CN113257984B - Temperature-adjustable flexible thermoelectric device and preparation method and application thereof - Google Patents
Temperature-adjustable flexible thermoelectric device and preparation method and application thereof Download PDFInfo
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- CN113257984B CN113257984B CN202110406971.6A CN202110406971A CN113257984B CN 113257984 B CN113257984 B CN 113257984B CN 202110406971 A CN202110406971 A CN 202110406971A CN 113257984 B CN113257984 B CN 113257984B
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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
- H10N10/13—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 heat-exchanging means at the junction
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Abstract
The application provides a flexible thermoelectric device can adjust temperature includes: a first flexible substrate, a first flexible electrode layer being laminated and bonded to a surface of the first flexible substrate; a thermoelectric layer including a plurality of pairs of thermoelectric pairs arranged at intervals, the thermoelectric pairs including a p-type semiconductor thermoelectric unit and an n-type semiconductor thermoelectric unit; a second flexible substrate having a second flexible electrode layer laminated and bonded to a surface thereof; wherein the thermoelectric layer is bonded between the first flexible electrode layer and the second flexible electrode layer, and the p-type semiconductor thermoelectric units and the n-type semiconductor thermoelectric units form a pi-type series structure; and the first flexible electrode layer and the second flexible electrode layer are connected in series through an external wire. The device can regulate and control the temperature to reach the required temperature in a short time, realizes the effect of regulating refrigeration or heating simultaneously, can stretch and bend materials, and can be widely applied to daily worn fabrics.
Description
Technical Field
The application belongs to the technical field of functional fabrics, and particularly relates to a temperature-adjustable flexible thermoelectric device and a preparation method and application thereof.
Background
Different kinds of functional fabrics have been developed in the prior art based on the human body's heat balance pattern of thermal radiation, thermal convection, thermal conduction and evaporation of sweat. These fabrics can achieve thermal management of the human body to some extent, but under extremely complicated conditions, such as severe cold or hot summer, there are many limitations to achieving warm keeping or cooling by means of only passive regulation of the fabrics, and the effect of making the human body comfortable is often not achieved.
The thermoelectric device provided at present mainly uses a ceramic substrate which is not bendable and has high brittleness as a base body, is only suitable for industrial use, and is applied to textiles or a human body, and a flexible wearable thermoelectric device is needed to be provided, so that the thermoelectric device can be conveniently integrated into fabrics for personalized human body thermal management.
At present, great research progress has been made on personal heat management fabrics, but the provided materials can only realize the effect of refrigeration or heating independently, and cannot switch between refrigeration and heating so as to deal with various complicated and variable conditions, so that the better heat management effect of the heating effect and the refrigeration effect cannot be realized, and further the wide application is influenced.
Disclosure of Invention
The application aims to provide a temperature-adjustable flexible thermoelectric device and a preparation method and application thereof, and aims to solve the problems that the thermoelectric material in the prior art is a non-stretchable material and can only realize the effect of refrigeration or heating independently.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a temperature-tunable flexible thermoelectric device comprising:
a first flexible substrate having a first flexible electrode layer laminated and bonded to a surface thereof;
a thermoelectric layer including a plurality of pairs of thermoelectric pairs arranged at intervals, the thermoelectric pairs including a p-type semiconductor thermoelectric unit and an n-type semiconductor thermoelectric unit;
a second flexible substrate having a second flexible electrode layer laminated and bonded to a surface thereof;
wherein the thermoelectric layer is bonded between the first flexible electrode layer and the second flexible electrode layer, and the p-type semiconductor thermoelectric units and the n-type semiconductor thermoelectric units form a pi-type series structure; and the first flexible electrode layer and the second flexible electrode layer are connected in series.
In a second aspect, the present application provides a method of making a temperature adjustable flexible thermoelectric device, comprising the steps of:
preprocessing a first flexible substrate and a second flexible substrate;
preparing a first flexible electrode and a second flexible electrode on any surface of the first flexible substrate and the second flexible substrate;
arranging and combining first end faces of thermoelectric pairs on the surface of the first flexible electrode at intervals, and combining the second flexible electrode with a second end face of the thermoelectric pair to obtain a composite layer structure, wherein the thermoelectric pairs comprise p-type semiconductor thermoelectric units and n-type semiconductor thermoelectric units, and each p-type semiconductor thermoelectric unit and each n-type semiconductor thermoelectric unit form a pi-type series structure;
and after the composite layer structure is cured and dried, connecting the first flexible electrode layer and the second flexible electrode layer in series to obtain the temperature-adjustable flexible thermoelectric device.
In a third aspect, the present application provides a use of the temperature adjustable flexible thermoelectric device in a textile.
