A flexible wearable p-type composite thermoelectric fabric power supply device, its preparation method and application

Abstract

This invention provides a flexible wearable p-type composite thermoelectric fabric power supply device, its preparation method, and its application, belonging to the technical field of flexible wearable thermoelectric fabrics. The preparation method of this invention uses only p-type thermoelectric materials, effectively solving the connection problem of the p / n junction in thermoelectric fabrics and the problem of p / n junction misalignment caused by human movement. This significantly improves the performance stability of wearable thermoelectric fabrics and meets the needs of wearable device applications. The flexible wearable p-type composite thermoelectric fabric power supply device of this invention maintains very stable thermoelectric performance even after 5000 folds.

Description

Technical Field

[0001] This invention belongs to the field of flexible wearable thermoelectric fabric technology, specifically relating to a flexible wearable p-type composite thermoelectric fabric power supply device, its preparation method, and its application. Background Technology

[0002] With the development of electronic information technology, electronic products have created a demand for flexible wearable power devices. Wearable thermoelectric power devices, as an ideal type of wearable power device, utilize the temperature gradient between human skin and the environment to promote carrier movement, providing a continuous and stable power supply for electronic devices. Organic polymer materials show great application potential in wearable thermoelectric power devices due to their flexibility, processability, and low cost.

[0003] Fabrics, as a crucial component of flexible materials, play a vital role in flexible wearable devices. The diverse needs of flexible wearable devices can typically be met by altering the type of yarn, weaving structure, thickness, size, and assembly methods. However, the development of thermoelectric fabrics still faces significant challenges. Maximizing the utilization of the vertical temperature gradient between human skin and the environment is essential to improve thermoelectric efficiency in assembling thermoelectric devices, thereby achieving higher output power. When using a single type of thermoelectric material (p-type or n-type), traditional weaving structures can lead to conflicts between like charge carriers, resulting in assembly failure. Although using both types of thermoelectric materials, including p-type and n-type, to form p / n junctions during weaving can maximize the utilization of the temperature gradient perpendicular to human skin, the fabrication process is complex, costly, and difficult to scale up. Furthermore, organic n-type thermoelectric materials are scarce and cannot maintain stable performance in the environment. Especially in thermoelectric fabrics, the p / n junction connection must be exposed to the human skin surface or the environment, making the weaving process extremely complex. In addition, misalignment of the p / n junctions caused by human movement can significantly reduce the thermoelectric performance of p / n junction-type devices.

[0004] Therefore, in order to meet the needs of wearable applications, there is an urgent need to develop wearable thermoelectric fabric devices with simple manufacturing processes and stable power performance. Summary of the Invention

[0005] This invention is made to solve the above-mentioned problems, and aims to provide a flexible wearable p-type composite thermoelectric fabric power supply device, its preparation method and application.

[0006] This invention provides a method for preparing a flexible wearable p-type composite thermoelectric fabric power device, characterized by the following steps: S10, dispersing aminated multi-walled carbon nanotubes and sodium dodecyl sulfate in a phosphate buffer solution to obtain a stable aminated multi-walled carbon nanotube dispersion; S20, adding filaments, p-phenylenediamine, and formaldehyde (aq) to the aminated multi-walled carbon nanotube dispersion, reacting and drying to obtain aminated multi-walled carbon nanotube modified filaments, denoted as modified filaments; S30, immersing the modified filaments in a mixture of aniline and hydrochloric acid, then adding ammonium persulfate (aq), reacting at low temperature and drying to obtain filaments with thermoelectric properties, denoted as thermoelectric filaments; S40, weaving the thermoelectric filaments into a fabric, bonding carbon cloth to both sides of the fabric with conductive adhesive, and extending the carbon cloth on both sides of the fabric in two opposite directions by a certain distance to obtain a flexible wearable p-type composite thermoelectric fabric power device.

[0007] The method for preparing the flexible wearable p-type composite thermoelectric fabric power supply device provided by the present invention may also have the following feature: in step S10, the pH range of the phosphate buffer solution is 6.3 to 6.8.

[0008] The method for preparing the flexible wearable p-type composite thermoelectric fabric power supply device provided by the present invention may also have the following feature: wherein, in step S10, the dispersion time is 2 hours.

