WO2020220566A1 - Procédé de préparation d'un matériau thermoélectrique à base de liquide polyionique - Google Patents

Procédé de préparation d'un matériau thermoélectrique à base de liquide polyionique Download PDF

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WO2020220566A1
WO2020220566A1 PCT/CN2019/106270 CN2019106270W WO2020220566A1 WO 2020220566 A1 WO2020220566 A1 WO 2020220566A1 CN 2019106270 W CN2019106270 W CN 2019106270W WO 2020220566 A1 WO2020220566 A1 WO 2020220566A1
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polyionic liquid
polyionic
thermoelectric material
based thermoelectric
liquid
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PCT/CN2019/106270
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Chinese (zh)
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张嘉恒
麦成康
王振元
王滨燊
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哈尔滨工业大学（深圳）
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/856—Thermoelectric active materials comprising organic compositions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/857—Thermoelectric active materials comprising compositions changing continuously or discontinuously inside the material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • the invention relates to the field of organic thermoelectric materials, in particular to a method for preparing polyionic liquid-based thermoelectric materials.
  • Thermoelectric materials are functional materials that use the movement of carriers inside a solid to directly realize the mutual conversion between heat and electric energy. It has simple structure, small size and weight. It has the advantages of light weight, no transmission parts, no noise, zero emission, easy control, long service life and high reliability. It is considered to be one of the most promising new energy materials.
  • inorganic semiconductor thermoelectric materials such as Bi 2 Te 3 , PbTe, etc.
  • raw materials are limited, expensive, difficult to process, toxic, and severely pollute the environment, which seriously hinders their industrial application.
  • organic thermoelectric materials are not only rich in resources, low in price, easy to synthesize, easy to process, light in weight, and low in thermal conductivity (usually 0.1- 0.5W ⁇ m -1 ⁇ K -1 or W/(m ⁇ K)), which has important application prospects.
  • the organic thermoelectric materials in the prior art have a low degree of order in the arrangement of polyionic liquids, resulting in the conductivity of organic thermoelectric materials being much lower than that of inorganic materials, resulting in the fact that the thermoelectricity of organic thermoelectric materials is still lower than that of inorganic materials. .
  • the technical problem to be solved by the present invention is to provide a method for preparing polyionic liquid-based thermoelectric materials in view of the above-mentioned defects of the prior art, which aims to solve the problem of the lack of order in the prior art of organic thermoelectric materials due to the arrangement of polyionic liquids. High, resulting in the electrical conductivity of organic thermoelectric materials being much lower than that of inorganic materials, causing the problem that the thermoelectric properties of organic thermoelectric materials are still lower than that of inorganic materials.
  • thermoelectric material a preparation method of polyionic liquid-based thermoelectric material, the specific steps are as follows:
  • step A the structural formula of the polyionic liquid is:
  • step A The preparation method of the polyionic liquid-based thermoelectric material, wherein in step A, the grinding time is 0.5-5h, and the molar ratio of the polyionic liquid to the macromolecular sulfonic acid is 1.5-2.0:1.
  • step A the macromolecular sulfonic acid is camphorsulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfonic acid and/or dinonylnaphthalenesulfonic acid acid.
  • step B The preparation method of the polyionic liquid-based thermoelectric material, wherein, in step B, the phenol solvent is m-cresol, p-cresol, ethyl phenol, 2-chlorophenol and/or 2-fluorophenol.
  • step B The preparation method of the polyionic liquid-based thermoelectric material, wherein, in step B, the stirring time is 1-24h, the stirring speed is 100-1000rpm, and the mass concentration of the polyionic liquid solution is 1wt % ⁇ l0wt%.
  • the nano-carbon material is carbon nanotube, graphene, carbon fiber or C60.
  • the mass concentration of the nano-carbon material in the polyionic liquid solution is 1 wt% to 90 wt%.
