has a very Wide range of use. At the same time, the flexible substrate can also be used as a carrier for thermoelectric elements, which can significantly improve the heat exchange efficiency between thermoelectric devices and heat sources, and can also effectively protect thermoelectric elements, prevent pollution and mechanical damage during work, and prolong the service life of devices. Long-term use stability. Further, forming a plurality of cutting partitions on the first flexible substrate or/and the second flexible substrate can make the entire flexible thermoelectric device have more deformation regions and larger deformation amounts, thereby making it multi-directionally bendable Due to the deformation characteristics, it can be suitable for heat sources with more and more complex shapes.

The present invention also provides a method for preparing the above-mentioned flexible thermoelectric device, comprising the following steps:

Cut the N-type semiconductor thermoelectric material sheet and the P-type semiconductor thermoelectric material sheet according to size to form a thermoelectric unit of a certain specification;

Preparing patterned first electrodes and second electrodes on a surface of the first flexible substrate and the second flexible substrate and dislocation arrangement of the first electrodes relative to the second electrodes;

placing a grid with a plurality of small holes corresponding to the first electrodes on the surface of the first flexible substrate with the second electrodes, and then placing a plurality of the N-type semiconductor thermoelectric units and the P-type The semiconductor thermoelectric units are alternately arranged in the grid, and one end surface of each of the N-type semiconductor thermoelectric units and the P-type semiconductor thermoelectric units is correspondingly connected to the second electrode and fixed on the first flexible on the substrate, and then remove the grid;

The second electrode on the second flexible substrate is correspondingly connected to the other end surfaces of the plurality of N-type semiconductor thermoelectric units and P-type semiconductor thermoelectric units on the first flexible substrate, so that each of the The N-type semiconductor thermoelectric unit and the P-type semiconductor thermoelectric unit form an electrical series and thermal parallel structure and are sandwiched between the first flexible substrate and the second flexible substrate.

As an optional step of the preparation method of the flexible thermoelectric device of the present invention, each of the N-type semiconductor thermoelectric units and the P-type semiconductor thermoelectric units forms an electrical series and thermal parallel structure and is sandwiched between the first flexible substrate and the After the second flexible substrate, on the first flexible substrate or/and the second flexible substrate, according to the electrical series structure area of the N-type semiconductor thermoelectric unit and the P-type semiconductor thermoelectric unit, cutting At least one partition is formed in such a way that the flexible thermoelectric device can be bent or deformed arbitrarily.

As an optional step of the preparation method of the flexible thermoelectric device of the present invention, each of the N-type semiconductor thermoelectric unit and the P-type semiconductor thermoelectric unit is connected and fixed to the first flexible substrate and the second flexible substrate by welding.

As an optional step of the preparation method of the flexible thermoelectric device of the present invention, in the step of fixedly connecting each of the N-type semiconductor thermoelectric unit and the P-type semiconductor thermoelectric unit to the first flexible substrate and the second flexible substrate, the mesh The grid is covered on the first flexible substrate, and solder is dripped on the first electrode in the small holes of the grid, and then the N-type semiconductor thermoelectric unit and the P-type semiconductor thermoelectric unit are put into the In the grid, heat to 170°C-180°C for welding, and remove the grid after cooling; then cover the grid on the second flexible substrate, and drop on the second electrode The solder is used to displace the first electrode relative to the second electrode and weld each of the N-type semiconductor thermoelectric units and the P-type semiconductor thermoelectric units.

The flexible thermoelectric device produced by the preparation method of the present invention has a high degree of compatibility with the existing device preparation process, does not require complicated processing equipment and molds, has a simple production process, short time, low cost, easy realization, and small thermal processing stress. It can better guarantee the mechanical performance of each component, and is easy to improve and innovate the existing processing technology, and has very high promotion value.

Description of drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following will briefly introduce the accompanying drawings that need to be used in the embodiments. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention. For Those of ordinary skill in the art can also obtain other drawings based on these drawings without making creative efforts.

Fig. 1 is a schematic cross-sectional view of a structural embodiment of a flexible thermoelectric device provided by the present invention;

Fig. 2 is a schematic diagram of arbitrarily bent and deformed sections obtained after cutting the structure embodiment of the flexible thermoelectric device provided by the present invention;

Fig. 3 is a top view of the structure of the first flexible substrate with cutting lines provided by the present invention;

FIG. 4 is a top view of the structure of the second flexible substrate with cutting lines provided by the present invention.

Detailed ways

In order to make the object, technical solution and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.

