CN214226945U - Thermoelectric power generation device with laminated structure - Google Patents
Thermoelectric power generation device with laminated structure Download PDFInfo
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- CN214226945U CN214226945U CN202022824652.0U CN202022824652U CN214226945U CN 214226945 U CN214226945 U CN 214226945U CN 202022824652 U CN202022824652 U CN 202022824652U CN 214226945 U CN214226945 U CN 214226945U
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Abstract
The utility model relates to a range upon range of structure's thermoelectric generation device, thermoelectric generation device structure is including thermoelectric material layer, insulating adhesive linkage, top electrode and bottom electrode, top insulating layer and bottom insulating layer, the adiabatic encapsulation layer of insulation of range upon range of setting, thermoelectric generation device has longer thermoelectric arm length, is favorable to drawing the big difference in temperature, can be used to the natural radiating thermoelectric generation environment of air. No gap exists between the N-type thermoelectric material and the P-type thermoelectric material, the proportion of the thermoelectric material in unit area is large, the structural internal resistance and the thermal resistance of the thermoelectric power generation module are effectively reduced, and the power generation efficiency is improved; the problems of moisture corrosion and the like can be eliminated by adopting simple edge packaging; the conductive connection between the N-type thermoelectric material and the P-type thermoelectric material adopts a simple spraying or sputtering process, and the insulating bonding layer of the connecting electrode is thinner, so that the thermal resistance of a heat transfer surface can be greatly reduced. The heat transfer surface of the thermoelectric power generation device can be processed into any shape, and is effectively attached to a curved surface heat source, so that the maximum thermoelectric power generation efficiency is obtained.
Description
Technical Field
The utility model belongs to the technical field of thermoelectric device, concretely relates to laminated structure's thermoelectric generation device.
Background
The thermoelectric power generation module is a device for converting heat energy into electric energy by utilizing the thermoelectric effect of a semiconductor, has the characteristics of no noise, long service life, stable and reliable work, portability and the like, can provide electric power for electric equipment and devices by utilizing various energy sources including solid, liquid and gaseous fuels, solar energy, nuclear energy, human body heating, waste heat and waste heat of various equipment and the like, and is suitable for the fields of aerospace, military, exploration, portable equipment, passive sensors and the like.
The structure and the manufacturing method of the current thermoelectric power generation module are generally to cut P-type and N-type thermoelectric materials into particles with designed sizes, and electrodes are plated at two ends of the particles. And preparing a connecting electrode on the ceramic substrate, placing the P/N particles on the ceramic substrate electrode, and welding the P-type particles and the N-type particles by using a welding material according to a mode of conducting electricity in series and conducting heat in parallel to form the thermoelectric device. The upper ceramic substrate and the lower ceramic substrate of the particle array form a cold surface and a hot surface of the thermoelectric generation sheet, the hot surface is contacted with a heat source, and the cold surface is contacted with a cold source (such as an air cooling radiating fin, a cooling circulating water radiating fin and the like), so that output voltage and current can be obtained from two output ends of the device, and thermoelectric generation is realized. The specific structure and the manufacturing method of the thermoelectric power generation module are disclosed in patents 200610130263.X, CN101409324A, CN201408783Y and the like.
However, since the conventional thermoelectric generation module is formed by assembling P-type and N-type thermoelectric material particles in an array manner. The following technical problems mainly exist: (1) the current thermoelectric power generation module can leave millimeter-grade gaps among P-type thermoelectric material particles and N-type thermoelectric material particles due to the insulation requirement among the particles, so that the occupation ratio of the thermoelectric material in unit area is not high, the heat flow transmission efficiency is lost, and the internal resistance of the power generation module is increased. The presence of voids can easily lead to moisture accumulation within the device in a humid environment, causing corrosion damage failure of the thermoelectric material. Therefore, the thermoelectric power generation module needs special packaging, and the manufacturing cost is increased. (2) In order to obtain the insulation between the structural support and the electrodes, the two ends of the thermoelectric material particles are respectively welded on the ceramic substrate deposited with the metal electrodes. Because the ceramic has low thermal conductivity coefficient, the ceramic substrate with a certain thickness can generate thermal resistance to influence the power generation efficiency of the power generation module. Due to the limitation of the processing technology, the ceramic substrate is generally of a planar structure, and the application of the power generation module in the case of a curved surface heat source is limited. (3) Thermoelectric power generation modules that utilize natural air heat dissipation typically require long thermoelectric arms to achieve sufficient temperature differentials. The existing thermoelectric power generation module is formed by arranging and welding P-type thermoelectric material particles and N-type thermoelectric material particles, and the heights (the lengths of thermoelectric arms) of the thermoelectric material particles are generally in the order of millimeters, so that higher thermoelectric conversion efficiency cannot be realized under the condition of natural air heat dissipation. The main reason that the length of the particles of the existing thermoelectric materials is only millimeter order is that the thermoelectric materials are brittle and difficult to cut into strips, and the thermoelectric materials with the strip structure are difficult to assemble into devices by adopting the existing technology and have higher structural strength. Although the length of the thermoelectric arm can be equivalently increased by adopting a mode of stacking the multistage power generation sheets, and the temperature difference is enlarged. However, since the thermoelectric material sheet of each stage of power generation sheet is mounted on the ceramic substrate, the ceramic substrate increases the weight and volume of the device. Moreover, each layer of ceramic plate can increase the longitudinal thermal resistance of the device, and seriously reduce the thermoelectric conversion efficiency of the system.
