CN115064636A - Flexible silver selenide-based thermoelectric device and preparation method thereof - Google Patents

Flexible silver selenide-based thermoelectric device and preparation method thereof Download PDF

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CN115064636A
CN115064636A CN202210293117.8A CN202210293117A CN115064636A CN 115064636 A CN115064636 A CN 115064636A CN 202210293117 A CN202210293117 A CN 202210293117A CN 115064636 A CN115064636 A CN 115064636A
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ink
thermoelectric
silver selenide
silver
flexible
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刘艳
张骐昊
张可忆
王连军
周蓓莹
郑琦
江莞
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Donghua University
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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
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    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0023—Digital printing methods characterised by the inks used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0047—Digital printing on surfaces other than ordinary paper by ink-jet printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0064—Digital printing on surfaces other than ordinary paper on plastics, horn, rubber, or other organic polymers
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    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/009—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using thermal means, e.g. infrared radiation, heat
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    • B82—NANOTECHNOLOGY
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    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
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    • 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
    • H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
    • H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
    • 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
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur

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Abstract

The invention relates to a flexible silver selenide based thermoelectric device and a preparation method thereof, wherein the thermoelectric device comprises: the flexible substrate, the silver selenide based thermoelectric material containing the inorganic semiconductor as the thermoelectric arm and the conductive ink as the electrode. The thermoelectric device has higher integration level, excellent thermoelectric performance and good flexibility, and can meet the requirements of applications such as flexibility and wearability.

Description

Flexible silver selenide-based thermoelectric device and preparation method thereof
Technical Field
The invention belongs to the field of thermoelectric devices, and particularly relates to a flexible silver selenide-based thermoelectric device and a preparation method thereof.
Background
In recent years, the thermoelectric conversion technology has attracted attention because it can directly utilize waste heat in life production to generate electricity to realize secondary utilization of energy without pollution. The thermoelectric material can utilize the temperature difference between the body temperature and the surrounding environment to realize thermoelectric conversion power generation, provides continuous energy supply for wearable electronic products, and has the advantages of environmental protection, safety and reliability, thereby having wide application prospect.
The current wearable electronic device gradually develops towards miniaturization, and conventional traditional block thermoelectric device is difficult to be applied to the wearable thermoelectric device in life because the rigidity is big, and is difficult to be crooked. In contrast, the flexible thermoelectric device can be closely attached to the surface of a heat source through the flexibility of the material, so that heat can be collected to the maximum extent, and the flexible thermoelectric device is expected to become a power source of wearable electronic equipment.
In order to realize the structure of the flexible thermoelectric device, some flexible thermoelectric devices are reported at home and abroad, and the current methods for preparing the flexible thermoelectric devices comprise a magnetron sputtering method and an electrochemical deposition method. The magnetron sputtering method has higher equipment cost and is difficult to realize large-scale application; and the flexible thermoelectric device prepared based on the electrochemical deposition method has poor performance. The ink-jet printing technology is an attractive alternative technology due to simple process, low cost and good applicability to the flexible substrate, and provides a new idea for the structural design and preparation of the flexible thermoelectric device.
At present, most of materials used for preparing flexible thermoelectric devices are organic thermoelectric materials, which are derived from the advantages of good flexibility, low thermal conductivity, safety, no pollution and the like of the organic thermoelectric materials. But their power factor is low, limiting the development of this class of materials. The inorganic thermoelectric material is expected to realize large-scale application of thermoelectric devices due to higher thermoelectric performance.
Bi 2 Te 3 The base thermoelectric material is one of the best thermoelectric properties near room temperature in the existing thermoelectric materials, can be used for preparing high-performance thermoelectric devices, but has more scarce component element Te, and is expensive and toxic. The silver selenide has no toxicity and environmental protection, and has higher Seebeck coefficient and conductivity near room temperature, thereby being expected to replace the traditional Bi 2 Te 3 It becomes one of the best choices for developing a new generation of flexible thermoelectric devices. The existing silver selenide based thermoelectric device usually utilizes a vacuum filtration or thermal evaporation method to prepare a thermoelectric arm on a flexible substrate, and then uses thermal evaporation to prepare an electrode or directly integrates metal silver, gold, copper wires and the like as connecting wires into the flexible thermoelectric device. For example, chinese patent CN 109293962a discloses a method for preparing a silver selenide/nylon flexible composite film, in which a silver selenide nanowire is synthesized by a wet chemical method, and then a silver selenide film with certain flexibility is prepared on a flexible nylon filter film substrate by a vacuum filtration method. The film prepared by the method has a porous structure, the compactness is lower (relative density is 70%), and the silver selenide crystal grains have obvious preferred orientation in the (00l) direction, so that the thermoelectric property of the film is still different from the property of bulk silver selenide. The subject group Cai et al (Cai et al. high performance n-type Ag 2 Se film on nylon membrane for flexible thermoelectric power generator, nat. Commun.2019,10,841) further cuts the film into 4 strip thermoelectric arms with the diameter of 20mm multiplied by 5mm, then Au electrodes are prepared at two ends of the strip thermoelectric arms by a thermal evaporation method, and then the Au electrodes are coated on a substrate as connecting leads by silver paste to form the flexible film thermoelectric power generator in series. Under the condition that the temperature difference is 30K, the open-circuit voltage of the device is 18mV, and the output power is 460 nW. However, the film prepared by the vacuum filtration method is not beneficial to the integrated construction of the device, and the patterning design and the application of the flexible thermoelectric device are limited.
