CN110289348B - Printing ink printing type preparation method and structure of photo-assisted thermoelectric device - Google Patents
Printing ink printing type preparation method and structure of photo-assisted thermoelectric device Download PDFInfo
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- CN110289348B CN110289348B CN201910331525.6A CN201910331525A CN110289348B CN 110289348 B CN110289348 B CN 110289348B CN 201910331525 A CN201910331525 A CN 201910331525A CN 110289348 B CN110289348 B CN 110289348B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
Abstract
The invention discloses a printing ink printing type preparation method of a photo-assisted thermoelectric device, which comprises the following steps: mixing a binder, a diluent and N-type or P-type thermoelectric material powder to obtain N-type thermoelectric ink and P-type thermoelectric ink; printing N-type or P-type thermoelectric ink on a substrate, and after drying, printing P-type or N-type thermoelectric ink on the substrate; curing the substrate printed with the thermoelectric printing ink, and connecting the N-type thermoelectric printing ink and the P-type thermoelectric printing ink in series by adopting a conductive material to form a thermoelectric power generation unit; and covering two or more light absorption materials with different absorptivities on the thermoelectric power generation unit to obtain the final light-assisted thermoelectric device. The prepared photo-assisted thermoelectric device comprises a substrate, a thermoelectric power generation unit covered on the substrate and a photo-thermal conversion unit covered on the thermoelectric power generation unit. The invention provides a photo-assisted thermoelectric device based on ink printing, which can collect light energy and heat energy simultaneously and has the characteristics of batch production and low cost.
Description
Technical Field
The invention relates to the technical field of new energy, in particular to a printing ink printing type preparation method and a printing ink printing type structure of a photo-assisted thermoelectric device.
Background
Today, the growth of the world population and advances in society, economy, and technology are not keeping away from increasingly using natural gas, coal, petroleum, and chemical batteries, among others. The limited reserves of traditional fossil fuels and their resulting global environmental impact have prompted researchers to actively search for renewable and sustainable clean energy sources. The effective renewable clean energy is developed, the energy crisis and the greenhouse effect are solved, and the sustainable development of the human society is promoted. In recent years, among various renewable clean energy technologies, photovoltaic and thermoelectric have been receiving more and more attention.
The solar energy is used as the most main energy source of the earth, has the characteristics of wide distribution, cleanness, safety and inexhaustibility, and is an ideal green energy source. The method has the advantages of high manufacturing cost, low power generation efficiency, large occupied area, and lack of devices for collecting light energy, simple process and low cost.
Thermal energy is a ubiquitous form of energy such as fuel combustion, waste industrial heat, geothermal heat, and human body. The thermoelectric power generation technology can directly convert heat energy into electric energy, and no mechanical movable part or liquid exists in the thermoelectric power generation technology, so that the thermoelectric power generation technology is free from maintenance, has no extra cost, has long service life and no size effect, can generate micro-watt-level electric power and kilowatt-level electric power in a limited space, can be applied to various scenes and has good application prospect. However, thermoelectric power generation has been limited to space applications for many years and its popularity has been limited by the disadvantages of low efficiency and high cost.
Therefore, the research on a novel device which has simple process and low cost and can simultaneously collect the light energy and the heat energy has important significance for popularizing the application of thermoelectricity and photoelectricity and relieving energy crisis and environmental pollution.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the traditional photoelectric conversion device or thermoelectric conversion device is complex in preparation process and high in cost, and the invention provides the ink printing type preparation method and structure of the photo-assisted thermoelectric device for solving the problems.
The invention is realized by the following technical scheme:
a printing ink type preparation method of a photo-assisted thermoelectric device comprises the following steps:
step A, preparing thermoelectric ink: mixing a binder, a diluent and N-type or P-type thermoelectric material powder to obtain N-type thermoelectric ink and P-type thermoelectric ink;
step B, preparing a thermoelectric power generation unit: printing N-type or P-type thermoelectric ink on a substrate, and after drying, printing P-type or N-type thermoelectric ink on the substrate; curing the substrate printed with the thermoelectric printing ink, and connecting the N-type thermoelectric printing ink and the P-type thermoelectric printing ink in series by adopting a conductive material to form a thermoelectric power generation unit;
step C, preparing a photothermal conversion unit: covering two or more light absorption materials with different absorptances on the thermoelectric power generation unit prepared in the step B to obtain a final light-assisted thermoelectric device;
and the printing method in the step B comprises screen printing, stencil printing and dispensing printing.