According to the temperature-adjustable flexible thermoelectric device provided by the first aspect of the application, a stretchable and wearable flexible hotspot device is constructed by adopting a flexible substrate, a flexible thermoelectric material and a flexible electrode; meanwhile, by combining the characteristics of thermoelectric materials, the device can change the cold and hot surfaces by adjusting the current direction in a passage, and in the using process, the conducting direction of the current is adjusted by adjusting the connection direction of a circuit, so that the current flows from a p-type semiconductor thermoelectric unit to an n-type semiconductor thermoelectric unit, the upper surface of a thermoelectric pair is a heating end, and the lower surface of the thermoelectric pair is a cooling end; changing the current direction changes the cold end and the hot end. The device can regulate and control to reach the required temperature in a short time, realizes the effect of simultaneously regulating refrigeration or heating, and has the advantages that the material can be stretched and bent, and the stretching strain capacity is more than 100 percent. Therefore, the obtained temperature-adjustable flexible thermoelectric device can be widely applied to daily-worn fabrics.
According to the preparation method of the temperature-adjustable flexible thermoelectric device, the preparation process is simple, the composite layer structure is well laminated and combined according to requirements and then is cured, and the temperature-adjustable flexible thermoelectric device can be obtained.
The gentle thermoelectric device of adjustable temperature that this application third aspect provided, the gentle thermoelectric device of adjustable temperature that the preparation obtained can adjust the temperature as required, realizes keeping human heat preservation and resisting severe cold under the low temperature environment again, realizes human cooling and resists hot and warm under high temperature environment, consequently can wide application in the fabrics.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a temperature-adjustable flexible thermoelectric device according to an embodiment of the present disclosure.
Fig. 2 is a schematic arrangement diagram of a first flexible electrode unit in a first flexible electrode layer provided in an embodiment of the present application.
Fig. 3 is a schematic arrangement diagram of a second flexible electrode unit in a second flexible electrode layer provided in an embodiment of the present application.
Fig. 4 is a schematic diagram of a thermoelectric pair provided in an embodiment of the present application.
Fig. 5 is a schematic view of a pi-type series structure provided in an embodiment of the present application.
Fig. 6 is a schematic diagram of a pi-type series structure provided in an embodiment of the present application.
Fig. 7 is a schematic diagram of a manufacturing process of a temperature adjustable flexible thermoelectric device according to an embodiment of the present application.
Fig. 8 is a schematic structural diagram of a temperature-adjustable flexible thermoelectric device according to an embodiment of the present application.
Fig. 9 is a schematic diagram of a temperature adjustable flexible thermoelectric device provided in an embodiment of the present application.
Detailed Description
In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of and not restrictive on the broad application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass described in the specification of the examples of the present application may be a mass unit known in the chemical field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another and are not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
A first aspect of an embodiment of the present application provides a temperature-adjustable flexible thermoelectric device, as shown in fig. 1, including:
a first flexible substrate 1, a first flexible electrode layer 2 laminated and bonded on the surface of the first flexible substrate 1;
a thermoelectric layer 3, the thermoelectric layer 3 comprising a plurality of pairs of thermoelectric pairs 31 arranged at intervals, and the thermoelectric pairs 31 comprising a p-type semiconductor thermoelectric unit 311 and an n-type semiconductor thermoelectric unit 312;
a second flexible substrate 5, a second flexible electrode layer 4 laminated and bonded on a surface of the second flexible substrate 5;
the thermoelectric layer 3 is bonded between the first flexible electrode layer 2 and the second flexible electrode layer 4, so that each p-type semiconductor thermoelectric unit 311 and each n-type semiconductor thermoelectric unit 312 form a pi-type series structure; and the first flexible electrode layer 2 and the second flexible electrode layer 4 are wired in series.
According to the temperature-adjustable flexible thermoelectric device provided by the first aspect of the application, a stretchable and wearable flexible hotspot device is constructed by adopting a flexible substrate, a flexible thermoelectric material and a flexible electrode; meanwhile, in combination with the characteristics of thermoelectric materials, the device can change the cold and hot surfaces by adjusting the direction of current in the path, and in the using process, the conducting direction of the current is adjusted by adjusting the direction of circuit connection, so that the current flows from the p-type semiconductor thermoelectric unit 311 to the n-type semiconductor thermoelectric unit 312, and then the upper surface of the thermoelectric pair 31 is a heating end and the lower surface is a cooling end; changing the direction of the current changes the cold end and the hot end. The device can regulate and control the temperature to reach the required temperature in a short time, realizes the effect of regulating refrigeration or heating simultaneously, and has the advantages of tensile and bending of the material and the tensile strain capacity of more than 100 percent. Therefore, the obtained temperature-adjustable flexible thermoelectric device can be widely applied to daily-worn fabrics.
Specifically, the temperature-adjustable flexible thermoelectric device comprises a first flexible substrate 1 and a second flexible substrate 5, wherein the first flexible substrate 1 and the second flexible substrate 5 are made of flexible substrate materials, and the obtained thermoelectric device is guaranteed to be a flexible device integrally and is beneficial to being used in textiles. The flexible substrate is provided to mainly serve as a support and a carrier for other materials.
In some embodiments, the materials of the first flexible substrate 1 and the second flexible substrate 5 are selected from at least one of polydimethylsiloxane, hydrogenated styrene-butadiene block copolymer, and Ecoflex series silicone rubber, and the materials are selected as the flexible substrates, and have excellent material properties, good flexibility, and an insulating effect, and can be applied well.
