KR102026838B1 - Multilayered thermoelectric modules and preparation method thereof - Google Patents

Abstract

The present invention is to provide a stacked thermoelectric module, a method for manufacturing the same, a thermoelectric device including the thermoelectric module, and a method for manufacturing the same. To this end, according to the stacked thermoelectric module, P- and N-type semiconductor regions are formed to alternately meet at a conductive support, and the conductive support is formed in a folded shape along a boundary line where the P- and N-type semiconductor regions meet in order to allow the P- and N-type semiconductor regions to face each other. Also, an insulating layer is positioned between the P- and N-type semiconductor regions, and an electrode unit where a semiconductor region is not formed, is positioned at one end and the other end of the conductive support. The thermoelectric device of the present invention comprises: a thermoelectric element in which the thermoelectric modules are electrically connected to each other in series through each electrode unit; and a flexible support including a space for accommodating each of the thermoelectric modules. According to the present invention, individual cutting and arranging of the thermoelectric element are unnecessary. Also, electrical contact resistance is reduced by forming only thermal contact while removing an electrical bonding process, thereby improving output and processability.

Description

Stacked thermoelectric module and manufacturing method thereof {MULTILAYERED THERMOELECTRIC MODULES AND PREPARATION METHOD THEREOF}

The present invention relates to a laminated thermoelectric module, a method of manufacturing the same, a thermoelectric device including the same, and a method of manufacturing a thermoelectric device.

Thermoelectric phenomenon refers to the reversible and direct energy conversion between heat and electricity, the movement of electrons and holes in the material, the generation of electrical energy due to the temperature difference applied to the material (seebeck effect) and vice versa It refers to the exothermic phenomenon or endothermic phenomenon (Peltier effect) of the material generated by the electrical energy loaded in the.

Using thermoelectric, not only is it possible to produce power using various heat sources such as industrial waste heat, natural heat, body heat, etc., but it is also possible to transform the environment-friendly energy of the future that can be precisely and rapidly cooled. In addition, the thermoelectric device using the same is used to directly convert the thermal energy into electrical energy, the electrical energy into thermal energy and can save energy is the technology that best meets the needs of the times.

Conventional thermoelectric devices have a structure in which the ends of a P-type thermoelectric material and an N-type thermoelectric material are connected in series by electrode bonding. Thermoelectric devices based on organic materials are generally made in a film form, and there is a problem in that high thermoelectric performance is difficult to achieve due to cutting and aligning films of several tens of nanometers in thickness and connecting each film.

Although the P-type thermoelectric material and the N-type thermoelectric material are connected by using a low resistivity material as an electrode, the interface or contact resistance generated between the electrode and the thermoelectric element increases the internal resistance, and thermal or mechanical shock When the interface breaks out or cracks are generated, the electrical resistance increases or the power decreases rapidly.

For example, Korean Patent Laid-Open Publication No. 10-2014-0101121 discloses a thermoelectric device, and specifically, a lower substrate, a first electrode stacked on the lower substrate, and a P-type cell stacked on the first electrode ( P type cell, an N-type cell stacked on the first electrode, a P-type cell and a second electrode stacked on the N-type cell, and an upper substrate stacked on the second electrode. And a cross-sectional area of the N-type cell is set larger than that of the P-type cell. However, since the thermoelectric element forms a P-type cell and an N-type cell, respectively, and separately forms an electrode for electrically connecting the same, there is a problem in that the process is complicated, the resistance is also increased structurally, and the interface is separated. It may occur, and there may be a problem of an increase in electrical resistance due to crack generation.

In addition, Korean Patent Laid-Open Publication No. 10-2018-0028157 discloses a thermoelectric device, specifically, disposed to face each other and spaced apart from each other, the first substrate and the second substrate having a plurality of through holes formed therein; A first electrode layer disposed on the bottom surface of the first substrate; A second electrode layer disposed on an upper surface of the second substrate; A first solder layer disposed on the through hole of the first substrate and an upper surface of the first electrode layer; A second solder layer disposed on the through hole of the second substrate and a lower surface of the second electrode layer; And a thermoelectric material disposed in the through hole of the first substrate and the through hole of the second substrate. However, the thermoelectric device is also electrically connected to the P-type semiconductor and the N-type semiconductor through a separate electrode, the same problem may occur as described above.

