CN114725278A - Manufacturing method of flexible thermoelectric device and flexible thermoelectric device obtained by manufacturing method - Google Patents

Manufacturing method of flexible thermoelectric device and flexible thermoelectric device obtained by manufacturing method Download PDF

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CN114725278A
CN114725278A CN202210230073.4A CN202210230073A CN114725278A CN 114725278 A CN114725278 A CN 114725278A CN 202210230073 A CN202210230073 A CN 202210230073A CN 114725278 A CN114725278 A CN 114725278A
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thermoelectric device
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谢燕楠
张思源
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Nanjing University of Posts and Telecommunications
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Nanjing University of Posts and Telecommunications
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Priority to PCT/CN2022/125263 priority patent/WO2023168942A1/en
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    • 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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    • H10N10/856—Thermoelectric active materials comprising organic compositions
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    • 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
    • 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

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Abstract

The invention provides a manufacturing method of a flexible thermoelectric device and the flexible thermoelectric device obtained by the same, wherein PPF thermoelectric hydrogel and PPI thermoelectric hydrogel are respectively prepared and cut into wafers with the diameter as a set value; arranging a plurality of first electrode plates on a first substrate frame at intervals, respectively arranging the bottom surfaces of the PPF thermoelectric hydrogel wafers and the PPI thermoelectric hydrogel wafers at two ends of each first electrode plate, attaching one end of each second electrode plate to the top surface of each PPF thermoelectric hydrogel wafer, and attaching the other end of each second electrode plate to the top surface of the adjacent PPI thermoelectric hydrogel wafer; and arranging a second substrate frame above the second electrode plate together, and leading out by using a copper wire to obtain the prepared flexible thermoelectric device. The flexible thermoelectric device obtained by the invention has a Seebeck coefficient larger than that of the traditional thermoelectric material, and can obtain high thermoelectric performance, excellent tensile performance and cyclic stress-strain performance.

Description

Manufacturing method of flexible thermoelectric device and flexible thermoelectric device obtained by manufacturing method
Technical Field
The invention relates to a manufacturing method of a flexible thermoelectric device and the flexible thermoelectric device obtained by the same, belonging to the technical field of thermoelectric application.
Background
A large amount of low-grade heat energy (<100 ℃) is widely distributed in the natural environment, such as electronic product heat dissipation, human body heat energy, sunlight heat energy and the like, but the energy is difficult to collect and utilize due to the lack of an effective energy technology; on the other hand, with the rapid development of human society, the problem of energy shortage is increasingly highlighted, and people pay attention to the low-grade heat energy and strive to develop corresponding collection technology to solve the problem of carbon emission as an important sustainable energy.
The thermoelectric technology, which utilizes the seebeck effect, is a new technology for converting thermal energy into electric energy, and has the remarkable advantages of zero emission, no noise and the like, so that the thermoelectric technology has attracted wide interest of researchers. Conventional thermoelectric materials are mainly based on solid semiconductors or conductive polymers such as carbon nanotubes, bismuth telluride, lead telluride, PEDOT, etc., and although these materials have been rapidly developed in recent years, there are the following problems: the Seebeck coefficient is low (usually μ V.K)-1) The elements used are rare and precious, and the material does not have excellent intrinsic stretchability and the like.
The new colloidal thermal battery is well able to solve the above problems. The material has the excellent characteristics of low cost, wide material source, good flexibility and the like, and most importantly, the Seebeck coefficient of the material is higher than that of the material by one order of magnitude, so that the mV.K is achieved-1A rank. The high seebeck coefficient can ensure that higher output voltage can be obtained under the condition of limited temperature difference, and the wearable flexible energy device has huge application potential, because the temperature difference between a human body and the environment is usually several K to dozens of K, the device with high seebeck is expected to output high voltage, the energy supply problem of small wearable electronic equipment is solved, and the self-driving of the system is realized.