  • step C The preparation method of the polyionic liquid-based thermoelectric material, wherein, in step C, the stirring time is 0.5-12h, the stirring speed is 100-1000 rpm; the drying conditions are: 20°C-80 Vacuum drying at °C for 24-120h.
  • a polyionic liquid-based thermoelectric material which is prepared by the method for preparing a polyionic liquid-based thermoelectric material as described above.
  • the present invention dissolves the polyionic liquid doped with sulfonic acid in the phenol solvent, and uses the chemical interaction force between the phenol solvent and the polyionic liquid molecule to influence the conformation of the polyionic liquid molecular chain, and initially improves the molecular chain of the polyionic liquid
  • the degree of order of arrangement through the combination of polyionic liquid and nano-carbon material, the ordered structure of nano-carbon material and the conjugation effect between nano-carbon and polyionic liquid molecules induce the orderly growth of polyionic liquid molecules to further improve
  • the order degree of ionic liquid molecular chain arrangement under the synergistic induction of phenol solvent and nano-carbon material, a highly ordered nano-carbon/polyionic liquid composite material with polyionic liquid molecular chain is obtained, thereby reducing the internal and inter-chain
  • the defect of the ⁇ - ⁇ conjugation effect formed by the disorderly arrangement of the molecular chains provides a high-performance polyionic liquid-based thermoelectric material.
  • the preparation method of the present invention
  • Fig. 1 is a flow chart of a preferred embodiment of the preparation method of the polyionic liquid-based thermoelectric material of the present invention.
  • the present invention provides a method for preparing a polyionic liquid-based thermoelectric material.
  • a polyionic liquid-based thermoelectric material In order to make the objectives, technical solutions and advantages of the present invention clearer and clearer, the present invention will be described in further detail below. It should be understood that the specific embodiments described here are only used to explain the present invention, but not to limit the present invention.
  • FIG. 1 is a flowchart of a preferred embodiment of the preparation method of a polyionic liquid-based thermoelectric material of the present invention, as shown in the figure, which includes the steps:
  • the structural formula of the polyionic liquid in this example is among them,
  • the structure of polyionic liquids contains asymmetric cations and anions. It not only has the high ionic conductivity, thermal stability, tunable solution properties and chemical stability of ionic liquids, but also has some polymer properties (processable , Physical and mechanical properties). Compared with ionic liquids, polyionic liquids have enhanced mechanical stability, improved processing performance, durability and spatial controllability, which promote polyionic liquids to become a new type of functional material.
  • the polyionic liquid in this embodiment consists of pyridine cation and tetraimidazole boron anion.
  • the macromolecular sulfonic acid in this embodiment is camphor sulfonic acid, dodecyl benzene sulfonic acid, p-toluene sulfonic acid and/or dinonyl naphthalene sulfonic acid.
  • the small-molecular inorganic acid will slowly release and corrode other devices during use. At the same time, the conductivity will decrease, and the reaction will be more violent in the high-temperature and humid environment. Therefore, the macro-molecular sulfonic acid is selected in this embodiment.
  • the polymer chain swells and the chain rotates to reduce the binding defects of the ⁇ bond on the skeleton, which enhances the delocalization effect of the polymer chain and enhances the conductivity.
  • the negatively charged sulfonic acid ions on the macromolecular sulfonic acid and the anions on the polyionic liquid undergo a complex decomposition reaction to replace the anions of the polyionic liquid with sulfonate ions, which enhances the hydrophobicity and aromaticity of the polyionic liquid , So that the polyionic liquid can be dissolved in organic solvents such as chloroform and phenols.
  • the molar ratio of the polyionic liquid to the macromolecular sulfonic acid in this embodiment is 1.5 to 2.0:1, and the mixed grinding is to use a grinder to grind for 0.5 to 5 hours, so that the polyionic liquid and the macromolecular sulfonic acid can be fully mixed.