In addition, recently ZHEN et al (ZHen)g et al.Microstructurally tailored thinβ-Ag 2 Se films handbards commercial flexible thermal electronics, adv. mater.2021,2104786) put the magnetron sputtered elemental silver film into the sodium sulfide aqueous solution dissolving selenium powder, and grow the silver selenide semiconductor film in situ through chemical reaction at room temperature. Particularly, when a flexible device is prepared, a thermoelectric arm needs to be prepared in a mask mode, an Au electrode is prepared by a thermal evaporation method, and then silver paste is coated on a substrate to be used as a connecting wire, so that the preparation process is complex.
Disclosure of Invention
At present, the manufacturing process flow of the flexible silver selenide-based thermoelectric device is complex, and the preparation method and the structure of the device are single, so that the practical application of the device is limited. The invention aims to solve the technical problem of providing a flexible silver selenide-based thermoelectric device and a preparation method thereof.
The present invention provides a flexible thermoelectric device, comprising: the flexible substrate, silver selenide based thermoelectric material containing inorganic semiconductor as thermoelectric arm, conductive ink as electrode; the thermoelectric arms of the silver selenide-based thermoelectric material containing the inorganic semiconductor are printed on the flexible substrate through ink-jet printing, and the thermoelectric arms are connected through conductive ink electrodes.
Preferably, the flexible substrate is any one of polyethylene terephthalate, polyimide and paper substrates.
The conductive ink is conductive silver ink or conductive copper ink with excellent conductivity.
The connection mode is that the conductive ink electrode and the silver selenide based thermoelectric material containing the inorganic semiconductor are used as two ends of the thermoelectric arm to form a series connection structure.
The series structure is in a linear series connection mode, a circular series connection mode or other series connection modes.
The invention provides a preparation method of a flexible thermoelectric device, which comprises the following steps:
(1) mixing the silver selenide nano material with a dispersing agent, and carrying out ultrasonic treatment to obtain silver selenide ink;
or mixing silver selenide ink and silver ink to obtain composite ink;
(2) carrying out ink-jet printing on the silver selenide ink or the composite ink obtained in the step (1) by using the flexible substrate as a receiving substrate, forming a thermoelectric arm on the flexible substrate, and carrying out vacuum drying to obtain a silver selenide-containing prefabricated thermoelectric arm;
(3) carrying out ink-jet printing on the silver selenide-containing prefabricated thermoelectric arm by taking the conductive ink as printing ink to form a conductive ink electrode and connect the thermoelectric arm so as to obtain a silver selenide-containing prefabricated thermoelectric device;
(4) and (3) carrying out vacuum drying and reducing atmosphere heat treatment on the silver selenide-containing prefabricated thermoelectric device to obtain the flexible thermoelectric device.
The preferred mode of the above preparation method is as follows:
the silver selenide nano material in the step (1) is specifically as follows: selenium source and silver source are used as reactants, then surfactant, solvent and reducer are selected and mixed evenly, and silver selenide based nano powder is obtained by a chemical solution method.
The molar ratio of the selenium source to the silver source is 1: 1.6-1: 2.4, the mass ratio of the surfactant to the solvent is 4-8%, and the volume ratio of the reaction solvent to the reducing agent is 1.4: 1-2.6: 1.
The reaction temperature of the chemical solution method is 90-200 ℃, and the reaction time is 6-18 h.