However, when a colloidal thermal battery material is used for preparing a thermoelectric device, redox counter ions are introduced in the process of colloid formation, and the electrode of the device is deposited on a substrate, so that the cost is high, and the time and the labor are wasted. The existing colloidal thermal battery is used for preparing the flexible thermoelectric device, the material preparation process is complex, and the electrode material adopts an evaporation process with high cost, so that the two points limit the large-scale production capacity of the flexible thermoelectric device; more importantly, it did not investigate the effect of ion concentration on the thermoelectric performance of the colloidal thermal battery, resulting in lower thermoelectric performance.
The above-mentioned problems are problems that should be considered and solved in the design and fabrication process of the flexible thermoelectric device.
Disclosure of Invention
The invention aims to provide a manufacturing method of a flexible thermoelectric device and the flexible thermoelectric device obtained by the manufacturing method, and solves the problems that thermoelectric performance needs to be improved, production difficulty is high, and large-scale processing and production are difficult in the prior art.
The technical solution of the invention is as follows:
a method for manufacturing a flexible thermoelectric device comprises the following steps,
s1, preparing PPF thermoelectric hydrogel and PPI thermoelectric hydrogel respectively;
s2, cutting the PPF thermoelectric hydrogel and the PPI thermoelectric hydrogel prepared in the step S1 into round pieces with the diameter being a set value;
s3, arranging a plurality of first electrode plates on the first substrate frame at intervals, respectively arranging two ends of each first electrode plate on the bottom surface of the PPF thermoelectric hydrogel wafer obtained in the step S2 and the bottom surface of the PPI thermoelectric hydrogel wafer, and arranging the PPF thermoelectric hydrogel wafer and the PPI thermoelectric hydrogel wafer in a staggered mode;
s4, attaching one end of a second electrode sheet to the top surface of the PPF thermoelectric hydrogel wafer, attaching the other end of the second electrode sheet to the top surface of an adjacent PPI thermoelectric hydrogel wafer, wherein the second electrode sheet and the first electrode sheet are not attached to the same PPI thermoelectric hydrogel wafer;
and S5, arranging a second substrate frame above the second electrode slice, respectively arranging electrode slices on the top surfaces of the PPF thermoelectric hydrogel wafer and the PPI thermoelectric hydrogel wafer at the head end and the tail end, and leading out by using copper wires to obtain the prepared flexible thermoelectric device.
Further, step S6 is included, after the silicone layer is encapsulated on the surface of the entire flexible thermoelectric device, the encapsulated flexible thermoelectric device is obtained.
Further, in step S1, a PPF thermoelectric hydrogel is prepared, specifically,
s11, preparing a prepolymer solution by using 10-25% of PVA powder and deionized water by mass ratio;
s12, transferring the prepolymer solution obtained in the step S1 into a Teflon groove, and repeating the freeze thawing process for 3 times to finally obtain PVA hydrogel;
s13, placing the PVA hydrogel obtained in the step S12 in a medium containing K with the concentration of 0.05M-0.8M4[Fe(CN)6]And K3[Fe(CN)6]Soaking the PVA hydrogel in the solution for 10 to 14 hours to introduce redox couple ions into the pore structure of the PVA hydrogel, and entering the next step S14;
and S14, washing away the redox counter ions remained on the surface by using deionized water, and finally preparing the PPF thermoelectric hydrogel.
Further, in step S11, a prepolymer solution is prepared using 15% by mass of PVA powder and deionized water, specifically, 1.5 g of PVA powder is mixed with 8.5ml of deionized water, and then the mixture is placed in an oil bath kettle at 90-95 ℃ to be continuously stirred until the solution becomes clear, so as to obtain the prepolymer solution.
Further, in step S12, the freeze-thaw process specifically includes placing the solution in a refrigerator at-15 ℃ to-20 ℃ for 0.8 to 1.2 hours, taking out the solid after the solution is frozen into the solid, placing the solid in a watch glass, sealing, and placing at room temperature for 8 to 12 hours.
Further, in step S1, a PPI thermoelectric hydrogel is prepared, specifically,
s15, placing the PVA hydrogel obtained in the step S12 in KI and KI with the concentration of 0.05M-0.8M3Soaking the PVA hydrogel in the solution for 10 to 14 hours to introduce redox counter ions into the pore structure of the PVA hydrogel, and then entering the next step S16;
and S16, washing away the redox counter ions remained on the surface by using deionized water, and finally preparing the PPI thermoelectric hydrogel.