P-type and N-type thermoelectric materials have to be repeatedly placed at high density for high power thermoelectric power generation in actual systems, but it is impossible to erect a film with a thickness of more than 100 micrometers in the vertical direction depending on the thermoelectric configuration. There was a problem that the loss is large. Therefore, it is urgent to develop a manufacturing process of a large area and high-density thermoelectric element while lowering the manufacturing cost based on the continuous process.

Republic of Korea Patent Publication No. 10-2014-0101121 Republic of Korea Patent Publication No. 10-2018-0028157

SUMMARY OF THE INVENTION An object of the present invention is to provide a stacked thermoelectric module, a method of manufacturing the same, and a thermoelectric device including the thermoelectric module and a method of manufacturing the same.

To this end, the present invention is formed such that the P-type semiconductor region and the N-type semiconductor region alternately contact the conductive support, and the P-type semiconductor region and the N-type so that the P-type semiconductor region and the N-type semiconductor region face each other The conductive support is folded along a boundary line where the semiconductor region is in contact with each other, and an insulating layer is disposed between the P-type semiconductor region and the N-type semiconductor region, and an electrode having no semiconductor region formed at one end portion and the other end portion of the conductive support. It provides a laminated thermoelectric module characterized in that the additional position.

In addition, the present invention by repeatedly printing a P-type dopant and an N-type dopant on the conductive support to form a P-type semiconductor region and an N-type semiconductor region repeatedly, the dopant is printed on one end and the other end of the conductive support Forming an electrode part in a manner not performed; Forming an insulating layer in a space between the P-type semiconductor region and the N-type semiconductor region; Folding the conductive support along a boundary line between the P-type semiconductor region and the N-type semiconductor region such that the P-type semiconductor region and the N-type semiconductor region face each other; And cutting the folded conductive support in a vertical or horizontal direction to a length direction in which the P-type dopant and the N-type dopant are printed.

Furthermore, the present invention provides a plurality of thermoelectric modules, the thermoelectric elements electrically interconnected in series through the respective electrode portion; And a flexible support including a space in which each of the plurality of thermoelectric modules is accommodated.

Furthermore, the present invention comprises the steps of fixing the plurality of thermoelectric modules to a flexible support including a space for receiving each of the plurality of thermoelectric modules; And electrically connecting the plurality of thermoelectric modules fixed to the flexible support to each other in series through respective electrode units.

The present invention as described above forms a P-type semiconductor region and an N-type semiconductor region on one conductive support by a continuous process, and continuously folds the thermoelectric element along a boundary line where the P-type semiconductor region and the N-type semiconductor region are in contact with each other. The fabrication eliminates the need for separate cutting and alignment of thermoelectric elements, and eliminates electrical bonding processes, resulting in only thermal contact, reducing electrical contact resistance, thereby improving output and processability. In addition, the formed thermoelectric element is cut into a plurality of small thermoelectric modules and inserted into a flexible support plate or arranged between upper and lower substrates, and then electrodes are connected to each other. There is an effect of greatly improving the process efficiency for manufacturing.

1 is a flow chart showing a thermoelectric device manufacturing process according to an embodiment of the present invention,
2 is a photograph of a thermoelectric device manufactured according to one embodiment of the present invention,
3 is an experimental result graph for confirming the thermoelectric properties of the P-type dopant used in the present invention,
4 is an experimental result graph for confirming the thermoelectric properties of the N-type dopant used in the present invention,
5 is a graph showing the power generation capacity of the thermoelectric device manufactured in one embodiment of the present invention,
6 is a photograph and a graph showing voltage and current experiments generated by body temperature with respect to the thermoelectric device manufactured in one embodiment of the present invention.
FIG. 7 is a graph showing a photograph of a thermoelectric device not forming a thermally conductive tape and a generating capacity thereof, and
8 is a photograph of a thermoelectric device manufactured in one embodiment of the present invention.

In the present invention, the "stacked type" refers to a form in which a plurality of thermoelectric modules are stacked while being in contact with each other.

In addition, in the present invention, 'thermoelectric module' means a unit capable of producing electricity from heat, and 'thermoelectric element' means that a plurality of thermoelectric modules are connected, and 'thermoelectric device' is different in such thermoelectric elements. In combination with the components, it means a structure.

