CN111584706A - Flexible thermoelectric device and preparation method thereof - Google Patents
Flexible thermoelectric device and preparation method thereof Download PDFInfo
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- CN111584706A CN111584706A CN202010360544.4A CN202010360544A CN111584706A CN 111584706 A CN111584706 A CN 111584706A CN 202010360544 A CN202010360544 A CN 202010360544A CN 111584706 A CN111584706 A CN 111584706A
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- H10N19/00—Integrated devices, or assemblies of multiple devices, comprising at least one thermoelectric or thermomagnetic element covered by groups H10N10/00 - H10N15/00
- H10N19/101—Multiple thermocouples connected in a cascade arrangement
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- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
- H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
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- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
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Abstract
A flexible thermoelectric device comprising: at least two power generation units arranged according to a design pattern; the power generation unit comprises a first electrode group, a thermoelectric leg group and a second electrode group which are sequentially arranged; the thermoelectric leg group is provided with at least two thermoelectric leg pairs which are arranged at intervals, and each thermoelectric leg pair comprises a pair of a first type thermoelectric leg and a second type thermoelectric leg which have the same size; one end of each pair of the first type thermoelectric leg and the second type thermoelectric leg is electrically connected with the same corresponding first flexible electrode; the second electrode group comprises second flexible electrodes which are in one-to-one correspondence with the first type thermoelectric legs in the thermoelectric leg pairs and third flexible electrodes which are in one-to-one correspondence with the second type thermoelectric legs, the other ends of the first type thermoelectric legs are electrically connected with the corresponding second flexible electrodes, and the other ends of the second type thermoelectric legs are electrically connected with the corresponding third flexible electrodes; at least two power generation units are connected in series in sequence. The flexible thermoelectric device has the capability of double-sided bending and stretching, and is well combined with a heat source.
Description
Technical Field
The invention relates to the technical field of thermoelectricity, in particular to a flexible thermoelectric device and a preparation method thereof.
Background
With the emergence of the era of internet of things and the wide use of electronic equipment capable of communicating anytime and anywhere, people have more and more strong interest in wearable electronic systems, and the wearable electronic systems have important application prospects in the fields of human artificial limbs, electronic skins, robots and the like. But before wearable electronic systems are widely used, the problem of frequent charging thereof has to be overcome. The most effective way to solve this problem is to combine the energy harvesting device with a wearable electronic device, making it a self-powered system.
Among the above self-powered systems, a thermoelectric device (TEG) is considered as an excellent energy supply module in an energy harvesting device. Thermoelectric devices can convert heat generated by the human body into electrical energy through the thermoelectric technology of Seebeck (Seebeck) effect, which has the advantages of cleanness, no pollution, no mechanical shock, high reliability, and the like, and is considered as a particularly attractive way to implement self-powered wearable systems.
When used in self-powered wearable systems, thermoelectric devices are required to have greater flexibility in order to provide thermal contact between the human body and the thermoelectric device that conforms to the surface of the human body, especially for larger sized thermoelectric devices. The current thermoelectric devices use a rigid ceramic substrate as a base, and P-type and N-type semiconductors arranged alternately are integrated between two ceramic plates by using solder. Although rigid materials such as ceramics have high thermal conductivity, the rigid materials also have the characteristics of inextensibility, high brittleness and the like, and the defects cause that the current thermoelectric device cannot be tightly attached to various shapes and complex curved surfaces, so that the thermoelectric device cannot fully utilize the heat generated by a human body, and the application range of the thermoelectric device is limited.
In order to realize the structure of the flexible thermoelectric device, technicians at home and abroad develop some flexible thermoelectric devices, for example, a thermoelectric device which is obtained by replacing a traditional commercial ceramic hard substrate with heat-conducting silica gel and toughening the substrate by using textile gauze is proposed in an issued patent CN 106206923B, but the thermoelectric device usually needs a high-temperature environment in a welding process, and textile cotton is usually denatured under the action of high temperature so as to lose the supporting function of the textile cotton; the granted patent CN104410331B proposes a method of punching holes in a flexible PDMS template and pouring a mixture of N-type and P-type thermoelectric materials and adhesives into the holes to form thermoelectric legs, which can effectively achieve the flexibility of the device, but this will lose the thermoelectric performance of the thermoelectric device, resulting in lower output power; the granted patent CN107046092B proposes a flexible wearing device with a hollowed-out structure substrate, which can make the whole device have a certain flexibility by hollowing out the substrate, but because the thermoelectric material used in the device is very fragile, when the thermoelectric device is subjected to repeated bending deformation, the fracture occurs at the interface of the electrode and the thermoelectric leg. Therefore, there is an urgent need in the art to develop a flexible thermoelectric device that is structurally stable, easy to produce, and has excellent performance.
