Preparation Method and Related Device of N-Type Organic Thermoelectric Aerogel Based on PBFDO

Abstract

The embodiments of the present application provide a preparation method and related device for an N-type organic thermoelectric aerogel based on PBFDO. The preparation method includes: stirring and mixing PBFDO, CMC, water, and GOPS to obtain a mixed dispersion; performing ultrasonic treatment on the mixed dispersion; performing freeze-solidification treatment on the ultrasonically treated mixed dispersion to obtain a solidified body; performing freeze-drying on the solidified body to obtain an N-type organic thermoelectric aerogel; using CMC as the support framework of this N-type organic thermoelectric aerogel and using GOPS as a cross-linking agent to ensure good mechanical properties of the N-type organic thermoelectric aerogel; the N-type organic thermoelectric aerogel based on PBFDO has stable thermoelectric properties in air.

Description

Technical Field

[0001] Embodiments of the present application relate to the field of sensors, and particularly to a preparation method and related device of an N-type organic thermoelectric aerogel based on PBFDO. Background Art

[0002] A thermoelectric generator uses P-type organic thermoelectric materials and N-type organic thermoelectric materials to form multiple consecutive PN junctions to generate electricity using temperature differences. The majority carriers of N-type organic thermoelectric materials are electrons, and in air, electrons are easily captured by water and oxygen, causing the thermoelectric performance of the N-type organic thermoelectric materials themselves to decrease sharply. To improve the thermoelectric performance of N-type organic thermoelectric materials, it is necessary to compound N-type organic thermoelectric materials with other inorganic materials. However, with the introduction of inorganic materials, there are also some problems such as pollution, high cost, and cumbersome production processes during their production, and the final products often also have low flexibility and high thermal conductivity. Summary of the Invention

[0003] The following is an overview of the subject matter described in detail in this article.

[0004] The purpose of the present application is to solve at least to a certain extent one of the technical problems existing in the related art. Embodiments of the present application provide a preparation method and related device of an N-type organic thermoelectric aerogel based on PBFDO, so that the prepared N-type organic thermoelectric aerogel has stable thermoelectric performance and good mechanical properties.

[0005] In an embodiment of the first aspect of the present application, a preparation method of an N-type organic thermoelectric aerogel includes:

[0006] Stir and mix polybenzodifurandione PBFDO, carboxymethyl cellulose CMC, water, and (3-glycidoxypropyl) trimethoxysilane GOPS to obtain a mixed dispersion;

[0007] Ultrasonically treat the mixed dispersion;

[0008] Freeze and solidify the ultrasonically treated mixed dispersion in a liquid nitrogen bath to obtain a solid;

[0009] Freeze-dry the solid to obtain an N-type organic thermoelectric aerogel.

[0010] According to certain embodiments of the first aspect of the present application, the mass fraction of the PBFDO added in water is 0.6%, the mass fraction of the CMC is 1.5%, and the volume fraction of the GOPS is 0.3%.

[0011] According to certain embodiments of the first aspect of the present application, the stirring and mixing of polybenzodifuran dione (PBFDO), carboxymethyl cellulose (CMC), water, and (3-glycidoxypropyl) trimethoxysilane (GOPS) includes:

[0012] Stir and mix polybenzodifuran dione (PBFDO), carboxymethyl cellulose (CMC), water, and (3-glycidoxypropyl) trimethoxysilane (GOPS) in an environment of 25 degrees Celsius for 24 hours.

[0013] According to certain embodiments of the first aspect of the present application, the time for ultrasonic treatment is 1 hour.

[0014] According to certain embodiments of the first aspect of the present application, the freeze-solidification treatment of the mixed dispersion after ultrasonic treatment includes:

[0015] Pour the mixed dispersion after ultrasonic treatment into a polytetrafluoroethylene mold, and perform freeze-solidification treatment in a liquid nitrogen bath for 10 minutes.

[0016] According to certain embodiments of the first aspect of the present application, the freeze-drying of the solid includes: performing freeze-drying on the solid for 24 hours.

[0017] According to certain embodiments of the first aspect of the present application, the PBFDO is in powder form; the powdered PBFDO is prepared as follows: Pour the PBFDO solution with dimethyl sulfoxide (DMSO) as the solvent into a glass dish, and perform evaporation treatment at 80 degrees to remove DMSO to obtain a PBFDO film; grind the PBFDO film to obtain powdered PBFDO.

[0018] In an embodiment of the second aspect of the present application, the flexible thermoelectric sensor is provided with a processing unit and an N-type organic thermoelectric gel, and the N-type organic thermoelectric gel is prepared according to the preparation method described above; the processing unit is used to sense the temperature difference between the two ends or the upper and lower surfaces of the N-type organic thermoelectric gel, and generate a corresponding thermoelectric voltage reading according to the temperature difference.