The grain size of the silver selenide nanometer material in the step (1) is less than or equal to 450 nm; the dispersing agent is glycol, absolute ethyl alcohol or glycerol; the mass percentage of the dispersing agent relative to the silver selenide-based nano powder is 0.1-5%; the mass percentage of the silver ink in the composite ink relative to the silver selenide ink is 0.5-60 percent; the ultrasonic treatment time is 40-150 min.
In the step (1), the silver particle size of the silver ink is 30-80 nm, and the silver content is 30-60 wt%.
The specific process of the step (2) is as follows: and (2) taking the flexible substrate as a receiving substrate, transferring the silver selenide ink or the composite ink obtained in the step (1) to an ink-jet printing device, adjusting printing parameters of the ink-jet printing device, performing ink-jet printing on the ink on the flexible substrate to form a prefabricated thermoelectric arm pattern which is arranged in parallel or in a ring shape according to the size and arrangement of the thermoelectric arms which are designed in advance, and performing vacuum drying to obtain the silver selenide-based prefabricated thermoelectric arm.
The technological parameters of the ink-jet printing in the step (2) are as follows: the substrate temperature is 40-60 ℃, the nozzle temperature is 30-50 ℃, and the ink drop distance is 10-25 μm.
Further, the inkjet printing process parameters in the step (2) are as follows: the substrate temperature is 40-60 ℃, the nozzle temperature is 30-50 ℃, the ink drop distance is 10-25 mu m, the number of printing layers is 10-100, after one layer is printed, the next layer is printed step by step after being dried for 30-60 s.
The flexible substrate in the step (2) is one of polyethylene glycol terephthalate, polyimide and a paper substrate; the thermoelectric arms are 0.1-30 mm long and 0.1-20 mm wide, the distance between the thermoelectric arms is 0.1-5 mm, and the number of the thermoelectric arms is not less than 1.
The step (3) is specifically as follows: the ink of the ink-jet printing device is replaced, the ink prepared based on the silver selenide-based nano powder is replaced by the conductive electrode ink, the printing parameters of the ink-jet printing device are adjusted, the electrodes are printed on the obtained prefabricated thermoelectric arms, the silver selenide thermoelectric arms can be sequentially connected, and finally, the electric series connection structure of the whole flexible thermoelectric device is realized.
The conductive ink in the step (3) is conductive silver ink or conductive copper ink. The particle size of silver in the conductive silver ink is 30-80 nm, and the silver content is 30-60 wt%; the conductive copper ink has a copper particle diameter of 30 to 80nm and a copper content of 30 to 60 wt%.
The technological parameters of the ink-jet printing in the step (3) are as follows: the temperature of the substrate is 40-60 ℃, the temperature of the spray head is 30-60 ℃, and the distance between ink drops is 40-70 mu m; the connection is realized by connecting the silver selenide-containing thermoelectric arms end to end in sequence by electrodes.
Further, the process parameters of the inkjet printing in the step (3) are as follows: the substrate temperature is 40-60 ℃, the nozzle temperature is 30-60 ℃, the ink drop distance is 40-70 mu m, the number of printing layers is set to be 1-20, after one layer is printed, the next layer is printed step by step after being dried for 50-90 s.
In the step (4), the vacuum drying temperature is 40-70 ℃, and the time is 6-12 h; the reducing atmosphere heat treatment is that the reducing atmosphere is argon-hydrogen mixed gas, the components of the reducing atmosphere are 5% of hydrogen and 95% of argon according to volume percentage, the heat treatment temperature is 200-450 ℃, the heating rate is 1-10 ℃/min, and the heat preservation time is 10-120 min.
The invention provides an application of the flexible thermoelectric device in waste heat collection, local temperature control, electronic skin or wearable electronic equipment.
The invention firstly utilizes a chemical solution method to synthesize silver selenide-based nano powder, and prepares a plurality of printable inks of silver selenide or silver selenide-based composite materials with good dispersibility and stability based on the synthesized nano powder. And sequentially printing the silver selenide-based thermoelectric arm and the conductive electrode on the flexible substrate by utilizing ink-jet printing equipment to form an electric series connection structure, and carrying out heat treatment after vacuum drying to obtain the flexible silver selenide-based thermoelectric device. The method has the advantages of convenient operation and low cost, and avoids the complicated process in the traditional thermoelectric device preparation process. The design of any pattern on various substrates can be realized, and the prepared thermoelectric device has higher integration level, excellent thermoelectric performance and good flexibility, and can meet the requirements of applications such as flexibility and wearability.