In an embodiment of the present invention, the material of the first flexible substrate 1 is selected from polydimethylsiloxane, and the material of the second flexible substrate 5 is selected from polydimethylsiloxane.
In some embodiments, the thicknesses of the first flexible substrate 1 and the second flexible substrate 5 are both 0.2-0.5 mm, and the thicknesses of the first flexible substrate 1 and the second flexible substrate 5 are controlled to be thin, so that the overall thickness of the obtained temperature-adjustable flexible hot spot device is moderate, and the temperature-adjustable flexible hot spot device is favorably applied to textiles.
Further, a first flexible electrode layer 2 is laminated and combined on the surface of the first flexible substrate 1, the first flexible electrode layer 2 is attached to the thermoelectric layer 3, and the arrangement of the electrode layer can facilitate the electric conduction and the heat conduction; meanwhile, the electrode layer is made of a flexible electrode layer material, the flexible electrode material can be bent and stretched, the stretching strain capacity can be more than 100%, and the problem that the traditional thermoelectric material is not stretchable can be solved.
Further, a second flexible electrode layer 4 is laminated and combined on the surface of the second flexible substrate 5, the second flexible electrode layer 4 is attached to the thermoelectric layer 3, and the arrangement of the electrode layer can be favorable for electric conduction and heat conduction; meanwhile, the electrode layer is made of a flexible electrode layer material, the flexible electrode material can be bent and stretched, the stretching strain capacity can be more than 100%, and the problem that the traditional thermoelectric material is not stretchable can be solved.
In some embodiments, as shown in fig. 2, the first flexible electrode layer is a gridded flexible electrode layer, and the first flexible electrode layer includes a plurality of first flexible electrode units arranged at intervals; wherein the first flexible electrode layer 2 comprises a plurality of first flexible electrode units 21 with a certain spacing between them for the purpose of bonding with the thermoelectric pair 31.
In some embodiments, as shown in fig. 3, the second flexible electrode layer is a gridded flexible electrode layer, and the second flexible electrode layer includes a plurality of second flexible electrode units arranged at intervals, wherein the second flexible electrode layer 4 includes a plurality of second flexible electrode units 41, and the second flexible electrode units have certain intervals therebetween.
In some embodiments, the first flexible electrode unit and the second flexible electrode unit are in a staggered arrangement. The purpose is to combine the p-type semiconductor thermoelectric element 311 and the n-type semiconductor thermoelectric element 312 with the first flexible electrode element and the second flexible electrode element, respectively, to form a pi-type series structure, in order to combine the thermoelectric pair 31 with each other in a stacked manner.
In some embodiments, the materials of the first flexible electrode layer 2 and the second flexible electrode layer 4 are selected from any one of copper, silver, gallium, and indium, and the materials of the flexible electrode layers are any one of the above materials, so that good electric conduction and heat conduction effects can be achieved, and meanwhile, the stretching effect is good, which is beneficial to use.
In some embodiments, the first flexible electrode layer 2 and the second flexible electrode layer 4 are each 20 to 50 microns thick; the thickness of the flexible electrode layer is controlled to be moderate, and if the thickness is too thin, the obtained temperature-adjustable flexible thermoelectric device is easy to break the electrode layer in the process of bending and stretching, so that the use is influenced; if the thickness is too thick, the overall thickness of the resulting temperature-adjustable flexible thermoelectric device may be too high, which may affect use in fabrics.
Specifically, the temperature-adjustable flexible thermoelectric device further comprises a thermoelectric layer 3, the thermoelectric layer 3 comprises a plurality of pairs of thermoelectric pairs 31 arranged at intervals, and as shown in fig. 4, the thermoelectric pairs 31 comprise a p-type semiconductor thermoelectric unit 311 and an n-type semiconductor thermoelectric unit 312.
In some embodiments, the thermoelectric pairs 31 in the thermoelectric layer 3 are spaced, wherein the spacing is selected from a longitudinal staggered spacing or a transverse staggered spacing or both.
In some embodiments, the thermoelectric layer 3 includes at least 5 pairs or more of thermoelectric pairs 31 in a pi-type series structure, and the more pairs of thermoelectric pairs 31 are provided, the better electric and thermal conductivity can be achieved, so that the performance is more excellent.
In some embodiments, the spacing between the spaced thermoelectric pairs 31 is 1.2mm to 1.4mm, which ensures that there is a distance between the thermoelectric pairs 31 that does not cause a short circuit.
Each thermoelectric pair 31 includes a p-type semiconductor thermoelectric unit 311 and an n-type semiconductor thermoelectric unit 312, and the p-type semiconductor thermoelectric unit 311 and the n-type semiconductor thermoelectric unit 312 are disposed opposite to each other.