  • phenolic compounds are compounds produced by replacing the hydrogen atoms on the benzene ring in aromatic hydrocarbons with hydroxyl groups, and are hydroxyl-containing derivatives of aromatic hydrocarbons, which can be divided into monohydric phenols and polyhydric phenols according to the number of hydroxyl groups contained in their molecules.
  • the polyionic liquid and the macromolecular sulfonic acid are mixed and ground to enhance the hydrophobicity and aromaticity of the polyionic liquid, thereby increasing the solubility of the polyionic liquid in the phenol solvent.
  • the sulfonic acid-doped polyionic liquid is further dissolved in a phenol solvent, and the hydroxyl group on the phenol solvent forms a hydrogen bond with the polyionic liquid or the ⁇ bond on the phenol solvent forms a ⁇ - ⁇ co-existence with the ⁇ bond on the polyionic liquid.
  • Conjugation uses the chemical interaction force between the phenol solvent and the polyionic liquid molecules to affect the conformation of the polyionic liquid molecular chain, and initially improves the order of the polyionic liquid chain arrangement.
  • the phenol solvent is m-methylphenol, p-methylphenol, ethylphenol, 2-chlorophenol and/or 2-fluorophenol.
  • m-methylphenol is selected as the phenol solvent in this embodiment, and sulfonic acid is mixed After the heteropoly ionic liquid is dissolved in m-cresol, the hydroxyl and benzene ring on the m-cresol form hydrogen bonds and ⁇ - ⁇ conjugation between the m-cresol and the polyionic liquid.
  • the intermolecular between m-cresol and polyionic liquid The chemical interaction force increases the order of the molecular chain arrangement of the polyionic liquid, thereby improving the thermoelectric properties of the polyionic liquid.
  • the stirring time in this embodiment is 8 hours, and the stirring speed is 500 rpm.
  • the concentration of the obtained polyionic liquid solution is 1wt% to 10wt%, so that the sulfonic acid-doped polyionic liquid can be completely dispersed in the phenol solvent, so that the polyionic liquid and the nanocarbon material can be combined in the phenol solvent in the subsequent steps .
  • carbon nanomaterials have unique structures and excellent physical properties, such as ordered structures with large specific surface area and high aspect ratio, light weight, good thermal conductivity, metal or semiconductor properties, good electrical conductivity, and outstanding mechanical properties. Strength etc. Combining polyionic liquid with carbon nanomaterials and introducing carbon nanomaterials into polyionic liquid can comprehensively utilize its superior characteristics.
  • the carbon nano material is carbon nanotube, graphene, carbon fiber or C60.
  • single-walled carbon nanotube is selected in this embodiment.
  • the tetraimidazole boron anion in the polyionic liquid has a strong affinity for the ⁇ electrons on the surface of the single-walled carbon nanotubes, and can form a tetraimidazole boron anion gel with the single-walled carbon nanotubes, which not only improves the conductivity of the polyionic liquid, And it solves the problems of polyionic liquid material with high dielectric constant and easy to be charged with static electricity.
  • the surface of carbon nanomaterials is chemically inert, making it difficult to control the surface.
  • the carbon surface has a surface confinement effect on polyionic liquids.
  • the arrangement guiding effect further improves the order degree of the molecular chain arrangement of the polyionic liquid, thereby improving the thermoelectric performance of the polyionic liquid.
  • the mass percentage of the nanocarbon material added in the embodiment in the polyionic liquid solution is 1 wt% to 90 wt%.
  • the nanocarbon material is added to the polyionic liquid solution and stirred for a period of time, and then a certain amount of the mixed solution is poured on the glass substrate.
  • the present invention also provides a polyionic liquid-based thermoelectric material, which is prepared by the above-mentioned preparation method.
  • the preparation method of the polyionic liquid-based thermoelectric material of the present invention initially improves the order of the molecular chains of the polyionic liquid through the interaction of the phenol solvent and the polyionic liquid molecule, and then combines with the nano-carbon material to induce polymerization by carbon nanotubes.
