Preparation method for pbfdo-based n-type organic thermoelectric aerogel, and related apparatus

Abstract

Embodiments of the present application provide a preparation method for a PBFDO-based N-type organic thermoelectric aerogel, and a related apparatus. The preparation method comprises: stirring and mixing PBFDO, CMC, water and GOPS, to obtain a mixed dispersion liquid; performing ultrasonic treatment on the mixed dispersion liquid; performing freezing solidification treatment on the mixed dispersion liquid which has undergone ultrasonic treatment, to obtain a solidified body; and freeze-drying the solidified body, to obtain an N-type organic thermoelectric aerogel. CMC is used as a supporting framework of the N-type organic thermoelectric aerogel, and GOPS is used as a cross-linking agent to ensure that the N-type organic thermoelectric aerogel has good mechanical properties. The thermoelectric properties of the PBFDO-based N-type organic thermoelectric aerogel in air are stable.

Description

Preparation method and related device of N-type organic thermoelectric gel based on PBFDO Technical Field

[0001] The embodiments of the present application relate to the field of sensors, and in particular to a preparation method and related devices of an N-type organic thermoelectric gel based on PBFDO. Background Art

[0002] Thermoelectric generators use P-type and N-type organic thermoelectric materials to form multiple continuous PN junctions to generate electricity using temperature differences. The majority carriers in N-type organic thermoelectric materials are electrons, which are easily captured by water and oxygen in the air, causing the thermoelectric performance of the N-type organic thermoelectric material to drop sharply. To improve the thermoelectric performance of N-type organic thermoelectric materials, they need to be compounded with other inorganic materials. However, the introduction of inorganic materials also brings with it problems such as pollution, high costs, and cumbersome manufacturing processes. Furthermore, the final product often suffers from low flexibility and high thermal conductivity. Summary of the Invention

[0003] The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.

[0004] The purpose of this application is to solve, at least to some extent, one of the technical problems existing in the related art. The embodiments of this application provide a method for preparing an N-type organic thermoelectric gel based on PBFDO and related devices, so that the thermoelectric performance of the prepared N-type organic thermoelectric gel is stable and the mechanical properties are good.

[0005] An embodiment of the first aspect of the present application provides a method for preparing an N-type organic thermoelectric gel, comprising:

[0006] Polybenzofurandione PBFDO, carboxymethyl cellulose CMC, water and (3-glycidyloxypropyl)trimethoxysilane GOPS are stirred and mixed to obtain a mixed dispersion;

[0007] subjecting the mixed dispersion to ultrasonic treatment;

[0008] The mixed dispersion after ultrasonic treatment is frozen and solidified in a liquid nitrogen bath to obtain a solidified body;

[0009] The solidified body is freeze-dried to obtain an N-type organic thermoelectric gel.

[0010] According to certain embodiments of the first aspect of the present application, the mass fraction of the PBFDO added to 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 polybenzofurandione PBFDO, carboxymethyl cellulose CMC, water and (3-glycidyloxypropyl)trimethoxysilane GOPS comprises:

[0012] Polybenzofurandione PBFDO, carboxymethyl cellulose CMC, water and (3-glycidyloxypropyl)trimethoxysilane GOPS were stirred and mixed at 25 degrees Celsius for 24 hours.

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

[0014] According to certain embodiments of the first aspect of the present application, the freezing and solidifying the mixed dispersion after ultrasonic treatment comprises:

[0015] The mixed dispersion after ultrasonic treatment was poured into a polytetrafluoroethylene mold and subjected to freeze-solidification treatment in a liquid nitrogen bath for 10 minutes.

[0016] According to certain embodiments of the first aspect of the present application, freeze-drying the solidified body comprises freeze-drying the solidified body 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: a PBFDO solution containing dimethyl sulfoxide (DMSO) as a solvent is poured into a glass dish and evaporated to dryness at 80 degrees Celsius to remove DMSO, thereby obtaining a PBFDO film; and the PBFDO film is ground to obtain the 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, wherein 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 thermovoltage indication based on the temperature difference.