In some embodiments, the p-type semiconductor thermoelectric unit 311 and the n-type semiconductor thermoelectric unit 312 are oppositely spaced, the spacing distance between the p-type semiconductor thermoelectric unit 311 and the n-type semiconductor thermoelectric unit 312 is 1.2 to 1.4mm, and the spacing distance between the p-type semiconductor thermoelectric unit 311 and the n-type semiconductor thermoelectric unit 312 is controlled, so that the size of the spacing distance between the p-type semiconductor thermoelectric unit 311 and the n-type semiconductor thermoelectric unit 312 can be ensured, and good electric conduction and heat conduction effects can be facilitated.
Further, the thermoelectric layer 3 is bonded between the first flexible electrode layer 2 and the second flexible electrode layer 4, and the p-type semiconductor thermoelectric cell 311 and the n-type semiconductor thermoelectric cell 312 form a pi-type series structure.
In some embodiments, a pi-type series structure is formed as shown in fig. 5 and 6, wherein first end faces of the p-type semiconductor thermoelectric unit 311 and the n-type semiconductor thermoelectric unit 312 are respectively bonded to surfaces of the two opposite first flexible electrode units 21 facing away from the first flexible substrate, and second end faces of the p-type semiconductor thermoelectric unit 311 and the n-type semiconductor thermoelectric unit 312 are jointly attached to surfaces of the second flexible electrode units 41 facing away from the second flexible substrate, which are offset from the two opposite first flexible electrodes, so that each of the p-type semiconductor thermoelectric unit 311 and the n-type semiconductor thermoelectric unit 312 forms the pi-type series structure. The thermoelectric material may be energized to apply a voltage to the thermoelectric pair 31 to heat or cool the object. The working principle is as follows: when current passes through the thermocouple pair formed by connecting one n-type semiconductor thermoelectric unit 312 and one p-type semiconductor thermoelectric unit 311, heat transfer occurs between the two ends, and the heat is transferred from one end to the other end, so that temperature difference is generated to form a cold end and a hot end. When current flows from the n-type semiconductor thermoelectric unit 312 to the junction of the p-type semiconductor thermoelectric unit 311, heat is absorbed and becomes a cold side; the heat is released from the p-type semiconductor thermoelectric element 311 to the junction of the n-type semiconductor thermoelectric element 312, and becomes a hot side.
In some embodiments, the p-type semiconductor thermoelectric unit 311 is a sheet-like member made of bismuth telluride, skutterudite, lead sulfide, lead selenide, or lead telluride; the materials are selected as the materials of the semiconductor thermoelectric unit, so that the effects of electric conduction and heat conduction can be realized.
In some embodiments, the n-type semiconductor thermoelectric element 312 is a sheet-like member made of a bismuth telluride, skutterudite, lead sulfide, lead selenide, or lead telluride material; the materials are selected as the materials of the semiconductor thermoelectric unit, so that the functions of electric conduction and heat conduction can be realized.
In some embodiments, the p-type semiconductor thermoelectric element 311 and the n-type semiconductor thermoelectric element 312 have dimensions of 1.2 to 1.4mm in length, 1.2 to 1.4mm in width, and 0.8 to 1.0mm in height. Among them, the p-type semiconductor thermoelectric element 311 and the n-type semiconductor thermoelectric element 312 have the same dimensions, and therefore, the same specifications are ensured during use, and excellent action effect of the obtained thermoelectric layer 3 is ensured.
Further, the first flexible electrode layer 2 and the second flexible electrode layer 4 are connected in series by an external connection wire. The upper surface of the thermoelectric couple 31 is a heating end, and the lower surface is a cooling end; changing the direction of the current changes the cold end and the hot end.
In some embodiments, the thickness of the temperature-adjustable flexible thermoelectric device is controlled to be 1.5-2 mm; the temperature-adjustable flexible thermoelectric device is controlled to be moderate, the temperature-adjustable flexible thermoelectric device can be applied to wearable textiles, and the service life is guaranteed.
A second aspect of the embodiments of the present application provides a method for manufacturing a temperature-adjustable flexible thermoelectric device, where the temperature-adjustable flexible thermoelectric device provided in the first aspect of the embodiments is manufactured by the method, and a manufacturing process of the temperature-adjustable flexible thermoelectric device is as shown in fig. 7, and includes the following steps:
s01, preprocessing a first flexible substrate 1 and a second flexible substrate 5;
s02, preparing a first flexible electrode and a second flexible electrode on any surface of the first flexible substrate 1 and the second flexible substrate 5;
s03, arranging and combining first end faces of thermoelectric pairs 31 on the surface of a first flexible electrode at intervals, and combining a second flexible electrode with second end faces of the thermoelectric pairs 31 to obtain a composite layer structure, wherein each thermoelectric pair 31 comprises a p-type semiconductor thermoelectric unit 311 and an n-type semiconductor thermoelectric unit 312, and each p-type semiconductor thermoelectric unit 311 and each n-type semiconductor thermoelectric unit 312 form a pi-type series structure;
and S04, curing and drying the composite layer structure, and connecting the first flexible electrode layer and the second flexible electrode layer in series to obtain the temperature-adjustable flexible thermoelectric device.
According to the preparation method of the temperature-adjustable flexible thermoelectric device, the preparation process is simple, the composite layer structure is well laminated and combined according to requirements and then is cured, and the temperature-adjustable flexible thermoelectric device can be obtained.