The method for manufacturing the flexible thermoelectric device by using the ink-jet printing technology can realize the printing of any pattern on the surface of various flexible substrates and the manufacturing of the flexible thermoelectric device; the ink jet printing method can realize devices of various structures, such as devices of in-plane parallel structure, and devices of radial structure.
Advantageous effects
(1) The invention adopts a chemical solution method to synthesize silver selenide-based nano powder, then adopts absolute ethyl alcohol as a dispersing agent to prepare printable ink with better dispersibility and stability, prepares a silver selenide thermoelectric arm with higher thermoelectric property through ink-jet printing, and then prints an electrode material by utilizing an ink-jet printing technology, thereby realizing the preparation of a flexible thermoelectric device of full ink-jet printing.
(2) Compared with the multi-step and tedious preparation and assembly process of the thermoelectric arm and the electrode of the traditional flexible thermoelectric device, the invention has the advantages of simple preparation process, low cost, convenient operation and control and the like. In addition, the ink-jet printing technology has high printing resolution, can realize the printing of high-precision and complex devices by setting printing parameters, and can flexibly be applied to various fields such as waste heat collection, local temperature control, electronic skin, wearable electronic equipment and the like by changing the types of thermoelectric materials in the devices, the sizes and the intervals of the thermoelectric arms and the shapes of the connecting electrodes to change the structure and the thermoelectric performance of the devices.
(3) The method has the advantages of simple and controllable process and short preparation period, and is suitable for large-scale industrial production. The thermoelectric material prepared by the method has higher power factor, and the assembled silver selenide based thermoelectric device has excellent thermoelectric performance and flexibility, and is suitable for application in the fields of wearability and the like.
Drawings
Fig. 1 is a flow chart of ink-jet printing preparation of a flexible silver selenide-based thermoelectric device and a device flexibility display diagram, wherein the device prepared by ink-jet printing has better flexibility;
FIG. 2 is Ag prepared by ink-jet printing according to example 1 2 Experimental results of Se thermoelectric devices (4 thermoelectric legs), wherein (a) is an optical photograph and an open-circuit voltage diagram of the device, and (b) is a graph showing the relationship between the output voltage and the output power of the device and the output current under different temperature differences;
FIG. 3 is Ag prepared by ink-jet printing in example 2 2 Experimental results of a thermoelectric device (4 thermoelectric arms) compounded by Se/Ag, wherein (a) is an optical photo and an open-circuit voltage graph of the device, and (b) is a schematic diagram of the relationship between output voltage and output power of the device and output current under different temperature differences;
FIG. 4 is Ag prepared by ink-jet printing according to example 3 2 Experimental results of a thermoelectric device (8 thermoelectric arms) of Se/Ag composition, wherein (a) is an optical photo and an open-circuit voltage chart of the device, and (b) is the output voltage and output power of the device under different temperature differencesThe relation diagram of the output current;
FIG. 5 is a graph showing the change in resistance with the number of bends of the device in example 4, and it can be seen that Ag 2 The Se and Ag composite flexible thermoelectric device has better flexibility;
FIG. 6 Ag prepared by ink-jet printing in example 5 2 Se ring structure thermoelectric device and high integration thermoelectric device, wherein (a) and (b) are optical photos of the ring device, and (c) is a device composed of 33 thermoelectric arms;
FIG. 7 is Ag prepared by ink-jet printing in comparative example 2 2 Se thermoelectric film, wherein (a) is Ag prepared by different heat preservation temperatures in the heat treatment process 2 A field emission scanning electron microscope image of the Se thermoelectric film, and (b) Ag with different heat preservation temperatures 2 Thermoelectric performance diagram of Se thin film.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Firstly, the source of raw materials
Selenium dioxide, silver nitrate, polyvinylpyrrolidone PVP (K-30, average molecular weight MW 40000), N-dimethylformamide DMF, and oleic acid OA, which are medicines used in the examples of the present invention, are all produced by alatin technologies, ltd. The conductive silver INK (BroadCON-INK550) is produced by Beijing Dahuabo Boke Intelligent science and technology Limited, the particle diameter of the silver powder is 50nm, and the silver content is 30-40 wt%.
Example 1
Ag 2 Preparation of Se flexible thermoelectric device (4 thermoelectric arms):
1) weighing 1.0g of PVP, dissolving in 40mL of DMF, carrying out magnetic stirring, then adding 52.6mg of selenium dioxide and 164.6mg of silver nitrate into the solution, adding 20mL of oleic acid, carrying out magnetic stirring at room temperature for 8-10 min, pouring into a 100mL reaction kettle, reacting for 12h at 120 ℃, centrifuging the obtained powder for multiple times, and washing to obtain the silver selenide nano powder (the particle size is about 100nm) meeting the requirements of ink-jet printing.