Disclosure of Invention
The flexible thermoelectric device mainly solves the technical problem of providing a flexible thermoelectric device with strong bending and stretching capabilities, and the flexible thermoelectric device can be better attached to heat sources with different bending conditions.
According to a first aspect, there is provided in one embodiment a flexible thermoelectric device comprising:
at least two power generation units arranged according to a design pattern;
the power generation unit comprises a first electrode group, a thermoelectric leg group and a second electrode group which are sequentially arranged;
the thermoelectric leg group is provided with at least two thermoelectric leg pairs which are arranged at intervals, each thermoelectric leg pair comprises a pair of a first type thermoelectric leg and a second type thermoelectric leg which have the same size, wherein the first type thermoelectric leg is a P type thermoelectric leg or an N type thermoelectric leg, and the second type thermoelectric leg is an N type thermoelectric leg or a P type thermoelectric leg which is different from the first type thermoelectric leg in type;
the first electrode group comprises first flexible electrodes which correspond to the thermoelectric leg pairs one by one, and one end of each of the first type thermoelectric leg and the second type thermoelectric leg of each thermoelectric leg pair is electrically connected with the same corresponding first flexible electrode;
the second electrode group comprises second flexible electrodes which are in one-to-one correspondence with the first type thermoelectric legs in the thermoelectric leg pairs and third flexible electrodes which are in one-to-one correspondence with the second type thermoelectric legs, the other ends of the first type thermoelectric legs are electrically connected with the corresponding second flexible electrodes, and the other ends of the second type thermoelectric legs are electrically connected with the corresponding third flexible electrodes;
along the arrangement direction of the thermoelectric leg pairs, the second flexible electrode corresponding to the previous thermoelectric leg pair is electrically connected with the third flexible electrode corresponding to the next thermoelectric leg pair;
an electric connector is arranged between the adjacent power generation units, so that at least two power generation units are sequentially connected in series;
one end of the electric connecting piece is connected with the second flexible electrode corresponding to the previous thermoelectric leg pair, and one end of the electric connecting piece is connected with the third flexible electrode corresponding to the next thermoelectric leg pair.
According to a second aspect, an embodiment provides a method of manufacturing a flexible thermoelectric device, comprising the steps of:
preparing a first type thermoelectric leg and a second type thermoelectric leg, cutting thermoelectric materials to obtain the first type thermoelectric leg and the second type thermoelectric leg with preset sizes and numbers, wherein the first type thermoelectric leg and the second type thermoelectric leg are used for forming at least two thermoelectric leg groups, each thermoelectric leg group is provided with at least two spaced thermoelectric leg pairs, each thermoelectric leg pair comprises a pair of the first type thermoelectric leg and the second type thermoelectric leg with the same size, the first type thermoelectric leg is a P type thermoelectric leg or an N type thermoelectric leg, and the second type thermoelectric leg is an N type thermoelectric leg or a P type thermoelectric leg with the type different from that of the first type thermoelectric leg;
preparing a first flexible electrode layer and a second flexible electrode layer, wherein the first flexible electrode layer comprises first electrode groups which are used for corresponding to the thermoelectric leg groups one by one, the first electrode groups comprise first flexible electrodes which are used for corresponding to the thermoelectric leg pairs one by one, and each first flexible electrode is respectively used for being electrically connected with one end of a first type thermoelectric leg and one end of a second type thermoelectric leg in the corresponding thermoelectric leg pair;
the second flexible electrode layer comprises an electric connecting piece and a second electrode group in one-to-one correspondence with the thermoelectric leg groups, the second electrode group comprises a second flexible electrode used for being in one-to-one correspondence with a first type thermoelectric leg in the thermoelectric leg group and a third flexible electrode used for being in one-to-one correspondence with the second type thermoelectric leg, the second flexible electrode is used for being electrically connected with the other end of the corresponding first type thermoelectric leg, the third flexible electrode is used for being electrically connected with the other end of the corresponding second type thermoelectric leg, and the second flexible electrode corresponding to the previous thermoelectric leg pair is electrically connected with the third flexible electrode corresponding to the next thermoelectric leg pair along the preset arrangement direction of the thermoelectric leg pairs;
the first electrode group, the thermoelectric leg group and the second electrode group which correspond to each other are used for forming a power generation unit, one end of the electric connecting piece is connected with the second flexible electrode corresponding to the previous thermoelectric leg pair along the preset arrangement direction of the power generation unit, and one end of the electric connecting piece is connected with the third flexible electrode corresponding to the next thermoelectric leg pair;
assembling a flexible thermoelectric device, namely welding one ends of a first type thermoelectric leg and a second type thermoelectric leg on corresponding first flexible electrodes respectively, welding the other end of the first type thermoelectric leg on corresponding second flexible electrodes, and welding the other end of the second type thermoelectric leg on a third flexible electrode to complete the assembly of the flexible thermoelectric device;
and packaging the flexible thermoelectric device by adopting a flexible insulating and heat-insulating medium, packaging the assembled flexible insulating device, and respectively wrapping the first type thermoelectric leg and the second type thermoelectric leg in the flexible insulating and heat-insulating medium, wherein the gap in the first electrode group and the gap in the second electrode group are respectively filled with the flexible insulating and heat-insulating medium.
