Flexible wearable p-type composite thermoelectric fabric power supply device and preparation method and application thereof

Abstract

The invention provides flexible wearable p-type composite thermoelectric fabric power supply equipment and a preparation method and application thereof, and belongs to the technical field of flexible wearable thermoelectric fabrics. According to the preparation method of the flexible wearable p-type composite thermoelectric fabric power supply equipment, only a p-type thermoelectric material is adopted in the preparation process, so that the problem of connection of p / n junctions of thermoelectric fabrics and the problem of dislocation of the p / n junctions caused by the human body movement process can be effectively solved; the performance stability of the wearable thermoelectric fabric is greatly improved, and the application requirements of wearable equipment can be met. The flexible wearable p-type composite thermoelectric fabric power supply device disclosed by the invention also has very stable thermoelectric performance after being folded for 5000 times.

Description

Technical Field

[0001] The present invention belongs to the technical field of flexible wearable thermoelectric fabrics, and specifically relates to a flexible wearable p-type composite thermoelectric fabric power supply device, a preparation method and an application thereof. Background Art

[0002] With the development of electronic information technology, electronic products have put forward the demand for flexible wearable power devices. As an ideal wearable power device, wearable thermoelectric power devices use the temperature gradient between human skin and the environment to promote carrier movement and provide continuous and stable power for electronic devices. Organic polymer materials show great application potential in wearable thermoelectric power devices due to their flexibility, processability and low cost.

[0003] As an important component of flexible materials, fabrics play an important role in flexible wearable devices. Generally, various requirements for flexible wearable devices can be met by changing the type of yarn, weaving structure, thickness, size and assembly method. However, the development of thermoelectric fabrics still faces major challenges. It is necessary to utilize the vertical temperature gradient between human skin and the environment as much as possible to improve the thermoelectric efficiency to assemble thermoelectric devices, thereby achieving higher output power. When a single type of thermoelectric material (p-type or n-type) is used, the traditional weaving structure will cause conflicts between the same charge carriers, resulting in assembly failure. Although two types of thermoelectric materials, including p-type and n-type, are applied to form a p / n junction during the weaving process, which can utilize the temperature gradient perpendicular to the human skin as much as possible, its preparation process is complicated, the cost is high, and it is difficult to prepare on a large scale. Moreover, organic n-type thermoelectric materials are scarce and cannot maintain stable performance in the environment. Especially in thermoelectric fabrics, the connection of the p / n junction must be exposed on the surface of human skin or in the environment, which makes the weaving process of thermoelectric fabrics extremely complicated. In addition, the dislocation of the p / n junction caused by the movement of the human body will greatly reduce the thermoelectric performance of the p / n junction type device.

[0004] Therefore, in order to meet the needs of wearable applications, it is urgent to develop wearable thermoelectric textile devices with simple preparation processes and stable power supply performance. Summary of the invention

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

[0006] The present invention provides a preparation method of a flexible wearable p-type composite thermoelectric fabric power supply device, which has the following characteristics and comprises 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 silk thread, p-phenylenediamine and formaldehyde (aq) into the aminated multi-walled carbon nanotube dispersion, drying after reaction to obtain aminated multi-walled carbon nanotube-modified silk thread, recorded as modified silk thread; S30, soaking the modified silk thread in a mixed solution of aniline and hydrochloric acid, then adding ammonium persulfate (aq) thereto, reacting under low temperature conditions and drying to obtain silk thread with thermoelectric properties, recorded as thermoelectric silk thread; S40, weaving the thermoelectric silk thread into a fabric, bonding carbon cloth on both sides of the fabric by conductive adhesive, and making the carbon cloth on both sides of the fabric extend a distance in two opposite directions, respectively, to obtain a flexible wearable p-type composite thermoelectric fabric power supply device.

[0007] In the preparation method of the flexible wearable p-type composite thermoelectric textile power supply device provided by the present invention, it can also have the following characteristics: wherein, in step S10, the pH range of the phosphate buffer solution is 6.3 to 6.8.

[0008] In the preparation method of the flexible wearable p-type composite thermoelectric textile power supply device provided by the present invention, it can also have the following characteristics: wherein, in step S10, the dispersion time is 2 hours.

[0009] In the preparation method of the flexible wearable p-type composite thermoelectric textile power supply device provided by the present invention, it can also have the following characteristics: wherein, in step S20, the reaction conditions are 35°C to 40°C for 24 hours.