SUMMERY OF THE UTILITY MODEL
In order to solve the above problems existing in the prior art, the utility model provides a temperature difference power generation device of laminated structure. Stacked structure's thermoelectric generation device, single device have longer thermoelectric arm length, are favorable to drawing big difference in temperature, can be used to the air natural cooling's thermoelectric generation environment. No gap exists between the N-type thermoelectric material and the P-type thermoelectric material, the proportion of the thermoelectric material in unit area is increased, the structural internal resistance and the thermal resistance of the thermoelectric power generation module can be effectively reduced, and the power generation efficiency is improved; the problems of moisture corrosion and the like can be eliminated by adopting simple edge encapsulation; the conductive connection between the N-type thermoelectric material and the P-type thermoelectric material adopts a simple spraying or sputtering process, and the insulating bonding layer of the connecting electrode is thinner, so that the thermal resistance of a heat transfer surface can be greatly reduced. Thermoelectric generation device's heat transfer surface can be processed into any shape, curved surface heat source can effectively laminate, obtains the biggest thermoelectric generation efficiency.
The utility model discloses the technical scheme who adopts does:
a thermoelectric power generation device of a laminated structure, the structure comprising:
the thermoelectric material layers are arranged in a stacked mode and comprise P-type thermoelectric sheets and N-type thermoelectric sheets, and the P-type thermoelectric sheets and the N-type thermoelectric sheets are alternately arranged;
the insulating bonding layer is arranged between the adjacent P-type thermoelectric thin sheets and the adjacent N-type thermoelectric thin sheets, and at least one layer of the insulating bonding layer is arranged;
top and bottom electrodes on top and bottom sides of the thermoelectric material layer, respectively, to electrically connect the P-type and N-type thermoelectric foils across the insulating adhesive layer to form a series structure;
the top insulating layer covers the surface of the top electrode, and the bottom insulating layer covers the surface of the bottom electrode;
and the insulating and heat-insulating packaging layer is positioned on the outermost layer of the device so as to package the peripheral side face.
The N-type thermoelectric thin sheet is a thin sheet with the thickness of 0.1-1000 μm, and the N-type thermoelectric material is selected from, but not limited to, BiTeSe-based semiconductor thermoelectric material of carrier electrons, Mg2Any one of Si-based semiconductor thermoelectric materials.
The P-type thermoelectric thin sheet is a thin sheet with the thickness of 0.1-1000 μm, and the P-type thermoelectric material is selected from but not limited to Sb with a hole as a current carrier2Te3Base semiconductor thermoelectric material, SnTe base semiconductor thermoelectric material, PbTe base semiconductor thermoelectric material, FeSi2Any one of the base semiconductor thermoelectric materials.
The P-type thermoelectric thin slice and the N-type thermoelectric thin slice can be prepared by wire cutting ingot processing, and can also be prepared by nanometer powder casting and silk screen printing.
The thickness of the insulating bonding layer is 10-100 mu m; the insulating bonding layer is of one or more layers of structures, and the insulating bonding layer is formed by compounding one or more layers of PMMA layers, polystyrene layers, mica layers, glass layers and quartz layers.
The top electrode and the bottom electrode are both strip-shaped metal electrodes, and the strip-shaped metal electrodes are made of any one of copper, nickel, aluminum, tin, gold and silver; the thickness of the strip-shaped metal electrode is 50-100 mu m. Preferably, the strip-shaped metal electrode can be formed by magnetron sputtering, evaporation or conductive paste spraying and printing after covering a mask.