In step S01, the first flexible substrate 1 and the second flexible substrate 5 are pretreated; the pretreatment steps are as follows: vacuum drying treatment is carried out for 10 to 15 minutes in order to eliminate bubbles.
In step S02, a first flexible electrode and a second flexible electrode are prepared on any one of the surfaces of the first flexible substrate 1 and the second flexible substrate 5.
In some embodiments, the first flexible electrode layer comprises a plurality of first flexible electrode units arranged at intervals, and the second flexible electrode layer comprises a plurality of second flexible electrode units arranged at intervals; and the first flexible electrode unit and the second flexible electrode unit are arranged in a staggered manner.
Providing a first flexible electrode with gridding and a second flexible electrode with gridding, wherein the specific operation method comprises the following steps: s021, providing a gridding mould frame, and respectively arranging the frame on the surfaces of the first flexible substrate 1 and the second flexible substrate 5; s022, respectively coating the stretchable electrodes on the surfaces of the first flexible substrate 1 and the second flexible substrate 5 according to the grids of the die frame to obtain a first flexible electrode and a second flexible electrode; wherein, the first flexible electrode and the second flexible electrode are arranged in a staggered manner.
In step S03, the first end surfaces of the thermoelectric pairs 31 are arranged at intervals and are combined on the surface of the first flexible electrode, and the second flexible electrode is combined with the second end surface of the thermoelectric pair 31 to obtain a composite layer structure, wherein the thermoelectric pair 31 includes a p-type semiconductor thermoelectric unit 311 and an n-type semiconductor thermoelectric unit 312, and each p-type semiconductor thermoelectric unit 311 and each n-type semiconductor thermoelectric unit 312 form a pi-type series structure.
In some embodiments, thermoelectric pair 31 includes a p-type semiconductor thermoelectric element 311 and an n-type semiconductor thermoelectric element 312, and in accordance with the above, the same material is selected, and p-type semiconductor thermoelectric element 311 and n-type semiconductor thermoelectric element 312 are cut to form a sheet in a size of 1.4mm long, 1.4mm wide, and 1.0mm high.
In some embodiments, the distance between the p-type semiconductor thermoelectric element 311 and the n-type semiconductor thermoelectric element 312 in each thermoelectric pair 31 is 1.4mm.
In some embodiments, the p-type semiconductor thermoelectric element 311 and the n-type semiconductor thermoelectric element 312 are connected to the first flexible electrode and the second flexible electrode by soldering.
In some embodiments, the method of welding comprises the steps of:
s031. Control the distance between the p-type semiconductor thermoelectric unit 311 and the n-type semiconductor thermoelectric unit 312,
s032, placing the p-type semiconductor thermoelectric unit 311 and the n-type semiconductor thermoelectric unit 312 on the surfaces of two different first flexible electrode units which are opposite to each other at intervals according to a provided distance;
s033, respectively welding a first end surface of the p-type semiconductor thermoelectric unit 311 and a first end surface of the n-type semiconductor thermoelectric unit 312 to surfaces of two different first flexible electrode units opposite to each other at an interval by using a conventional soldering technique;
s034, providing a second flexible electrode, and welding the second end face of the p-type semiconductor thermoelectric unit 311 and the second end face of the n-type semiconductor thermoelectric unit 312 to the surface of the same second flexible electrode which is arranged in a staggered manner with the first electrode by adopting the traditional soldering technology; a composite layer structure is obtained, and each of the p-type semiconductor thermoelectric cells 311 and the n-type semiconductor thermoelectric cells 312 forms a pi-type series structure.
In step S04, after the composite layer structure is cured and dried, the first flexible electrode layer and the second flexible electrode layer are connected in series to obtain the temperature-adjustable flexible thermoelectric device.
In some embodiments, the composite layer structure is dried at 60 to 70 ℃ for 4 to 5 hours to yield a temperature adjustable flexible thermoelectric device.
Further, after curing and drying treatment, an external wire is provided, the first flexible electrode layer 2 and the second flexible electrode layer 4 are connected in series through the external wire, so that the cold and hot surfaces can be changed according to the direction of current in a channel, and if a human body feels heat (or external environment heat), the direction of the current can be adjusted to enable the side close to the skin to be refrigerated. If the human body feels cold (or the external environment is cold), the current direction is changed, so that the side close to the skin heats. Both cases are achieved by varying the current level. To change the heating or cooling effect. When the current flows from p to n, the upper surface is a heating end, the lower surface is a cooling end, and the cold end and the hot end change the current direction.
A third aspect of embodiments of the present application provides a use of a temperature-tunable and flexible thermoelectric device in a textile.
The temperature-adjustable flexible thermoelectric device prepared by the temperature-adjustable flexible thermoelectric device provided by the third aspect of the application can adjust the temperature as required, so that the human body can be kept warm and resists severe cold under the low-temperature environment, and the human body can be cooled and resists hot and cold under the high-temperature environment, so that the temperature-adjustable flexible thermoelectric device can be widely applied to textiles.