[0010] In the preparation method of the flexible wearable p-type composite thermoelectric textile power supply device provided by the present invention, it can also have the following characteristics: wherein, in step S20, the silk thread is a protein silk thread, and the protein silk thread includes silk thread.

[0011] In the preparation method of the flexible wearable p-type composite thermoelectric textile power supply device provided by the present invention, it can also have the following characteristics: wherein, in steps S10 to S20, the mass ratio of the amino 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, and the concentration of formaldehyde (aq) is 35% to 40%.

[0012] In the preparation method of the flexible wearable p-type composite thermoelectric textile power supply device provided by the present invention, it can also have the following characteristics: wherein, 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 mixed solution after adding ammonium persulfate (aq) is 0.09% to 0.36%.

[0013] In the preparation method of the flexible wearable p-type composite thermoelectric textile power supply device provided by the present invention, it can also have the following characteristics: wherein, in step S30, the immersion time is 2 hours and the reaction time is 24 hours.

[0014] The present invention also provides a flexible wearable p-type composite thermoelectric fabric power supply device, which has the following characteristics and is prepared by any of the preparation methods of the flexible wearable p-type composite thermoelectric fabric power supply device described above.

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

[0016] Functions and Effects of the Invention

[0017] According to the flexible wearable p-type composite thermoelectric fabric power supply device and its preparation method and application involved in the present invention, since 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 body movement can be effectively solved, which greatly improves the performance stability of the wearable thermoelectric fabric and can meet the application needs of wearable devices. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

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

[0021] Figure 4 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 is a curve showing the change of output voltage with temperature difference of samples 1, 2 and 3 in the test example of the present invention;

[0023] Figure 6 It is a comparison of the maximum output power and power density of the comparative sample, sample 1, sample 2 and sample 3 in the test example of the present invention at a temperature difference of 90°C;

[0024] Figure 7The output voltage and internal resistance of sample 3 in the test example of the present invention change at a temperature difference of 90° C. during 5000 foldings. DETAILED DESCRIPTION

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

[0026] <Example>

[0027] Figure 1 It is a flowchart of a method for preparing a flexible wearable p-type composite thermoelectric textile power supply device according to an embodiment of the present invention; Figure 2 It is a schematic diagram of a method for preparing a flexible wearable p-type composite thermoelectric textile 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 textile power supply device, comprising the following steps:

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

[0030] S20, adding 0.33g silk thread, 0.03g p-phenylenediamine and 0.06g formaldehyde (aq) with a concentration of 35% to 40% into the dispersion of amino multi-walled carbon nanotubes, reacting at 38°C for 24h, and drying after the reaction to obtain amino multi-walled carbon nanotube-modified silk thread, recorded as modified silk thread.

[0031] S30, soaking the modified silk thread in 80 mL of a mixed solution of aniline and hydrochloric acid (wherein the aniline content is 90 μL to 360 μL) for 2 h, then adding 20 mL of ammonium persulfate (aq) thereto, reacting in an ice-water bath for 24 h and then drying to obtain a silk thread with thermoelectric properties, which is recorded as a thermoelectric silk thread.

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

[0033] S40, weaving the thermoelectric wires into a fabric, bonding carbon cloth on both sides of the fabric with conductive adhesive, and making the carbon cloth on both sides of the fabric extend a distance in two opposite directions, so as to obtain a flexible wearable p-type composite thermoelectric fabric power supply device.

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

[0035] This embodiment also provides a flexible wearable p-type composite thermoelectric textile power supply device, whose structure is as follows: Figure 3 It is prepared by the preparation method of a flexible wearable p-type composite thermoelectric textile power supply device provided in this embodiment.

[0036] A flexible wearable p-type composite thermoelectric textile power supply device 100 of the present embodiment includes a textile 10 , a carbon cloth 20 and a conductive adhesive 30 .

[0037] The fabric 10 is the fabric woven by the thermoelectric wires in the aforementioned step S40 .

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

[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 textile power supply devices were prepared using the aforementioned method for preparing a flexible wearable p-type composite thermoelectric textile power supply device, which were respectively recorded as sample 1, sample 2, and sample 3.

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

[0042] Figure 4 3 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.

[0043] like Figure 4 As shown, the amino-modified multi-walled carbon nanotubes are tightly riveted on the surface of the silk thread and entangled with each other to form a conductive path. Polyaniline is further wrapped on the surface of the amino-modified multi-walled carbon nanotube layer to form a composite thermoelectric wire.