The thicknesses of the top insulating layer and the bottom insulating layer are both 100-1000 mu m; the top insulating layer and the bottom insulating layer are made of heat-conducting silica gel or high-heat-conducting ceramic. The high thermal conductivity ceramics can be selected from aluminum nitride, boron nitride and the like.
The thickness of the insulating and heat-insulating packaging layer is 1-5mm, and the insulating and heat-insulating packaging layer is made of low-heat-conductivity ceramic or low-heat-conductivity resin. The low heat-conducting resin can be selected from epoxy resin and polystyrene plastic, and the low heat-conducting ceramic can be selected from alumina ceramic.
A method for manufacturing a thermoelectric power generation device with a laminated structure comprises the following steps:
(1) preparing P-type thermoelectric slices and N-type thermoelectric slices with designed thicknesses;
(2) spin-coating insulating glue on two surfaces of the P-type thermoelectric slice and the N-type thermoelectric slice in the step (1);
(3) alternately laminating and pressing the P-type thermoelectric thin sheet and the N-type thermoelectric thin sheet coated with the insulating glue according to the designed layer number, and then airing to form a bonding block;
(4) after the insulating glue is completely dried, cutting off the side edge of the bonding block according to the designed size and shape and polishing to obtain a smooth top heat-conducting surface and a smooth bottom heat-conducting surface;
(5) covering the top heat-conducting surface and the bottom heat-conducting surface in the step (4) by using a mask plate respectively, and then spraying conductive metal paste, wherein the conductive metal paste penetrates through a cavity of the mask plate to connect the P-type thermoelectric thin sheet and the N-type thermoelectric thin sheet at the top and the bottom respectively to form a top electrode and a bottom electrode, and the P-type thermoelectric thin sheet and the N-type thermoelectric thin sheet are connected end to end through the top electrode and the bottom electrode to realize series connection;
(6) respectively spraying or bonding a top insulating layer on the surface of the top electrode, spraying or bonding a bottom insulating layer on the surface of the bottom electrode, and packaging the top electrode and the bottom electrode by using the top insulating layer and the bottom insulating layer to obtain a composite thermoelectric block;
(7) and finally, packaging a layer of insulating and heat-insulating packaging layer on the peripheral side surface of the composite thermoelectric block to obtain the thermoelectric power generation device with the laminated structure.
The preparation method of the P-type thermoelectric thin slice and the N-type thermoelectric thin slice is selected from any one of a crystal ingot linear cutting method, a screen printing method and a magnetron sputtering method.
In the step (5), the top heat-conducting surface and the bottom heat-conducting surface are planes or curved surfaces.
The utility model has the advantages that:
(1) the thermoelectric power generation device with the laminated structure has the advantages that the thermoelectric power generation device with the laminated structure comprises the thermoelectric material layers which are laminated, the P-type thermoelectric thin slices and the N-type thermoelectric thin slices in the thermoelectric material layers are alternately arranged, and the insulating bonding layers are filled between the adjacent P-type thermoelectric thin slices and the N-type thermoelectric thin slices, so that no gap exists, and the problem that the thermoelectric material is corroded and fails due to moisture gathered in the gap in the structure of the traditional thermoelectric power generation device is solved;
(2) stacked structure's thermoelectric generation device, the thermoelectric arm length of single device can reach centimetre level, can effectively enlarge the difference in temperature, can be used for the radiating thermoelectric generation of air nature to use.
(3) Stacked structure's thermoelectric generation device, thermoelectric material accounts for than higher in the unit area, has lower structural resistance and thermal resistance, is favorable to improving power generation module's thermoelectric conversion efficiency.
(4) Stacked structure's thermoelectric generation device, the material of top insulating layer and bottom insulating layer is heat conduction silica gel or high heat conduction pottery, can provide on the one hand and fully contact with the heat source flexibility, on the other hand can have thinner thickness and reduce the thermal resistance.
(5) Stacked structure's thermoelectric generation device, any shapes such as curved surface can be processed into to top electrode and bottom electrode to effectively laminating heat source surface improves thermoelectric conversion efficiency.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a perspective view of the thermoelectric power generation device with a laminated structure according to the present invention;
FIG. 2 is a cross-sectional view of the thermoelectric power generation device with a stacked structure according to the present invention;
in the figure, 1-N type thermoelectric sheet, 2-insulating adhesive layer, 3-P type thermoelectric sheet, 4-bottom electrode, 5-bottom insulating layer, 6-insulating heat-insulating packaging layer, 7-top electrode, 8-top insulating layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be described in detail below. It is to be understood that the embodiments described are only some embodiments of the invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by a person skilled in the art without creative efforts belong to the protection scope of the present invention.