  • the orderly accumulation of ionic liquid molecules further enhances the order of arrangement of polyionic liquid molecular chains to obtain high-performance polyionic liquid-based thermoelectric materials.
  • the prepared camphorsulfonic acid-doped polyionic liquid powder was added to 6 mL of m-cresol, and stirred at a stirring speed of 500 rpm at room temperature for 8 hours to obtain a polyionic liquid solution. 0.03 mL of the polyionic liquid solution was extracted and poured onto a glass substrate with an area of 20 ⁇ 20 mm 2 , and the solvent was removed by vacuum drying at 60° C. for 48 hours to obtain a polyionic liquid film.
  • the prepared camphorsulfonic acid-doped polyionic liquid powder was added to 6 mL of m-cresol, and stirred at a stirring speed of 500 rpm at room temperature for 8 hours to obtain a polyionic liquid solution.
  • Single-walled carbon nanotubes with a mass of 0.372g were added to the polyionic liquid solution, stirred at room temperature at 500rpm for 2h, and 0.03mL of the solution was also extracted and poured onto a glass substrate with an area of 20 ⁇ 20mm 2 .
  • the solvent was removed by vacuum drying at 60°C for 48 hours to obtain a carbon nanotube/polyionic liquid composite film with a carbon nanotube mass percentage of 64%.
  • the conductivity ⁇ of the prepared polyionic liquid film is 339S/cm
  • the Seebeck coefficient S is 33 ⁇ V/K
  • the thermal conductivity ⁇ is 0.34W/( m ⁇ K)
  • the prepared camphorsulfonic acid-doped polyionic liquid powder was added to 6 mL of m-cresol, and stirred at a stirring speed of 500 rpm at room temperature for 8 hours to obtain a polyionic liquid solution.
  • Single-walled carbon nanotubes with a mass of 2.409g were added to the polyionic liquid solution, stirred at room temperature for 2 hours at a stirring speed of 500rpm, and 0.03mL of the solution was also extracted and poured onto a glass substrate with an area of 20 ⁇ 20mm 2 .
  • the solvent was removed by vacuum drying at 60°C for 48 hours to obtain a carbon nanotube/polyionic liquid composite film with a carbon nanotube mass percentage of 89%.
  • the conductivity meter ⁇ of the prepared polyionic liquid film is 341S/cm
  • the Seebeck measurement system S is 34 ⁇ V/K
  • the thermal conductivity ⁇ is 0.39W. /(m ⁇ K)
  • ZT S 2 ⁇ T/ ⁇
  • the ZT value of the prepared polyionic liquid film at 300K is 0.030.
  • the conductivity ⁇ of the prepared polyionic liquid block is 70S/cm
  • the Seebeck coefficient S is 15 ⁇ V/K
  • the thermal conductivity ⁇ is 0.3W/ (m ⁇ K)
  • ZT S 2 ⁇ T/ ⁇
  • the ZT value of the prepared polyionic liquid block at 300K is 0.002.
  • the conductivity ⁇ of the prepared polyionic liquid block is 90S/cm
  • the Seebeck coefficient S is 35 ⁇ V/K
  • the thermal conductivity ⁇ is 0.6W/ (m ⁇ K)
  • ZT S 2 ⁇ T/ ⁇
  • the ZT value of the prepared polyionic liquid block at 300K is 0.006.
  • Single-walled carbon nanotubes with a mass of 1.767g were added to the above polyionic liquid solution (the content of polyionic liquid was 0.093g), and the stirring speed was 500rpm at room temperature for 1 hour; then 1mL of the polyionic liquid solution was taken first Dry naturally at room temperature in a fume hood to remove most of the solvent, and then put it in a vacuum drying oven at 60°C for 72 hours to obtain a single-walled carbon nanotube/polyionic liquid with a carbon nanotube content of 89% by mass Composite block.