Preferably, the thermoelectric material comprises bismuth telluride, antimony telluride, or lead telluride; the particle size of the thermoelectric material powder is less than 37 μm.
Preferably, the adhesive is an epoxy adhesive prepared by mixing an epoxy resin, a curing agent and a catalyst; the epoxy resin is a mixture of bisphenol F epoxy resin and polypropylene glycol diglycidyl ether; the curing agent is methyl hexahydrophthalic anhydride; the catalyst is 1-cyanoethyl-2-ethyl-4-methylimidazole; the diluent is butyl acetate.
Preferably, the two epoxy resins of bisphenol F epoxy resin and polypropylene glycol diglycidyl ether are mixed in a ratio of 1: 1; wherein the epoxy value of the bisphenol F epoxy resin is 0.58eq/100g, and the epoxy value of the polypropylene glycol diglycidyl ether is 0.32eq/100 g.
Preferably, the mass ratio of the N-type thermoelectric material powder to the epoxy resin binder is 1: 6; the mass ratio of the P-type thermoelectric material powder to the epoxy resin adhesive is 1: 5.
Preferably, among the light absorbing materials, the light absorbing material with higher absorptivity comprises polydimethylsiloxane polymer doped with carbon powder or black PVC insulating tape; the light absorbing materials with lower absorption include titanium oxide doped polydimethylsiloxane polymers or white PVC insulating tape.
Preferably, in the step B, the drying temperature is 90 ℃; the curing operation is carried out in a vacuum environment and under an inert gas atmosphere, and the curing temperature is 300 ℃.
The photo-assisted thermoelectric device prepared by the ink printing preparation method of the photo-assisted thermoelectric device comprises a substrate, a thermoelectric power generation unit covered on the substrate and a photo-thermal conversion unit covered on the thermoelectric power generation unit.
Preferably, the thermoelectric generation unit includes an N-type thermoelectric arm, a P-type thermoelectric arm, and a conductive connection part; the N-type thermoelectric arms and the P-type thermoelectric arms are alternately arranged at intervals, and the axes of the N-type thermoelectric arms and the P-type thermoelectric arms are parallel to each other; the conductive connecting part is connected with two ends of the adjacent N-type thermoelectric arm and the adjacent P-type thermoelectric arm to form a snake-shaped arrangement structure.
Preferably, the photothermal conversion unit includes a high absorbance absorbing material layer and a low absorbance absorbing material layer; the high-absorptivity light-absorbing material layer and the low-absorptivity light-absorbing material layer are arranged in an abutting mode along the axial direction of the N-type thermoelectric arm or the P-type thermoelectric arm, and the long axis direction of the high-absorptivity light-absorbing material layer and the long axis direction of the low-absorptivity light-absorbing material layer are in the same direction as the snake-shaped arrangement extending direction.
The invention has the following advantages and beneficial effects:
the invention provides a photo-assisted thermoelectric device based on ink printing, which can collect light energy and heat energy simultaneously and has the characteristics of batch production and low cost.
1. The improved epoxy resin system is used as the adhesive of the thermoelectric material to prepare the corresponding thermoelectric ink, and the epoxy resin molecules shrink in the curing process of the ink, so that the thermoelectric material is more tightly combined together, and a thermoelectric arm with good toughness, stable performance and excellent electrical property can be formed;
2. the invention adopts the mode of ink printing, can select the processes of screen printing, stencil printing or dispensing printing and the like, has simple process, mature technology and low cost, can realize the batch preparation of devices, thereby solving the problem of large-scale production, reducing the cost of the devices and having wide application prospect;
3. the invention provides a light-assisted thermoelectric device which comprises a thermoelectric power generation unit and a photo-thermal conversion unit. The thermoelectric power generation unit is based on the Seebeck effect, and the Seebeck effect is a phenomenon that when temperature difference exists between two different electric conductors or semiconductors, voltage is generated between the two substances. Therefore, when the temperature difference exists between the two ends of the thermoelectric generator, voltage is generated, and the conversion from heat energy to electric energy is completed; the photothermal conversion unit generates a temperature difference according to different absorption rates of different materials or colors to the spectrum, and further converts heat energy into electric energy by using the thermoelectric generation unit. Therefore, the light-assisted thermoelectric generator provided by the invention can collect light energy and heat energy simultaneously, and is a novel high-efficiency clean energy collecting device.