Further, in step S3, the first electrode sheet and the second electrode sheet are both made of aluminum sheets.
Further, the first substrate frame and the second substrate frame are both made of polyimide.
A flexible thermoelectric device is manufactured by adopting the manufacturing method of any one of the flexible thermoelectric devices.
The invention has the beneficial effects that:
the flexible thermoelectric device is prepared by using PPF thermoelectric hydrogel and PPI thermoelectric hydrogel different types of colloidal thermal battery materials, and has a Seebeck coefficient larger than that of the traditional thermoelectric material; meanwhile, due to the hydrogel framework, the composite material has excellent tensile property and cyclic stress-strain property.
Secondly, the thermoelectric material used in the invention has simple preparation process and low cost, and is more beneficial to large-scale commercialization. The invention can well study the relation between the thermoelectric property and the ion concentration, and can obtain the flexible thermoelectric device with high thermoelectric property.
Third, the specific relation exists between the thermoelectric performance and the ion concentration of the flexible thermoelectric device, so that the prepared PPF and PPI can reach the maximum power output under the solution concentration of 0.2M and 0.4M respectively, and the performance of the flexible thermoelectric device provides a good basis for semi-permanent endurance of wearable flexible electronic equipment.
The flexible thermoelectric device has excellent flexibility, generates voltage and current under the condition of temperature difference, and can realize self-driving when being used as a power supply of small wearable electronic equipment.
Drawings
FIG. 1 is a flow chart of a method for manufacturing a flexible thermoelectric device according to an embodiment of the present invention.
FIG. 2 is a schematic view showing a structure of a flexible thermoelectric device obtained by the method of manufacturing a flexible thermoelectric device according to the embodiment; the method includes the steps of (a) obtaining a back structure schematic diagram of the flexible thermoelectric device obtained by the manufacturing method of the flexible thermoelectric device of the embodiment, (b) obtaining a three-dimensional structure schematic diagram of the flexible thermoelectric device obtained by the manufacturing method of the flexible thermoelectric device of the embodiment, (c) obtaining a front structure schematic diagram of the flexible thermoelectric device obtained by the manufacturing method of the flexible thermoelectric device of the embodiment, and (d) obtaining a side structure schematic diagram of the flexible thermoelectric device obtained by the manufacturing method of the flexible thermoelectric device of the embodiment.
Fig. 3 is a schematic view illustrating the principle of a flexible thermoelectric device obtained by the method of manufacturing the flexible thermoelectric device according to the embodiment.
FIG. 4 is a schematic illustration of SEM microtopography of the PPF and PPI thermoelectric hydrogels obtained in the examples at different concentrations of material.
Fig. 5 is a power curve diagram of the PPF thermoelectric hydrogel and the PPI thermoelectric hydrogel obtained in the example at different concentrations of materials, wherein (a) is a power curve diagram of the PPF thermoelectric hydrogel at different concentrations of materials, and (b) is a power curve diagram of the PPI thermoelectric hydrogel at different concentrations of materials.
FIG. 6 is a schematic power curve of the flexible thermoelectric device obtained by the method for fabricating the flexible thermoelectric device according to the embodiment when p-n pairs are constructed using an optimal concentration of PPF of 0.2M as p-type and PPI of 0.4M as n-type.
FIG. 7 is a schematic circuit diagram of the flexible thermoelectric device obtained in the example as an excitation power source of the lactate sensor.
Wherein: the manufacturing method comprises the following steps of 1-a first substrate frame, 2-a wafer of PPF thermoelectric hydrogel, 3-a wafer of PPI thermoelectric hydrogel, 4-a first electrode slice, 5-a second electrode slice, 6-a second substrate frame, 7-a copper wire and 8-a silica gel layer.
Detailed Description
Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
Examples
A method for manufacturing a flexible thermoelectric device, as shown in FIG. 1, comprises the following steps,
s1, preparing PPF thermoelectric hydrogel and PPI thermoelectric hydrogel respectively;
in step S1, a PPF thermoelectric hydrogel is prepared, specifically,
s11, preparing a prepolymer solution by using 10-25% by mass of polyvinyl alcohol powder (PVA powder) and deionized water; preferably, 1.5 g of PVA powder is mixed with 8.5ml of deionized water, and then the mixture is placed in an oil bath kettle at 91 ℃ to be continuously stirred until the solution becomes clear, so that a prepolymer solution is obtained.