[0019] An embodiment of the third aspect of the present application is a flexible thermoelectric generator, comprising an N-type thermoelectric module, a P-type thermoelectric module and a substrate, wherein 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 by the preparation method according to any one of claims 1 to 7; the N-type thermoelectric modules and the P-type thermoelectric modules are alternately embedded in the substrate, and the N-type thermoelectric modules and the P-type thermoelectric modules 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 in the following manner: soaking a polyurethane sponge in a P-type organic thermoelectric material for 24 hours; drying the polyurethane sponge containing the P-type organic thermoelectric material at 60 degrees Celsius 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).

[0021] The above scheme has at least the following beneficial effects: CMC is used as the supporting skeleton of this N-type organic thermoelectric gel, and (3-glycidyloxypropyl)trimethoxysilane GOPS is used as a cross-linking agent, thereby ensuring that the aerogel has good mechanical properties; the thermoelectric performance of the N-type organic thermoelectric gel in air is stable, 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 accompanying drawings are used to provide a further understanding of the technical solution of the present application and constitute a part of the specification. Together with the embodiments of the present application, they are used to explain the technical solution of the present application and do not constitute a limitation on the technical solution of the present application.

[0023] FIG1 is a step diagram of a method for preparing an N-type organic thermoelectric gel based on PBFDO;

[0024] FIG2 is a side view of a flexible thermoelectric generator;

[0025] FIG3 is a top view of a flexible thermoelectric generator. DETAILED DESCRIPTION

[0026] In order to make the purpose, technical solutions and advantages of this application more clear, the following further describes this application in detail with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain this application and are not intended to limit this application.

[0027] It should be noted that although the device schematics illustrate functional module divisions and the flowcharts illustrate logical sequences, in certain circumstances, the steps shown or described may be performed in a sequence that differs from the module divisions in the device or the sequence in the flowcharts. The terms "first," "second," and the like in the specification, claims, or accompanying drawings are used to distinguish similar items and are not necessarily used to describe a specific sequence or precedence.

[0028] The embodiments of the present application are further described below with reference to the accompanying drawings.

[0029] An embodiment of the present application provides an N-type organic thermoelectric gel based on PBFDO.

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

[0031] The PBFDO-based N-type organic thermoelectric gel was prepared according to the following preparation method.

[0032] 1 , a method for preparing an N-type organic thermoelectric gel based on PBFDO includes:

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

[0034] Step S200, subjecting the mixed dispersion to ultrasonic treatment;

[0035] Step S300, freezing and solidifying the mixed dispersion after ultrasonic treatment to obtain a solidified body;

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

[0037] Natural cellulose is the most widely distributed and abundant polysaccharide in nature, with abundant sources. Carboxymethyl cellulose (CMC), obtained through carboxymethylation of cellulose, has aqueous solutions with thickening and film-forming properties. CMC serves as the backbone of this N-type organic thermoelectric gel, while (3-glycidoxypropyl)trimethoxysilane (GOPS) serves as a crosslinker, ensuring the aerogel's excellent mechanical properties.

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

[0039] PBFDO is in powder form. The powdered PBFDO is prepared as follows: a PBFDO solution in dimethyl sulfoxide (DMSO) is poured into a glass dish; the glass dish containing the DMSO solution is placed in an oven set to 80 degrees Celsius; the DMSO is removed by evaporation at 80 degrees Celsius to obtain a PBFDO film; the PBFDO film is scraped off with a sterile knife and ground in a quartz mortar until it is powdered.

[0040] The PBFDO solution with dimethyl sulfoxide (DMSO) as the solvent is not conducive to freeze-drying. The DMSO in the PBFDO solution with dimethyl sulfoxide (DMSO) as the solvent is evaporated at 80 degrees to remove it. This allows the obtained PBFDO powder to be prepared into an aqueous dispersion and then freeze-dried to prepare an N-type organic thermoelectric gel.