In addition, the thermoelectric ink provided by the invention can be printed on a flexible substrate to prepare a flexible device so as to adapt to a complex curved environment or be applied to wearable equipment, so that the application range of the thermoelectric ink is enlarged.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention. In the drawings:
FIG. 1 is an exploded view of a light-assisted thermoelectric device of the present invention;
FIG. 2 is a top view of a light assisted thermoelectric device of the present invention;
FIGS. 3 and 4 are temperature response curves of the photo-assisted thermoelectric device of the present invention;
FIGS. 5 and 6 reflect the flexible nature of the photo-assisted thermoelectric device of the present invention;
FIG. 7(a) is a schematic diagram of a photo-assisted thermoelectric device of the present invention placed on the back of the hand to collect thermal energy, (b) placing a photo-assisted thermoelectric device on the back of the hand to collect the output voltage of the thermal energy; not placed in the sun;
fig. 8(a) is a schematic diagram of a photo-assisted thermoelectric device of the present invention placed in sunlight to collect light energy and heat energy, and (b) is an output voltage of the photo-assisted thermoelectric device placed in sunlight to collect light energy and heat energy.
Reference numbers and corresponding part names in the drawings: 1-substrate, 2-high absorptivity light absorption material layer, 3-low absorptivity light absorption material layer, 4-N type thermoelectric arm, 5-P type thermoelectric arm and 6-conductive connecting part.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples and accompanying drawings, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not meant to limit the present invention.
Example 1
The embodiment provides an ink printing type preparation method of a photo-assisted thermoelectric device, which comprises the following specific steps:
And 4, mixing the thermoelectric material powder, the epoxy resin adhesive and a diluent, wherein the mass ratio of the N-type thermoelectric powder to the epoxy resin adhesive is 1:6, the mass ratio of the P-type thermoelectric powder to the epoxy resin adhesive is 1:5, dispersing thermoelectric particles by using a magnetic stirrer, and stirring at the rotating speed of 1800r/min for 10min to respectively prepare the N-type thermoelectric ink and the P-type thermoelectric ink.
And 5, printing the N-type thermoelectric ink on a polyimide substrate by using screen printing, wherein a 150-mesh screen printing plate is selected, and the thickness of the thermoelectric ink layer is about 40 mu m. And (3) drying the printed sample in a forced air drying oven at the drying temperature of 90 ℃ for 30 min.
And 6, printing the P-type thermoelectric ink on the polyimide substrate in the step 5 by using screen printing, wherein a 150-mesh screen printing plate is selected, and the thickness of the thermoelectric ink layer is about 40 microns. Putting the printed sample into a vacuum drying oven for curing, introducing pure nitrogen, removing air in the oven, wherein the curing temperature is 300 ℃, and the curing time is 6 hours; and finally forming the N-type thermoelectric arm and the P-type thermoelectric arm on the substrate after curing.
And 7, connecting the N-type thermoelectric arm and the P-type thermoelectric arm in series by using commercial conductive silver adhesive.
And 8, covering the upper layer of the thermoelectric power generation unit with light absorption materials with different absorption rates on the spectrum by using a rolling method. The high-absorptivity light-absorbing material adopts polydimethylsiloxane doped with carbon powder, and the mass percentage of the carbon powder is 10%; the light absorption material with low absorptivity adopts polydimethylsiloxane doped with titanium oxide, and the mass percentage of the titanium oxide is 20%. Covering the light absorption material with the thickness of 0.5mm, and drying the sample in a forced air drying oven at the drying temperature of 90 ℃ for 1 h. The rolling method is characterized in that an adhesive tape with uniform thickness is adhered to the periphery of a pattern of a thermoelectric power unit of a sample, a certain amount of polydimethylsiloxane is poured above the pattern, and a glass rod is utilized to roll back and forth, so that the polydimethylsiloxane with a certain thickness covers the upper layer of the thermoelectric power generator.
Example 2
The embodiment provides an ink printing type preparation method of a photo-assisted thermoelectric device, which comprises the following specific steps:
And 4, mixing the thermoelectric material powder, the epoxy resin adhesive and a diluent, wherein the mass ratio of the N-type thermoelectric powder to the epoxy resin adhesive is 1:6, the mass ratio of the P-type thermoelectric powder to the epoxy resin adhesive is 1:5, dispersing thermoelectric particles by using an electric stirrer, and stirring at 1800r/min for 10min to obtain the N-type thermoelectric ink and the P-type thermoelectric ink.
And 5, printing the N-type thermoelectric ink on a polyimide substrate by using screen printing, wherein a 150-mesh screen printing plate is selected, and the thickness of the thermoelectric ink layer is about 40 mu m. And (3) drying the printed sample in a forced air drying oven at the drying temperature of 90 ℃ for 30 min.