[0019] In an embodiment of the third aspect of the present application, a flexible thermoelectric generator includes an N-type thermoelectric module, a P-type thermoelectric module, and a substrate. The N-type thermoelectric module is made of an N-type organic thermoelectric gel, the P-type thermoelectric module is made of a P-type organic thermoelectric material, and the N-type organic thermoelectric gel is prepared according to the above preparation method; the N-type thermoelectric module and the P-type thermoelectric module are alternately embedded in the substrate, and the N-type thermoelectric module and the P-type thermoelectric module are alternately connected by a conductive material.

[0020] According to certain embodiments of the third aspect of the present application, the P-type thermoelectric module is prepared as follows: Soak the polyurethane sponge in the P-type organic thermoelectric material for 24 hours; Dry the polyurethane sponge containing the P-type organic thermoelectric material in an environment of 60 degrees Celsius for 1 hour to obtain the P-type thermoelectric module; wherein, the P-type organic thermoelectric material is poly(3,4-ethylenedioxythiophene):polystyrene sulfonic acid.

[0021] The above solution has at least the following beneficial effects: Using CMC as the supporting framework of this N-type organic aerogel and using (3-glycidoxypropyl)trimethoxysilane GOPS as the cross-linking agent ensures good mechanical properties for this aerogel; The thermoelectric performance of the N-type organic aerogel is stable in air, and the thermoelectric generator formed has high biocompatibility and can be used as a flexible wearable thermoelectric generator or wearable sensor attached to the skin surface. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] The drawings are used to provide a further understanding of the technical solutions of the present application, and constitute a part of the specification. They are used together with the embodiments of the present application to explain the technical solutions of the present application, and do not constitute a limitation to the technical solutions of the present application.

[0023] Figure 1 is a step diagram of the preparation method of the N-type organic aerogel based on PBFDO;

[0024] Figure 2 is a side view of the flexible thermoelectric generator;

[0025] Figure 3 is a top view of the flexible thermoelectric generator. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0026] In order to make the objectives, technical solutions and advantages of the present application clearer, the present application will be further described in detail below with reference to the drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0027] It should be noted that although the functional modules are divided in the device schematic diagram and the logical order is shown in the flowchart, in some cases, the steps shown or described may be executed in a different order from the module division in the device or the flowchart. Terms such as "first" and "second" in the specification, claims or the above drawings are used to distinguish similar objects and do not necessarily need to describe a specific order or sequence.

[0028] The following will further elaborate on the embodiments of the present application with reference to the drawings.

[0029] Embodiments of the present application provide an N-type organic thermoelectric aerogel based on PBFDO.

[0030] An aerogel is a novel lightweight solid material composed of colloidal particles or polymer molecules aggregated with each other to form a micro-nano porous network structure, and filled with an air dispersion medium in the pores. It is usually used as a thermal insulation material, a flame retardant material, a sound insulation material, a high-efficiency adsorption material, a catalyst carrier material, an optical device, and an electrode energy material.

[0031] The N-type organic thermoelectric aerogel based on PBFDO is prepared according to the following preparation method.

[0032] Refer to Figure 1 , the preparation method of the N-type organic thermoelectric aerogel based on PBFDO includes:

[0033] Step S100, stirring and mixing polybenzodifurandione, carboxymethyl cellulose, water, and (3-glycidoxypropyl)trimethoxysilane to obtain a mixed dispersion;

[0034] Step S200, ultrasonically treating the mixed dispersion;

[0035] Step S300, subjecting the ultrasonically treated mixed dispersion to freeze-solidification treatment to obtain a solidified body;

[0036] Step S400, freeze-drying the solidified body to obtain the N-type organic thermoelectric aerogel based on PBFDO.

[0037] Natural cellulose is the most widely distributed and most abundant polysaccharide in nature, with a very rich source. After carboxymethylation of cellulose, carboxymethyl cellulose CMC is obtained, and its aqueous solution has functions such as thickening and film-forming. Using CMC as the supporting skeleton of this N-type organic thermoelectric aerogel and using (3-glycidoxypropyl)trimethoxysilane GOPS as a cross-linking agent provides guarantee for the good mechanical properties of this aerogel.

[0038] For step S100, polybenzodifurandione PBFDO, carboxymethyl cellulose CMC, water, and (3-glycidoxypropyl)trimethoxysilane GOPS are stirred and mixed to obtain a mixed dispersion.

[0039] PBFDO is in powder form. The PBFDO in powder form is prepared as follows: Pour the PBFDO solution with dimethyl sulfoxide (DMSO) as the solvent into a glass dish; Place the glass dish containing the PBFDO solution with dimethyl sulfoxide (DMSO) as the solvent into an oven, and set the oven to 80 degrees Celsius; Perform evaporation treatment at 80 degrees to remove DMSO, thereby obtaining a PBFDO film; Scrape the PBFDO film with a sterile knife and place it in a quartz mortar for grinding until it becomes powder to obtain PBFDO in powder form.