According to the present invention, the P-type semiconductor region and the N-type semiconductor region are formed such that the P-type semiconductor region and the N-type semiconductor region are alternately in contact with the conductive support, and are configured such that the P-type semiconductor region and the N-type semiconductor region face each other. The conductive support is folded along the adjacent boundary line, and an insulating layer is positioned between the P-type semiconductor region and the N-type semiconductor region, and an electrode portion where no semiconductor region is formed is disposed at one end portion and the other end portion of the conductive support. It provides a laminated thermoelectric module characterized in that.

Hereinafter, the laminated thermoelectric module of the present invention will be described in detail for each configuration.

The laminated thermoelectric module of the present invention includes a P-type semiconductor region and an N-type semiconductor region that are alternately and repeatedly formed on the conductive support, wherein the conductive support is folded along a boundary line between the P-type semiconductor region and the N-type semiconductor region. As the conductive support is folded, the P-type semiconductor region and the N-type semiconductor region face each other, and an insulating layer is positioned between the P-type semiconductor region and the N-type semiconductor region. In addition, in the stacked thermoelectric module of the present invention, a semiconductor region is not formed at one end portion and the other end portion of the conductive support so that an electrode portion serving as an electrode is positioned.

The conductive support of the present invention may be one kind of fiber selected from the group consisting of carbon nanotubes, graphene, carbon graphite, graphene oxide, carbon black, carbon nanofibers, and conductive polymers. In addition, in consideration of the electrical conductivity, the carbon nanotube fibers may be aligned in bundles and in a porous form.

Wherein the P-type semiconductor region is 2,3,5,6-tetrafluorolu-tetracyanoquinomidimethane, 7,7,8,8-tetracyanoquinomidimethane, HAuCl ₄ , FeCl ₃ , nitric acid, and sulfuric acid It may be made of one or more selected from the group consisting of, it may be made of FeCl ₃ in that it is environmentally friendly and cheap.

N-type semiconductor regions include benzyl viologen, triphenylphosphine, polyethyleneimine, polyaniline, polyazine, poly (4-aminostyrene), poly (4-vinylpyridine), polyarylamine, polyvinylamine, hydrazine, ethylenediamine , Triethylamine, ethylamine and pyrrolidine, and may be composed of one or more selected from the group consisting of benzyl viologen in terms of permeability and simple molecular structure.

In the present invention, a plastic polymer or a curable polymer may be used as the insulating layer, and when the curable polymer is used, the insulating layer may be fixed to the P-type semiconductor region or the N-type semiconductor region by using an adhesive, or both surfaces of the insulating layer Silver epoxy or ceramic insulating bonding material may be applied.

The concentration of the P-type dopant forming the P-type semiconductor region of the present invention may range from 0.01 mM to 20 mM, and the concentration of the N-type dopant forming the N-type semiconductor region may range from 0.1 mM to 100 mM. . In addition, the concentration of the P-type dopant is more preferably in the range of 1 mM to 10 mM, more preferably, the concentration of the N-type dopant is in the range of 5 mM to 100 mM.

Despite the small size, the thermoelectric module according to the present invention has a high output and also has an advantage that a plurality of thermoelectric modules can be easily electrically connected through an electrode portion formed therein.

The present invention also provides a method of manufacturing a stacked thermoelectric module.

Method for manufacturing a laminated thermoelectric module according to the present invention

By alternately printing the P-type dopant and the N-type dopant on the conductive support, the P-type semiconductor region and the N-type semiconductor region are repeatedly formed, but do not print the dopant on one end and the other end of the conductive support. Forming a portion;

Is an insulating layer formed in a space between the P-type semiconductor region and the N-type semiconductor region? step;

Folding the conductive support along a boundary line between the P-type semiconductor region and the N-type semiconductor region such that the P-type semiconductor region and the N-type semiconductor region face each other; And

And cutting the folded conductive support in a vertical or horizontal direction to a length direction in which the P-type dopant and the N-type dopant are printed.

Hereinafter, the present invention will be described in detail for each step.