Above-mentioned flexible thermoelectric device has designed the power generation unit that a plurality of thermoelectric legs are constituteed, and the upper and lower both sides of power generation unit are connected with flexible electrode electricity respectively, and it is located thermoelectric device surface ceramic substrate to remove to compare with traditional device for its cost is lower, and life is longer, and the person of wearing this device is also more comfortable. And the power generation units for removing the constraint of the ceramic substrate are connected in series through the electric connectors, so that enough space is reserved for the deformation of the flexible thermoelectric device, the whole flexible thermoelectric device has the capability of double-sided bending and stretching, and the flexible thermoelectric device can be applied to heat sources with different bending conditions. The preparation method of the flexible thermoelectric device is simple in process and strong in operability.
Drawings
FIG. 1 is a schematic structural diagram of a flexible thermoelectric device according to an embodiment of the present application;
FIG. 2 is a schematic structural diagram of a power generation unit according to an embodiment of the present application;
FIG. 3 is a schematic structural diagram of a first flexible electrode layer according to an embodiment of the present disclosure;
FIG. 4 is a schematic structural diagram of a second flexible electrode layer according to an embodiment of the present disclosure;
FIG. 5 is a schematic structural view of a profiled electrical connector according to an embodiment of the present disclosure;
FIG. 6 is a schematic view of another alternative profiled electrical connector according to an embodiment of the present disclosure;
FIG. 7 is a schematic view of a protective casing according to an embodiment of the present application;
FIG. 8 is a flow chart of a process for fabricating a flexible thermoelectric device according to an embodiment of the present application;
fig. 9 is a current-voltage curve and an output power curve of a power generation device worn by a human body under an ambient temperature condition of 20 ℃.
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and accompanying drawings. Wherein like elements in different embodiments are numbered with like associated elements. In the following description, numerous details are set forth in order to provide a better understanding of the present application. However, those skilled in the art will readily recognize that some of the features may be omitted or replaced with other elements, materials, methods in different instances. In some instances, certain operations related to the present application have not been shown or described in detail in order to avoid obscuring the core of the present application from excessive description, and it is not necessary for those skilled in the art to describe these operations in detail, so that they may be fully understood from the description in the specification and the general knowledge in the art.
Furthermore, the features, operations, or characteristics described in the specification may be combined in any suitable manner to form various embodiments. Also, the various steps or actions in the method descriptions may be transposed or transposed in order, as will be apparent to one of ordinary skill in the art. Thus, the various sequences in the specification and drawings are for the purpose of describing certain embodiments only and are not intended to imply a required sequence unless otherwise indicated where such sequence must be followed.
The numbering of the components as such, e.g., "first", "second", etc., is used herein only to distinguish the objects as described, and does not have any sequential or technical meaning. The term "connected" and "coupled" when used in this application, unless otherwise indicated, includes both direct and indirect connections (couplings).
The first type thermoelectric leg and the second type thermoelectric leg described in the present application may be a P-type thermoelectric leg and an N-type thermoelectric leg, respectively, or may be an N-type thermoelectric leg and a P-type thermoelectric leg, respectively. The P-type thermoelectric legs and the N-type thermoelectric legs can be made of Bi2Te3, MgSi2, Mg3Sb2, GeSi, PbTe or CoSb 3; or made of half-heller or organic thermoelectric materials.
In the embodiment of the invention, the power generation units with the flexible electrodes at the upper part and the lower part are designed, and the power generation units are sequentially connected in series through the electric connecting pieces, so that enough space is reserved for the deformation of the flexible thermoelectric device.
Referring to fig. 1 to 4, the flexible thermoelectric device provided in this embodiment includes at least two power generation units 100 arranged according to a design pattern, a flexible encapsulation layer 200 and an insulation layer 300, where the at least two power generation units 100 are sequentially connected in series through an electrical connection member 40, and a reasonable distance is maintained between adjacent power generation units 100, so as to provide a sufficient deformation space for the entire flexible thermoelectric device.