[0040] The PBFDO solution with dimethyl sulfoxide (DMSO) as the solvent is not conducive to freeze-drying. Removing DMSO in the PBFDO solution with dimethyl sulfoxide (DMSO) as the solvent by evaporation treatment at 80 degrees enables the prepared PBFDO powder to be formulated into an aqueous dispersion, and then an N-type organic thermoelectric aerogel can be prepared by the method of freeze-drying.

[0041] Add PBFDO powder with a mass fraction of 0.6%, CMC with a mass fraction of 1.5%, and GOPS with a volume fraction of 0.3% to water, and stir at high speed for 24 hours in an environment at room temperature (25 degrees Celsius).

[0042] For step S200, perform ultrasonic treatment on the mixed dispersion for 1 hour.

[0043] For step S300, pour the ultrasonically treated mixed dispersion into a polytetrafluoroethylene mold, and perform freeze-solidification treatment in a liquid nitrogen bath for ten minutes to obtain a solidified body.

[0044] For step S400, perform freeze-drying on the freeze-solidified module using a freeze-dryer for 24 hours, and after demolding the freeze-dried module, obtain the N-type organic thermoelectric aerogel based on PBFDO.

[0045] The embodiments of the present application provide a flexible thermoelectric sensor.

[0046] The flexible thermoelectric sensor is provided with a processing unit and an N-type organic thermoelectric aerogel based on PBFDO.

[0047] The N-type organic thermoelectric aerogel based on PBFDO has a stable Seebeck coefficient in air. The Seebeck coefficient is used to describe the thermoelectric properties of a substance and is the rate of change of the thermoelectromotive force with temperature at a given temperature. The stable Seebeck coefficient of this N-type organic thermoelectric aerogel indicates that the rate of change of the thermoelectromotive force of the N-type organic thermoelectric aerogel with temperature is stable.

[0048] As a thermoelectric material, N-type organic thermoelectric aerogel can achieve the mutual conversion between thermal energy and electrical energy; thermoelectric aerogel is a Wiener porous structure material with thermoelectric properties made of thermoelectric materials. This structure enables the thermoelectric material to have a lower thermal conductivity and a specific thermoelectric transport mechanism, with high electrical conductivity, Seebeck coefficient, low thermal conductivity, and flexibility.

[0049] The processing unit is used to sense the temperature difference between the two ends or the upper and lower surfaces of the N-type organic thermoelectric aerogel and generate a thermal voltage reading according to the temperature difference. The thermal voltage value has a linear relationship with the temperature difference.

[0050] An embodiment of the present application provides a flexible thermoelectric generator.

[0051] Refer to Figure 2 and Figure 3 , the principle of the thermoelectric generator is to utilize the Seebeck effect in the thermoelectric effect, that is, connecting two different materials into a closed loop. When the temperatures at the joints of the two materials are different, a thermoelectric potential will be generated in this closed loop. Using P-type organic thermoelectric materials and N-type organic thermoelectric materials to form multiple continuous PN junctions to generate electricity using the temperature difference is the assembly method of the thermoelectric generator.

[0052] The flexible thermoelectric generator includes an N-type thermoelectric module, a P-type thermoelectric module, and a substrate 2. The N-type thermoelectric module is made of N-type organic thermoelectric aerogel, and the P-type thermoelectric module is made of P-type organic thermoelectric material; the N-type thermoelectric module and the P-type thermoelectric module are alternately embedded in the substrate 2, and the N-type thermoelectric module and the P-type thermoelectric module are alternately connected by a conductive material 1.

[0053] The preparation method of the flexible thermoelectric generator is as follows:

[0054] Cut the N-type organic thermoelectric aerogel into N-type thermoelectric modules using a sterile knife.

[0055] Soak the polyurethane sponge in poly(3,4-ethylenedioxythiophene):polystyrene sulfonate PEDOT:PSS for 24 hours; dry the polyurethane sponge containing PEDOT:PSS in an environment of 60 degrees Celsius for 1 hour, and cut it using a sterile knife to obtain a P-type thermoelectric module;

[0056] Alternately embed the N-type thermoelectric module and the P-type thermoelectric module into the flexible polydimethylsiloxane PDMS substrate 2, and connect them alternately up and down with copper tape to obtain a flexible thermoelectric generator.

[0057] In other embodiments, the P-type organic thermoelectric material used to make the P-type organic thermoelectric module can also be other types of materials; the substrate 2 can also be other types of materials, such as polyurethane sponge, etc.; the conductive material 1 can also be other types of materials, such as silver.