In the method of manufacturing a stacked thermoelectric module according to the present invention, the P-type semiconductor region and the N-type dopant are alternately printed on the conductive support so as to repeatedly form the P-type semiconductor region and the N-type semiconductor region, but at one end of the conductive support. And forming an electrode portion at the other end portion by a method not printing a dopant.

The conductive support of the present invention can be, for example, a wide conductive support. In the manufacturing method of the present invention, the P-type dopant and the N-type dopant are alternately formed so that the P-type semiconductor region, the N-type semiconductor region adjacent thereto and the P-type semiconductor region adjacent thereto may be continuously and repeatedly formed on the conductive support. Print so that they touch each other.

On the other hand, the step of repeatedly forming the P-type semiconductor region and the N-type semiconductor region to form the electrode portion by the method do not print the dopant on one end and the other end of the conductive support. As such, when the plurality of stacked thermoelectric modules are formed by cutting the electrode part by a method of not printing the dopant, the plurality of thermoelectric modules may be electrically connected to each other through the electrode part.

In this step, the method of printing the P-type and N-type dopant may be performed by one method selected from the group consisting of a brush casting method, a screen printing method and a spray coating method, in particular, the mask in the doping step Brush casting can be used in view of ease of process that doping can be performed on a specific site without using.

At this time, the concentration of the P-type dopant and N-type dopant is 0.01 mM to 20 mM, and 0.1 mM to 100, respectively, in terms of smoothly doping in performing the doping by a method such as brush casting method, rather than supporting. mM, and furthermore, the concentrations may be 1 mM to 10 mM, and 5 mM to 50 mM, respectively.

P-type dopants include 2,3,5,6-tetrafluororu-tetracyanoquinomidimethane, 7,7,8,8-tetracyanoquinomidimethane, HAuCl ₄ , FeCl ₃ , nitric acid, and sulfuric acid. One or more selected from the group consisting of may be used, and FeCl ₃ may be used in that it is environmentally friendly and inexpensive.

As a solvent for the P-type dopant, one or more solvents selected from the group consisting of 1,2-dichlorobenzene, methanol, ethanol and toluene may be used, and ethanol may be used in that it is environmentally friendly and has low boiling point.

N-type dopants include benzyl viologen, triphenylphosphine, polyethyleneimine, polyaniline, polyazine, poly (4-aminostyrene), poly (4-vinylpyridine), polyarylamine, polyvinylamine, hydrazine, ethylenediamine , At least one selected from the group consisting of triethylamine, ethylamine and pyrrolidine may be used, and benzyl viologen may be used in view of its permeability and simple molecular structure.

As the solvent for the N-type dopant, one or more solvents selected from the group consisting of 1,2-dichlorobenzene, methanol, ethanol and toluene can be used, and toluene can be used in view of excellent volatility.

In this step, the conductive support may be one fiber selected from the group consisting of carbon nanotubes, graphene, carbon graphite, graphene oxide, carbon black, carbon nanofibers, and conductive polymers.

When the conductive support used in the step is a carbon nanotube fiber, the carbon nanotube fiber is direct spinning, coagulation spinning, liquid-crystalline spinning, and brush spinning It can be produced by one method selected from the group consisting of, in particular, it can be produced using a direct spinning method in terms of increasing electrical conductivity. In addition, in consideration of the electrical conductivity, the carbon nanotube fibers may be aligned in bundles and in a porous form.

The method of manufacturing a stacked thermoelectric module according to the present invention includes folding a conductive support along a boundary line between the P-type semiconductor region and the N-type semiconductor region such that the P-type semiconductor region and the N-type semiconductor region face each other. A thermoelectric module is formed by folding the conductive support so that the P-type semiconductor region and the N-type semiconductor region face each other along the boundary line of the P-type semiconductor region and the N-type semiconductor region that are alternately repeatedly formed on the conductive support.

The manufacturing method according to the present invention may further include evaporating a solvent included in each dopant after the formation of the P-type semiconductor region and the N-type semiconductor region, and before folding the conductive support, wherein the evaporation is performed by, for example, hot wind. It can be done in a blowing manner.

