Preparation method of n-p type alternating flexible thermoelectric fiber based on thermochemical cell

Abstract

This invention relates to the field of materials science, specifically a method for preparing N-P type alternating flexible thermoelectric fibers based on thermoelectric cells. Thermoelectric materials directly convert thermal energy into electrical energy based on the Seebeck effect, which originates from carrier diffusion driven by temperature gradients. However, currently commercially available thermoelectric materials are mainly rigid solid blocks, which are not suitable for wearable systems. The method for preparing N-P type alternating flexible thermoelectric fibers based on thermoelectric cells provided in this invention has a simple production process, low cost, and is suitable for large-scale production. The thermoelectric fibers prepared by the method in this application have good mechanical properties, good stretchability and elasticity, and are comfortable to wear, making them suitable for use in most aspects of daily life. The thermoelectric fiber material prepared by the method for preparing N-P type alternating flexible thermoelectric fibers based on thermoelectric cells provided in this invention has a tight bond at the P-N interface, and the lengths of the P and N segments are controllable, making it suitable for weaving.

Description

Technical fields:

[0001] This invention relates to the field of materials science, specifically to a method for preparing NP-type alternating flexible thermoelectric fibers based on thermochemical cells. Background technology:

[0002] With continuous breakthroughs in miniaturization and integration of electronic devices, wearable electronic devices and smart fabrics are receiving increasing attention. To meet the dispersed energy demands of the Internet of Things (IoT), various new energy extraction strategies from the environment are being researched, such as piezoelectric power generation, triboelectric power generation, and solar power generation. Among these, thermoelectric power generation has unique advantages in wearable electronic devices because it does not require continuous mechanical movement, is unaffected by day-night cycles, and benefits from the constant temperature difference between the body and the environment.

[0003] Thermoelectric materials convert heat energy directly into electrical energy based on the Seebeck effect, which originates from carrier diffusion driven by temperature gradients. However, currently commercially available thermoelectric materials are mainly rigid solid blocks, unsuitable for wearable systems. Thermochemical batteries can also directly convert heat energy into electrical energy, utilizing temperature-related entropy changes during ion redox reactions and electron transfer between electrodes. Because their reactions typically occur in liquids, they are inherently fluid and flexible. Furthermore, the optimal operating temperature of ordinary thermochemical batteries is usually below 100°C, making them more suitable for everyday use. However, most current thermochemical batteries use rigid and inelastic substrates to support the liquid working medium, masking the advantages of their material's flexibility and stretchability. In addition, devices containing substrates have poor breathability, affecting wearing comfort, and long-term wear can lead to health problems. Summary of the Invention:

[0004] The purpose of this invention is to solve the existing problems and provide a method for preparing NP-type alternating flexible thermoelectric fibers based on thermochemical cells.

[0005] The technical solution of the present invention is as follows: A method for preparing NP-type alternating flexible thermoelectric fibers based on thermochemical cells, characterized by comprising the following steps:

[0006] Step 1: Mix 10 g of acrylamide monomer (AM), 240 mg of N,N'-methylenebisacrylamide (MBA), 100 mg of ammonium persulfate (APS), and 100 mg of 3-(trimethoxysilane)propyl acrylate (TMSPMA) as silane coupling agents with 50 mL of deionized water to prepare a hydrogel precursor solution;

[0007] Step 2: Place the hydrogel precursor solution in a polytetrafluoroethylene tube and polymerize it at 60-90 degrees Celsius for 10-30 minutes;

[0008] Step 3: The hydrogel precursor liquid polymerized in Step 2 is extruded from the tube to obtain the shaped PAAm hydrogel fiber. The PAAm hydrogel fiber is completely washed with deionized water and freeze-dried to form PAAm aerogel fiber. The PAAm aerogel fiber is cut into PAAm aerogel fiber segments of uniform length.

[0009] Step 4: Mix 0.1 g of conductive material and 1 g of polydimethylsiloxane (PDMS) evenly in 50-150 mL of anhydrous hexachloroane and stir. Add 0.1 g of curing agent to the prepared mixture and stir again for 30 minutes.

[0010] Step 5: The mixture from Step 4 is stirred and evaporated to form a liquid PDMS conductive composite material; PAAm aerogel segments are sequentially bonded to the prepared liquid PDMS conductive composite material and cured at 80 degrees Celsius to form aerogel fibers.

[0011] Step 6: Dissolve the electrolytes of P-type and N-type thermal batteries in deionized water to form solutions; immerse the aerogel fibers in deionized water to restore them to their hydrogel form;

[0012] Step 7: Alternately add 2 μL of 0.1-1 mol / L P-type and N-type electrolyte solutions to the aerogel section;

[0013] Step 8: Mix the PDMS base material and curing agent with triethoxyvinylsilane (TEOVS), then dip the bare P / N alternating hydrogel fibers into the mixture and cure them in a vacuum drying oven to form np-type alternating flexible thermoelectric fibers.