The utility model provides a range upon range of structure's thermoelectric generation device, as shown in figure 1 and figure 2, the structure is including thermoelectric material layer, insulating adhesive linkage, top electrode and bottom electrode, top insulating layer and bottom insulating layer, the adiabatic encapsulated layer of insulation of range upon range of setting.
The thermoelectric material layer comprises P-type thermoelectric sheets and N-type thermoelectric sheets, and the P-type thermoelectric sheets and the N-type thermoelectric sheets are alternately arranged; the insulating bonding layer is arranged between the adjacent P-type thermoelectric thin sheets and the adjacent N-type thermoelectric thin sheets, and at least one layer of insulating bonding layer is arranged; the top electrode and the bottom electrode are respectively positioned on the top side and the bottom side of the thermoelectric material layer so as to electrically connect the P-type thermoelectric thin sheet and the N-type thermoelectric thin sheet to form a series connection structure by crossing the insulating adhesive layer; the top insulating layer covers the surface of the top electrode, and the bottom insulating layer covers the surface of the bottom electrode; the insulating and heat-insulating packaging layer is positioned at the outermost layer of the device to package the peripheral side (see fig. 2).
In an alternative embodiment, the N-type thermoelectric sheet is a sheet having a thickness of 0.1 to 1000 μm, and the N-type thermoelectric material is a BiTeSe-based semiconductor thermoelectric material in which a carrier is an electron, Mg2Any one of Si-based semiconductor thermoelectric materials.
In an alternative embodiment, the P-type thermoelectric sheet is a sheet having a thickness of 0.1 to 1000 μm, and the P-type thermoelectric material is Sb in which carriers are holes2Te3Base semiconductor thermoelectric material, SnTe base semiconductor thermoelectric material, PbTe base semiconductor thermoelectric material, FeSi2Any one of the base semiconductor thermoelectric materials.
In an alternative embodiment, the thickness of the insulating adhesive layer is 10 to 100 μm; the insulating bonding layer is of one or more layers of structures, and the insulating bonding layer is formed by compounding one or more layers of PMMA layers, polystyrene layers, mica layers, glass layers and quartz layers. For example, a P-type thermoelectric thin film or an N-type thermoelectric thin film may be sputtered on a quartz plate, and then the quartz plates with the thermoelectric thin films attached thereto may be bonded with PMMA. The P-type thermoelectric thin sheets and the N-type thermoelectric thin sheets are alternately bonded into a block structure through the insulating bonding layers.
As an alternative embodiment, the top electrode and the bottom electrode are both strip-shaped metal electrodes, and the strip-shaped metal electrodes are made of any one of copper, nickel, aluminum, tin, gold and silver; the thickness of the strip-shaped metal electrode is 50-100 mu m. The top and bottom electrodes connect the stacked P-type and N-type thermoelectric sheets end-to-end to form a series path, and two output electrodes are led out at the top or bottom end face of the device. For the sake of good lead-out, the two output electrodes that are usually led out are located on the same end face, for example, both on the top end face or both on the bottom end face.
In an alternative embodiment, the thickness of the top insulating layer and the bottom insulating layer are both 100-1000 μm; the top insulating layer and the bottom insulating layer are made of heat-conducting silica gel or high-heat-conducting ceramic, and the high-heat-conducting ceramic is made of aluminum nitride, boron nitride and the like as an optional implementation mode and mainly aims at insulation and heat conduction. The flexibility of the top insulating layer and the bottom insulating layer can enable the thermoelectric generation device to be easily attached to a heat source. The top insulating layer and the bottom insulating layer are thin, so that thermal resistance can be reduced to the greatest extent, and thermoelectric conversion efficiency of the device is improved.
In an alternative embodiment, the thickness of the insulating and heat-insulating packaging layer is 1-5mm, and the material of the insulating and heat-insulating packaging layer is low-heat-conductivity ceramic or low-heat-conductivity resin which has low heat conductivity and good insulation and waterproof properties. In an alternative embodiment, the low thermal conductive ceramic is alumina ceramic, and the low thermal conductive resin is epoxy resin, polystyrene plastic, or the like. The insulating and heat-insulating packaging layer is positioned on the outermost layer and is a packaging layer surrounding the periphery of the thermoelectric generation module, and the insulating and heat-insulating packaging layer mainly has the effect of isolating the humidity and the heat of the environment.
