CN113140666A - Composite thermoelectric material and preparation method thereof - Google Patents
Composite thermoelectric material and preparation method thereof Download PDFInfo
- Publication number
- CN113140666A CN113140666A CN202110341431.4A CN202110341431A CN113140666A CN 113140666 A CN113140666 A CN 113140666A CN 202110341431 A CN202110341431 A CN 202110341431A CN 113140666 A CN113140666 A CN 113140666A
- Authority
- CN
- China
- Prior art keywords
- acid
- solution
- thermoelectric material
- doped
- metal complex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 196
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 38
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 239000002109 single walled nanotube Substances 0.000 claims abstract description 30
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 14
- 230000000536 complexating effect Effects 0.000 claims abstract description 6
- 230000003993 interaction Effects 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 54
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 claims description 17
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000007800 oxidant agent Substances 0.000 claims description 16
- 230000001590 oxidative effect Effects 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- -1 transition metal salt Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 description 13
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- MIOPJNTWMNEORI-XVKPBYJWSA-N (R)-camphorsulfonic acid Chemical compound C1C[C@]2(CS(O)(=O)=O)C(=O)C[C@H]1C2(C)C MIOPJNTWMNEORI-XVKPBYJWSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003384 small molecules Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Classifications
-
- 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
- H10N10/01—Manufacture or treatment
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to a composite thermoelectric material and a preparation method thereof, wherein the composite thermoelectric material comprises a metal complex of an acid-doped aniline polymer and a single-walled carbon nanotube, the single-walled carbon nanotube is combined with the metal complex of the acid-doped aniline polymer through weak interaction force, and the metal complex of the acid-doped aniline polymer is obtained by coordination complexing the acid-doped aniline polymer and transition metal ions. The composite material based on the invention has excellent thermoelectric performance.
Description
Technical Field
The invention belongs to the technical field of thermoelectric materials, and particularly relates to a composite thermoelectric material and a preparation method thereof.
Background
The thermoelectric material can directly convert waste heat into electric energy, and becomes one of effective schemes for dealing with energy crisis and environmental deterioration in the world at present, most of researches are concentrated on inorganic thermoelectric materials at present, and the application of the inorganic thermoelectric materials is limited due to the problems of high cost, complex manufacturing process, heavy metal pollution and the like. In contrast, organic thermoelectric materials have the advantages of low cost, good flexibility, abundant raw material resources, and the like, and thus become the main focus of research. Among conductive polymers, Polyaniline (PANI) is considered as one of the most promising thermoelectric materials, and has better conductivity, diversified structures, unique doping mechanism, excellent physical properties and good environmental stability, so that the polyaniline becomes the key point for conductive polymer research, but the thermoelectric properties of the polyaniline still need to be improved.
Disclosure of Invention
The technical problem solved by the invention is as follows: provides a composite thermoelectric material and a preparation method thereof, which are used for solving the problems of low conductivity and low Seebeck coefficient of a conductive polymer taking polyaniline as a main component in the prior art. The composite material of the present invention comprises a metal complex of an acid-doped aniline multimer and a single-walled carbon nanotube, and has excellent thermoelectric properties compared to polyaniline.
The specific solution provided by the invention is as follows:
the invention provides a composite thermoelectric material which comprises a metal complex of an acid-doped aniline polymer and a single-wall carbon nanotube, wherein the single-wall carbon nanotube is combined with the metal complex of the acid-doped aniline polymer through weak interaction force, and the metal complex of the acid-doped aniline polymer is obtained by coordination complexing the acid-doped aniline polymer and transition metal ions.
Based on the technical scheme of the invention, the aniline polymer is a small molecule, has more advantages than polyaniline in molecular expansibility and self-assembly capability, and particularly has greatly improved conductivity and thermoelectric property after being complexed with transition metal ions; the single-walled carbon nanotube has good thermal stability, good electrical property and mechanical property, and can greatly improve the conductivity and the processability of the polymer under small load capacity. Therefore, the composite material with excellent thermoelectric performance can be obtained by compounding the single-walled carbon nanotube and the metal organic complex obtained by coordinating the acid-doped aniline polymer with the transition metal ions.
Specifically, the single-walled carbon nanotube and the metal complex of the acid-doped aniline polymer have weak acting forces such as pi-pi, hydrogen bonds and the like.