[0014] As a preferred technical solution, the polymerization time of the thermoelectric fiber precursor in step 2 is 10-60 minutes.

[0015] As a preferred technical solution, the conductive material in step 4 includes, but is not limited to, one of single-walled carbon nanotubes (SWCNTs), multi-walled carbon nanotubes (MWCNTs), and carbon powder.

[0016] As a preferred technical solution, the electrolyte for P-type thermal batteries includes, but is not limited to, K3Fe(CN)6 / K4Fe(CN)6.

[0017] As a preferred technical solution, the electrolyte for N-type thermal batteries includes, but is not limited to, FeCl3 / FeCl2.

[0018] As a preferred technical solution, in step 3, the PAAm aerogel fiber is cut into uniform PAAm aerogel fiber segments with a length of 5 mm.

[0019] As a preferred technical solution, the curing agent is mainly composed of silanes and olefins.

[0020] The beneficial effects of this invention are as follows:

[0021] 1. The preparation method of NP-type alternating flexible thermoelectric fiber based on thermochemical cell provided in this invention has a simple production process, low cost, and is suitable for large-scale production.

[0022] 2. The thermoelectric fibers prepared by the method described in this application have good mechanical properties, good stretchability and elasticity, and are comfortable to wear, making them suitable for use in most aspects of daily life.

[0023] 3. The thermoelectric fiber material prepared by the method for preparing NP-type alternating flexible thermoelectric fibers based on thermochemical cells provided in this invention has a tight bond at the PN interface, and the lengths of the P and N segments are controllable, making it suitable for weaving. Attached image description:

[0024] Figure 1 This is a schematic diagram of the preparation process of the present invention;

[0025] Figure 2 This is a schematic diagram of the thermoelectric performance of the present invention;

[0026] Figure 3 This is a curve of 1000 contraction cycles of the present invention; Detailed implementation method:

[0027] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0028] Example 1:

[0029] like Figure 1-3 As shown, a method for preparing NP-type alternating flexible thermoelectric fibers based on thermochemical cells is characterized by comprising the following steps:

[0030] Step 1: Mix 10 g of acrylamide monomer (AM), 240 mg of N,N'-methylenebisacrylamide (MBA), 100 mg of ammonium persulfate (APS), and 100 mg of 3-(trimethoxysilane)propyl acrylate (TMSPMA) as silane coupling agents with 50 mL of deionized water to prepare a hydrogel precursor solution;

[0031] Step 2: Polymerize the degassed hydrogel precursor solution in a polytetrafluoroethylene tube at 80 degrees Celsius for 15 minutes;

[0032] Step 3: After extruding the hydrogel precursor solution polymerized in Step 2 from the tube, the PAAm hydrogel fibers are completely washed with deionized water and then freeze-dried to form PAAm aerogel fibers. The PAAm aerogel fibers are then cut into uniform 5mm length segments.

[0033] Step 4: Mix 0.1 g of multi-walled carbon nanotubes (MWCNTs) and 1 g of polydimethylsiloxane (PDMS) uniformly in 100 mL of anhydrous hexachloroane and stir at room temperature for 30 minutes. Then, add 0.1 g of curing agent to the prepared mixture and stir again for 30 minutes.

[0034] Step 5: The mixture from Step 4 is stirred and evaporated to form a liquid PDMS / CNT composite material. PAAm aerogel segments are then bonded to the prepared liquid PDMS / CNT composite material in sequence and cured in an oven at 80 degrees Celsius to form aerogel fibers.

[0035] Step 6: Dissolve K4Fe(CN)6, K3Fe(CN)6, FeCl3, and FeCl2 in deionized water to form 0.1 mol / L P-type and N-type electrolyte solutions, respectively. Immerse the aerogel fibers in deionized water to restore them to their hydrogel form.

[0036] Step 7: Alternately add 2 μL of 0.1 mol / L P-type and N-type electrolyte solutions to the aerogel segment;

[0037] Step 8: Mix the PDMS base material and curing agent with triethoxyvinylsilane (TEOVS), then dip the bare P / N alternating hydrogel fibers into the PDMS mixture and cure them in a vacuum drying oven to form NP-type alternating flexible thermoelectric fibers.

[0038] Example 2:

[0039] A method for preparing NP-type alternating flexible thermoelectric fibers based on thermochemical cells, characterized by comprising the following steps:

[0040] Step 1: Mix 10 g of acrylamide monomer (AM), 240 mg of N,N'-methylenebisacrylamide (MBA), 100 mg of ammonium persulfate (APS), and 100 mg of 3-(trimethoxysilane)propyl acrylate (TMSPMA) as silane coupling agents with 50 mL of deionized water to prepare a hydrogel precursor solution;

[0041] Step 2: Polymerize the degassed hydrogel precursor solution in a polytetrafluoroethylene tube at 80 degrees Celsius for 15 minutes;

[0042] Step 3: After extruding the hydrogel precursor solution polymerized in Step 2 from the tube, the PAAm hydrogel fibers are completely washed with deionized water and then freeze-dried to form PAAm aerogel fibers. The PAAm aerogel fibers are then cut into uniform 5mm length segments.