2) 0.05g of Ag 2 Dispersing Se nano powder in 10mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 60min to obtain silver selenide ink with good dispersibility, and transferring the obtained ink to an ink-jet printing device. Then, using flexible polyimide as a flexible substrate, printing 4 parallel Ag strips with an ink jet printer (model DMP-2850) 2 Se thermoelectric arms, each thermoelectric arm is a rectangular strip 8mm long, 4mm wide and 1 μm thick, and the distance between the thermoelectric arms is 2 mm. In which the substrate temperature for ink-jet printing was set to 40 c, the head temperature was set to 30 c, and the pitch between ink droplets was 20 μm. The number of printing layers is set to 40, after one layer is printed, the next layer is printed step by step after drying is carried out for 30-60 s, and when the number of printing layers is 40, the thermoelectric arm is manufactured.
3) Changing printing ink of an ink-jet printing device, changing ink prepared based on silver selenide nano powder into conductive silver ink, adjusting printing parameters of the ink-jet printing device, wherein the temperature of a substrate for ink-jet printing is set to be 40 ℃, the temperature of a spray head is set to be 30 ℃, the distance between ink drops is 60 mu m, printing silver electrodes on the obtained prefabricated thermoelectric arms, sequentially connecting the silver selenide thermoelectric arms which are arranged in parallel end to end, the number of printing layers is set to be 8, after one layer is printed, printing the next layer step by step after drying for 50-90 s, and stopping printing when the number of printing layers is 8, namely obtaining the prefabricated flexible silver selenide thermoelectric device containing 4 thermoelectric arms.
4) Then placing the printed prefabricated device in a vacuum oven, drying for 12h at 60 ℃, placing the prefabricated device in a tube furnace, setting the heating rate to be 5 ℃/min under the argon-hydrogen mixed (5% hydrogen and 95% argon) atmosphere, preserving heat for 10min when the temperature reaches 450 ℃, and obtaining the flexible Ag after the natural cooling is finished 2 A Se thermoelectric device. The device has good flexibility and its optical photograph is shown in figure 1.
To measure the flexible Ag 2 The output voltage and output power of the Se thermoelectric device are used for testing the Ag by using the self-built device output performance test system 2 Output performance of Se deviceThe test system mainly comprises a Peltier patch, an infrared thermal imager (FOTRIC 226), a nano-voltmeter (Keithley 2182A), a rheostat and the like. During the test, the output voltage of the device was recorded using a peltier chip, an infrared thermal imager (FOTRIC 226) and a nanovoltmeter (Keithley 2182A). Then connecting the ink-jet printed Ag with silver wires respectively 2 And a rheostat box and a nanovolt instrument (Keithley 2182A) are connected in series at the silver electrodes of the starting end and the terminal of the Se thermoelectric device, and the external load of the device is changed by connecting the rheostat box and the device in series, so that the output power under different loads is obtained. And recording the current under different loads through the nano-volt meter, thereby calculating the output power under different loads. As shown in fig. 2, flexible Ag 2 The output performance of the Se thermoelectric device, fig. 2(a), is the variation trend of the open circuit voltage of the device along with the temperature difference, the open circuit voltage of the device increases linearly along with the continuous increase of the temperature difference, and the open circuit voltage generated by the device under the temperature difference of 50K is 23.85 mV. Fig. 2(b) shows the output power of the device under different temperature differences, and it can be seen that the maximum output power of the device is 110nW when the temperature difference is 50K.
Example 2
Ag 2 Preparation of a Se and Ag composite flexible thermoelectric device (4 thermoelectric arms):
1) preparing Ag by adopting a chemical solution method 2 The specific process of the Se nanopowder is the same as that of the step (1) in the example 1.
2) 0.05g of Ag 2 Dispersing Se nano powder in 10mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 60min to obtain silver selenide ink with better dispersibility, and then mixing the silver selenide ink with a certain volume of commercial silver ink to obtain Ag/Ag with the mass percentage of the silver ink relative to the silver selenide ink being 30% 2 Se composite ink, transferring the composite ink to an ink-jet printing device. Then, using flexible polyimide as flexible substrate, printing 4 parallel Ag/Ag lines with ink jet printer (model DMP-2850) 2 Se thermoelectric arms, each thermoelectric arm is a rectangular strip 8mm long, 4mm wide and 1 μm thick, and the distance between the thermoelectric arms is 2 mm. In which the substrate temperature for ink-jet printing was set to 40 c, the head temperature was set to 30 c, and the pitch between ink droplets was 20 μm. The number of printing layers is set to 40, and after one layer is printedAnd after drying for 30-60 s, printing the next layer step by step, and when the number of printing layers is 40, finishing Ag/Ag 2 And preparing a Se thermoelectric arm.