[0009] The method for preparing the flexible wearable p-type composite thermoelectric fabric power supply device provided by the present invention may also have the following feature: in step S20, the reaction conditions are 35℃~40℃ for 24h.

[0010] The method for preparing the flexible wearable p-type composite thermoelectric fabric power supply device provided by the present invention may also have the following feature: in step S20, the thread is a protein thread, and the protein thread includes silk thread.

[0011] The method for preparing the flexible wearable p-type composite thermoelectric fabric power supply device provided by the present invention may also have the following feature: in steps S10 to S20, the mass ratio of aminated multi-walled carbon nanotubes, sodium dodecyl sulfate, filaments, p-phenylenediamine, and formaldehyde (aq) is 0.6:0.24:3.3:0.3:0.6, and the concentration of formaldehyde (aq) is 35% to 40%.

[0012] The method for preparing the flexible wearable p-type composite thermoelectric fabric power supply device provided by the present invention may also have the following feature: in step S30, the molar ratio of aniline, hydrochloric acid and ammonium persulfate is 3:3:1, and the volume concentration of aniline in the mixture after adding ammonium persulfate (aq) is 0.09% to 0.36%.

[0013] The preparation method of the flexible wearable p-type composite thermoelectric fabric power supply device provided by the present invention may also have the following features: in step S30, the soaking time is 2h and the reaction time is 24h.

[0014] The present invention also provides a flexible wearable p-type composite thermoelectric fabric power supply device, which is characterized by being prepared by the preparation method of the flexible wearable p-type composite thermoelectric fabric power supply device of any of the preceding claims.

[0015] The present invention also provides an application of a flexible wearable p-type composite thermoelectric fabric power supply device in providing power to electronic devices.

[0016] The role and effect of invention

[0017] The present invention relates to a flexible wearable p-type composite thermoelectric fabric power supply device, its preparation method, and its application. Because only p-type thermoelectric materials are used in the preparation process, the connection problem of the p / n junction of the thermoelectric fabric and the problem of p / n junction misalignment caused by human movement can be effectively solved, greatly improving the performance stability of the wearable thermoelectric fabric and meeting the needs of wearable device applications. Attached Figure Description

[0018] Figure 1 This is a flowchart illustrating a method for preparing a flexible wearable p-type composite thermoelectric fabric power supply device according to an embodiment of the present invention.

[0019] Figure 2 This is a schematic diagram illustrating a method for preparing a flexible wearable p-type composite thermoelectric fabric power supply device according to an embodiment of the present invention;

[0020] Figure 3 This is a side view of the flexible wearable p-type composite thermoelectric fabric power supply device according to an embodiment of the present invention;

[0021] Figure 4 This is a SEM image of the thermoelectric wire obtained in step S30 of the preparation process of sample 1 in the embodiment of the present invention;

[0022] Figure 5 These are the output voltage curves of samples 1, 2, and 3 in the test examples of this invention as a function of temperature difference;

[0023] Figure 6 This is a comparison of the maximum output power and power density of the control sample, sample 1, sample 2 and sample 3 in the test examples of the present invention at a temperature difference of 90°C.

[0024] Figure 7The changes in output voltage and internal resistance of sample 3 in the test example of this invention during 5000 folds at a temperature difference of 90°C. Detailed Implementation

[0025] To make the technical means, creative features, objectives and effects of the present invention easy to understand, the following embodiments, in conjunction with the accompanying drawings, specifically illustrate a flexible wearable p-type composite thermoelectric fabric power supply device, its preparation method and application.

[0026] <Example>

[0027] Figure 1 This is a flowchart illustrating a method for preparing a flexible wearable p-type composite thermoelectric fabric power supply device according to an embodiment of the present invention. Figure 2 This is a schematic diagram illustrating a method for preparing a flexible wearable p-type composite thermoelectric fabric power supply device according to an embodiment of the present invention.

[0028] like Figure 1 and 2 As shown, this embodiment provides a method for preparing a flexible wearable p-type composite thermoelectric fabric power supply device, including the following steps:

[0029] S10: 0.06 g of aminated multi-walled carbon nanotubes and 0.024 g of sodium dodecyl sulfate were dispersed in 100 mL of phosphate buffer solution at pH 6.5 for 2 h to obtain a stable aminated multi-walled carbon nanotube dispersion.