[0044] <Test example>

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

[0046] The heating table is used as the heat source and the Peltier sheet is used as the cold source. The upper and lower surfaces of the sample are respectively placed on the heat source and the cold source, and a temperature difference is 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 is connected with a wire, and the output voltage of the sample under different temperature differences is collected using a Gisley 2400 source meter.

[0047] The internal resistance of the sample was measured using a two-wire method, using wires to connect the carbon cloth on the upper and lower surfaces of the sample, and a Gisley 2400 source meter was used to measure the internal resistance of the sample.

[0048] Figure 5 1 is a curve showing the change of output voltage with temperature difference of samples 1, 2 and 3 in the test example of the present invention.

[0049] like Figure 5 As shown in the figure, the output voltage of all samples increases with the increase of temperature difference. The Seebeck coefficient of the samples decreases with the increase of polyaniline content, among which the Seebeck coefficient of sample 1 is the largest and that of sample 3 is 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 textile power supply device in the embodiment, and was recorded as the comparative sample. The preparation process of the comparative sample is generally similar to the preparation process of samples 1, 2 and 3, and the content of the added amino-modified multi-walled carbon nanotubes is 0.06g. The only difference is that aniline is not added in step S30 of the preparation process of the comparative sample.

[0051] Figure 6 It 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 example 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 makes the Seebeck coefficient and internal resistance of the sample decrease synchronously. Overall, the maximum output power and maximum output power density of the sample increase with the increase of polyaniline content.

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

[0054] like Figure 7 As shown, sample 3 in the test example of the present invention still has very stable thermoelectric performance after being folded 5000 times, and its internal resistance and output voltage are maintained at about 1.7 kΩ and 0.8 mV.

[0055] Those skilled in the art should understand that the present invention is not limited to the above embodiments, and the above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, and these changes and improvements fall within the scope of the present invention to be protected. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. A method for preparing a flexible wearable p-type composite thermoelectric textile power supply device, characterized in that: The following steps are involved: S10, dispersing the 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 silk thread, p-phenylenediamine and formaldehyde (aq) into the dispersion of the aminated multi-walled carbon nanotubes, and drying after the reaction to obtain silk thread modified with the aminated multi-walled carbon nanotubes, which is recorded as modified silk thread; S30, soaking the modified silk thread in a mixture of aniline and hydrochloric acid, then adding ammonium persulfate (aq) thereto, reacting under low temperature conditions and drying to obtain a silk thread with thermoelectric properties, which is recorded as a thermoelectric silk thread; S40, weaving the thermoelectric wires into a fabric, bonding carbon cloth on both sides of the fabric with conductive adhesive, and making the carbon cloth on both sides of the fabric extend a distance in two opposite directions, so as to obtain a flexible wearable p-type composite thermoelectric fabric power supply device.

2. The method for preparing the flexible wearable p-type composite thermoelectric textile power supply device according to claim 1, characterized in that: in, In step S10, the pH of the phosphate buffer solution is in the range of 6.3 to 6.

8.

3. The method for preparing the flexible wearable p-type composite thermoelectric textile power supply device according to claim 1, characterized in that: in, In step S10, the dispersion time is 2 hours.

4. The method for preparing the flexible wearable p-type composite thermoelectric textile power supply device according to claim 1, characterized in that: in, In step S20, the reaction condition is 35° C. to 40° C. for 24 hours.

5. The method for preparing the flexible wearable p-type composite thermoelectric textile power supply device according to claim 1, characterized in that: in, In step S20, the silk thread is a protein silk thread, The protein thread includes silk thread.

6. The method for preparing the flexible wearable p-type composite thermoelectric textile power supply device according to claim 1, characterized in that: in, In steps S10 to S20, the mass ratio of the aminated 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% to 40%.

7. The method for preparing the flexible wearable p-type composite thermoelectric textile power supply device according to claim 1, characterized in that: in, In step S30, the molar ratio of aniline, hydrochloric acid and ammonium persulfate is 3:3:

1. The volume concentration of aniline in the mixed solution after adding ammonium persulfate (aq) is 0.09% to 0.36%.

8. The method for preparing the flexible wearable p-type composite thermoelectric textile power supply device according to claim 1, characterized in that: in, In step S30, the soaking time is 2 hours. The reaction time is 24h.

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

10. The flexible wearable p-type composite thermoelectric textile power supply device as claimed in claim 9 is used to provide power for electronic devices.

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