And 6, printing the P-type thermoelectric ink on the polyimide substrate in the step 5 by using screen printing, wherein a 150-mesh screen printing plate is selected, and the thickness of the thermoelectric ink layer is about 40 microns. Putting the printed sample into a vacuum drying oven for curing, introducing pure nitrogen, removing air in the oven, wherein the curing temperature is 300 ℃, and the curing time is 6 hours; and forming an N-type thermoelectric arm and a P-type thermoelectric arm on the substrate after curing.
And 7, connecting the N-type thermoelectric arm and the P-type thermoelectric arm in series by using commercial conductive carbon paste, wherein the main component in the conductive carbon paste is graphite.
And 8, covering the upper layer of the thermoelectric power generation unit with light absorption materials with different absorption rates on the spectrum by adopting a rolling method. The high-absorptivity light-absorbing material adopts polydimethylsiloxane doped with carbon powder, and the mass percentage of the carbon powder is 10%; the light absorption material with low absorptivity adopts polydimethylsiloxane doped with titanium oxide, and the mass percentage of the titanium oxide is 20%. The thickness of the light absorption material layer is 0.5mm, and the sample is placed into a forced air drying oven to be dried, wherein the drying temperature is 90 ℃ and the drying time is 1 h.
Example 3
The embodiment provides an ink printing type preparation method of a photo-assisted thermoelectric device, which comprises the following specific steps:
And 4, mixing the thermoelectric material powder, the epoxy resin adhesive and a diluent, wherein the mass ratio of the N-type thermoelectric powder to the epoxy resin adhesive is 1:6, the mass ratio of the P-type thermoelectric powder to the epoxy resin adhesive is 1:5, dispersing thermoelectric particles by using an electric stirrer, and stirring at 1800r/min for 10min to obtain the N-type thermoelectric ink and the P-type thermoelectric ink.
And 5, printing the N-type thermoelectric ink on a polyimide substrate by using screen printing, wherein a 150-mesh screen printing plate is selected, and the thickness of the thermoelectric ink layer is about 40 mu m. And (3) drying the printed sample in a forced air drying oven at the drying temperature of 90 ℃ for 30 min.
And 6, printing the P-type thermoelectric ink on the polyimide substrate in the step 5 by using screen printing, wherein a 150-mesh screen printing plate is selected, and the thickness of the thermoelectric ink layer is about 40 microns. Putting the printed sample into a vacuum drying oven for curing, introducing pure nitrogen, removing air in the oven, wherein the curing temperature is 300 ℃, and the curing time is 6 hours; and forming an N-type thermoelectric arm and a P-type thermoelectric arm on the substrate after curing.
And 7, connecting the N-type thermoelectric arm and the P-type thermoelectric arm in series by using commercial conductive carbon paste, wherein the main component in the conductive carbon paste is graphite.
And 8, covering light absorption materials with different absorption rates to the spectrum on the upper layer of the thermoelectric power generation unit. The high-absorptivity light-absorbing material is a black PVC insulating adhesive tape, and the high-absorptivity light-absorbing material is a white PVC insulating adhesive tape and is directly adhered to the thermoelectric power generation unit.
Example 4
The embodiment provides an ink printing type preparation method of a photo-assisted thermoelectric device, which comprises the following specific steps:
And 4, mixing the thermoelectric material powder, the epoxy resin adhesive and a diluent, wherein the mass ratio of the N-type thermoelectric powder to the epoxy resin adhesive is 1:6, the mass ratio of the P-type thermoelectric powder to the epoxy resin adhesive is 1:5, dispersing thermoelectric particles by using an electric stirrer, and stirring at 1800r/min for 10min to obtain the N-type thermoelectric ink and the P-type thermoelectric ink.
And 5, printing the N-type thermoelectric ink on the substrate by using stencil printing, wherein the thickness of the thermoelectric ink layer is about 100 mu m. And (3) drying the printed sample in a forced air drying oven at 90 ℃ for 30 min.
And 6, printing the P-type thermoelectric ink on the substrate in the step 5 by using stencil printing, wherein the thickness of the thermoelectric ink layer is about 100 mu m. Putting the printed sample into a vacuum drying oven for curing, introducing pure nitrogen, removing air in the oven, wherein the curing temperature is 300 ℃, and the curing time is 6 hours; and forming an N-type thermoelectric arm and a P-type thermoelectric arm on the substrate after curing.
