CN109301060B - Preparation method of composite aerogel thermoelectric material - Google Patents
Preparation method of composite aerogel thermoelectric material Download PDFInfo
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- 239000004964 aerogel Substances 0.000 title claims abstract description 55
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- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention relates to a preparation method of a composite aerogel thermoelectric material, which solves the technical problems that the thermal conductivity is increased and the overall electrical conductivity is reduced when the aerogel is prepared by compounding PEDOT with carbon materials and inorganic materials, and comprises the following steps: (1) mixing bacterial cellulose and EDOT monomer according to the mass ratio of 1: (9-11) mixing in the water solution, fully stirring, and adding 1.35-3.51 mmol of Fe3+Fully stirring the aqueous solution for 24-48 h, and washing the aqueous solution by using HCL and deionized water to prepare a composite material mixed solution; (2) mixing the prepared solution with nano conductive fillers with different proportional contents, stirring and carrying out ultrasonic treatment to obtain a solution, freezing the solution at the temperature of-10 to-50 ℃, and then carrying out vacuum freeze drying to obtain aerogel; (3) and (3) processing the aerogel prepared in the step (2) by using a powder tablet machine to obtain the BC-PEDOT multi-component composite sheet with the porous structure. The invention is widely applied to the field of thermoelectric material preparation.
Description
Technical Field
The invention relates to the field of thermoelectric materials, in particular to a preparation method of a composite aerogel thermoelectric material.
Background
At present, traditional non-renewable energy sources such as traditional petroleum, coal and the like are not enough to support the long-term development of human society, in addition, along with advocating environmental protection, the call for sustainable development is higher and higher, and the development of novel environment-friendly energy materials and devices also becomes a hotspot in scientific research. The thermoelectric material is a material capable of realizing mutual conversion of heat energy and electric energy, and the manufactured thermoelectric device has the advantages of small volume, no noise in work, long service life, no environmental pollution and the like, and can utilize the movement of current carriers to generate electricity only by depending on temperature difference. However, at present, the conversion efficiency is low, and the device is commonly applied to places with low power supply voltage, such as power supply of equipment worn by human bodies. The development performance of traditional inorganic materials such as bismuth telluride and alloys thereof, lead telluride and alloys thereof and the like is greatly improved through research, but the content of the elements on the earth is relatively low, and the elements do not have flexibility and are difficult to process, so that the development of high-performance organic thermoelectric materials with abundant materials, convenient processing and flexibility is important.
The organic thermoelectric material mostly adopts conductive polymers, carbon nanotubes and composite materials thereof. PEDOT is one of the current high-thermoelectric-performance conductive polymer materials, and is usually coated on a flexible substrate to prepare a flexible material, and the high-performance thermoelectric material is prepared by compounding carbon nanotubes, inorganic nano materials and the like to improve the Seebeck coefficient, but the thermal conductivity of the material is often improved by compounding.
In order to further reduce the thermal conductivity and improve the thermoelectric performance, in recent years, researches are carried out to construct conductive networks, wherein the conductive networks are connected by wires or sheet layers at the micron or even nanometer level, and air or insulating polymers are filled among the conductive networks. This structure greatly reduces the thermal conductivity. Wang et al prepared a tubular graphene framework by a template method and then deposited polyaniline to prepare a high-performance aerogel thermoelectric material. [ Wang L, Bi H, Yao Q, et al, three-dimensional structural graphene/polyaniline Composites as high-performance electronics [ J ]. Composites Science & Technology,2017,150.135-140 ]. Shaobo Han et al, using PEDOT: PSS and cellulose to composite an ultra-light, low thermal conductivity, Temperature-sensitive, pressure-sensitive, dual-inductive aerogel thermoelectric material [ Han S, Jiano F, Khan Z U, et al.
However, the material prepared in the mode has high porosity, so that the overall electrical conductivity is greatly reduced, and the overall thermoelectric performance of the aerogel is greatly reduced. Therefore, in the case of ensuring low thermal conductivity, it is important to improve the electrical conductivity.
Disclosure of Invention
The invention aims to solve the problems that the thermal conductivity is increased and the overall electrical conductivity of the prepared aerogel is reduced due to the compounding of PEDOT, carbon materials and inorganic materials, and provides a simple and effective preparation and treatment method of a PEDOT, bacterial cellulose and conductive filler multi-component composite aerogel material.