[0030] S20: 0.33g of silk thread, 0.03g of p-phenylenediamine and 0.06g of formaldehyde (aq) with a concentration of 35% to 40% were added to an aminated multi-walled carbon nanotube dispersion and reacted at 38°C for 24 hours. After the reaction, the aminated multi-walled carbon nanotube modified thread was obtained and denoted as modified thread.

[0031] S30: The modified filament is immersed in an 80 mL mixture of aniline and hydrochloric acid (the aniline content is 90 μL to 360 μL) for 2 h. Then, 20 mL of ammonium persulfate (aq) is added to it. After reacting under ice-water bath conditions for 24 h, the filament with thermoelectric properties is obtained and is called thermoelectric filament.

[0032] In this step, the molar ratio of aniline, hydrochloric acid, and ammonium persulfate is controlled to be 3:3:1.

[0033] S40, thermoelectric wires are woven into fabric, and carbon cloth is bonded to both sides of the fabric with conductive adhesive, so that the carbon cloth on both sides of the fabric extends a certain distance in two opposite directions, to obtain a flexible wearable p-type composite thermoelectric fabric power device.

[0034] Figure 3This is a side view of the flexible wearable p-type composite thermoelectric fabric power supply device according to an embodiment of the present invention.

[0035] This embodiment also provides a flexible wearable p-type composite thermoelectric fabric power supply device, the structure of which is as follows: Figure 3 As shown, it is prepared by a method for fabricating a flexible wearable p-type composite thermoelectric fabric power supply device provided in this embodiment.

[0036] A flexible wearable p-type composite thermoelectric fabric power supply device 100 according to this embodiment includes fabric 10, carbon cloth 20 and conductive adhesive 30.

[0037] Fabric 10 is the fabric woven from thermoelectric wires in the aforementioned step S40.

[0038] Carbon cloth 20 is bonded to both sides of fabric 10 by conductive adhesive 30, wherein the carbon cloth 20 on both sides of fabric 10 extends a distance in two opposite directions.

[0039] Specifically, the conductive adhesive 30 in this embodiment is made of conductive carbon adhesive.

[0040] In this embodiment, three flexible wearable p-type composite thermoelectric fabric power devices were prepared using the aforementioned method for preparing a flexible wearable p-type composite thermoelectric fabric power device, which are referred to as Sample 1, Sample 2, and Sample 3, respectively.

[0041] The difference between Sample 1, Sample 2 and Sample 3 is that the amount of aniline added in step S30 of the preparation process is 90 μL, 180 μL and 360 μL respectively. All other parameters are the same and will not be repeated.

[0042] Figure 4 This is a SEM image of the thermoelectric wire obtained in step S30 of the preparation process of sample 1 in an embodiment of the present invention.

[0043] like Figure 4 As shown, aminated multi-walled carbon nanotubes are tightly anchored to the surface of the silk thread, intertwined to form a conductive path, and polyaniline is further wrapped around the surface of the aminated multi-walled carbon nanotube layer to form a composite thermoelectric wire.

[0044] <Test Example>

[0045] This test case conducts relevant performance tests on samples 1, 2, and 3 in the embodiment, thereby providing an application of a flexible wearable p-type composite thermoelectric fabric power supply device in providing power to electronic devices.

[0046] A heating stage was used as the heat source, and Patek plates were used as the cold source. The upper and lower surfaces of the sample were placed in close contact with the heat source and the cold source, respectively. A temperature difference was generated on the sample surface by controlling the temperature of the heat source and the cold source. The carbon cloth on the upper and lower surfaces of the sample was connected by wires, and the output voltage of the sample under different temperature differences was collected using a Gisley 2400 source meter.

[0047] The internal resistance of the sample was measured using the two-wire method. The carbon cloth on the upper and lower surfaces of the sample was connected by wires, and the internal resistance of the sample was measured using a Gishley 2400 source meter.

[0048] Figure 5 These are the output voltage curves of samples 1, 2, and 3 in the test examples of this invention, as a function of temperature difference.