[0058] It should be noted that the temperature difference of the fabricated flexible thermoelectric generator is in the vertical direction, and the upper and lower surfaces of the substrate 2 become the hot end and the cold end of each PN thermoelectric module; the fabricated flexible thermoelectric generator can be attached to the human skin surface to form a wearable thermoelectric generator, where the human body surface serves as the hot end and the environment serves as the cold end.

[0059] The N-type organic thermoelectric aerogel based on PBFDO has relatively stable thermoelectric performance in air, and the thermoelectric generator formed has high biocompatibility and can be used as a flexible wearable thermoelectric generator or a wearable sensor attached to the skin surface.

[0060] The above is a specific description of the preferred embodiment of the present application, but the present application is not limited to the embodiment. Those skilled in the art can make various equivalent deformations or substitutions without departing from the spirit of the present application, and these equivalent deformations or substitutions are all included within the scope defined by the claims of the present application.

Claims

1. A preparation method of an N-type organic thermoelectric aerogel based on PBFDO, characterized in that, Including: Stir and mix polybenzobisfurandione PBFDO, carboxymethyl cellulose CMC, water and (3-glycidoxypropyl)trimethoxysilane GOPS to obtain a mixed dispersion; Perform ultrasonic treatment on the mixed dispersion; Perform freeze-solidification treatment on the ultrasonically treated mixed dispersion to obtain a solidified body; Perform freeze-drying on the solidified body to obtain an N-type organic thermoelectric aerogel based on PBFDO; Wherein, the mass fraction of PBFDO added to water is 0.6%, the mass fraction of CMC is 1.5%, and the volume fraction of GOPS is 0.3%.

2. The preparation method of an N-type organic thermoelectric aerogel based on PBFDO according to claim 1, wherein, The step of stirring and mixing polybenzobisfurandione PBFDO, carboxymethyl cellulose CMC, water and (3-glycidoxypropyl)trimethoxysilane GOPS includes: Stir and mix polybenzobisfurandione PBFDO powder, carboxymethyl cellulose CMC, water and (3-glycidoxypropyl)trimethoxysilane GOPS in an environment of 25 °C for 24 hours.

3. The preparation method of an N-type organic thermoelectric aerogel based on PBFDO according to claim 1, characterized in that, The time for ultrasonic treatment is 1 hour.

4. The preparation method of an N-type organic thermoelectric aerogel based on PBFDO according to claim 1, wherein The step of performing freeze-solidification treatment on the ultrasonically treated mixed dispersion includes: Pour the ultrasonically treated mixed dispersion into a polytetrafluoroethylene mold, and perform freeze-solidification treatment in a liquid nitrogen bath for 10 minutes.

5. A preparation method of an N-type organic thermoelectric aerogel based on PBFDO according to claim 1, characterized in that, The step of performing freeze-drying on the solidified body includes: performing freeze-drying on the solidified body for 24 hours.

6. The preparation method of an N-type organic thermoelectric aerogel based on PBFDO according to claim 1, wherein The PBFDO is in powder form; the powdered PBFDO is prepared as follows: pour a PBFDO solution with dimethyl sulfoxide DMSO as the solvent into a glass dish, and perform evaporation treatment at 80 °C to remove DMSO to obtain a PBFDO film; Grind the PBFDO film to obtain powdered PBFDO.

7. A flexible thermoelectric sensor, characterized in that, The flexible thermoelectric sensor is provided with a processing unit and an N-type organic thermoelectric aerogel, and the N-type organic thermoelectric aerogel is prepared according to the preparation method described in any one of claims 1 to 6; the processing unit is used to sense the temperature difference between the two ends or the upper and lower surfaces of the N-type organic thermoelectric aerogel, and generate a corresponding thermoelectric voltage indication according to the temperature difference.

8. A flexible thermoelectric generator, characterized in that, Including an N-type thermoelectric module, a P-type thermoelectric module and a substrate, the N-type thermoelectric module is made of an N-type organic thermoelectric aerogel, the P-type thermoelectric module is made of a P-type organic thermoelectric material, and the N-type organic thermoelectric aerogel is prepared according to the preparation method described in any one of claims 1 to 6; the N-type thermoelectric module and the P-type thermoelectric module are alternately embedded in the substrate, and the N-type thermoelectric module and the P-type thermoelectric module are alternately connected by a conductive material.

9. The flexible thermoelectric generator according to claim 8, characterized in that, The P-type thermoelectric module is prepared as follows: soak a polyurethane sponge in a P-type organic thermoelectric material for 24 hours; dry the polyurethane sponge containing the P-type organic thermoelectric material in an environment of 60 °C for 1 hour to obtain a P-type thermoelectric module; wherein, the P-type organic thermoelectric material is poly(3,4-ethylenedioxythiophene):polystyrene sulfonic acid.

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