The power generating unit 100 comprises a first electrode group 10, a thermoelectric leg group and a second electrode group 20, which are sequentially arranged, wherein the thermoelectric leg group has at least two thermoelectric leg pairs which are arranged at intervals, each thermoelectric leg pair comprises a pair of a first-type thermoelectric leg 31 and a second-type thermoelectric leg 32 with the same size, the number of the thermoelectric leg pairs is preferably 2 to 4, in the embodiment, the thermoelectric leg group has two thermoelectric leg pairs, namely two pairs of the first-type thermoelectric leg 31 and the second-type thermoelectric leg 32, and the two thermoelectric leg pairs are parallel, so that the thermoelectric legs in the power generating unit 100 are distributed in an array.
As shown in fig. 3, the first electrode group 10 includes first flexible electrodes 11 corresponding to the thermoelectric leg pairs one to one, one end of each of the first type thermoelectric leg 31 and the second type thermoelectric leg 32 of each thermoelectric leg pair is welded to the same corresponding first flexible electrode 11, for example, the upper surfaces of the first type thermoelectric leg 31 and the second type thermoelectric leg 32 are welded to the first flexible electrode 11, and the area of the first flexible electrode 11 is matched with the upper surfaces of the corresponding two thermoelectric legs, such that the area of the first flexible electrode 11 is minimized, the space occupied by the power generation unit 100 can also be reduced, and a larger space is provided for deformation of the flexible thermoelectric device.
By means of soldering with the first flexible electrode 11, an electrical connection between the thermoelectric legs of the first type 31 and the thermoelectric legs of the second type 32 within the same thermoelectric leg pair can be achieved. In the present embodiment, each power generation unit 100 includes two first flexible electrodes 11.
As shown in fig. 4, the second electrode group 20 includes a second flexible electrode 21 corresponding to the first type thermoelectric leg 31 in the thermoelectric leg pair one by one, and a third flexible electrode 22 corresponding to the second type thermoelectric leg 32 one by one, and the other end of the first type thermoelectric leg 31 is welded to the corresponding second flexible electrode 21, and the other end of the second type thermoelectric leg 32 is welded to the corresponding third flexible electrode 22, for example, the lower surface of the first type thermoelectric leg 31 is welded to the second flexible electrode 21, and the lower surface of the second type thermoelectric leg 32 is welded to the third flexible electrode 22. In the present embodiment, each power generation unit 100 includes two second flexible electrodes 21 and two third flexible electrodes 22.
The second flexible electrode 21 corresponding to the previous pair of thermoelectric legs is electrically connected to the third flexible electrode 22 corresponding to the next pair of thermoelectric legs along the arrangement direction of the pairs of thermoelectric legs, so that the first-type thermoelectric legs 31 in the previous pair of thermoelectric legs are electrically connected to the second-type thermoelectric legs 32 in the next pair of thermoelectric legs, thereby realizing the sequential series connection of the pairs of thermoelectric legs in the power generation unit 100.
The first electrode group 10 and the second electrode group 20, in addition to the function of connecting the entire conductive circuit of the thermoelectric device in series, also take on the deformation of the thermoelectric device caused by external forces such as tensile, compressive, bending and shearing.
One end of the electrical connection member 40 is connected to the second flexible electrode 21 corresponding to the previous pair of thermoelectric legs and the other end of the electrical connection member 40 is connected to the third flexible electrode 22 corresponding to the next pair of thermoelectric legs along the arrangement direction of the power generation cells 100, so that the first-type thermoelectric leg 31 in the previous pair of thermoelectric legs is electrically connected to the second-type thermoelectric leg 32 in the next pair of thermoelectric legs between the adjacent power generation cells 100, thereby sequentially connecting the power generation cells 100 in series. To enhance the bending resistance of electrical connector 40, the surface of electrical connector 40 may be coated with a polyimide film.
The purpose of adopting the power generation units 100 to connect in sequence is to enhance the flexibility of the thermoelectric device and ensure that the thermoelectric device does not lose excessive power, and the packing density of the thermoelectric legs inside the power generation units 100 is equivalent to that of the traditional thermoelectric device.
The flexible packaging layer 200 is filled with a flexible insulating and heat insulating medium, so that the first type thermoelectric leg 31 and the second type thermoelectric leg 32 are respectively wrapped in the flexible insulating and heat insulating medium, and the gap in the first electrode group 10 and the gap in the second electrode group 20 are respectively filled with the flexible insulating and heat insulating medium. The gaps in the first electrode group 10 refer to gaps between adjacent first flexible electrodes 11, and the gaps in the second electrode group 20 refer to gaps between adjacent second flexible electrodes 21, between adjacent third flexible electrodes 22, and between adjacent second flexible electrodes 21 and third flexible electrodes 22. In fig. 2, parts of the flexible insulating and heat insulating medium on the surface of the thermoelectric legs are omitted for better viewing of the first type thermoelectric legs 31 and the second type thermoelectric legs 32.