It should be noted that when an element is referred to as being “fixed on” or “disposed on” another element, it may be directly on the other element or there may be an intervening element at the same time. When an element is referred to as being "connected to" another element, it can be directly connected to the other element or intervening elements may also be present.

It should also be noted that in the embodiments of the present invention, "length direction", "width direction", "upper", "lower", "inner", "outer", "one surface (end) surface" or "another Orientation terms such as "surface (end) surface" are only relative concepts or refer to the normal use state of the product, or refer to the position shown in the drawings, and are only for the convenience of describing the present invention and simplifying the description. , rather than indicating or implying that the device or element referred to must have a particular orientation, be constructed, and operate in a particular orientation, and thus should not be considered limiting.

In addition, the terms "first" and "second" are used for descriptive purposes only, and cannot be interpreted as indicating or implying relative importance or implicitly specifying the quantity of indicated technical features. Thus, a feature defined as "first" and "second" may explicitly or implicitly include one or more of these features. In the description of the present invention, "plurality" means two or more, unless otherwise specifically defined.

Referring to FIG. 1, the present invention provides an embodiment structure of a flexible thermoelectric device, including a first flexible substrate 1, a second flexible substrate 3 and a thermoelectric unit 5. The thermoelectric element 5 includes a plurality of smaller thermoelectric elements formed by cutting thermoelectric materials. The N-type semiconductor thermoelectric unit 51 and the P-type semiconductor thermoelectric unit 52 of uniform size, the N-type semiconductor thermoelectric unit 51 and the P-type semiconductor thermoelectric unit 52 are arranged in pairs, and are interlaced and arranged at intervals, and can be staggered vertically and The thermoelectric elements 5 are formed after being arranged in a staggered interval in the transverse direction, and the first end face 54 and the second end face 53 opposite to each other are formed along its length or width direction; one surface 11 of the first flexible substrate 1 has a plurality of formed area, a plurality of first electrodes 2 with a certain interval in a patterned area layout can be formed, each of the first electrodes 2 is adapted to the arrangement of the N-type semiconductor thermoelectric unit 51 and the P-type semiconductor thermoelectric unit 52, and roughly The size is larger than that of the N-type semiconductor thermoelectric unit 51 and the P-type semiconductor thermoelectric unit 52 . After the first electrode 2 is fixed on the first flexible substrate 1, it has an outward surface 21, and the surface 21 is connected and fixed to the first end surface 54 on the N-type semiconductor thermoelectric unit 51 and the P-type semiconductor thermoelectric unit 52. That is, the arranged N-type semiconductor thermoelectric units 51 and P-type semiconductor thermoelectric units 52 are pasted and fixed on the surfaces 21 of the first electrodes 2 respectively. At the same time, the surface 31 of the second flexible substrate 3 also has a plurality of formation areas, which can form a plurality of second electrodes 4 with a certain interval in a patterned area layout, for connecting the second end surface 53 of the thermoelectric unit 5 . Similarly, each second electrode 4 is arranged in the same way as the N-type semiconductor thermoelectric unit 51 and the P-type semiconductor thermoelectric unit 52, and is slightly larger than the size of the N-type semiconductor thermoelectric unit 51 and the P-type semiconductor thermoelectric unit 52, but is opposite to the first electrode. 2 Displacement arrangement, that is, the first electrode 2 is arranged in a dislocation relative to the second electrode 4 in an N-type semiconductor thermoelectric unit 51 or a P-type semiconductor thermoelectric unit 52 . When connecting, the surface 41 of the second electrode 4 opposite to the thermoelectric unit 5 is aligned and fixedly connected to the second end surface 53 of the thermoelectric unit 5 . Since the first electrode 2 is arranged in a dislocation relative to the second electrode 4 , an electrical series and thermal parallel connection structure can be formed between each N-type semiconductor thermoelectric unit 51 and P-type semiconductor thermoelectric unit 52 . And because the first flexible substrate 1 and the second flexible substrate 3 have deformable flexibility, the N-type semiconductor thermoelectric unit 51 and the P-type semiconductor thermoelectric unit fixed between the first flexible substrate 1 and the second flexible substrate 3 are sandwiched 52 are small in size and arranged at intervals, so they can deform with the deformation of the first flexible substrate 1 and the second flexible substrate 3, so that the thermoelectric device of the present invention forms a flexible structure that can adapt to the shape of the outer surface of the heat source.