  • the conductivity ⁇ of the prepared polyionic liquid block is 390S/cm
  • the Seebeck coefficient S is 57 ⁇ V/K
  • thermoelectric performance index comparison table of the polyionic liquid-based thermoelectric materials prepared in Examples 1-6 is shown in Table 1:
  • the conductivity ⁇ of the pure polyionic liquid is 1*10 -4 S/cm
  • the Seebeck coefficient S is about 20 ⁇ V/K
  • the ZT value of the pure polyionic liquid at 300K is 0.6*10 -8
  • the above table 1 is the polyionic liquid prepared in Example 1-6
  • the conductivity ⁇ and ZT value of the polyionic liquid-based thin film thermoelectric material prepared by adding a certain proportion of carbon nanotubes to the polyionic liquid doped with sulfonic acid have improved, and the carbon nanotubes
  • the electrical conductivity ⁇ and ZT value of the polyionic liquid film thermoelectric material with a mass content of 89% and the polyionic liquid-based film thermoelectric material with a carbon nanotube mass content of 64% are basically the same.
  • the conductivity, Seebeck coefficient and ZT value of the polyionic liquid-based bulk thermoelectric material prepared by adding a certain proportion of carbon nanotubes to the polyionic liquid doped with sulfonic acid have improved.
  • the conductivity and ZT value of the polyionic liquid-based bulk thermoelectric material with a carbon nanotube mass content of 89% are significantly higher than those of the polyionic liquid-based bulk thermoelectric material with a carbon nanotube mass content of 64%.
  • the present invention discloses a preparation method of polyionic liquid-based thermoelectric material.
  • the preparation method includes mixing and grinding polyionic liquid with macromolecular sulfonic acid to obtain a polyionic liquid doped with sulfonic acid;
  • the acid-doped polyionic liquid is dissolved in a phenol solvent and stirred to obtain a polyionic liquid solution; then the nanocarbon material is added to the polyionic liquid solution, stirred and dried to obtain a polyionic liquid-based thermoelectric material.
  • the order of arrangement of the molecular chains of the polyionic liquid is initially improved through the interaction of the phenol solvent and the polyionic liquid molecules, and then the orderly accumulation of the polyionic liquid molecules is achieved through the induction of carbon nanotubes by compounding with the nano-carbon material, and further Enhancing the order of arrangement of polyionic liquid molecular chains to obtain high-performance polyionic liquid-based thermoelectric materials.

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Abstract

L'invention concerne un procédé de préparation d'un matériau thermoélectrique à base de liquide polyionique, comprenant : le mélange et le broyage d'un liquide polyionique et d'acide sulfonique macromoléculaire pour obtenir un liquide polyionique dopé à l'acide sulfonique ; la dissolution du liquide polyionique dopé à l'acide sulfonique dans un solvant phénol et l'agitation de la solution mélangée pour obtenir une solution de liquide polyionique ; et l'ajout d'un matériau nanocarboné à la solution de liquide polyionique, l'agitation et le séchage du mélange pour obtenir le matériau thermoélectrique à base de liquide polyionique. Le procédé augmente le degré d'orientation des chaînes moléculaires du liquide polyionique au moyen de l'interaction du solvant phénol et des molécules de liquide polyionique, puis, par combinaison avec le matériau nanocarboné, réalise l'accumulation ordonnée des molécules de liquide polyionique au moyen de l'induction des nanotubes de carbone, et améliore encore le degré d'orientation des chaînes moléculaires du liquide polyionique pour obtenir le matériau thermoélectrique à base de liquide polyionique à hautes performances.
PCT/CN2019/106270 2019-04-29 2019-09-17 Procédé de préparation d'un matériau thermoélectrique à base de liquide polyionique WO2020220566A1 (fr)

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CN110197869B (zh) * 2019-04-29 2021-11-09 哈尔滨工业大学（深圳） 一种聚离子液体基热电材料的制备方法
CN113594346B (zh) * 2021-06-30 2023-11-17 南方科技大学 一种有机热电薄膜及其制备方法

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