The flexible insulating and heat insulating medium is made of an organic material which is flexible, breathable, low in heat conductivity and high in biological friendliness, such as Polydimethylsiloxane (PDMS), the PDMS has good electrical insulation and low heat conductivity, heat flow loss can be effectively reduced, the temperature difference between the hot end and the cold end of the flexible thermoelectric device is facilitated to be constructed, the power generation capacity of the device is improved, and the PDMS can be simultaneously deformed with the thermoelectric unit to protect the thermoelectric unit.
The insulating layer 300 is respectively attached to the outer surfaces of the first flexible electrode 11, the second flexible electrode 21, the third flexible electrode 22 and the electrical connection member 40 (only the surface of the first flexible electrode 11 is shown in fig. 2), and the insulating layer 300 is used for insulating the electrodes, and generally selects a high-thermal-conductivity insulating adhesive to avoid electric leakage when worn, reduce the interface thermal resistance between the device and a heat source, and optimize the output power of the device.
The flexible thermoelectric device comprises a plurality of power generation units 100 connected in series, and each power generation unit 100 comprises a plurality of thermoelectric leg pairs, so that the loss of power caused by the flexibility of the device is avoided. The areas outside the power generation unit 100 and the electrical connector 40 are filled with flexible insulating media, so that the whole flexible thermoelectric device has strong double-sided bending and stretching capabilities.
When the thermoelectric device is subjected to an external force, the electrical connection member 40 is deformed first, and in some embodiments, the electrical connection member 40 is a profiled structure including at least one tensile bend 41. The following examples are given.
For example, as shown in fig. 4, there are two types of the electrical connecting members 40, wherein one type of the electrical connecting member 40 has only one stretch bending portion 41, so that the electrical connecting member 40 is similar to an arc structure, and the number of the stretch bending portions 41 of the other type of the electrical connecting member 40 is two, and the two stretch bending portions 41 are symmetrical and have two ends respectively connected to the power generating cells 100 on two sides.
For another example, as shown in fig. 5 to 6, the number of the stretch folds 41 is at least two, at least two stretch folds 41 are sequentially connected between two power generation cells 100, and the convex sides of at least two stretch folds 41 are sequentially and alternately facing to two sides of the electrical connector 40, so that the electrical connector 40 is in a wave shape.
The electrical connector 40, particularly the electrical connector 40 having more than two tensile bends 41, can be deformed first when the thermoelectric device is subjected to an external force, so that the internal connection of the thermoelectric device is not damaged, and the requirement of basic flexibility of the thermoelectric device is met.
In some embodiments, as shown in fig. 7, the power generation unit 100 further includes a rigid protective cover 50, the protective cover 50 is located between the first electrode group 10 and the second electrode group 20, through holes 51 penetrating through the protective cover 50 are provided on the protective cover 50, the number of the through holes 51 matches with the total number of the first type thermoelectric legs 31 and the second type thermoelectric legs 32 included in the power generation unit 100 corresponding to the protective cover 50, the first type thermoelectric legs 31 and the second type thermoelectric legs 32 are respectively embedded in the corresponding through holes 51, the thermoelectric legs and the through holes 51 may adopt an interference fit, and in the case of an assembly error, the bonding strength of the two may be further enhanced by filling a sealant.
The protective sleeve 50 can protect the thermoelectric legs in the entire power generation unit 100 from stress concentration, and can prevent the thermoelectric legs from breaking and failing under the action of external force.
The invention also provides a preparation method of the flexible thermoelectric device, as shown in fig. 8, comprising the following steps:
step S1, preparing a first type thermoelectric leg 31 and a second type thermoelectric leg 32.
In this step, the thermoelectric material may be cut by a wire cutting method to obtain the first type thermoelectric legs 31 and the second type thermoelectric legs 32 with a predetermined size and number. In order to improve the welding performance of the thermoelectric material, a barrier isolation layer can be electroplated on a joint surface of the thermoelectric leg for welding with the electrode through an electroplating process, and then the processed thermoelectric leg is cleaned through ultrasonic cleaning.
The resulting first type 31 and second type 32 thermoelectric legs are used to form at least two thermoelectric leg sets having at least two spaced thermoelectric leg pairs, each thermoelectric leg pair comprising a pair of first type 31 and second type 32 thermoelectric legs of the same size.
Step S2, preparing a first flexible electrode layer and a second flexible electrode layer.