And 7, connecting the N-type thermoelectric arm and the P-type thermoelectric arm in series by using commercial conductive carbon paste, wherein the main component in the conductive carbon paste is graphite.
And 8, covering the upper layer of the thermoelectric power generation unit with light absorption materials with different absorption rates on the spectrum by using a rolling method. The high-absorptivity light-absorbing material adopts polydimethylsiloxane doped with carbon powder, and the mass percentage of the carbon powder is 10%; the light absorption material with low absorptivity adopts polydimethylsiloxane doped with titanium oxide, and the mass percentage of the titanium oxide is 20%. The thickness of the light absorption material layer is 0.5mm, and the sample is placed into a forced air drying oven to be dried, wherein the drying temperature is 90 ℃ and the drying time is 1 h.
Example 5
The embodiment provides a photo-assisted thermoelectric device, which is prepared by the method provided in embodiment 2, and has the following specific structure: comprises a substrate 1, a thermoelectric power generation unit covered on the substrate 1 and a photo-thermal conversion unit covered on the thermoelectric power generation unit. The thermoelectric power generation unit comprises an N-type thermoelectric arm 4, a P-type thermoelectric arm 5 and a conductive connecting part 6, wherein the conductive connecting part 6 is formed by coating conductive silver paste or conductive carbon paste on a substrate, and the conductive carbon paste is adopted in the embodiment. The N-type thermoelectric arms 4 and the P-type thermoelectric arms 5 are alternately arranged at intervals, the axes of the N-type thermoelectric arms 4 and the axes of the P-type thermoelectric arms 5 are mutually parallel, and the axial lengths of the N-type thermoelectric arms 4 and the axial lengths of the P-type thermoelectric arms 5 are equal; the conductive connecting part 6 connects the ends of the adjacent N-type thermoelectric arms 4 and P-type thermoelectric arms 5, so that all the N-type thermoelectric arms 4 and P-type thermoelectric arms 5 on the substrate 1 are connected in series to form a serpentine arrangement structure.
The photothermal conversion unit comprises a high absorbance absorbing material layer 2 and a low absorbance absorbing material layer 3; the high-absorptivity light-absorbing material layer 2 and the low-absorptivity light-absorbing material layer 3 are arranged adjacently along the axial direction of the N-type thermoelectric arm 4 or the P-type thermoelectric arm 5, and the long axis direction of the high-absorptivity light-absorbing material layer 2 and the low-absorptivity light-absorbing material layer 3 is the same as the extending direction of the snake-shaped arrangement.
Example 6
The photo-assisted thermoelectric device prepared in example 5 was subjected to the following performance tests:
the test method comprises the following steps:
in this example, a digital multimeter model DM3068, manufactured by Rigol, was used to measure voltage and SR570 was used to measure current. In order to control the temperature difference between the two ends of the thermoelectric device, a constant temperature heating table is adopted to heat one end of the thermoelectric device, the other end of the thermoelectric device is arranged in the external environment, and a thermocouple thermometer is adopted to measure the temperature of the two ends of the thermoelectric device in real time. The prepared thermoelectric device is directly connected with a DM3068 digital multimeter and an SR570 respectively, and the open-circuit voltage and the short-circuit current of the thermoelectric device under different temperature difference states are measured.
Second, test results
1. Thermoelectric performance
As shown in FIG. 3, the temperature difference increased from 5 ℃ to 50 ℃, the open-circuit voltage increased from 4.5mV to 63.1mV, and the short-circuit current increased from 28. mu.A to 68.8. mu.A.
The prepared thermoelectric device is connected in series with a 1k omega resistor, the voltage at two ends of the resistor under different temperature differences is measured by a DM3068 digital multimeter, so that the output power of the thermoelectric device under different temperature differences is obtained, as shown in FIG. 4, the output voltage and the output power of the thermoelectric device are increased along with the increase of the temperature difference, when the temperature difference is increased from 5 ℃ to 50 ℃, the output voltage is increased from 2mV to 29.3mV, and the output power is increased from 0.004 muW to 0.859 muW.