In the thermoelectric module, an insulator is formed between the P-type semiconductor region and the N-type semiconductor region. In the manufacturing method of the present invention, a P-type semiconductor region and an N-type semiconductor region are formed on a conductive support, and an insulating layer is formed on one surface thereof. After forming a, the conductive support is folded along the boundary to form a thermoelectric module, or to form a P-type semiconductor region and an N-type semiconductor region on the conductive support, and after folding the conductive support to some extent along the boundary, P-type After the insulating layer is formed between the semiconductor region and the N-type semiconductor region, the thermoelectric module may be formed by completely folding the insulating layer. That is, the step of forming the insulating layer according to the present invention may be performed before the folding of the conductive support, or may be performed after the folding of the conductive support.

In the manufacturing method of the present invention, the insulating layer may be carried out by one method selected from the group consisting of spin coating, drop casting, doctor blading, spray coating and bar coating, or an adhesive is formed. PET double sided tape can also be used.

As the insulating layer, a plastic polymer or a curable polymer may be used, and when using a curable polymer, an adhesive may be used to fix the insulating layer to the P-type semiconductor region or the N-type semiconductor region, or both surfaces of the insulating layer may be epoxy or ceramic. The insulating bonding material of the system may be applied.

The manufacturing method according to the present invention includes cutting the folded conductive support in a vertical or horizontal direction to the longitudinal direction in which the P-type dopant and the N-type dopant are printed. As in the manufacturing method of the present invention, a plurality of stacked thermoelectric modules can be manufactured by a simple method by cutting the folded conductive support in a vertical or horizontal direction to the printed length direction of the P-type dopant and the N-type dopant.

In this case, the cutting may be performed by one or more methods selected from the group consisting of shearing cutting, gas cutting, plasma cutting, laser cutting, saw cutting and knife cutting.

In addition, the present invention is a plurality of thermoelectric modules are thermoelectric elements electrically interconnected in series through the respective electrode portion; And

It provides a thermoelectric device comprising a flexible support including a space in which each of the plurality of thermoelectric modules are accommodated.

Hereinafter, the thermoelectric device according to the present invention will be described in detail for each component.

The thermoelectric device according to the present invention includes a thermoelectric device in which a plurality of thermoelectric modules are electrically interconnected in series through respective electrode units. As such, there is an effect of increasing the voltage generated by electrically connecting the plurality of thermoelectric modules in series. In addition, the thermoelectric device according to the present invention has an advantage of forming a thermoelectric element by a very simple method because the plurality of thermoelectric modules according to the present invention including an electrode part are interconnected through the electrode part.

In this case, the series connection of the plurality of thermoelectric modules may be performed by electrically connecting the surface of the P-type semiconductor region of one thermoelectric module and the surface of the N-type semiconductor region of another thermoelectric module. A silver, a metal such as aluminum, copper, gold, silver, or a composite thereof, a conductive polymer, or a carbon nanotube material may be used, and silver paste may be used in view of commercialization and easy availability.

The thermoelectric device of the present invention includes a flexible support including a space accommodating each thermoelectric module of the thermoelectric element as described above. The thermoelectric device according to the present invention not only has the advantage that a plurality of thermoelectric modules are connected in series to increase the voltage of electricity generated from heat, and each of the plurality of thermoelectric modules is fixed to a flexible support, thereby providing flexibility. Since the device can be obtained, there is an advantage that can be applied to various types of heating surface.

In this case, the flexible support may use a material having excellent flexibility and elasticity, for example, a silicon-based polymer material including PDMS (polydimethyl siloxane) or a composite or carbon-based polymer material thereof may be used. In terms of flexibility and stability, the use of silicone-based polymer materials can be considered.

As the flexible support, a material having a thermal conductivity of 1 W / m · K or less may be used. By using a material having low thermal conductivity as the flexible support, more electricity can be generated even at the same temperature difference between the hot portion and the cold portion.

In addition, the thermoelectric device of the present invention may further include a flexible heat sink on the side in contact with the low temperature portion of the thermoelectric module for more efficient heat dissipation and thereby efficient power generation. In this case, the flexible heat sink may have a mesh form or another form.

Furthermore, the thermoelectric device of the present invention may further include a heat transfer passage on the surface of the thermoelectric module in contact with the high temperature portion or the high temperature portion and the low temperature portion for more efficient heat transfer and thus efficient power generation, wherein the heat transfer passage is, for example, thermally conductive. It may be formed of a tape, wherein the aluminum foil may be attached to the opposite side of the surface in which the thermal conductive tape is in contact with the thermoelectric module.