[0043] Step 4: Mix 0.1 g of single-walled carbon nanotubes (SWCNTs) and 1 g of polydimethylsiloxane (PDMS) uniformly in 100 mL of anhydrous hexachloroane and stir for 30 minutes. Then, add 0.1 g of curing agent to the prepared mixture and stir again for 30 minutes.

[0044] Step 5: The mixture from Step 4 is stirred and evaporated to form a liquid PDMS / CNT composite material. PAAm aerogel segments are then bonded to the prepared liquid PDMS / CNT composite material in sequence and cured in an oven at 80 degrees Celsius to form aerogel fibers.

[0045] Step 6: Prepare P-type and N-type electrolyte solutions of 1 mol / L by dissolving K4Fe(CN)6, K3Fe(CN)6, and FeCl3 / FeCl2 in deionized water, respectively. Immerse the aerogel fibers in deionized water to restore them to their hydrogel form.

[0046] Step 7: Alternately add 2 μL of 1 mol / L P-type and N-type electrolyte solutions to the aerogel segment;

[0047] Step 8: Mix the PDMS base material and curing agent with triethoxyvinylsilane (TEOVS), then dip the bare P / N alternating hydrogel fibers into the mixture and cure them in a vacuum drying oven to form NP-type alternating flexible thermoelectric fibers.

[0048] Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing NP-type alternating flexible thermoelectric fibers based on thermochemical cells, characterized in that, Includes the following steps: Step 1: Mix 10 g of acrylamide monomer (AM), 240 mg of N,N'-methylenebisacrylamide (MBA), 100 mg of ammonium persulfate (APS), and 100 mg of 3-(trimethoxysilane)propyl acrylate (TMSPMA) as silane coupling agents with 50 mL of deionized water to prepare a hydrogel precursor solution; Step 2: Place the hydrogel precursor solution in a polytetrafluoroethylene tube and polymerize it at 60-90 degrees Celsius for 10-30 minutes; Step 3: The hydrogel precursor liquid polymerized in Step 2 is extruded from the tube to obtain the shaped PAAm hydrogel fiber. The PAAm hydrogel fiber is completely washed with deionized water and freeze-dried to form PAAm aerogel fiber. The PAAm aerogel fiber is cut into PAAm aerogel fiber segments of uniform length. Step 4: Mix 0.1 g of conductive material and 1 g of polydimethylsiloxane (PDMS) evenly in 50-150 mL of anhydrous hexachloroane and stir. Add 0.1 g of curing agent to the prepared mixture and stir again for 30 minutes. Step 5: The mixture from Step 4 is stirred and evaporated to form a liquid PDMS conductive composite material; PAAm aerogel segments are sequentially bonded to the prepared liquid PDMS conductive composite material and cured at 80 degrees Celsius to form aerogel fibers. Step 6: Dissolve the electrolytes of P-type and N-type thermal batteries in deionized water to form solutions; immerse the aerogel fibers in deionized water to restore them to their hydrogel form; Step 7: Alternately add 2 μL of 0.1-1 mol / L P-type and N-type electrolyte solutions to the aerogel section; Step 8: Mix the PDMS base material and curing agent with triethoxyvinylsilane (TEOVS), then dip the bare P / N alternating hydrogel fibers into the mixture and cure them in a vacuum drying oven to form NP-type alternating flexible thermoelectric fibers.

2. The method for preparing an NP-type alternating flexible thermoelectric fiber based on a thermochemical cell as described in claim 1, characterized in that: The polymerization time in step 2 is 10-60 minutes.

3. The method for preparing an NP-type alternating flexible thermoelectric fiber based on a thermochemical cell as described in claim 1, characterized in that: The conductive material in step 4 includes one of single-walled carbon nanotubes (SWCNTs), multi-walled carbon nanotubes (MWCNTs), and carbon powder.

4. The method for preparing an NP-type alternating flexible thermoelectric fiber based on a thermochemical cell as described in claim 1, characterized in that: The electrolyte for the P-type thermal battery includes K3Fe(CN)6 / K4Fe(CN)6.

5. The method for preparing an NP-type alternating flexible thermoelectric fiber based on a thermoelectric cell as described in claim 1, characterized in that: The electrolyte for the N-type thermal battery includes FeCl3 / FeCl2.

6. The method for preparing an NP-type alternating flexible thermoelectric fiber based on a thermoelectric cell according to claim 1, characterized in that: In step 3, the PAAm aerogel fibers are cut into uniform PAAm aerogel fiber segments with a length of 5 mm.

7. The method for preparing an NP-type alternating flexible thermoelectric fiber based on a thermoelectric cell according to claim 1, characterized in that: The curing agent is composed of silane and olefin.

Images