Example 1
The embodiment provides a preparation method of the thermoelectric generation device with the laminated structure, which comprises the following steps:
(1) sb2Te3Cutting the crystal ingot line of the base semiconductor thermoelectric material into P-type thermoelectric slices with the thickness of 400-1000 mu m, cutting the crystal ingot line of the BiTeSe-based semiconductor thermoelectric material into N-type thermoelectric slices with the thickness of 400-1000 mu m, and polishing the two sides of the P-type thermoelectric slices and the N-type thermoelectric slices by a polishing machine, wherein the surface roughness is lower than 10 mu m;
(2) spin-coating insulating glue polystyrene layers on two surfaces of the P-type thermoelectric slice and the N-type thermoelectric slice in the step (1), wherein the thickness of the polystyrene layers is 5-50 mu m;
(3) alternately laminating and pressing the P-type thermoelectric thin sheet and the N-type thermoelectric thin sheet coated with the polystyrene layer according to the designed layer number, and then airing to form a bonding block;
(4) after the polystyrene layer is completely dried, cutting off the side edge of the bonding block according to the design size and polishing to obtain a flat and smooth top heat-conducting surface and a flat and smooth bottom heat-conducting surface, wherein the top heat-conducting surface and the bottom heat-conducting surface are both planes as shown in fig. 2;
(5) covering the top heat-conducting surface and the bottom heat-conducting surface in the step (4) by using a mask plate respectively, and then spraying conductive silver paste, wherein the conductive silver paste penetrates through the hole of the mask plate to connect the P-type thermoelectric thin sheet and the N-type thermoelectric thin sheet at the top and the bottom respectively to form a top electrode and a bottom electrode, and the thicknesses of the top electrode and the bottom electrode are controlled to be 50-100 mu m; the P-type thermoelectric thin slice and the N-type thermoelectric thin slice are connected end to end through the top electrode and the bottom electrode to realize series connection;
(6) respectively spraying heat-conducting silica gel on the surfaces of the top electrode and the bottom electrode to respectively form a top insulating layer and a bottom insulating layer, wherein the thicknesses of the top insulating layer and the bottom insulating layer are both 100-1000 mu m; after the heat-conducting silica gel is cured, packaging the top electrode and the bottom electrode to obtain a composite thermoelectric block;
(7) and finally, packaging the periphery of the composite thermoelectric block (the top surface and the bottom surface are not packaged) in an alumina ceramic shell, wherein the thickness of the insulating and heat-insulating packaging layer is 1-5mm, and thus the thermoelectric power generation device with the laminated structure is obtained.
Example 2
The embodiment provides a preparation method of a thermoelectric power generation device with a laminated structure, which comprises the following steps:
(1) respectively adopting a screen printing method to prepare a P-type thermoelectric slice and an N-type thermoelectric slice which are 10-200 mu m thick;
wherein, the preparation of the N-type thermoelectric thin sheet comprises the following steps:
bi of 1000 meshes2Te2.7Se0.3Adding 95% alcohol into the powder, mixing with agate balls, sealing in an agate grinding tank, exhausting air by using nitrogen, and placing in a planetary ball mill at the rotation speed of 300-500rpm for 24 hours to obtain the slurry of the ultrafine powder. Taking a quartz substrate with the thickness of 500 mu m, placing the quartz substrate at the lower end of a silk screen printing machine, coating slurry on the silk screen, and scraping the silk screen by a scraper to finish printing. After the printed film is dried by a hot air gun at 80 ℃, the operation can be repeated to obtain the N-type thermoelectric film with the thickness of 10-200 mu m and the positive correlation between the thickness and the layer number, namely the N-type thermoelectric slice.
Preparing the P-type thermoelectric sheet:
bi of 1000 meshes0.5Sb1.5Te3Adding 95% alcohol into the powder, mixing with agate balls, sealing in an agate grinding tank, exhausting air by using nitrogen, and placing in a planetary ball mill at the rotation speed of 300-500rpm for 24 hours to obtain the slurry of the ultrafine powder. The quartz substrate with the thickness of 50 μm is placed at the lower end of the screen of a screen printer, and the screen is coated with slurry and scraped through the screen by a scraper to complete printing. After the printed film is dried by a hot air gun at 80 ℃, the operation can be repeated to obtain the P-type thermoelectric film with the thickness of 10-200 mu m and the positive correlation between the thickness and the layer number, namely the P-type thermoelectric sheet.