Furthermore, the present invention comprises the steps of fixing the plurality of thermoelectric modules to a flexible support including a space for receiving each of the plurality of thermoelectric modules; And electrically connecting the plurality of thermoelectric modules fixed to the flexible support to each other in series through respective electrode units.

Hereinafter, a method of manufacturing a thermoelectric device according to the present invention will be described in detail for each step.

A method of manufacturing a thermoelectric device according to the present invention includes electrically connecting a plurality of thermoelectric modules in series through respective electrode portions, thereby increasing a voltage generated by electrically connecting the plurality of thermoelectric modules in series. It can be effected. In addition, since the present invention interconnects a plurality of thermoelectric modules including an electrode part through the electrode part as described above, an additional configuration is unnecessary for mutual electrical connection, and thus the connection step is greatly simplified.

In this case, electrically connecting the plurality of thermoelectric modules in series may be performed by electrically connecting the surface of the P-type semiconductor region of one thermoelectric module and the surface of the N-type semiconductor region of another thermoelectric module. It can be performed using a metal such as silver aluminum, copper, gold, silver, or a composite thereof, a conductive polymer, or a carbon nanotube material, and may use a silver paste from the viewpoint of being commercially available.

As the method of electrically connecting as described above, a dry deposition method such as sputtering, electron beam deposition, thermal evaporation deposition, or the like, or a wet deposition method such as screen printing or electroplating may be used, or a brush casting method may be used.

In the method of manufacturing a thermoelectric device of the present invention, after fixing the plurality of thermoelectric modules to a flexible support including a space accommodating each thermoelectric module, a plurality of thermoelectric modules are electrically connected through each electrode unit as described above. Can be interconnected. The thermoelectric device thus formed has the advantage that a plurality of thermoelectric modules are connected in series to increase the voltage of electricity generated from heat, and each of the plurality of thermoelectric modules is fixed to a flexible support, thereby providing flexibility. Since it can be obtained, there is an advantage that can be applied to various types of heating surface.

In this case, the flexible support may use a material having excellent flexibility and elasticity, for example, a silicon-based polymer material including PDMS (polydimethyl siloxane) or a composite or carbon-based polymer material thereof may be used. In terms of flexibility and stability, the use of silicone-based polymer materials can be considered.

As the flexible support, a material having a thermal conductivity of 1 W / m · K or less may be used. By using a material having low thermal conductivity as the flexible support, more electricity can be generated even at the same temperature difference between the hot portion and the cold portion.

In addition, the manufacturing method of the thermoelectric device of the present invention may include the step of forming a flexible heat sink on the side in contact with the low temperature portion of the thermoelectric module for more efficient heat dissipation and thereby efficient power generation. In this case, the flexible heat sink may have a mesh form or another form.

Furthermore, the manufacturing method of the thermoelectric device of the present invention may include the step of forming a heat transfer passage on the surface of the thermoelectric module in contact with the hot or hot and cold portion for more efficient heat transfer and thus efficient power generation, wherein the heat transfer passage For example, may be formed of a thermally conductive tape, wherein the aluminum foil may be attached to the opposite side of the surface that the thermally conductive tape is in contact with the thermoelectric module.

According to the manufacturing method of the present invention, it is possible to manufacture a flexible thermoelectric device by a simple method, there is an advantage to manufacture a thermoelectric device that can be applied to the application field having a variety of types of surface, furthermore the power generation efficiency through heat There is an advantage that can be greatly improved.

Hereinafter, the present invention will be described in more detail through Examples and Experimental Examples. The following Examples and Experimental Examples are only intended to explain the present invention in detail, and the scope of the present invention is not limited by the following contents.

<Example 1>

Manufacturing of thermoelectric modules

A wide carbon nanotube web (manufactured by Soongsil University) 8 cm X 30 cm was used as the conductive support.

8.1 mg of FeCl ₃ was added to 10 mL of ethanol and stirred uniformly to prepare a P-type dopant. 0.2 g of benzyl viologen was dissolved in 10 mL of distilled water, and 10 mL of toluene was added thereto, and 7.5 g of sodium borohydride was added to the resulting separation layer, followed by storage for 1 day to prepare an N-type dopant. The concentration of the prepared P-type dopant was 5 mM and the concentration of the N-type dopant was 50 mM.