Therefore, the invention provides a preparation method of a composite aerogel thermoelectric material, which comprises the following steps:
(1) preparing a composite material mixed solution: mixing bacterial cellulose and EDOT monomer according to the mass ratio of 1: (9-11) mixing in the water solution, fully stirring, and adding 1.35-3.51 mmol of Fe3+Fully stirring the aqueous solution for 24-48 h, and washing the aqueous solution by using HCL and deionized water to prepare a composite material mixed solution; (2) preparing aerogel: mixing the composite material mixed solution prepared in the step (1) with nano conductive fillers with different proportion contents, stirring and carrying out ultrasonic treatment to obtain a solution, freezing the solution for 4 hours at the temperature of between 10 ℃ below zero and 50 ℃ below zero, and then carrying out vacuum freeze drying to obtain aerogel; (3) and (3) treating the aerogel: and (3) processing the aerogel prepared in the step (2) by using a powder tablet machine to obtain the BC-PEDOT multi-component composite sheet with a porous structure.
Preferably, the nanowire filler in step (2) is one or more of a single-walled carbon nanotube, a double-walled carbon nanotube, a multi-walled carbon nanotube, and a tellurium nanowire.
Preferably, in the step (3), the pressure is 5-50 MPa, the pressurizing time is 0.1-30 min, and the pressurizing temperature is 0-100 ℃.
The invention also provides a preparation method of the composite aerogel thermoelectric material, which comprises the following steps: (1) preparing a composite material mixed solution: mixing a bacterial cellulose solution with a PEDOT (Poly ethylene terephthalate) PSS (Poly ethylene styrene) solution to prepare a composite material mixed solution; (2) preparing aerogel: mixing the composite material mixed solution prepared in the step (1) with nano conductive fillers with different proportion contents, stirring and carrying out ultrasonic treatment to obtain a solution, freezing the solution at the temperature of-10 to-50 ℃, and then carrying out vacuum freeze drying to obtain aerogel; (3) and (3) treating the aerogel: treating the aerogel prepared in the step (2) by using a powder tabletting machine to obtain BC-PEDOT with a porous structure: PSS multi-element composite sheet.
The invention has the following beneficial effects:
(1) according to the invention, bacterial cellulose with low thermal conductivity is used as a supporting material to form a three-dimensional network framework, an EDOT monomer is used for in-situ polymerization or a PEDOT/PSS is used for coating to form a communicated conductive network, a nano conductive filler is added to reach a percolation threshold to form another communicated conductive network, an energy filtering effect can be formed at the interface and the conductive network joint due to the difference of materials to improve Seebeck, and the whole system forms a double-communicated network structure to form a P-type thermoelectric material.
(2) The composite sheet material is subjected to thermoelectric performance test, and the P-type sheet material and the n-type sheet material prepared by the method are sequentially connected to form the thermoelectric device. And keeping different temperature differences at the two ends, and carrying out device performance test.
(3) The invention adopts a freeze-drying method to prepare the dual-communicated porous lamellar composite thermoelectric material, and has the characteristics of simple and convenient manufacturing process, rich raw materials, low price, environmental friendliness and better flexibility of the product.
(4) The invention adopts a simple aerogel tabletting mode, the porosity can still reach about 40 percent after tabletting, the thermoelectric electrical conductivity of the aerogel is greatly improved, the thermal conductivity is not greatly increased, in addition, the peroxidation phenomenon caused by removing oxygen in the air in the vacuum freeze drying process is eliminated, and the Seebeck coefficient of the sheet prepared by the invention is a bit higher compared with that of the sheet formed by vacuum filtration film forming.
Drawings
FIG. 1a is a SEM image of a torn section of a BC-PEDOT sheet layer composite thermoelectric material prepared in example 1 of the invention;
FIG. 1b is a high power SEM image of a BC-PEDOT sheet layer composite thermoelectric material prepared in example 1 of the present invention;
FIG. 1c is a graph comparing the Seebeck coefficient over time for sheets formed by compression of BC/PEDOT aerogel prepared in example 1 of the present invention with the Seebeck coefficient over time for films made by suction filtration.
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as described in the claims.