(2) Spin-coating PMMA layers on two surfaces of the P-type thermoelectric slice and the N-type thermoelectric slice in the step (1), wherein the thickness of the PMMA layers is 5-50 mu m;
(3) alternately laminating and compressing the P-type thermoelectric thin sheet and the N-type thermoelectric thin sheet coated with the PMMA layer according to the designed layer number, and then airing to form a bonding block;
(4) after the PMMA layer is completely dried, cutting off the side edge of the bonding block according to the designed size and shape and polishing to obtain a smooth top heat-conducting surface and a smooth bottom heat-conducting surface; as shown in fig. 2, the top and bottom thermally conductive surfaces are both planar;
(5) respectively covering the top heat-conducting surface and the bottom heat-conducting surface in the step (B4) by using a mask plate, and then spraying conductive copper paste, wherein the conductive copper paste penetrates through the hollow hole of the mask plate to respectively connect the P-type thermoelectric thin sheet and the N-type thermoelectric thin sheet at the top and the bottom to form a top electrode and a bottom electrode, and the thicknesses of the top electrode and the bottom electrode are controlled to be 50-100 mu m; the P-type thermoelectric thin slice and the N-type thermoelectric thin slice are connected end to end through the top electrode and the bottom electrode to realize series connection;
(6) respectively bonding high-thermal-conductivity aluminum nitride ceramic plates on the surfaces of the top electrode and the bottom electrode to respectively form a top insulating layer and a bottom insulating layer, wherein the thicknesses of the top insulating layer and the bottom insulating layer are both 100-1000 mu m; packaging the top electrode and the bottom electrode by using the aluminum nitride ceramic wafer to obtain a composite thermoelectric block;
(7) and finally, encapsulating the periphery (the top surface and the bottom surface are not encapsulated) of the composite thermoelectric block by using epoxy resin, wherein the thickness of the insulating and heat-insulating encapsulating layer is 1-5mm, and thus the thermoelectric power generation device with the laminated structure is obtained.
Example 3
The embodiment provides a preparation method of a thermoelectric power generation device with a laminated structure, which comprises the following steps:
(1) respectively adopting a magnetron sputtering method to prepare a P-type thermoelectric slice and an N-type thermoelectric slice with the thickness of 0.1-10 mu m;
wherein, the preparation of the N-type thermoelectric thin sheet comprises the following steps:
and (3) ultrasonically cleaning a quartz substrate with the thickness of 50 micrometers by deionized water, ethanol and acetone, then airing, and loading into a magnetron sputtering sample table. Adding Bi2Te2.7Se0.3The target material is loaded into a target table of the magnetron sputtering equipment and is vacuumized to reach the back pressure of 5 multiplied by 10- 4And Pa, filling argon according to the flow rate of 50-100sccm, and maintaining the air pressure in the cavity at 0.5-3Pa by adjusting the air extraction valve. Heating the substrate to 200-400 ℃, starting the direct current sputtering power supply to enable the sputtering power to be 10-30W, and controlling the film deposition time to obtain the N-type thermoelectric film with the thickness of 0.1-10 mu m on the quartz substrate, namely the N-type thermoelectric slice.
Preparing the P-type thermoelectric sheet:
and (3) ultrasonically cleaning a quartz substrate with the thickness of 50 micrometers by deionized water, ethanol and acetone, then airing, and loading into a magnetron sputtering sample table. Adding Bi0.5Sb1.5Te3The target material is loaded into a target table of the magnetron sputtering equipment and is vacuumized to reach the back pressure5x10- 4And Pa, filling argon according to the flow rate of 50-100sccm, and maintaining the air pressure in the cavity at 0.5-3Pa by adjusting the air extraction valve. Heating the substrate to 200-400 ℃, starting the direct current sputtering power supply to enable the sputtering power to be 10-30W, and controlling the film deposition time to obtain the P-type thermoelectric film with the thickness of 0.1-10 mu m on the quartz substrate, namely the N-type thermoelectric sheet.