[0041] 0.6% by mass of PBFDO powder, 1.5% by mass of CMC, and 0.3% by volume of GOPS were added to water and stirred at high speed for 24 hours at room temperature (25 degrees Celsius).

[0042] In step S200 , the mixed dispersion is subjected to ultrasonic treatment for 1 hour.

[0043] In step S300 , the mixed dispersion after ultrasonic treatment is poured into a polytetrafluoroethylene mold and subjected to a freeze-solidification treatment in a liquid nitrogen bath for ten minutes to obtain a solidified body.

[0044] In step S400 , the frozen solidified module is freeze-dried for 24 hours using a freeze dryer, and the freeze-dried module is demolded to obtain a PBFDO-based N-type organic thermoelectric gel.

[0045] An embodiment of the present application provides a flexible thermoelectric sensor.

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

[0047] The PBFDO-based N-type organic thermoelectric gel exhibits a stable Seebeck coefficient in air. The Seebeck coefficient describes the thermoelectric properties of a material 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 gel indicates that the rate of change of the thermoelectromotive force with temperature is stable.

[0048] N-type organic thermoelectric gel, as a thermoelectric material, can realize the mutual conversion between thermal energy and electrical energy; thermoelectric gel is a Wiener porous structure material with thermoelectric properties made from thermoelectric materials. This structure makes the thermoelectric material have lower thermal conductivity and has its own specific thermoelectric transmission mechanism, with higher electrical conductivity and Seebeck coefficient, lower 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 gel and generate a thermovoltage reading based on the temperature difference. The thermovoltage value is linearly related to the temperature difference.

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

[0051] Referring to Figures 2 and 3, the principle of a thermoelectric generator is to utilize the Seebeck effect, a thermoelectric effect. This involves connecting two dissimilar materials into a closed loop. When the temperatures at the junction of the two materials differ, a thermoelectric potential is generated within this closed loop. Thermoelectric generators are assembled by using P-type and N-type organic thermoelectric materials to form multiple continuous PN junctions, generating electricity from temperature differences.

[0052] A 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 an N-type organic thermoelectric gel, and the P-type thermoelectric module is made of a 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] The N-type organic thermoelectric gel was cut into N-type thermoelectric modules using a sterile knife.

[0055] The polyurethane sponge was soaked in poly (3,4-ethylenedioxythiophene):polystyrene sulfonate) PEDOT:PSS for 24 hours. The polyurethane sponge containing PEDOT:PSS was dried at 60 degrees Celsius for 1 hour and cut with a sterile knife to obtain a P-type thermoelectric module.

[0056] N-type thermoelectric modules and P-type thermoelectric modules are alternately embedded in a flexible polydimethylsiloxane (PDMS) substrate 2 and alternately connected 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 may also be made of other types of materials; the substrate 2 may also be made of other types of materials, such as polyurethane sponge, etc.; the conductive material 1 may also be made of other types of materials, such as silver.

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

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

[0060] The above is a specific description of the preferred implementation of the present application, but the present application is not limited to the embodiments. Those skilled in the art may make various equivalent modifications or substitutions without violating the spirit of the present application, and these equivalent modifications or substitutions are all included in 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-glycidyloxypropyl)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 gel based on PBFDO.

2. The preparation method of an N-type organic thermoelectric aerogel based on PBFDO according to claim 1, 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%.

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

4. 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.

5. The preparation method of an N-type organic thermoelectric aerogel based on PBFDO according to claim 1, characterized in that, 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.

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

7. The preparation method of an N-type organic thermoelectric aerogel based on PBFDO according to claim 1, characterized in that, 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.

8. A flexible thermoelectric sensor, characterized in that, 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 in any one of claims 1 to 7; 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 thermovoltage indication according to the temperature difference.

9. 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 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 preparation method described in any one of claims 1 to 7; 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.

10. A flexible thermoelectric generator according to claim 9, 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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