It can be seen from the structure of the above-mentioned flexible thermoelectric device that the thermoelectric unit 5 of the present invention is composed of a plurality of smaller N-type semiconductor thermoelectric units 51 and P-type semiconductor thermoelectric units 52 combined and connected. The structural size is enough, and there is no need to use complex thermoelectric unit molding equipment or process the thermoelectric unit into a shape that matches the heat source, which greatly simplifies the processing and preparation of the device and is low in cost. The thermal stress caused by the change is small, which greatly improves the stability of the device. Further, since the thermoelectric units are small in size and arranged at intervals, they can be arranged and combined according to needs, which facilitates the connection with the first flexible substrate 1 and the second flexible substrate 3, which is beneficial to the first flexible substrate 1 and the second flexible substrate. 2. Deformation of the flexible substrate 3 . At the same time, the first flexible substrate 1 and the second flexible substrate 3 are made of flexible materials, which are very compatible with the outer surface of the heat source, and can also be used as the carrier of the thermoelectric unit, effectively fixing and protecting the thermoelectric unit, and preventing pollution during the working process It is free from mechanical damage, prolongs the service life of the device, and has long-term stability.

The invention has a high degree of combination with heat sources, is beneficial to the utilization of various heat sources, and can significantly improve the heat exchange efficiency of thermoelectric devices and heat sources. Due to the simple arrangement and structure of the thermoelectric units, it has a high degree of fit with the existing device preparation process, and is easy to improve and innovate the existing processing technology.

Further referring to Fig. 2-Fig. 4, the present invention can also set at least one partition 6 on the first flexible substrate 1 or the second flexible substrate 3 according to the shape of the heat source or/and actual needs, or at least one partition 6 can be installed on the first flexible substrate 1 and the second flexible substrate 3 at the same time. Different positions of the second flexible substrate 3 are provided with a plurality of partitions 6. The partitions 6 can be formed by cutting, specifically according to the electrical connection area of the N-type semiconductor thermoelectric unit 51 and the P-type semiconductor thermoelectric unit 52, so as to ensure that each N-type semiconductor The electrical series and thermal parallel connection structures between the semiconductor thermoelectric unit 51 and the P-type semiconductor thermoelectric unit 52 are not separated. With this structural arrangement, since the first flexible substrate 1 and/or the second flexible substrate 3 have multiple cutting partitions, the flexible thermoelectric device as a whole is not disconnected, so that the entire flexible thermoelectric device can be further deformed. area and greater deformation, so that it has the characteristics of multi-directional bending deformation, which can be suitable for more and more complex shapes of heat sources, and this structure is obtained on the basis of the above structure by cutting and processing as needed, It is simple, fast and convenient, and has a higher degree of fit with the heat source.

In the structure of the embodiment of the present invention, the first flexible substrate 1 and the second flexible substrate 3 are both made of polyimide flexible material, which is bendable, has good thermoplasticity, does not deform at high temperatures above 400°C, and has relatively high High insulation performance, very suitable for making flexible substrates of thermoelectric devices. It can be understood that the first flexible substrate 1 and the second flexible substrate 3 can also be made of other flexible materials, as long as they can well carry the thermoelectric unit 5 and have good thermoplasticity and thermal conductivity, they are all in accordance with the present invention. protected range.

In the structure of the embodiment of the present invention, the N-type semiconductor thermoelectric unit 51 and the P-type semiconductor thermoelectric unit 52 are selected from one of the following thermoelectric materials: Bi ₂ Te ₃ , MgSi ₂ , Mg ₃ Sb ₂ , GeSi, PbTe or CoSb ₃ material; or half-hesuler or organic thermoelectric material. The above materials are made into sheet-shaped components, and then cut into sheet-shaped thermoelectric units with a length of 0.1-5 mm, a width of 0.1-5 mm, and a height of 0.05-5 mm. The cut N-type semiconductor thermoelectric unit 51 and P-type semiconductor thermoelectric unit 52 are the simplest sheet-like structure, small in size, easy to process, easy to deform with the first flexible substrate 1 and the second flexible substrate 3 when they are arranged at intervals, and can It achieves a smaller radius of curvature and is applicable to various shapes and sizes of heat sources.