(2) Spin-coating insulating glue on two surfaces of the P-type thermoelectric slice and the N-type thermoelectric slice in the step (1), wherein the thickness of the insulating glue is 5-50 μm;
(3) alternately laminating and pressing the P-type thermoelectric thin sheet and the N-type thermoelectric thin sheet coated with the insulating glue according to the designed layer number, and then airing to form a bonding block;
(4) after the insulating glue is completely dried, cutting off the side edge of the bonding block according to the designed size and shape and polishing to obtain a smooth top heat-conducting surface and a smooth bottom heat-conducting surface; as shown in fig. 2, the top and bottom thermally conductive surfaces are both planar;
(5) covering the top heat-conducting surface and the bottom heat-conducting surface in the step (4) by using a mask plate respectively, and then spraying conductive nickel slurry, wherein the conductive nickel slurry penetrates through the cavity of the mask plate to connect the P-type thermoelectric thin sheet and the N-type thermoelectric thin sheet at the top and the bottom respectively to form a top electrode and a bottom electrode, and the thicknesses of the top electrode and the bottom electrode are controlled to be 50-100 mu m; the P-type thermoelectric thin slice and the N-type thermoelectric thin slice are connected end to end through the top electrode and the bottom electrode to realize series connection;
(6) bonding high-thermal-conductivity boron nitride ceramic plates on the surfaces of the top electrode and the bottom electrode respectively to form a top insulating layer and a bottom insulating layer respectively, wherein the thicknesses of the top insulating layer and the bottom insulating layer are both 100-1000 mu m; packaging the top electrode and the bottom electrode by using the boron nitride ceramic wafer to obtain a composite thermoelectric block;
(7) and finally, encapsulating the periphery of the composite thermoelectric block (the top surface and the bottom surface are not encapsulated) by using polystyrene plastic, wherein the thickness of the insulating and heat-insulating encapsulating layer is 1-5mm, and thus the thermoelectric power generation device with the laminated structure is obtained.
Example 4
The embodiment provides a preparation method of a thermoelectric power generation device with a laminated structure, which comprises the following steps:
(1) respectively adopting a magnetron sputtering method to prepare 0.1-10 mu m thick PbTe-based P-type thermoelectric thin slices and Mg2A Si-based N-type thermoelectric sheet;
(2) spin-coating insulating glue on two surfaces of the P-type thermoelectric slice and the N-type thermoelectric slice in the step (1), wherein the thickness of the insulating glue is 5-50 μm;
(3) alternately laminating and pressing the P-type thermoelectric thin sheet and the N-type thermoelectric thin sheet coated with the insulating glue according to the designed layer number, and then airing to form a bonding block;
(4) after the insulating glue is completely dried, cutting off the side edge of the bonding block according to the designed size and shape and polishing to obtain a smooth top heat-conducting surface and a smooth bottom heat-conducting surface; as shown in fig. 2, the top and bottom thermally conductive surfaces are both planar;
(5) covering the top heat-conducting surface and the bottom heat-conducting surface in the step (4) by using a mask plate respectively, and then spraying conductive aluminum paste, wherein the conductive aluminum paste penetrates through the cavity of the mask plate to connect the P-type thermoelectric thin sheet and the N-type thermoelectric thin sheet at the top and the bottom respectively to form a top electrode and a bottom electrode, and the thicknesses of the top electrode and the bottom electrode are controlled to be 50-100 mu m; the P-type thermoelectric thin slice and the N-type thermoelectric thin slice are connected end to end through the top electrode and the bottom electrode to realize series connection;
(6) respectively spraying heat-conducting silica gel on the surfaces of the top electrode and the bottom electrode to respectively form a top insulating layer and a bottom insulating layer, wherein the thicknesses of the top insulating layer and the bottom insulating layer are both 100-1000 mu m; after the heat-conducting silica gel is cured, packaging the top electrode and the bottom electrode to obtain a composite thermoelectric block;
(7) and finally, encapsulating the periphery of the composite thermoelectric block (the top surface and the bottom surface are not encapsulated) by using polystyrene plastic, wherein the thickness of the insulating and heat-insulating encapsulating layer is 1-5mm, and thus the thermoelectric power generation device with the laminated structure is obtained.
Example 5
Example 5 differs from example 3 only in that: in the step (1), the P-type thermoelectric slice is an SnTe-based semiconductor thermoelectric material, and is of an N typeThermoelectric sheet is Mg2The Si-based semiconductor thermoelectric material was the same as in example 3.
Example 6
Example 5 differs from example 3 only in that: in the step (2), insulating glue is coated on two surfaces of the P-type thermoelectric slice and the N-type thermoelectric slice in a spinning mode, and the thickness of the insulating glue is 5-50 mu m. The rest was the same as in example 3.
Example 7
Example 6 differs from example 3 only in that: in the step (4), the top heat-conducting surface and the bottom heat-conducting surface are cut into curved surfaces according to the shape of a heat source, and then the curved surfaces are polished to be smooth by a polishing device, and then the subsequent operation procedures are carried out.