3) Replacing printing ink of ink-jet printing device with Ag/Ag 2 Se ink is replaced by conductive silver ink, printing parameters of an ink-jet printing device are adjusted, wherein the temperature of a substrate for ink-jet printing is set to be 40 ℃, the temperature of a spray head is set to be 30 ℃, the distance between ink drops is 60 mu m, electrodes are printed on the obtained prefabricated thermoelectric arm, and Ag/Ag arranged in parallel can be printed on the prefabricated thermoelectric arm 2 The Se thermoelectric arms are connected end to end in sequence, and finally, the electric series connection structure of the whole flexible thermoelectric device is realized.
4) Then placing the printed prefabricated part in a vacuum oven, drying for 12h at 60 ℃, placing the prefabricated part in a tube furnace, setting the heating rate to be 5 ℃/min under the atmosphere of argon-hydrogen mixture (5% of hydrogen and 95% of argon), preserving heat for 10min when the temperature reaches 450 ℃, and obtaining the flexible Ag/Ag after the natural cooling is finished 2 A Se thermoelectric device. The device has good flexibility and its optical image is shown in figure 3.
To measure the flexible Ag/Ag 2 The output voltage and output power of the Se thermoelectric device are equal, and the Ag/Ag is tested by the self-built device output performance test system 2 The output performance of the Se device is tested, and the test system mainly comprises a Peltier patch, an infrared thermal imager (FOTRIC 226), a nanovoltmeter (Keithley 2182A), a rheostat and the like. During the test, the output voltage of the device was recorded using a peltier chip, an infrared thermal imager (FOTRIC 226) and a nanovoltmeter (Keithley 2182A). Then connecting the ink-jet printed Ag/Ag by silver wires 2 The silver electrodes at the starting end and the terminal end of the Se thermoelectric device are connected with a rheostat box and a nano-meter (Keithley 2182A) in series, and the external load of the device is changed by connecting the rheostat box and the device in series, so that the output power under different loads is obtained. And recording the current under different loads through the nano-volt meter, thereby calculating the output power under different loads. FIG. 3 shows a flexible Ag/Ag 2 The output performance of the Se thermoelectric device is shown in FIG. 3(a), which shows the variation trend of the open-circuit voltage of the device along with the temperature difference, the open-circuit voltage of the device increases linearly along with the increase of the temperature difference, when the maximum temperature difference is 50K,the open circuit voltage is 20.68mV, and the output power is 460 nW.
Example 3
Ag 2 Preparation of Se and Ag composite flexible thermoelectric device (8 thermoelectric arms):
in order to increase the output voltage, according to example 2, the number of the thermoelectric arms in step (2) of example 2 was changed to 8, and the rest was the same as example 2, thereby obtaining flexible Ag/Ag consisting of 8 thermoelectric arms 2 A photograph of the Se composite thermoelectric device is shown in fig. 4. Furthermore, it can be seen from the output voltage and output power with the output current variation at different temperature differences (fig. 4) that the output voltage of the device increases with the increase of the temperature gradient when the temperature difference increases from 10K to 50K, and the open circuit voltage reaches 39.45mV when the temperature difference is 50K. The output current and voltage of the device are inversely proportional, and the output power of the device increases along with the increase of the output voltage and current under a certain temperature difference. Therefore, when the temperature gradient is increased, the output power of the device is increased, and the output power and the current are in a parabolic relation. As shown in FIG. 4(b), when the temperature difference was 50K, the maximum output power of the device was 1.27. mu.W.
Example 4
Mechanical stability is an important indicator for evaluating the performance of flexible thermoelectric devices. Ag from example 3 2 The bending performance test of the Se and Ag composite flexible thermoelectric device (8 thermoelectric arms) is carried out, wherein the bending radius is 4mm, fig. 5 is a relation graph of the resistance change and the bending times of the device, as can be seen from the graph, the resistance of the device is gradually increased along with the increase of the bending cycle times, after 100 times of bending, the resistance of the device is only increased by 4.8%, after the bending cycle times reach 800 times, the resistance of the device is increased by 15.8%, after 1600 times of bending cycles, the internal resistance of the device is increased by about 20%, and it can be seen that Ag 2 The Se and Ag composite flexible thermoelectric device has excellent flexibility.