The following description is given with reference to specific examples.
Example 1
Temperature-adjustable flexible thermoelectric device and preparation method thereof
Temperature-adjustable flexible thermoelectric device
A first flexible substrate 1, a first flexible electrode layer 2 laminated and bonded on the surface of the first flexible substrate 1;
a thermoelectric layer 3, the thermoelectric layer 3 comprising a plurality of pairs of thermoelectric pairs 31 arranged at intervals, and the thermoelectric pairs 31 comprising p-type semiconductor thermoelectric units 311 and n-type semiconductor thermoelectric units 312;
a second flexible substrate 5, a second flexible electrode layer 4 being laminated and bonded on a surface of the second flexible substrate 5;
wherein, the thermoelectric layer 3 is combined between the first flexible electrode layer 2 and the second flexible electrode layer 4, so that each p-type semiconductor thermoelectric unit 311 and each n-type semiconductor thermoelectric unit 312 form a pi-type series connection structure; the first flexible electrode layer 2 and the second flexible electrode layer 4 are connected in series through an external wire;
the p-type semiconductor thermoelectric unit 311 is a sheet-shaped member made of bismuth telluride;
the n-type semiconductor thermoelectric unit 312 is a sheet-like member made of bismuth telluride;
the material of the first flexible electrode layer 2 is selected from conductive silver adhesive;
the material of the second flexible electrode layer 4 is selected from conductive silver adhesive;
the material of the first flexible substrate 1 is selected from polydimethylsiloxane;
the material of the second flexible substrate 5 is selected from polydimethylsiloxane;
the dimensions of the p-type semiconductor thermoelectric element 311 and the n-type semiconductor thermoelectric element 312 are 1.4mm long, 1.4mm wide, and 1.0mm high;
the thickness of the first flexible electrode layer 2 is 20 microns;
the thickness of the second flexible electrode layer 4 is 20 micrometers;
the first flexible substrate 1 is 0.3 mm;
the second flexible substrate 5 is 0.3 mm.
Preparation method of temperature-adjustable flexible thermoelectric device
The method comprises the following steps:
(1) Carrying out vacuum drying treatment on the first flexible substrate 1 and the second flexible substrate 5 for 10-15 minutes;
(2) Providing a gridding mould frame, and respectively arranging the frame on the surfaces of the first flexible substrate 1 and the second flexible substrate 5; respectively coating the stretchable electrodes on the surfaces of the first flexible substrate 1 and the second flexible substrate 5 according to the grids of the die frame to obtain a first flexible electrode and a second flexible electrode; the first flexible electrode and the second flexible electrode are arranged in a staggered mode;
(3) Arranging and combining first end faces of thermoelectric pairs 31 on the surface of the first flexible electrode at intervals, and combining second flexible electrodes with second end faces of the thermoelectric pairs 31 to obtain a composite layer structure, wherein the thermoelectric pairs 31 comprise p-type semiconductor thermoelectric units 311 and n-type semiconductor thermoelectric units 312, and each p-type semiconductor thermoelectric unit 311 and each n-type semiconductor thermoelectric unit 312 form a pi-type series structure;
(4) And drying the composite layer structure at 60 ℃ for 4 hours to obtain the temperature-adjustable flexible thermoelectric device.
Example 2
Temperature-adjustable flexible thermoelectric device and preparation method thereof
Temperature-adjustable flexible thermoelectric device
A first flexible substrate 1, a first flexible electrode layer 2 laminated and bonded on the surface of the first flexible substrate 1;
a thermoelectric layer 3, the thermoelectric layer 3 comprising a plurality of pairs of thermoelectric pairs 31 arranged at intervals, and the thermoelectric pairs 31 comprising p-type semiconductor thermoelectric units 311 and n-type semiconductor thermoelectric units 312;
a second flexible substrate 5, a second flexible electrode layer 4 being laminated and bonded on a surface of the second flexible substrate 5;
wherein, the thermoelectric layer 3 is combined between the first flexible electrode layer 2 and the second flexible electrode layer 4, so that each p-type semiconductor thermoelectric unit 311 and each n-type semiconductor thermoelectric unit 312 form a pi-type series connection structure; the first flexible electrode layer 2 and the second flexible electrode layer 4 are connected in series through an external wire;
the p-type semiconductor thermoelectric unit 311 is a sheet-shaped member made of lead sulfide;
the n-type semiconductor thermoelectric unit 312 is a sheet-like member made of lead sulfide;
the material of the first flexible electrode layer 2 is selected from gallium layers;
the material of the second flexible electrode layer 4 is selected from gallium layers;
the material of the first flexible substrate 1 is selected from hydrogenated styrene-butadiene block copolymers;
the material of the second flexible substrate 5 is selected from hydrogenated styrene-butadiene block copolymers;
the dimensions of the p-type semiconductor thermoelectric element 311 and the n-type semiconductor thermoelectric element 312 were 1.2mm long, 1.2mm wide, and 0.9mm high;
the thickness of the first flexible electrode layer 2 is 30 microns;
the thickness of the second flexible electrode layer 4 is 30 microns;
the first flexible substrate 1 is 0.3 mm;
the second flexible substrate 5 is 0.3 mm.