Example 8
Example 5 differs from example 3 only in that: in the step (5), the conductive metal paste is conductive gold paste. The rest was the same as in example 3.
Stacked structure's thermoelectric generation device, thermoelectric material layer, insulating adhesive linkage, top electrode and bottom electrode, top insulating layer and bottom insulating layer, the adiabatic encapsulation layer of insulation that the structure includes range upon range of setting, thermoelectric generation device has longer thermoelectric arm length, is favorable to drawing the big difference in temperature, can be used to the air natural cooling's thermoelectric generation environment. No gap exists between the N-type thermoelectric material and the P-type thermoelectric material, the proportion of the thermoelectric material in unit area is large, the internal resistance and the thermal resistance of the thermoelectric power generation module are effectively reduced, and the power generation efficiency is improved; the problems of moisture corrosion and the like can be eliminated by adopting simple edge packaging; the conductive connection between the N-type thermoelectric material and the P-type thermoelectric material adopts a simple spraying or sputtering process, and the insulating bonding layer of the connecting electrode is thinner, so that the thermal resistance of a heat transfer surface can be greatly reduced. The heat transfer surface of the thermoelectric power generation device can be processed into any shape, and is effectively attached to a curved surface heat source, so that the maximum thermoelectric power generation efficiency is obtained.
The above description is only for the specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto, and any person skilled in the art can easily think of the changes or substitutions within the technical scope of the present invention, and all should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (6)
1. A thermoelectric power generation device of a laminated structure, characterized in that the structure comprises:
the thermoelectric material layer is arranged in a stacked mode and comprises P-type thermoelectric sheets and N-type thermoelectric sheets, and the P-type thermoelectric sheets and the N-type thermoelectric sheets are alternately arranged; the N-type thermoelectric thin sheet is a thin sheet with the thickness of 0.1-1000 μm, and the N-type thermoelectric material is selected from but not limited to BiTeSe-based semiconductor thermoelectric material with electron carriers, Mg2Any one of Si-based semiconductor thermoelectric materials; the P-type thermoelectric thin sheet is a thin sheet with the thickness of 0.1-1000 μm, and the P-type thermoelectric material is selected from but not limited to Sb with a hole as a current carrier2Te3Base semiconductor thermoelectric material, SnTe base semiconductor thermoelectric material, PbTe base semiconductor thermoelectric material, FeSi2Any one of the base semiconductor thermoelectric materials;
the insulating bonding layer is arranged between the adjacent P-type thermoelectric thin sheets and the adjacent N-type thermoelectric thin sheets, and at least one layer of the insulating bonding layer is arranged; the thickness of the insulating bonding layer is 10-100 mu m; the insulating bonding layer is of one or more layers of structures, and is a composite of one or more layers of a PMMA layer, a polystyrene layer, a mica layer, a glass layer and a quartz layer;
top and bottom electrodes on top and bottom sides of the thermoelectric material layer, respectively, to electrically connect the P-type and N-type thermoelectric sheets across the insulating adhesive layer to form a series structure;
the top insulating layer covers the surface of the top electrode, and the bottom insulating layer covers the surface of the bottom electrode;
and the insulating and heat-insulating packaging layer is positioned on the outermost layer of the device so as to package the peripheral side face.
2. The thermoelectric power generation device of a laminated structure according to claim 1, wherein the top electrode and the bottom electrode are both strip-shaped metal electrodes made of any one of copper, nickel, aluminum, tin, gold, and silver; the thickness of the strip-shaped metal electrode is 50-100 mu m.
3. The thermoelectric power generation device of a laminated structure as claimed in claim 1, wherein the top insulating layer and the bottom insulating layer each have a thickness of 100-1000 μm.
4. The thermoelectric power generation device of a laminated structure according to claim 1, wherein the top insulating layer and the bottom insulating layer are made of thermally conductive silica gel or highly thermally conductive ceramic.
5. The stacked-structure thermoelectric power generation device according to claim 1, wherein the thickness of the insulating and heat-insulating encapsulation layer is 1 to 5mm, and the insulating and heat-insulating encapsulation layer is made of low thermal conductive resin or low thermal conductive ceramic.
6. The stacked-structure thermoelectric power generation device according to claim 1, wherein the surface of the top electrode is a flat surface or a curved surface, and the surface of the bottom electrode is a flat surface or a curved surface.
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