Example 5
The invention can efficiently prepare Ag with different shapes 2 Se-based flexible devices, such as ring-configured thermoelectric devices, high integration flexible thermoelectric devices, and the results are shown in fig. 6.
In summary, the method of the present invention synthesizes silver selenide-based nano powder by using a chemical solution method, and then obtains the flexible silver selenide and the thermoelectric arm formed by the composite material thereof based on the inkjet printing technology. The manufacturing method has the advantages of controllable cost and simple and convenient operation. The problems of expensive use equipment and complicated processing steps of the conventional device preparation are solved through the full ink-jet printing technology, and the full ink-jet printing device has a good application prospect.
Comparative example 1
Preparation of Ag by ultrasonic method 2 Se nano powder
(1) Firstly, 15mL of ethylenediamine is weighed in a three-neck flask, 0.51g of silver nitrate and 0.12g of selenium powder are sequentially added in the three-neck flask, and after the mixture is uniformly stirred by magnetic force, the three-neck flask is placed in an ultrasonic dispersion instrument for 30-60 min by ultrasonic treatment.
(2) After the reaction is completed, centrifuging the reacted solution for 5min at the rotating speed of 5000rpm, removing the upper layer solution, sequentially adding water and ethanol, centrifuging for 5min at the rotating speed of 5000rpm, and finally drying the centrifuged powder for 6h under the vacuum condition at 60 ℃.
(3) For the obtained Ag 2 Se powder is characterized, and Ag prepared by the method is found 2 Se powder is seriously agglomerated, and the size of the powder is in the order of several micrometers to tens of micrometers. Due to the need to control Ag in the ink-jet printing process 2 The Se nano particle size is smaller than 1/10 (the nozzle diameter is 21 mu m) of the nozzle diameter, and the nano powder has good dispersibility and stability in the dispersing agent. Thus preparing Ag by ultrasonic method 2 Se nano powder can not be prepared into Ag meeting the ink-jet printing requirement 2 Se ink.
Comparative example 2
The heat treatment process can eliminate the defects in the film, thereby achieving the purpose of improving the thermoelectric property of the film material.
Ag 2 Synthesis procedure of Se nanopowder As shown in example 1, 0.05g of Ag 2 Dispersing Se nano powder in 10mL absolute ethyl alcohol, and performing ultrasonic treatment for 60min to obtain the Se nano powderTo silver selenide ink with good dispersibility, flexible polyimide is selected as a substrate, and an ink-jet printer (model DMP-2850) is used for printing Ag 2 A thermoelectric thin film of Se in which the substrate temperature for ink-jet printing was set to 40 ℃, the head temperature was set to 30 ℃, and the pitch between ink droplets was 20 μm. The number of printing layers is set to 40, after one layer is printed, the next layer is printed step by step after drying for 30-60 s, and when the number of printing layers is 40, the prefabricated Ag is finished 2 And (3) preparing the Se thermoelectric film. Placing the vacuum-dried prefabricated film in a tube furnace, setting the heating rate to be 5 ℃/min under the atmosphere of argon-hydrogen mixture (5% of hydrogen and 95% of argon, wherein 5% and 95% are volume percent), keeping the temperature for 10min when the temperature reaches 200 ℃, and obtaining the flexible Ag after the natural cooling is finished 2 Se thermoelectric film, as can be seen from scanning FIG. 7(a), Ag is observed when the incubation temperature is low 2 The Se film contains a large amount of pores, Ag 2 The Se nano particles are connected with the particles, the crystal grains can not grow and are combined with other crystal grains, the compactness of the film is low, the electrical property of the film is low, the electrical conductivity is 315S/cm, and the Seebeck coefficient is only-58 muV/K.
The heat-preservation temperature in the heat treatment process is increased from 200 ℃ to 450 ℃, and the rest is the same. From the scanned graph, it can be seen that Ag increases with the annealing temperature 2 Porosity reduction of Se film, Ag 2 Se crystal grains grow large and are combined with other crystal grains, so that the compactness of the film is greatly improved, and the electrical property of the film is further improved, as shown in figure 7(b), the electrical conductivity of the film is improved to 650S/cm, the Seebeck coefficient is-98 mu V/K, and the power factor is 624.26 mu W/m -1 k -2 . Based on high-performance Ag 2 Se thermoelectric film preparation method, in example 1, Ag with higher thermoelectric property is prepared by further designing a printing pattern 2 Se thermoelectric arms are assembled into a prefabricated silver selenide thermoelectric device, and then the optimized heat treatment process is adopted to prepare the flexible Ag with higher thermoelectric property 2 A Se thermoelectric device.