S12, transferring the prepolymer solution obtained in the step S1 to a Teflon groove with the thickness of 1mm, and repeating the freeze thawing process for 3 times to finally obtain PVA hydrogel; wherein the freeze-thaw process is specifically freezing for 1h in a refrigerator at-18 ℃; after 1h, the solution was frozen to a solid, which was taken out, placed in a petri dish and sealed, and left at room temperature for 10 h.
S13, placing the PVA hydrogel obtained in the step S12 in a medium containing K with the concentration of 0.05M-0.8M4[Fe(CN)6]And K3[Fe(CN)6]Soaking the PVA hydrogel in the solution for 10 to 14 hours to introduce redox couple ions into the pore structure of the PVA hydrogel, and entering the next step S14;
and S14, washing away the redox counter ions remained on the surface by using deionized water, and finally preparing the PPF thermoelectric hydrogel.
In step S1, a PPI thermoelectric hydrogel is prepared, specifically,
s15, placing the PVA hydrogel obtained in the step S12 in KI and KI with the concentration of 0.05M-0.8M3Soaking the PVA in the solution for 10 to 14 hours so as to introduce redox couple ions into the hole structure of the PVA, and then entering the next step S16;
and S16, washing away the redox counter ions remained on the surface by using deionized water, and finally preparing the PPI thermoelectric hydrogel.
S2, cutting the PPF thermoelectric hydrogel and the PPI thermoelectric hydrogel prepared in the step S1 into circular sheets with the diameter as a set value;
s3, arranging a plurality of first electrode plates 4 on the first substrate frame 1 at intervals, respectively arranging two ends of each first electrode plate 4 on the bottom surface of the PPF thermoelectric hydrogel wafer 2 and the bottom surface of the PPI thermoelectric hydrogel wafer 3 obtained in the step S2, and arranging two different types of the PPF thermoelectric hydrogel wafer 2 and the PPI thermoelectric hydrogel wafer 3 in a staggered mode;
s4, attaching one end of a second electrode slice 5 to the top surface of the PPF thermoelectric hydrogel wafer 2, attaching the other end of the second electrode slice 5 to the top surface of an adjacent PPI thermoelectric hydrogel wafer 3, wherein the second electrode slice 5 and the first electrode slice 4 are not attached to the same PPI thermoelectric hydrogel wafer 3;
s5, arranging a second substrate frame 6 above the second electrode slice 5, respectively arranging electrode slices on the top surfaces of the PPF thermoelectric hydrogel wafer and the PPI thermoelectric hydrogel wafer at the head end and the tail end, and leading out by using copper wires 7 to obtain the prepared flexible thermoelectric device.
Step S6, after the silicon gel layer 8ecoflex is packaged on the surface of the whole flexible thermoelectric device, the packaged flexible thermoelectric device is obtained.
A flexible thermoelectric device, as shown in FIG. 2, is manufactured by using the method for manufacturing the flexible thermoelectric device.
According to the manufacturing method of the flexible thermoelectric device and the flexible thermoelectric device obtained by the manufacturing method, the PPF thermoelectric hydrogel and PPI thermoelectric hydrogel different types of colloidal thermal battery materials are used for preparing the flexible thermoelectric device, and the Seebeck coefficient is larger than that of the traditional thermoelectric material; meanwhile, due to the hydrogel framework, the composite material has excellent tensile property and cyclic stress-strain property.
According to the manufacturing method of the flexible thermoelectric device and the flexible thermoelectric device obtained by the manufacturing method, after the hydrogel is successfully prepared, redox counter ions are introduced, and deionized water is used for washing out the residual redox counter ions on the surface, so that smooth gelling can be ensured, and the problem that the PVA cannot be gelled due to the fact that the redox counter ions are introduced in the PVA dissolving process in the conventional method for preparing the thermoelectric hydrogel and the PVA is dissolved due to the influence of overhigh concentration of the redox counter ions is well solved.