In this step, the obtained first flexible electrode layer includes, as shown in fig. 4, first electrode groups 10 for one-to-one correspondence to the thermoelectric leg groups, where the first electrode groups 10 include first flexible electrodes 11 for one-to-one correspondence to the thermoelectric leg pairs, and each of the first flexible electrodes 11 is respectively used for electrically connecting with one end of the first-type thermoelectric leg 31 and one end of the second-type thermoelectric leg 32 in the corresponding thermoelectric leg pair.
The obtained second flexible electrode layer is shown in fig. 5, and comprises an electrical connector 40 and a second electrode group 20 corresponding to the thermoelectric leg groups one by one, wherein the second electrode group 20 comprises a second flexible electrode 21 corresponding to the first-type thermoelectric leg 31 in the thermoelectric leg group one by one, and a third flexible electrode 22 corresponding to the second-type thermoelectric leg 32 one by one, the second flexible electrode 21 is electrically connected to the other end of the corresponding first-type thermoelectric leg 31, the third flexible electrode 22 is electrically connected to the other end of the corresponding second-type thermoelectric leg 32, and the second flexible electrode 21 corresponding to the previous thermoelectric leg pair is electrically connected to the third flexible electrode 22 corresponding to the next thermoelectric leg pair along the preset arrangement direction of the thermoelectric leg pairs.
The corresponding first electrode group 10, the corresponding thermoelectric leg group and the second electrode group 20 are used to form the power generation unit 100, and along the preset arrangement direction of the power generation unit 100, one end of the electrical connection member 40 is connected to the second flexible electrode 21 corresponding to the previous thermoelectric leg pair, and the other end of the electrical connection member 40 is connected to the third flexible electrode 22 corresponding to the next thermoelectric leg pair.
In this step, the first flexible electrode layer and the second flexible electrode layer may be prepared in two ways.
First, pure copper with a thickness of 0.1mm, i.e., copper foil, is selected as an electrode material. The copper foil is cut using a laser machining technique to obtain the first electrode group 10, the second electrode group 20 and the electrical connection members 40.
Secondly, the first electrode group 10, the second electrode group 20 and the electrical connection members 40 are respectively prepared on two polyimide substrates by using an electroplating process.
Step S3, assembling the flexible thermoelectric device.
In this step, one end of each of the first type thermoelectric leg 31 and the second type thermoelectric leg 32 is welded to the corresponding first flexible electrode 11, the other end of the first type thermoelectric leg 31 is welded to the corresponding second flexible electrode 21, and the other end of the second type thermoelectric leg 32 is welded to the third flexible electrode 22, thereby completing the assembly of the flexible thermoelectric device.
Specifically, the method comprises the following steps: (1) and preparing an assembly mold of the flexible thermoelectric device. And milling a pattern corresponding to the shape of the first flexible electrode layer on the upper die and milling a pattern corresponding to the shape of the second flexible electrode layer on the lower die by utilizing a milling machine processing technology, so that the hollow area of the die corresponds to the area of the flexible electrode layer provided with the electrode.
(2) And (6) welding for the first time. The second flexible electrode layer is maintained to correspond to the pattern of the lower mold, and the second flexible electrode 21 and the third flexible electrode 22 in the second flexible electrode layer are fixedly arranged on the lower surface of the lower mold, respectively. High-temperature solder with the melting point of 200-270 ℃ is selected as the solder used for the first welding, such as Sn/Ag3.0/Cu0.5 solder. The solder is uniformly spread on the die surface of the lower die, i.e., the upper surface thereof, by a doctor blade. Then, the first-type thermoelectric legs 31 and the second-type thermoelectric legs 32 are regularly arranged on the solder, a certain pressure is applied to the upper portions of the thermoelectric legs, and finally, the first soldering is completed by using a reflow soldering process.
(3) And (5) welding for the second time. The first flexible electrode layer is maintained to correspond to the pattern of the upper mold, and the first flexible electrode 11 is fixedly arranged on the upper surface of the upper mold. The low-temperature solder with the melting point of 140-150 ℃ is selected as the solder used for the second welding, such as Sn58/Sb42 solder. The solder is uniformly spread on the die surface of the upper die, i.e., the lower surface thereof, by a doctor blade. And buckling the first type thermoelectric leg 31 and the second type thermoelectric leg 32 which are welded on the upper template for the first time, completing the second welding in a reflow furnace, and finally, dismantling the upper die and the lower die. At this point, the assembly of the flexible thermoelectric device is completed.
If the first and second flexible electrode layers are prepared on the polyimide substrate by the plating process, it is also necessary to cut off regions of the polyimide substrate except for the first electrode group 10, the second electrode group 20, and the electrical connection members 40.
Step S4, packaging the flexible thermoelectric device.