Preparation method of temperature-adjustable flexible thermoelectric device
The method comprises the following steps:
(1) Carrying out vacuum drying treatment on the first flexible substrate 1 and the second flexible substrate 5 for 10-15 minutes;
(2) Providing a gridding mould frame, and respectively arranging the frames on the surfaces of the first flexible substrate 1 and the second flexible substrate 5; respectively coating the stretchable electrodes on the surfaces of the first flexible substrate 1 and the second flexible substrate 5 according to the grids of the die frame to obtain a first flexible electrode and a second flexible electrode; the first flexible electrode and the second flexible electrode are arranged in a staggered mode;
(3) Arranging and combining first end faces of the thermoelectric pairs 31 on the surfaces of the first flexible electrodes at intervals, and combining second flexible electrodes with second end faces of the thermoelectric pairs 31 to obtain a composite layer structure, wherein the thermoelectric pairs 31 comprise p-type semiconductor thermoelectric units 311 and n-type semiconductor thermoelectric units 312, and each p-type semiconductor thermoelectric unit 311 and each n-type semiconductor thermoelectric unit 312 form a pi-type series structure;
(4) And drying the composite layer structure at 65 ℃ for 4 hours to obtain the temperature-adjustable flexible thermoelectric device.
Example 3
Temperature-adjustable flexible thermoelectric device and preparation method thereof
Temperature-adjustable flexible thermoelectric device
A first flexible substrate 1, a first flexible electrode layer 2 laminated and bonded on a surface of the first flexible substrate 1;
a thermoelectric layer 3, the thermoelectric layer 3 comprising a plurality of pairs of thermoelectric pairs 31 arranged at intervals, and the thermoelectric pairs 31 comprising p-type semiconductor thermoelectric units 311 and n-type semiconductor thermoelectric units 312;
a second flexible substrate 5, a second flexible electrode layer 4 being laminated and bonded on a surface of the second flexible substrate 5;
the thermoelectric layer 3 is bonded between the first flexible electrode layer 2 and the second flexible electrode layer 4, so that each p-type semiconductor thermoelectric unit 311 and each n-type semiconductor thermoelectric unit 312 form a pi-type series structure; the first flexible electrode layer 2 and the second flexible electrode layer 4 are connected in series through an external wire;
the p-type semiconductor thermoelectric unit 311 is a sheet-shaped member made of lead sulfide;
the n-type semiconductor thermoelectric unit 312 is a sheet-like member made of lead sulfide;
the material of the first flexible electrode layer 2 is selected from gallium layers;
the material of the second flexible electrode layer 4 is selected from gallium layers;
the material of the first flexible substrate 1 is selected from hydrogenated styrene-butadiene block copolymers;
the material of the second flexible substrate 5 is selected from hydrogenated styrene-butadiene block copolymers;
the dimensions of the p-type semiconductor thermoelectric element 311 and the n-type semiconductor thermoelectric element 312 are 1.2mm long, 1.2mm wide, and 0.9mm high;
the thickness of the first flexible electrode layer 2 is 30 micrometers;
the thickness of the second flexible electrode layer 4 is 30 microns;
the first flexible substrate 1 is 0.3 mm;
the second flexible substrate 5 is 0.3 mm.
Preparation method of temperature-adjustable flexible thermoelectric device
The method comprises the following steps:
(1) Carrying out vacuum drying treatment on the first flexible substrate 1 and the second flexible substrate 5 for 10-15 minutes;
(2) Providing a gridding mould frame, and respectively arranging the frame on the surfaces of the first flexible substrate 1 and the second flexible substrate 5; respectively coating the stretchable electrodes on the surfaces of the first flexible substrate 1 and the second flexible substrate 5 according to the grids of the die frame to obtain a first flexible electrode and a second flexible electrode; the first flexible electrode and the second flexible electrode are arranged in a staggered mode;
(3) Arranging and combining first end faces of thermoelectric pairs 31 on the surface of the first flexible electrode at intervals, and combining second flexible electrodes with second end faces of the thermoelectric pairs 31 to obtain a composite layer structure, wherein the thermoelectric pairs 31 comprise p-type semiconductor thermoelectric units 311 and n-type semiconductor thermoelectric units 312, and each p-type semiconductor thermoelectric unit 311 and each n-type semiconductor thermoelectric unit 312 form a pi-type series structure;
(4) And drying the composite layer structure at 70 ℃ for 4 hours to obtain the temperature-adjustable flexible thermoelectric device.
Determination of Properties and analysis of results
1. The resulting temperature-adjustable flexible thermoelectric device prepared in example 1, as shown in fig. 8 and 9, can be used directly as a bendable and stretchable material.