It is worth mentioning that the thermoelectric material used in the embodiment has simple preparation process and low cost, and is more beneficial to large-scale commercialization. The invention can well study the relation between the thermoelectric property and the ion concentration, and can obtain the flexible thermoelectric device with high thermoelectric property. In the examples, PPF: polyvinyl alcohol + Potashium hexacyanoferrate, polyvinyl alcohol + Potassium hexacyanoferrate, and a p-type colloidal thermal battery obtained by introducing iron hexacyanoferrate/ferrous hexacyanoferrate ions into polyvinyl alcohol hydrogel. PPI: polyvinyl alcohol + Potashium iodide + Potashium triiodide, polyvinyl alcohol + Potassium iodide + Potassium triiodide, and iodine/iodine triions are introduced into polyvinyl alcohol hydrogel to obtain the n-type colloidal thermal battery.
The temperature difference that this kind of flexible thermoelectric device usable human body temperature and surrounding environment exist converts it into the electric energy, can supply the drive of flexible wearable electronic equipment, realizes electronic equipment's self-actuation. The prepared thermoelectric device has excellent flexibility, generates voltage and current under the condition of temperature difference, and can realize self-driving when being used as a power supply of small wearable electronic equipment.
A specific example of the method of fabricating the flexible thermoelectric device of the embodiment is as follows to fabricate a flexible thermoelectric device based on a redox couple:
preparing materials: firstly, 1.5 g of PVA powder is mixed with 8.5ml of deionized water, then the mixture is placed in an oil bath pan at 91 ℃ to be continuously stirred until the solution becomes clear, then the prepolymer solution is moved to a Teflon groove with the thickness of 1mm, and the mixture is placed in a refrigerator at-18 ℃ to be frozen for 1 hour; after 1h, after the solution is frozen into solid, taking out the solid, placing the solid in a watch glass, sealing, placing the watch glass at room temperature for 10h, and repeating the freezing and thawing process for 3 times to finally obtain the PVA hydrogel. For PPF gels, PVA hydrogels were placed at different concentrations of K4[Fe(CN)6]/K3[Fe(CN)6]Soaking in the solution for 12h (so as to introduce redox counter ions into the hole structure of PVA), and then washing away the residual redox counter ions on the surface by using a large amount of deionized water, thereby finally preparing the PPF thermoelectric hydrogel; similarly, for PPI thermoelectric hydrogel, only the solution needs to be replaced by KI/KI3And the other operation steps are consistent, and finally the PPI thermoelectric hydrogel is prepared.
As shown in fig. 2, the flexible thermoelectric device is prepared: cutting the prepared PPF and PPI thermoelectric hydrogel into circular slices with the diameter of 12mm by using a cutter, as shown in figure 2(a), placing two different types of circular slices in a staggered mode in a Polyimide (PI) frame (48 multiplied by 32 multiplied by 1mm) with a first electrode slice 4(29 multiplied by 13mm) stuck in advance, then sticking a second electrode slice 5 made of an aluminum slice on the other side (ensuring that the aluminum slice is fully contacted with the colloidal circular slices), as shown in figure 2(b) and figure 2(c), leading out the head end and the tail end by using copper wires 7, as shown in figure 2(b) and figure 2(d), avoiding the dehydration of the thermoelectric hydrogel due to the contact with air for a long time, improving the stability of the thermoelectric device, and finally packaging an ecoflex layer on the surface of the whole thermoelectric device.
As shown in fig. 3, the implementation principle of the flexible thermoelectric device obtained by the manufacturing method of the flexible thermoelectric device is described as follows, taking the cold end of the second electrode plate in a lower temperature environment and the hot end of the first electrode plate in a higher temperature environment as an example for description, and the thermal battery converts thermal energy into electric energy mainly based on two important processes: (1) oxidation-reduction reaction occurs at the contact surface of the electrode and the electrolyte at the cold end and the hot end due to the difference of Gibbs free energy; (2) diffusion occurs at both the hot and cold ends due to the concentration difference between the oxidizing ions and the reducing ions. The two processes together form a large cycle inside the thermal battery. Similarly, when the first electrode sheet is at the cold end of the lower temperature environment and the second electrode sheet is at the hot end of the higher temperature environment, the current in the direction opposite to that in fig. 3 is generated.