[0049] like Figure 5 As shown, the output voltage of all samples increases with increasing temperature difference. However, the Seebeck coefficient of the samples decreases with increasing polyaniline content, with sample 1 having the largest Seebeck coefficient and sample 3 having the smallest.

[0050] In this test example, a comparative sample was prepared according to the preparation method of the flexible wearable p-type composite thermoelectric fabric power device in the embodiments, and is referred to as the comparative sample. The preparation process of the comparative sample is generally similar to that of samples 1, 2 and 3, with the content of added aminated multi-walled carbon nanotubes being 0.06g. The only difference is that aniline is not added in step S30 of the comparative sample preparation process.

[0051] Figure 6 This is a comparison of the maximum output power and power density of the control sample, sample 1, sample 2 and sample 3 in the test examples of the present invention at a temperature difference of 90°C.

[0052] like Figure 6 As shown, with the increase of aniline addition, the polyaniline content in the sample increases, which causes the Seebeck coefficient and internal resistance of the sample to decrease simultaneously. Overall, the maximum output power and maximum output power density of the sample increase with the increase of polyaniline content.

[0053] Figure 7 The changes in output voltage and internal resistance of sample 3 in the test example of this invention during 5000 folds at a temperature difference of 90°C.

[0054] like Figure 7 As shown, sample 3 in the test example of the present invention still has very stable thermoelectric properties after undergoing 5000 folds, with its internal resistance and output voltage remaining at around 1.7kΩ and 0.8mV, respectively.

[0055] Those skilled in the art should understand that this invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to this invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the invention as claimed. The scope of protection of this invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a flexible wearable p-type composite thermoelectric fabric power device, characterized in that, The method comprises the following steps: S10, dispersing amino-functionalized multi-walled carbon nanotubes and sodium dodecyl sulfate in a phosphate buffer solution to obtain a stable amino-functionalized multi-walled carbon nanotube dispersion; S20, putting a silk thread, p-phenylenediamine, and formaldehyde (aq) into the amino-functionalized multi-walled carbon nanotube dispersion, drying after reaction to obtain an amino-functionalized multi-walled carbon nanotube modified silk thread, denoted as a modified silk thread; S30, soaking the modified silk thread in a mixture of aniline and hydrochloric acid, then putting ammonium persulfate (aq) into the mixture, drying after reaction under low-temperature conditions to obtain a thermoelectric silk thread, denoted as a thermoelectric silk thread; S40, weaving the thermoelectric silk thread into a fabric, adhering carbon cloth on both sides of the fabric by using conductive adhesive, and making the carbon cloth on both sides of the fabric extend in two opposite directions for a distance, to obtain a flexible wearable p-type composite thermoelectric fabric power supply device.

2. The method according to claim 1, wherein: wherein In step S10, the pH of the phosphate buffer solution ranges from 6.3 to 6.

8.

3. The method according to claim 1, wherein: wherein In step S10, the dispersion time is 2 hours.

4. The method according to claim 1, wherein: wherein, In step S20, the reaction condition is 35-40℃ for 24 hours.

5. The method according to claim 1, wherein: wherein In step S20, the silk thread is a protein silk thread, The protein silk thread comprises a silk thread.

6. The method according to claim 1, wherein: wherein In steps S10-S20, the mass ratio of amino-functionalized multi-walled carbon nanotubes, sodium dodecyl sulfate, silk thread, p-phenylenediamine, and formaldehyde (aq) is 0.6:0.24:3.3:0.3:0.6; The concentration of formaldehyde (aq) is 35-40%.

7. The method according to claim 1, wherein: wherein In step S30, the molar ratio of aniline, hydrochloric acid, and ammonium persulfate is 3:3:1, The volume concentration of aniline in the mixture after adding ammonium persulfate (aq) is 0.09-0.36%.

8. The method according to claim 1, wherein: wherein, In step S30, the soaking time is 2 hours, The reaction time is 24 hours.

9. A flexible wearable p-type composite thermoelectric fabric power device, characterized by, The flexible wearable p-type composite thermoelectric fabric power supply device is prepared by the method according to any one of claims 1-8.

10. The flexible wearable p-type composite thermoelectric fabric power supply device according to claim 9 is applied to provide power for electronic devices.

Images