In the step, Polydimethylsiloxane (PDMS) is selected as a flexible insulating and heat-insulating medium for packaging. Specifically, Polydimethylsiloxane (PDMS) and a hardener are prepared in a certain ratio. The mixture of the two is stirred uniformly, bubbles are pumped out in a vacuum furnace, the mixture of the two is poured on the assembled flexible thermoelectric device, and the packaging of the flexible thermoelectric device is completed after drying, so that the flexible thermoelectric device is obtained.
Fig. 9 is a current-voltage curve and an output power curve of the flexible thermoelectric device in fig. 1 worn by a human body to generate power under an ambient temperature condition of 20 ℃. Experiments show that the flexible thermoelectric device has great application potential in the fields of wearable equipment and the Internet of things.
The present invention has been described in terms of specific examples, which are provided to aid understanding of the invention and are not intended to be limiting. For a person skilled in the art to which the invention pertains, several simple deductions, modifications or substitutions may be made according to the idea of the invention.
Claims (10)
1. A flexible thermoelectric device, comprising:
at least two power generation units arranged according to a design pattern;
the power generation unit comprises a first electrode group, a thermoelectric leg group and a second electrode group which are sequentially arranged;
the thermoelectric leg group is provided with at least two thermoelectric leg pairs which are arranged at intervals, each thermoelectric leg pair comprises a first type thermoelectric leg and a second type thermoelectric leg, wherein the first type thermoelectric leg is a P type thermoelectric leg or an N type thermoelectric leg, and the second type thermoelectric leg is an N type thermoelectric leg or a P type thermoelectric leg which is different from the first type thermoelectric leg in type;
the first electrode group comprises first flexible electrodes which correspond to the thermoelectric leg pairs one by one, and one end of each of the first type thermoelectric leg and the second type thermoelectric leg of each thermoelectric leg pair is electrically connected with the corresponding first flexible electrode;
the second electrode group comprises second flexible electrodes which are in one-to-one correspondence with the first type thermoelectric legs in the thermoelectric leg pairs and third flexible electrodes which are in one-to-one correspondence with the second type thermoelectric legs, the other ends of the first type thermoelectric legs are electrically connected with the corresponding second flexible electrodes, and the other ends of the second type thermoelectric legs are electrically connected with the corresponding third flexible electrodes;
along the arrangement direction of the thermoelectric leg pairs, the second flexible electrode corresponding to the previous thermoelectric leg pair is electrically connected with the third flexible electrode corresponding to the next thermoelectric leg pair;
an electric connector is arranged between the adjacent power generation units, so that at least two power generation units are sequentially connected in series;
one end of the electric connecting piece is connected with the second flexible electrode corresponding to the previous thermoelectric leg pair, and the other end of the electric connecting piece is connected with the third flexible electrode corresponding to the next thermoelectric leg pair along the arrangement direction of the power generation units.
2. The flexible thermoelectric device according to claim 1, wherein the power generation unit further comprises a protective sheath of a rigid structure and located between the first and second electrode sets;
be equipped with the through-hole that runs through the protective sheath on the protective sheath, the total number that the first type thermoelectric leg and the second type thermoelectric leg that the generating unit contained are corresponded to the figure of through-hole and protective sheath matches, first type thermoelectric leg and second type thermoelectric leg inlay respectively and locate in the through-hole that corresponds.
3. The flexible thermoelectric device according to claim 1, wherein the electrical connection is a profiled structure comprising at least one tensile bend.
4. The flexible thermoelectric device according to claim 3, wherein the number of the stretch-bending parts is at least two, at least two of the stretch-bending parts are connected between two power generation cells in sequence, and convex sides of at least two of the stretch-bending parts face to both sides of the electrical connection member in sequence alternately.
5. The flexible thermoelectric device according to claim 3, wherein the number of the stretch bending portions is two, and the two stretch bending portions are symmetrical and have two ends respectively connected to the two power generation units.
6. The flexible thermoelectric device as claimed in claim 1, further comprising a flexible packaging layer, wherein the flexible packaging layer is located in the power generating unit and filled with a flexible insulating and heat-insulating medium, the first type thermoelectric leg and the second type thermoelectric leg are respectively wrapped in the flexible insulating and heat-insulating medium, and the gap in the first electrode group and the gap in the second electrode group are respectively filled with the flexible insulating and heat-insulating medium.
7. The flexible thermoelectric device according to claim 6, further comprising an insulating layer attached to outer surfaces of the first flexible electrode, the second flexible electrode, the third flexible electrode, and the electrical connection member, respectively.