FIG. 4 is a schematic illustration of SEM microtopography of the PPF and PPI thermoelectric hydrogels obtained in the examples at different concentrations of material. As can be seen from FIG. 4, the effect of different concentrations of ionic solution on the pore structure of PVA hydrogels was different, for PPF, at a concentration of 0.2M K4[Fe(CN)6]/K3[Fe(CN)6]PPF holes prepared in the solution are the best in diameter and penetrability, and the structure is more favorable for the flow of ions in the PPF holes, so that the prepared material has the most outstanding thermoelectric property; similarly, for PPI, the thermoelectric properties of PPI are best achieved at a solution concentration of 0.4M.
Fig. 5 is a power curve diagram of the PPF thermoelectric hydrogel and the PPI thermoelectric hydrogel obtained in the example at different concentrations of materials, wherein (a) is a power curve diagram of the PPF thermoelectric hydrogel at different concentrations of materials, and (b) is a power curve diagram of the PPI thermoelectric hydrogel at different concentrations of materials. As can be seen from fig. 5, the flexible thermoelectric device obtained by the embodiment has a specific relationship between thermoelectric performance and ion concentration: the prepared PPF and PPI respectively reach maximum power output under the solution concentration of 0.2M and 0.4M, and the performance of the PPF and the PPI provides a semi-permanent endurance possibility for the wearable flexible electronic device.
Fig. 6 is a schematic diagram of a power curve of the flexible thermoelectric device obtained by the method for manufacturing the flexible thermoelectric device according to the embodiment when p-n pairs are constructed by using the PPF with the optimal concentration, that is, 0.2M as the p-type and 0.4M PPI as the n-type, in fig. 6, straight lines indicate the corresponding voltage and current of the thermoelectric device under different applied load values (for measuring the optimal matching impedance), curves indicate the power (corresponding to the right ordinate), the product of the voltage and the current represented by each origin, and the highest point of the curve indicates the maximum power that the thermoelectric device can output.
One specific example of use of the resulting flexible thermoelectric device is as follows:
as shown in FIG. 7, the flexible thermoelectric device obtained in the example was used as an excitation power source of a lactate sensor, the electrochemical workstation was used as a detection instrument of the lactate sensor, the thermoelectric device was first attached to the surface of a hot cup with a temperature difference of 30K from the environment, the lactate sensor was then immersed in a 10mM lactate solution, and the current display of the electrochemical workstation for the lactate solution with the concentration was recorded, and the result is shown in FIG. 7.
As can be seen from the results in fig. 7, under the action of the excitation voltage generated by the flexible thermoelectric device obtained in the embodiment, a current with a certain range of magnitude can be generated, and the lactic acid concentration can be estimated according to the magnitude of the current in practical application, so that the lactic acid concentration can be used as a basis for diagnosing the health level of a human body.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.

Claims (9)

1. A manufacturing method of a flexible thermoelectric device is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
s1, preparing PPF thermoelectric hydrogel and PPI thermoelectric hydrogel respectively;
s2, cutting the PPF thermoelectric hydrogel and the PPI thermoelectric hydrogel prepared in the step S1 into round pieces with the diameter being a set value;
s3, arranging a plurality of first electrode plates on the first substrate frame at intervals, respectively arranging two ends of the first electrode plates on the bottom surface of the PPF thermoelectric hydrogel wafer obtained in the step S2 and the bottom surface of the PPI thermoelectric hydrogel wafer, and arranging the PPF thermoelectric hydrogel wafer and the PPI thermoelectric hydrogel wafer in a staggered manner;
s4, attaching one end of a second electrode sheet to the top surface of the PPF thermoelectric hydrogel wafer, attaching the other end of the second electrode sheet to the top surface of an adjacent PPI thermoelectric hydrogel wafer, wherein the second electrode sheet and the first electrode sheet are not attached to the same PPI thermoelectric hydrogel wafer;
s5, arranging a second substrate frame above the second electrode slice, arranging electrode slices on the top surfaces of the PPF thermoelectric hydrogel wafers and the PPI thermoelectric hydrogel wafers at the head end and the tail end respectively, and leading out the electrode slices by using copper wires to obtain the prepared flexible thermoelectric device.