Example 1
(1) Preparing a composite material mixed solution: diluting 10ml (2mg/ml) of bacterial cellulose with 20ml of deionized water, mixing with 1.27mmol of EDOT monomer in an aqueous solution, fully stirring, adding 1.35mmol of aqueous solution prepared from nine water, ferric nitrate and 3ml of deionized water, fully stirring for 24h, washing with HCL (0.1mol/L) and deionized water for at least 3 times, and finally preparing a composite material mixed solution with the concentration of 2 mg/ml.
(2) Preparing aerogel: the resulting solution was frozen at-50 ℃ for 4 hours and then vacuum freeze-dried for 48 hours to give an aerogel.
(3) And (3) treating the aerogel: pressing for 15min at 50 ℃ under 5MPa by using a powder tablet press to obtain the BC-PEDOT multi-component composite sheet with the porous structure.
Example 2
(1) Preparing a composite material mixed solution: diluting 10ml (2mg/ml) of bacterial cellulose with 20ml of deionized water, mixing with 1.27mmol of EDOT monomer in an aqueous solution, fully stirring, adding 1.35mmol of aqueous solution prepared from nine water, ferric nitrate and 3ml of deionized water, fully stirring for 24h, washing with HCL (0.1mol/L) and deionized water for at least 3 times, and finally preparing a composite material mixed solution with the concentration of 2 mg/ml.
(2) Preparing aerogel: mixing the solution (1) with DWCNT with different proportion content, stirring, and ultrasonic treating. The resulting solution was frozen at-10 ℃ for 4 hours and then freeze-dried in vacuo for 48 hours to give an aerogel.
(3) And (3) treating the aerogel: pressing with a powder tablet machine at 50MPa and 0 deg.C for 0.1min to obtain the porous BC-PEDOT multi-component composite sheet.
Example 3
(1) Preparing a composite material mixed solution: diluting 10ml (2mg/ml) of bacterial cellulose with 20ml of deionized water, mixing with 1.41mmol of EDOT monomer in an aqueous solution, fully stirring, adding 2.43mmol of aqueous solution prepared from nine water, ferric nitrate and 3ml of deionized water, fully stirring for 36h, respectively using HCL (0.1mol/L) and deionized water for 3 times, and finally preparing a composite material mixed solution with the concentration of 2 mg/ml.
(2) Preparing aerogel: mixing the solution (1) with MWNT with different proportion contents, stirring and carrying out ultrasonic treatment. The resulting solution was frozen at-30 ℃ for 4 hours and then freeze-dried in vacuo for 48 hours to give an aerogel.
(3) And (3) treating the aerogel: pressing for 10min at 50 ℃ under 25MPa by using a powder tablet press to obtain the BC-PEDOT multi-component composite sheet with the porous structure.
Example 4
(1) Preparing a composite material mixed solution: 10ml (2mg/ml) of bacterial cellulose was mixed with PEDOT: PSS (pH1000) in different proportions and stirred well.
(2) Preparing aerogel: the resulting solution was frozen at-50 ℃ for 4 hours and then vacuum freeze-dried for 48 hours to give an aerogel.
(3) And (3) treating the aerogel: pressing for 0.1min at 100 ℃ under 10MPa by using a powder tablet press to obtain the BC-PEDOT/PSS multi-component composite sheet with the porous structure.
Example 5
(1) Preparing a composite material mixed solution: diluting 10ml (2mg/ml) of bacterial cellulose with 20ml of deionized water, mixing the diluted bacterial cellulose with 1.55mmol of EDOT monomer in an aqueous solution, fully stirring, adding 3.51mmol of ferric chloride and 8ml of deionized water to prepare an aqueous solution, fully stirring for 48 hours, respectively using HCL (0.1mol/L) and deionized water for 3 times, and finally preparing a composite material mixed solution with the concentration of 2 mg/ml.
(2) Preparing aerogel: mixing the solution (1) with SWCNT with different proportion contents, stirring and carrying out ultrasonic treatment. The resulting solution was frozen at-30 ℃ for 4 hours and then freeze-dried in vacuo for 48 hours to give an aerogel.
(3) And (3) treating the aerogel: pressing for 0.5min at 100 ℃ under 5MPa by using a powder tablet press to obtain the BC-PEDOT multi-component composite sheet with the porous structure.