2. Flexibility performance
The thermoelectric device prepared in this example had excellent curved surface adaptability. As shown in FIG. 5, when the bending radius is 5cm and the device is bent in the A-A '(axial) and B-B' (radial) directions, respectively, the internal resistance change rate of the thermoelectric device is within 1.8% after 1000 times of bending. Fig. 6 shows the relationship between the internal resistance of the thermoelectric device and the bending radius, and the smaller the bending radius, the greater the rate of change of the internal resistance of the thermoelectric device. Along the direction B-B', when the bending radius reaches 3cm, the internal resistance change rate reaches 3.6 percent at most. The above results indicate that the device prepared by the above processing method has excellent curved surface adaptability, and can be applied to wearable equipment to collect heat energy of human body, and fig. 7 and 8 show output voltages for collecting heat energy and light energy when the device is placed on a hand.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (7)
1. A printing ink printing type preparation method of a photo-assisted thermoelectric device is characterized by comprising the following steps:
step A, preparing thermoelectric ink: mixing a binder, a diluent and N-type or P-type thermoelectric material powder to obtain N-type thermoelectric ink and P-type thermoelectric ink;
step B, preparing a thermoelectric power generation unit: printing N-type or P-type thermoelectric ink on a substrate, and after drying, printing P-type or N-type thermoelectric ink on the substrate; curing the substrate printed with the thermoelectric printing ink, and connecting the N-type thermoelectric printing ink and the P-type thermoelectric printing ink in series by adopting a conductive material to form a thermoelectric power generation unit;
step C, preparing a photothermal conversion unit: covering two or more light absorption materials with different absorptances on the thermoelectric power generation unit prepared in the step B to obtain a final light-assisted thermoelectric device;
the printing method in the step B comprises screen printing, stencil printing and dispensing printing;
the thermoelectric material comprises bismuth telluride, antimony telluride or lead telluride;
the adhesive is an epoxy resin adhesive prepared by mixing epoxy resin, a curing agent and a catalyst;
the epoxy resin is bisphenol F epoxy resin and polypropylene glycol diglycidyl ether, and the two epoxy resins are mixed according to the mass ratio of 1:1, wherein the epoxy value of the bisphenol F epoxy resin is 0.58eq/100g, and the epoxy value of the polypropylene glycol diglycidyl ether is 0.32eq/100 g; the curing agent is methyl hexahydrophthalic anhydride; 1-cyanoethyl-2-ethyl-4-methylimidazole is selected as a catalyst;
the diluent adopts butyl acetate;
among the light absorption materials, the light absorption material with higher absorptivity comprises polydimethylsiloxane polymer doped with carbon powder or black PVC insulating tape; the light absorbing materials with lower absorption include titanium oxide doped polydimethylsiloxane polymers or white PVC insulating tape.
2. The method of claim 1, wherein the thermoelectric material powder has a particle size of less than 37 μm.
3. The method for preparing a photo-assisted thermoelectric device by printing ink according to claim 1, wherein the mass ratio of the N-type thermoelectric material powder to the epoxy resin binder is 1: 6; the mass ratio of the P-type thermoelectric material powder to the epoxy resin adhesive is 1: 5.
4. The method for preparing a photo-assisted thermoelectric device by printing ink according to claim 1, wherein in the step B, the drying temperature is 90 ℃; the curing operation was carried out under an inert gas atmosphere at a curing temperature of 300 ℃.
5. The photo-assisted thermoelectric device prepared by the ink printing type preparation method of the photo-assisted thermoelectric device according to any one of claims 1 to 4, which is characterized by comprising a substrate (1), a thermoelectric power generation unit covered on the substrate (1) and a photo-thermal conversion unit covered on the thermoelectric power generation unit.
6. A light-assisted thermoelectric device according to claim 5, characterized in that the thermoelectric generation unit comprises an N-type thermoelectric leg (4), a P-type thermoelectric leg (5) and an electrically conductive connection (6); the N-type thermoelectric arms (4) and the P-type thermoelectric arms (5) are alternately arranged at intervals, and the axes of the N-type thermoelectric arms (4) and the P-type thermoelectric arms (5) are arranged in parallel; the conductive connecting part (6) is connected with two ends of the N-type thermoelectric arm (4) and the P-type thermoelectric arm (5) which are adjacent to each other to form a snake-shaped arrangement structure.
7. A light-assisted thermoelectric device according to claim 5, characterized in that the photothermal conversion unit comprises a layer of high absorbance absorbing material (2) and a layer of low absorbance absorbing material (3); the high-absorptivity light-absorbing material layer (2) and the low-absorptivity light-absorbing material layer (3) are arranged adjacently along the axial direction of the N-type thermoelectric arm (4) or the P-type thermoelectric arm (5), and the long axis direction of the high-absorptivity light-absorbing material layer (2) and the long axis direction of the low-absorptivity light-absorbing material layer (3) are in the same direction with the snake-shaped arrangement extending direction.
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