Claims (10)

1. A flexible thermoelectric device, comprising: the flexible substrate, silver selenide based thermoelectric material containing inorganic semiconductor as thermoelectric arm, conductive ink as electrode; the thermoelectric arms of the silver selenide-based thermoelectric material containing the inorganic semiconductor are printed on the flexible substrate through ink-jet printing, and the thermoelectric arms are connected through a conductive ink electrode.
2. A method for preparing a flexible thermoelectric device comprises the following steps:
(1) mixing the silver selenide nano material with a dispersing agent, and carrying out ultrasonic treatment to obtain silver selenide ink;
or mixing silver selenide ink and silver ink to obtain composite ink;
(2) carrying out ink-jet printing on the silver selenide ink or the composite ink obtained in the step (1) by using the flexible substrate as a receiving substrate, forming a thermoelectric arm on the flexible substrate, and carrying out vacuum drying to obtain a silver selenide-containing prefabricated thermoelectric arm;
(3) carrying out ink-jet printing on the silver selenide-containing prefabricated thermoelectric arm by taking the conductive ink as printing ink to form a conductive ink electrode and connect the thermoelectric arm so as to obtain a silver selenide-containing prefabricated thermoelectric device;
(4) and (3) carrying out vacuum drying and reducing atmosphere heat treatment on the silver selenide-containing prefabricated thermoelectric device to obtain the flexible thermoelectric device.
3. The preparation method according to claim 2, wherein the silver selenide nanomaterial in the step (1) is specifically: selenium source and silver source are used as reactants, then surfactant, solvent and reducer are selected and mixed evenly, and silver selenide based nano powder is obtained by a chemical solution method.
4. The preparation method according to claim 2, wherein the particle size of the silver selenide nano-material in the step (1) is less than or equal to 450 nm; the dispersing agent is glycol, absolute ethyl alcohol or glycerol; the mass percentage of the dispersing agent relative to the silver selenide-based nano powder is 0.1-5%; the mass percentage of the silver ink in the composite ink relative to the silver selenide ink is 0.5-60 percent; the ultrasonic treatment time is 40-150 min.
5. The manufacturing method according to claim 2, wherein the inkjet printing in the step (2) has the following process parameters: the substrate temperature is 40-60 ℃, the nozzle temperature is 30-50 ℃, and the ink drop distance is 10-25 μm.
6. The preparation method according to claim 2, wherein the flexible substrate in the step (2) is one of ethylene terephthalate, polyimide and paper substrate; the thermoelectric arms are 0.1-30 mm long and 0.1-20 mm wide, the distance between the thermoelectric arms is 0.1-5 mm, and the number of the thermoelectric arms is not less than 1.
7. The method according to claim 2, wherein the conductive ink in the step (3) is a conductive silver ink or a conductive copper ink.
8. The method for preparing a composite material according to claim 2, wherein the process parameters of the ink-jet printing in the step (3) are as follows: the temperature of the substrate is 40-60 ℃, the temperature of the spray head is 30-60 ℃, and the distance between ink drops is 40-70 mu m; the connection is realized by connecting the silver selenide-containing thermoelectric arms end to end in sequence by electrodes.
9. The preparation method according to claim 2, wherein the vacuum drying temperature in the step (4) is 40-70 ℃ and the time is 6-12 h; the reducing atmosphere heat treatment is that the reducing atmosphere is argon-hydrogen mixed gas, the components of the reducing atmosphere are 5% of hydrogen by volume percentage and 95% of argon by volume percentage, the heat treatment temperature is 200-450 ℃, the heating rate is 1-10 ℃/min, and the heat preservation time is 10-120 min.
10. Use of the flexible thermoelectric device of claim 1 in waste heat collection, topical temperature control, electronic skin, or wearable electronics.
CN202210293117.8A 2022-03-24 2022-03-24 Flexible silver selenide-based thermoelectric device and preparation method thereof Pending CN115064636A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117812985A (en) * 2024-03-01 2024-04-02 中北大学 Flexible photo-thermal electric detection device based on spraying method and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117812985A (en) * 2024-03-01 2024-04-02 中北大学 Flexible photo-thermal electric detection device based on spraying method and preparation method thereof
CN117812985B (en) * 2024-03-01 2024-05-14 中北大学 Flexible photo-thermal electric detection device based on spraying method and preparation method thereof

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