In the structure of the embodiment of the present invention, the first end surface 54 connected to the first electrode 2 and the second end surface 53 connected to the second electrode 4 of the N-type semiconductor thermoelectric unit 51 and the P-type semiconductor thermoelectric unit 52 are provided with an isolation layer (not shown). The isolation layer can be any single metal layer in Ni, Co, Fe, In, Pt, Ag, Au, Ti or Zn, or an alloy layer composed of two or more of the above metals, preferably a nickel layer. It can be processed by spraying, electroplating or magnetron sputtering. Nickel metal has high thermal conductivity and electrical conductivity, stable properties, and is conducive to heat transfer, and the thermal expansion coefficient of thermoelectric materials matches, and is also suitable for dripping solder, which is convenient for fixed connection with the first electrode 2 and the second electrode 4, It can also effectively protect the thermoelectric unit 5 and prevent the solder from diffusing into the thermoelectric unit 5 at high temperature. It can be understood that the isolation layer is not limited to the ones listed above, and can also be formed in other ways, as long as it can facilitate the connection between the N-type semiconductor thermoelectric unit 51 and the P-type semiconductor thermoelectric unit 52 and the first electrode 2 and the second electrode. 4. It only needs to be connected, be able to match the thermal expansion coefficient of the thermoelectric material and be conducive to electricity and heat conduction.

The present invention also provides a method for preparing a flexible thermoelectric device, comprising the following steps:

S1 selects n/p type Bi ₂ Te ₃ , MgSi ₂ , Mg ₃ Sb ₂ , PbTe, CoSb ₃ , GeSi-based thermoelectric material sheet, half-hesuler material sheet or organic thermoelectric material sheet, and then according to the size of the target object according to the length 0.1 -5 mm, width 0.1-5 mm, and height 0.05-5 mm are cut to form sheet-shaped N-type semiconductor thermoelectric units 51 and P-type semiconductor thermoelectric units 52 .

This step can be performed after electroplating, and a nickel layer with a thickness of 0.04-0.6 mm can be plated on the thermoelectric material sheet, and then cut into thermoelectric units.

S2 Process and pattern the first electrode 2 and the second electrode 4 on the first flexible substrate 1 and the second flexible substrate 3 according to the size of the N-type semiconductor thermoelectric unit 51 and the P-type semiconductor thermoelectric unit 52 .

In this step, the size of the first electrode 2 and the second electrode 4 should be slightly larger than the size of the N-type semiconductor thermoelectric unit 51 and the P-type semiconductor thermoelectric unit 52, so as to ensure that the size of each first electrode 2 and the second electrode 4 can completely cover Each pair of N-type semiconductor thermoelectric unit 51 and P-type semiconductor thermoelectric unit 52 . And each first electrode 2 and second electrode 4 correspond according to the arrangement of the thermoelectric elements 5 , so that the first electrode 2 has an N-type semiconductor thermoelectric unit 51 or a P-type semiconductor thermoelectric unit 52 arranged in a dislocation arrangement relative to the second electrode 4 .

S3 process a stainless steel perforated steel mesh adapted to the size of the first electrode 2 according to the size of the first flexible substrate 1 (or the second flexible substrate 3), and then cover the grid on the first flexible substrate 1. On the surface 21 of the electrode 2, and in each small hole, drop a connecting material (the present embodiment selects the Sn42/Bi58 solder with a melting point of 138° C.) on the first electrode 2, and then a plurality of N-type semiconductor thermoelectric units 51 and The P-type semiconductor thermoelectric units 52 are alternately arranged in the grid, and the first end faces 54 of the N-type semiconductor thermoelectric units 51 and the P-type semiconductor thermoelectric units 52 are attached to the first electrode 2, and the infrared heater is used to , heating to 170° C.-180° C. for welding, so that each N-type semiconductor thermoelectric unit 51 and P-type semiconductor thermoelectric unit 52 are correspondingly connected to the surface 21 of the first electrode 2 . After each N-type semiconductor thermoelectric unit 51 and P-type semiconductor thermoelectric unit 52 are firmly fixed on the first flexible substrate 1 , the grid is removed.

This step is mainly to connect the first flexible substrate 1 to the first end surface 54 of the N-type semiconductor thermoelectric unit 51 and the P-type semiconductor thermoelectric unit 52 by means of reflow soldering. It can be understood that the connection method between the first flexible substrate 1 and the N-type semiconductor thermoelectric unit 51 and the P-type semiconductor thermoelectric unit 52 is not limited to welding, as long as the connection between the first flexible substrate 1 and the N-type semiconductor thermoelectric unit 51 and the P-type semiconductor thermoelectric unit 52 can be guaranteed. It is sufficient that the P-type semiconductor thermoelectric unit 52 is reliably connected and can ensure the performance of electricity and heat transfer.