Example 6
(1) Preparing a composite material mixed solution: diluting 10ml (2mg/ml) of bacterial cellulose with 20ml of deionized water, mixing with 1.55mmol of EDOT monomer in an aqueous solution, fully stirring, adding 3.51mmol of aqueous solution prepared from nine water, ferric nitrate and 8ml of deionized water, fully stirring for 48h, respectively using HCL (0.1mol/L) and deionized water for 3 times, and finally preparing a composite material mixed solution with the concentration of 2 mg/ml.
(2) Preparing aerogel: and (2) mixing the solution (1) with SWCNT with a certain proportion of content and tellurium nanowires with different proportions of content, stirring and carrying out ultrasonic treatment. The resulting solution was frozen at-50 ℃ for 4 hours and then vacuum freeze-dried for 48 hours to give an aerogel.
(3) And (3) treating the aerogel: pressing for 30min at 50 ℃ under 25MPa by using a powder tablet press to obtain the BC-PEDOT multi-component composite sheet with the porous structure.
Comparative example
(1) Preparing a composite material mixed solution: diluting 10ml (2mg/ml) of bacterial cellulose with 20ml of deionized water, mixing the diluted bacterial cellulose with 1.27mmol of EDOT monomer in an aqueous solution, fully stirring, adding 1.35mmol of aqueous solution prepared from nonahydrate and ferric nitrate and 3ml of deionized water, respectively preparing samples stirred for 24 hours, 39 hours, 42 hours, 45 hours and 48 hours, washing the samples for at least 3 times by using HCL (0.1mol/L) and deionized water, and finally preparing a composite material mixed solution with the concentration of 2 mg/ml.
(2) And (3) carrying out suction filtration on the solution obtained in the step (1) on a nanofiber filter membrane in a vacuum reduced pressure suction filtration mode, and then drying at room temperature to obtain a self-supporting BC-PEDOT composite membrane as a comparison sample.
TABLE 1 film Material Performance parameters
And (4) conclusion: the data of the comparative example and the example 1 are that the BC-PEDOT solution which is prepared simultaneously and reacts for 39 hours is respectively prepared by the aerogel tabletting method and the traditional suction filtration method, and the Seebeck coefficient prepared by the method is higher, the thermal conductivity is lower and the thermoelectric property is more favorable.
Claims (4)
1. A preparation method of a composite aerogel thermoelectric material is characterized by comprising the following steps:
(1) preparing a composite material mixed solution: mixing bacterial cellulose and EDOT monomer according to the mass ratio of 1: (9-11) mixing in the water solution, fully stirring, and adding 1.35-3.51 mmol of Fe3+Fully stirring the aqueous solution for 24-48 h, and washing the aqueous solution by using HCL and deionized water to prepare a composite material mixed solution;
(2) preparing aerogel: mixing the composite material mixed solution prepared in the step (1) with nano conductive fillers with different proportion contents, stirring and carrying out ultrasonic treatment to obtain a solution, freezing the solution at the temperature of-10 to-50 ℃, and then carrying out vacuum freeze drying to obtain aerogel;
(3) and (3) treating the aerogel: and (3) processing the aerogel prepared in the step (2) by using a powder tablet machine to obtain the BC-PEDOT multi-component composite sheet with a porous structure.
2. The method of claim 1, wherein the nanowire filler in step (2) is one or more of single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, tellurium nanowires.
3. The method for preparing a composite aerogel thermoelectric material as claimed in claim 1, wherein the pressure in the step (3) is 5 to 50MPa, the pressurizing time is 0.1 to 30min, and the pressurizing temperature is 0 to 100 ℃.
4. A preparation method of a composite aerogel thermoelectric material is characterized by comprising the following steps:
(1) preparing a composite material mixed solution: mixing a bacterial cellulose solution with a PEDOT (Poly ethylene terephthalate) PSS (Poly ethylene styrene) solution to prepare a composite material mixed solution;
(2) preparing aerogel: mixing the composite material mixed solution prepared in the step (1) with nano conductive fillers with different proportion contents, stirring and carrying out ultrasonic treatment to obtain a solution, freezing the solution at the temperature of-10 to-50 ℃, and then carrying out vacuum freeze drying to obtain aerogel;
(3) and (3) treating the aerogel: treating the aerogel prepared in the step (2) by using a powder tabletting machine to obtain BC-PEDOT with a porous structure: PSS multi-element composite sheet.
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