Among the dopants, first, a P-type dopant was printed in a straight line with a width of 0.5 cm in a direction horizontal to the longitudinal direction of the wide carbon nanotube web conductive support to form a P-type semiconductor region on the conductive support. At this time, printing was performed using a brush casting method.

Next, after the insulating layer having the same area as the formed P-type semiconductor region was attached to the P-type semiconductor region, the N-type semiconductor region was formed in the same manner using the prepared N-type dopant.

The conductive support was folded along the boundary between the P-type semiconductor region and the N-type semiconductor region, and the P-type semiconductor region and the N-type semiconductor region were bonded to each other with an insulating layer interposed therebetween.

By forming the P-type semiconductor region, attaching the insulating layer, and repeating the process of forming the N-type semiconductor region 20 times and folding 20 times, 20 P-type semiconductor regions and 20 N-type semiconductor regions are repeated. To form.

On the other hand, electrode portions were formed at both ends by a method of not forming a semiconductor region at a width of 0.5 cm at both ends of the wide carbon nanotube web.

The laminated conductive thermoelectric module was manufactured by cutting the folded conductive support through a knife using a knife in a direction perpendicular to the length direction in which the P-type dopant and the N-type dopant were printed.

<Example 2>

Manufacture of thermoelectric devices

Polydimethyl siloxane (PDMS) having a size of 2 cm X 4 cm was used as the flexible support, and the flexible support is formed with a groove into which the thermoelectric module can be inserted and fixed. A plurality of stacked thermoelectric modules prepared in Example 1 were inserted into and fixed in the grooves of the flexible support.

A plurality of stacked thermoelectric modules inserted into and fixed in the grooves of the flexible support were electrically connected in series using silver paste and brush casting to manufacture thermoelectric devices and thermoelectric devices. At this time, the thermoelectric element is composed of six thermoelectric modules of 2 X 3 and each thermoelectric module is formed of 20 P-N pairs.

In order to uniformize the heat transfer of the thermoelectric elements located between the high temperature part and the low temperature part, and to maximize the temperature difference, a thermoelectric tape was attached to the upper and lower plates of the thermoelectric element to manufacture a thermoelectric device, and a photograph of the manufactured thermoelectric device is shown in FIG. 2. .

Experimental Example 1

Comparison of Thermoelectric Properties of Conductive Supports According to Dopant Concentration in Doping with Brush Casing

In order to realize the optimal thermoelectric performance of the P-type semiconductor region and the N-type semiconductor region formed by the brush casting method, which is one of the characteristics of the present invention, and to fabricate the thermoelectric module accordingly, the thermoelectric performance was measured according to each dopant concentration. Table 1 and Figures 3 and 4 are shown. A wide carbon nanotube web (manufactured by Soongsil University) was cut into 2 cm X 2 cm and used as a conductive support, and the dopants of the concentrations described in Table 1 were applied to the conductive support by brush casting, and then thermoelectric performance was measured for each. . Specifically, the electrical conductivity was measured using a standard van der Pauw direct-current four-probe method using a Keithley 195A digital multimeter and a Keithley 220 programmable current source at room temperature, and the Seebeck coefficient was LSR-3 (Linseis, Germany). Was measured using.

Dopant Dopant Concentration (mM) Electrical conductivity
(S cm ^-1 ) Seebeck coefficient
(μV K ^-1 ) Power factor
(μW m ^-1 K ^-2 ) Sample 1 none 0 998.4 39.2 153.4 Sample 2 FeCl ₃ 0.01 1010.2 43.4 190.3 Sample 3 FeCl ₃ 0.1 1034.9 60.8 382.6 Sample 4 FeCl ₃ 0.5 1212.3 77.0 718.8 Sample 5 FeCl ₃ One 1414.3 93.8 1244.4 Sample 6 FeCl ₃ 5 2305.3 82.2 2165.8 Sample 7 FeCl ₃ 10 3689.6 73.8 2009.5 Sample 8 Benzyl viologen 0.01 976.6 37.4 136.6 Sample 9 Benzyl viologen 0.1 968.2 35.1 119.3 Sample 10 Benzyl viologen 0.5 954.1 20.9 41.7 Sample 11 Benzyl viologen One 946.4 7.6 5.5 Sample 12 Benzyl viologen 5 1006.2 -75.6 575.1 Sample 13 Benzyl viologen 10 1105.8 -94.2 981.2 Sample 14 Benzyl viologen 50 1132.4 -102.6 1192.1 Sample 15 Benzyl viologen 100 1140.5 -89.4 911.5