2. The method of manufacturing a flexible thermoelectric device as claimed in claim 1, wherein: and step S6, encapsulating the silicon gel layer on the surface of the whole flexible thermoelectric device to obtain the encapsulated flexible thermoelectric device.
3. A method of manufacturing a flexible thermoelectric device as claimed in claim 1 or 2, characterized in that: in step S1, a PPF thermoelectric hydrogel is prepared, specifically,
s11, preparing a prepolymer solution by using 10-25% of PVA powder and deionized water by mass ratio;
s12, transferring the prepolymer solution obtained in the step S1 into a Teflon groove, and repeating the freeze thawing process for 3 times to finally obtain PVA hydrogel;
s13, placing the PVA hydrogel obtained in the step S12 in a solution containing K with the concentration of 0.05M-0.8M4[Fe(CN)6]And K3[Fe(CN)6]Soaking the PVA hydrogel in the solution for 10 to 14 hours to introduce redox counter ions into the pore structure of the PVA hydrogel, and then entering the next step S14;
and S14, washing away the redox counter ions remained on the surface by using deionized water, and finally preparing the PPF thermoelectric hydrogel.
4. A method of manufacturing a flexible thermoelectric device as claimed in claim 3, characterized in that: in step S11, a prepolymer solution is prepared using 15% by mass of PVA powder and deionized water, specifically, 1.5 g of PVA powder is mixed with 8.5ml of deionized water, and then the mixture is placed in an oil bath kettle at 90 ℃ to 95 ℃ to be continuously stirred until the solution becomes clear, so as to obtain a prepolymer solution.
5. A method of manufacturing a flexible thermoelectric device as claimed in claim 3, characterized in that: in the step S12, the freeze-thaw process specifically comprises freezing the solution in a refrigerator at-15 deg.C to-20 deg.C for 0.8 to 1.2h, taking out the solid, placing the solid in a watch glass, sealing, and placing at room temperature for 8 to 12 h.
6. A method of manufacturing a flexible thermoelectric device as claimed in claim 3, characterized in that: in step S1, a PPI thermoelectric hydrogel is prepared, specifically,
s15, placing the PVA hydrogel obtained in the step S12 in a medium containing KI and KI with the concentration of 0.05M-0.8M3Soaking the PVA hydrogel in the solution for 10 to 14 hours to introduce redox couple ions into the pore structure of the PVA hydrogel, and entering the next step S16;
and S16, washing away the redox couple ions remained on the surface by using deionized water, and finally preparing the PPI thermoelectric hydrogel.
7. A method of manufacturing a flexible thermoelectric device as claimed in claim 1 or 2, characterized in that: the first electrode plate and the second electrode plate are both made of aluminum sheets.
8. A method of manufacturing a flexible thermoelectric device as claimed in claim 1 or 2, characterized in that: the first substrate frame and the second substrate frame are both made of polyimide.
9. A flexible thermoelectric device, characterized by: the flexible thermoelectric device according to any one of claims 1 to 8.
CN202210230073.4A 2022-03-08 2022-03-08 Manufacturing method of flexible thermoelectric device and flexible thermoelectric device obtained by manufacturing method Pending CN114725278A (en)

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WO2020106883A1 (en) * 2018-11-20 2020-05-28 The Regents Of The University Of California Flexible thermoelectric devices
CN113881068B (en) * 2021-11-01 2022-09-09 南开大学 Preparation method and application of high-performance thermoelectric hydrogel based on ion conduction
CN114725278A (en) * 2022-03-08 2022-07-08 南京邮电大学 Manufacturing method of flexible thermoelectric device and flexible thermoelectric device obtained by manufacturing method

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WO2023168942A1 (en) * 2022-03-08 2023-09-14 南京邮电大学 Method for manufacturing flexible thermoelectric device, and flexible thermoelectric device obtained by same

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