8. A method for preparing a flexible thermoelectric device is characterized by comprising the following steps:
preparing a first type thermoelectric leg and a second type thermoelectric leg, cutting thermoelectric materials to obtain the first type thermoelectric leg and the second type thermoelectric leg with preset sizes and numbers, wherein the first type thermoelectric leg and the second type thermoelectric leg are used for forming at least two thermoelectric leg groups, each thermoelectric leg group is provided with at least two spaced thermoelectric leg pairs, each thermoelectric leg pair comprises a pair of the first type thermoelectric leg and the second type thermoelectric leg with the same size, the first type thermoelectric leg is a P type thermoelectric leg or an N type thermoelectric leg, and the second type thermoelectric leg is an N type thermoelectric leg or a P type thermoelectric leg with the type different from that of the first type thermoelectric leg;
preparing a first flexible electrode layer and a second flexible electrode layer, wherein the first flexible electrode layer comprises first electrode groups which are used for corresponding to the thermoelectric leg groups one by one, the first electrode groups comprise first flexible electrodes which are used for corresponding to the thermoelectric leg pairs one by one, and each first flexible electrode is respectively used for being electrically connected with one end of a first type thermoelectric leg and one end of a second type thermoelectric leg in the corresponding thermoelectric leg pair;
the second flexible electrode layer comprises an electric connecting piece and a second electrode group in one-to-one correspondence with the thermoelectric leg groups, the second electrode group comprises a second flexible electrode used for being in one-to-one correspondence with a first type thermoelectric leg in the thermoelectric leg group and a third flexible electrode used for being in one-to-one correspondence with the second type thermoelectric leg, the second flexible electrode is used for being electrically connected with the other end of the corresponding first type thermoelectric leg, the third flexible electrode is used for being electrically connected with the other end of the corresponding second type thermoelectric leg, and the second flexible electrode corresponding to the previous thermoelectric leg pair is electrically connected with the third flexible electrode corresponding to the next thermoelectric leg pair along the preset arrangement direction of the thermoelectric leg pairs;
the corresponding first electrode group, the corresponding thermoelectric leg group and the corresponding second electrode group are used for forming a power generation unit, one end of the electric connecting piece is connected with the corresponding second flexible electrode of the previous thermoelectric leg pair along the preset arrangement direction of the power generation unit, and the other end of the electric connecting piece is connected with the corresponding third flexible electrode of the next thermoelectric leg pair;
assembling a flexible thermoelectric device, namely welding one ends of a first type thermoelectric leg and a second type thermoelectric leg on corresponding first flexible electrodes respectively, welding the other end of the first type thermoelectric leg on corresponding second flexible electrodes, and welding the other end of the second type thermoelectric leg on a third flexible electrode to complete the assembly of the flexible thermoelectric device;
and packaging the flexible thermoelectric device by adopting a flexible insulating and heat-insulating medium, packaging the assembled flexible insulating device, and respectively wrapping the first type thermoelectric leg and the second type thermoelectric leg in the flexible insulating and heat-insulating medium, wherein the gap in the first electrode group and the gap in the second electrode group are respectively filled with the flexible insulating and heat-insulating medium.
9. The method of claim 8, wherein the step of preparing the first and second flexible electrode layers comprises: and cutting the copper foil by using a laser processing technology to obtain the first electrode group, the second electrode group and the electric connector.
10. The method of claim 8, wherein the step of preparing the first and second flexible electrode layers comprises: respectively preparing the first electrode group, the second electrode group and the electric connecting piece on the polyimide substrate by adopting an electroplating process;
in the step of assembling the flexible thermoelectric device, after the other end of the second type thermoelectric leg is welded on the third flexible electrode, the method further comprises the following steps: and cutting out the areas of the polyimide substrate except the first electrode group, the second electrode group and the electric connecting piece.
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| CN112615565A (en) * | 2020-12-03 | 2021-04-06 | 大连海事大学 | Substance identification device based on micro thermoelectric power generation and identification method thereof |
| CN114335065A (en) * | 2021-12-09 | 2022-04-12 | 武汉大学 | Thermoelectric array display and preparation method thereof |
| CN115061514A (en) * | 2022-05-17 | 2022-09-16 | 南方科技大学 | Artificial limb temperature sense system and preparation method thereof |
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| CN112615565A (en) * | 2020-12-03 | 2021-04-06 | 大连海事大学 | Substance identification device based on micro thermoelectric power generation and identification method thereof |
| CN112615565B (en) * | 2020-12-03 | 2023-02-10 | 大连海事大学 | Substance identification device based on micro thermoelectric power generation and identification method thereof |
| CN114335065A (en) * | 2021-12-09 | 2022-04-12 | 武汉大学 | Thermoelectric array display and preparation method thereof |
| CN114335065B (en) * | 2021-12-09 | 2022-10-25 | 武汉大学 | Thermoelectric array display and preparation method thereof |
| CN115061514A (en) * | 2022-05-17 | 2022-09-16 | 南方科技大学 | Artificial limb temperature sense system and preparation method thereof |
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