S4 cover the grid on the second flexible substrate 3 again, make each small hole correspond to the second electrode 4, and make the second electrode 4 opposite to the first electrode 4 on the first flexible substrate 1, and then Sn42/Bi58 solder with a melting point of 138°C is dripped on the second electrode 4, and then the second electrode 4 on the second flexible substrate 3 is bonded to the second end surface 53 of the N-type semiconductor thermoelectric unit 51 and the P-type semiconductor thermoelectric unit 52 , and then use an infrared heater to heat the solder to 170°C-180°C, so that the second flexible substrate 3 is soldered to the second end surface 53 of each N-type semiconductor thermoelectric unit 51 and P-type semiconductor thermoelectric unit 52. After connection, the N-type semiconductor thermoelectric unit 51 and the P-type semiconductor thermoelectric unit 52 are arranged in combination and sandwiched between the second flexible substrate 3 and the first flexible substrate 1, and each row of N-type semiconductor thermoelectric units 51 and P-type semiconductor thermoelectric units The cells 52 form an electrical series structure through the second electrodes 4 and the first electrodes 2, and each column forms a thermal parallel structure (see FIG. 1).

Similarly, in this step, the connection method between the second flexible substrate 3 and the N-type semiconductor thermoelectric unit 51 and the P-type semiconductor thermoelectric unit 52 is not limited to welding, as long as the connection between the second flexible substrate 3 and the N-type semiconductor thermoelectric unit can be ensured. It is only necessary that the unit 51 and the P-type semiconductor thermoelectric unit 52 be reliably connected and that the performance of electricity and heat transfer can be guaranteed.

Further referring to Fig. 2-Fig. 4, after the above steps are completed, N-type semiconductor thermoelectric units 51 and P-type semiconductor thermoelectric units can also be installed on the first flexible substrate 1 or/and the second flexible substrate 3 according to the size of the heat source. 52 for cutting the electrical connection area, that is, cutting according to the electrical series structure of the N-type semiconductor thermoelectric unit 51 and the P-type semiconductor thermoelectric unit 52 (the first electrode 2 and the second electrode 4 cannot be cut off, and the whole cannot be cut off). As shown in Figure 3 or Figure 4, cutting can be carried out according to the cutting line A or B shown in the figure, so that a plurality of partitions 6 are formed on the first flexible substrate 1 or the second flexible substrate 3, the first flexible substrate 1 or the second flexible substrate The two flexible substrates 3 are not completely connected together as a whole. In this way, the part disconnected by the partition 6 can be opened at a certain angle as required because it is not pulled, so that the whole flexible thermoelectric device has the characteristic of multi-directional bendability (see Figure 2).

It should be noted that the above illustrated embodiment is the preparation process of the flexible thermoelectric device of the present invention. In actual use, multiple flexible thermoelectric devices can be combined and arranged according to the structure of the heat source, which is very convenient. And because the thermoelectric unit 5 of the present invention is composed of sheet-like thermoelectric units with smaller dimensions, various shapes can be formed after combination, so the shape of the flexible thermoelectric device of the present invention is not limited to the multi-segment arc described in the above-mentioned embodiments, and can also be It is rectangular, polygonal, conical or other special-shaped, etc., and can be pre-cut to form a certain size during production and processing according to needs, so as to meet the needs of industrialized mass production, and then instantly combined into various shapes according to on-site needs , so it has a very wide range of use, can meet the needs of various heat sources, and is of great significance to promote the utilization of resources and reduce environmental pollution.

The above are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements or improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention Inside.

Claims (11)

1. flexible thermo-electric device, which is characterized in that including：

Thermoelectric element, including it is multiple staggeredly and the combination that is distributed in distance N-type semiconductor thermoelectric unit and P-type semiconductor thermoelectricity list Member；

First flexible substrate a, wherein surface has and each N-type semiconductor thermoelectric unit and the P-type semiconductor thermoelectricity list The corresponding first electrode of member, the first electrode and each N-type semiconductor thermoelectric unit and the P-type semiconductor thermoelectric unit End face be correspondingly connected with；

Second flexible substrate a, wherein surface has and each N-type semiconductor thermoelectric unit and the P-type semiconductor thermoelectricity list The corresponding second electrode of member, the second electrode and each N-type semiconductor thermoelectric unit and the P-type semiconductor thermoelectric unit Other end connection and so that each N-type semiconductor thermoelectric unit and the P-type semiconductor thermoelectric unit is located in described the Make each N-type semiconductor thermoelectric unit and P-type semiconductor heat between one flexible base board and the second flexible substrate Electric unit constitutes electrically coupled in series, hot parallel-connection structure.