2. The temperature change of the two surfaces of the thermoelectric material after being electrified is observed through infrared thermal imaging, the temperature of the heating surface of the thermoelectric material can be increased by about 5 ℃ within 10s, and the temperature of the cooling surface can be decreased by about 5 ℃ within 10 s. The temperature is quickly increased and decreased on one side, and the temperature control device has excellent temperature control performance.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (5)
1. A method of making a temperature adjustable flexible thermoelectric device for application to a fabric, the method comprising the steps of:
preprocessing a first flexible substrate and a second flexible substrate; wherein the pretreatment comprises the following steps: vacuum drying for 10-15 min;
preparing a gridded first flexible electrode and a gridded second flexible electrode on any surface of the first flexible substrate and the second flexible substrate, wherein the gridded first flexible electrode and the gridded second flexible electrode comprise: providing a gridding mould frame, respectively arranging the mould frame on the surfaces of the first flexible substrate and the second flexible substrate, respectively coating stretchable electrodes on the surfaces of the first flexible substrate and the second flexible substrate according to the grids of the mould frame, and respectively obtaining a first flexible electrode and a second flexible electrode;
arranging and combining first end faces of thermoelectric pairs on the surface of the first flexible electrode at intervals, and combining the second flexible electrode with a second end face of the thermoelectric pair to obtain a composite layer structure, wherein the thermoelectric pairs comprise p-type semiconductor thermoelectric units and n-type semiconductor thermoelectric units, and each p-type semiconductor thermoelectric unit and each n-type semiconductor thermoelectric unit form a pi-type series structure;
after the composite layer structure is cured and dried, the first flexible electrode layer and the second flexible electrode layer are connected in series to obtain a temperature-adjustable flexible thermoelectric device; wherein the curing and drying comprises drying for 4 hours at the temperature of 60-70 ℃;
the p-type semiconductor thermoelectric unit and the n-type semiconductor thermoelectric unit are sheet-shaped members made of lead sulfide or lead selenide, the first flexible electrode layer and the second flexible electrode layer are made of any one of copper and gallium, the first flexible substrate and the second flexible substrate are made of at least one of polydimethylsiloxane, hydrogenated styrene-butadiene block copolymer and Ecoflex series silicone rubber, the p-type semiconductor thermoelectric unit and the n-type semiconductor thermoelectric unit are 1.2-1.4 mm long, 1.2-1.4 mm wide and 0.8-1.0 mm high, the p-type semiconductor thermoelectric unit and the n-type semiconductor thermoelectric unit are consistent in size, the first flexible electrode layer is 20-50 micrometers thick, the second flexible electrode layer is 20-50 micrometers thick, and the temperature-adjustable flexible thermoelectric device is 1.5-2 millimeters thick.
2. A method of making a temperature-tunable flexible thermoelectric device as in claim 1, wherein the p-type and n-type semiconductor thermoelectric cells are connected to the first and second compliant electrodes by soldering.
3. A temperature-tunable flexible thermoelectric device prepared according to the preparation method of claim 1 or 2, wherein the temperature-tunable flexible thermoelectric device is applied to a fabric, and comprises:
a first flexible substrate, a first flexible electrode layer being laminated and bonded to a surface of the first flexible substrate;
a thermoelectric layer including a plurality of pairs of thermoelectric pairs arranged at intervals, the thermoelectric pairs including a p-type semiconductor thermoelectric unit and an n-type semiconductor thermoelectric unit;
a second flexible substrate having a second flexible electrode layer laminated and bonded to a surface thereof;
wherein the thermoelectric layer is bonded between the first flexible electrode layer and the second flexible electrode layer, and the p-type semiconductor thermoelectric units and the n-type semiconductor thermoelectric units form a pi-type series structure; and the first flexible electrode layer and the second flexible electrode layer are connected in series, the p-type semiconductor thermoelectric unit and the n-type semiconductor thermoelectric unit are sheet members made of lead sulfide or lead selenide materials, the first flexible electrode layer and the second flexible electrode layer are made of any one of copper and gallium, the first flexible substrate and the second flexible substrate are made of at least one of polydimethylsiloxane, hydrogenated styrene-butadiene block copolymer and Ecoflex series silicone rubber, the p-type semiconductor thermoelectric unit and the n-type semiconductor thermoelectric unit have the size of 1.2-1.4 mm in length, 1.2-1.4 mm in width and 0.8-1.0 mm in height, the p-type semiconductor thermoelectric unit and the n-type semiconductor thermoelectric unit have the same size, the separation distance between the p-type semiconductor thermoelectric unit and the n-type semiconductor thermoelectric unit is 1.2-1.4 mm, the thickness of the first flexible electrode layer is 20-50 micrometers, the second flexible electrode layer has the adjustable thickness of 20-50 micrometers, and the adjustable thickness of the heat is 1.2-1.4 mm.
4. A tuneable flexible thermoelectric device according to claim 3, wherein the first flexible electrode layer comprises a plurality of first flexible electrode units arranged at intervals and the second flexible electrode layer comprises a plurality of second flexible electrode units arranged at intervals; and the first flexible electrode unit and the second flexible electrode unit are arranged in a staggered manner.
5. Use of a temperature adjustable flexible thermoelectric device according to claim 3 or 4 in a textile.
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