As can be seen in Table 1, in the case of the P-type doping formed by the brush casting method using FeCl ₃ solution, the power factor value obtained by multiplying the electric conductivity value and the square value of the Seebeck coefficient is the optimal value at 5 mM concentration. It can be seen that, when the concentration is 1 mM or more, it can be seen that the power factor value is very excellent. Furthermore, when the concentration is 10 mM, it can be seen that the power factor value is lower than that of 5 mM.

In the case of N-type doping with benzyl viologen, the N-type semiconductor was not formed in the low concentration region of 1 mM or less, and showed the best thermoelectric value at 50 mM concentration. It can be seen that the power factor value is very excellent when the concentration is 5 mM or more, and furthermore, when the concentration is 100 mM, it can be seen that the power factor value is lower than when the concentration is 50 mM.

In case of P-type, the effect of doping by brush casting method was not good when the concentration of FeCl ₃ solution was 1 mM or less. In case of N-type, the Seebeck coefficient of the conductive support was positive when the concentration of benzyl viologen was 1 mM or less. N-type doping was not performed by brush casting.

Experimental Example 2

As a result of measuring the generated voltage and the generated current according to the temperature difference using the thermoelectric device manufactured in Example 2 of the present invention, the power generation capacity of 17.41 μW was shown by the temperature difference of 3.3 K (FIG. 5). The generation density divided by the total generation capacity of the manufactured thermoelectric device was calculated to be 2.17 μW cm ⁻² . Furthermore, when the temperature difference was generated by human body heat by touching the top of the device with a finger, electrical signals of 22 mV and 179 μA were obtained (FIG. 6).

Experimental Example 3

As a result of comparing the power generation capacity of the thermoelectric device manufactured according to Example 2 of the present invention with the thermoelectric device manufactured by the same method but without the thermal conductive tape, the temperature of 3.3 K was not applied. Although the power generation capacity was 10.22 μW due to the difference (FIG. 7), the thermoelectric device according to the second embodiment of the present invention with the thermal conductive tape attached improved the power generation capacity to about 17% by 17.41 μW at the same temperature difference. Could get

Claims (11)

delete delete delete The P-type semiconductor region and the N-type semiconductor region are repeatedly formed on both sides of the conductive support in the longitudinal direction of the conductive support so as to alternately contact the P-type dopant and the N-type dopant, and one end portion and the other end portion of the conductive support are formed. Forming an electrode part by a method not printing a dopant;
Forming an insulating layer in a space between the P-type semiconductor region and the N-type semiconductor region;
Folding the conductive support along a boundary line between the P-type semiconductor region and the N-type semiconductor region such that the P-type semiconductor region and the N-type semiconductor region face each other; And
And cutting the folded conductive support in a direction perpendicular to the lengthwise direction in which the P-type dopant and the N-type dopant are printed.
The method of claim 4, wherein
The printing is a method of manufacturing a laminated thermoelectric module, characterized in that carried out by one method selected from the group consisting of a brush casting method, a screen printing method and a spray coating method.
The method of claim 4, wherein
The concentration of the P-type dopant is 0.01 mM to 20 mM, the concentration of the N-type dopant is a method of manufacturing a stacked thermoelectric module, characterized in that 0.1 to 100 mM.
delete delete delete Fixing a plurality of thermoelectric modules manufactured by the method of claim 4 to a flexible support including a space for receiving each of the plurality of thermoelectric modules; And
And interconnecting the plurality of thermoelectric modules fixed to the flexible support electrically in series through respective electrode units.
The method of claim 10,
The method of manufacturing a thermoelectric device further comprising the step of forming a flexible heat sink on the side in contact with the low temperature portion of the thermoelectric module.

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