2. flexibility thermo-electric device as described in claim 1, which is characterized in that in the first flexible substrate or/and described the On two flexible base boards, area can be electrically connected by the N-type semiconductor thermoelectric unit and the P-type semiconductor thermoelectric unit by also having Domain, at least one partition formed by cutting mode.

3. flexibility thermo-electric device as described in claim 1, which is characterized in that the first flexible substrate and second flexibility Substrate is made of polyimide flex material.

4. flexibility thermo-electric device as described in claim 1, which is characterized in that the N-type semiconductor thermoelectric unit and the p-type Semiconductor heat electric unit uses Bi₂Te₃、MgSi₂、Mg₃Sb₂, GeSi, PbTe or CoSb₃Material is made；Either use half- Hesuler or Organic thermoelectric material are made.

5. flexibility thermo-electric device as described in claim 1, which is characterized in that each N-type semiconductor thermoelectric unit and the P The surface that type semiconductor heat electric unit is connect with the first electrode and the second electrode is equipped with separation layer.

6. flexibility thermo-electric device as claimed in claim 5, which is characterized in that the separation layer is Ni, Co, Fe, In, Pt, Ag, The alloy-layer of the metal layer of any simple substance or above two and two or more metals composition in Au, Ti or Zn.

7. flexibility thermo-electric device as claimed in any one of claims 1 to 6, which is characterized in that the N-type and the P-type semiconductor Thermoelectric unit size is long 0.1-5mm, wide 0.1-5mm, high 0.05-5mm.

8. flexible thermo-electric device preparation method, which is characterized in that include the following steps：

N-type semiconductor thermoelectric material chips and P-type semiconductor thermoelectric material chips are cut to size to the thermoelectricity list to form certain specification Member；

A surface in the first flexible substrate and the second flexible substrate prepares patterned first electrode and second Electrode and make the relatively described second electrode Heterogeneous Permutation of the first electrode；

Grid with multiple apertures corresponding with the first electrode is placed in the electric with second of the first flexible substrate On the surface of pole, multiple N-type semiconductor thermoelectric units and the P-type semiconductor thermoelectric unit are then alternately arranged placement In in the grid, and make the end face of each N-type semiconductor thermoelectric unit and the P-type semiconductor thermoelectric unit with it is described Second electrode is correspondingly connected with and is fixed in the first flexible substrate, then grid is removed；

By the second electrode in the second flexible substrate and multiple N-type semiconductors in the first flexible substrate The other end of thermoelectric unit and P-type semiconductor thermoelectric unit is correspondingly connected with, and makes each N-type semiconductor thermoelectric unit and described P-type semiconductor thermoelectric unit forms electrically coupled in series, hot parallel-connection structure and is located in the first flexible substrate and second flexibility Between substrate.

9. flexibility thermo-electric device preparation method as claimed in claim 8, which is characterized in that in each N-type semiconductor thermoelectricity Unit and the P-type semiconductor thermoelectric unit form electrically coupled in series, hot parallel-connection structure and are located in the first flexible substrate and institute After stating between second flexible substrate, in the first flexible substrate or/and the second flexible substrate, according to the N-type half Conductor thermoelectric unit and the electrically coupled in series structural region of P-type semiconductor thermoelectric unit form at least one partition using cutting mode, Make the flexible thermo-electric device arbitrarily bending or deformation.

10. flexibility thermo-electric device preparation method as claimed in claim 8 or 9, which is characterized in that each N-type semiconductor heat Electric unit and the P-type semiconductor thermoelectric unit pass through welding manner and the first flexible substrate and the second flexible substrate It is connected and fixed.

11. flexibility thermo-electric device preparation method as claimed in claim 10, which is characterized in that in each N-type semiconductor heat Electric unit and P-type semiconductor thermoelectric unit are fixedly connected in the step of the first flexible substrate and second flexible substrate, are Grid is covered in the first flexible substrate, and solder is added dropwise in first electrode in the grid aperture, then will The N-type semiconductor thermoelectric unit and the P-type semiconductor thermoelectric unit are put into the grid, are heated to 170 DEG C -180 DEG C It is welded, is removed the grid after cooling；Then grid is covered in the second flexible substrate again, described second Solder is added dropwise on electrode, make after first electrode second electrode dislocation relatively with each N-type semiconductor thermoelectric unit It is welded with the P-type semiconductor thermoelectric unit.