Further, the transition metal ion is selected from Cu2+、Ag+、Fe3+、Co2+、Mn2+、Ni2+Any one of them.
Specifically, the transition metal ion is Ag+Then, the metal complex of the acid-doped aniline polymer is obtained by carrying out coordination complexing on the acid-doped aniline polymer and transition metal ions according to the ratio of 2:1, wherein the transition metal ions are Cu2+、Co2+、Mn2+、Ni2+Then, the metal complex of the doped aniline polymer is obtained by carrying out coordination complexing on the acid doped aniline polymer and transition metal ions according to the ratio of 4:1, wherein the transition metal ions are Fe3+When the metal complex of the doped aniline polymer is obtained by carrying out coordination complexing on the acid-doped aniline polymer and transition metal ions according to the ratio of 6: 1.
The aniline tetramer is used as a matrix, and is subjected to targeted design with proper metal ions, so that the Fermi level, band gap, state density and the like of the composite material can be changed, and the charge transmission performance of the aniline multimer can be regulated.
Further, the mass ratio of the metal complex of the acid-doped aniline polymer to the single-wall multi-carbon nano tube is (1-9) to (1-9).
Further, the composite thermoelectric material is obtained by assembling the metal complex of the acid-doped aniline polymer and the single-walled carbon nanotube in an organic solvent, wherein the organic solvent is selected from N, N-Dimethylformamide (DMF) and methanol (CH)4O), chlorobenzene (C)6H5Cl) and dimethyl sulfoxide (DMSO), or a mixture of more than one of them.
The preparation method has the advantages of simple process, high efficiency and low cost, and can realize industrial mass production, and the prepared metal complex/single-walled carbon nanotube composite material of the acid-doped aniline polymer has good thermoelectric property, no pollution and no toxicity, and has wide application prospects in the fields of thermoelectric power generation, thermoelectric refrigeration, flexible thermoelectric power generation and the like.
Further, the metal complex of the acid-doped aniline multimer is a metal complex of an acid-doped aniline tetramer, and the preparation method of the composite thermoelectric material comprises the following steps:
s1, carrying out acid doping on the aniline tetramer to obtain the acid-doped aniline tetramer, and then dissolving the acid-doped aniline tetramer in the organic solvent to obtain a solution A; dispersing the single-walled carbon nanotube in the organic solvent to obtain a dispersion liquid B; dissolving a transition metal salt in the organic solvent to obtain a solution C;
s2, mixing the solution C with the solution A to obtain a solution of the metal complex of the acid-doped aniline tetramer;
and S3, mixing the solution of the metal complex of the acid-doped aniline tetramer with the dispersion liquid B, stirring for 1-6h, and carrying out solid-liquid separation to obtain the composite thermoelectric material of the metal complex of the acid-doped aniline tetramer and the single-walled carbon nanotube.
The invention takes aniline tetramer as a matrix, improves the conductivity of the polyaniline tetramer by acid doping, then carries out targeted design on the polyaniline tetramer and proper metal ions, and regulates and controls the charge transmission performance of the polyaniline multimer by changing the Fermi level, band gap, state density and the like of a composite material; the scheme adopts micromolecular aniline tetramer, which has more advantages than polyaniline in molecular expansibility and self-assembly capability, and particularly after the polyaniline tetramer is complexed with transition metal ions, the conductivity and the thermoelectric property of the polyaniline tetramer are greatly improved; the carbon nano tube has research value in the aspects of mechanical property, thermoelectric property and the like, and after the carbon nano tube is mixed with the acid-doped aniline polymer, the single-walled carbon nano tube and the metal complex of the acid-doped aniline polymer are assembled through weak interaction forces of pi-pi, hydrogen bonds and the like to obtain the composite thermoelectric material.
Can obviously improve the thermoelectric property of the material.
Specifically, the upper limit of the concentration of the transition metal salt is determined by its solubility in the organic solvent.
Preferably, the concentration of the acid-doped aniline tetramer in the solution A is 0.001-1mol/L, and the concentration of the transition metal salt in the solution C is 0.001-1 mol/L.
Further, the process for preparing the acid-doped aniline tetramer by acid-doping the aniline tetramer in the S1 comprises the following steps:
and dispersing the aniline tetramer into 0.5-2mol/L protonic acid solution, stirring for 1-6h, then carrying out solid-liquid separation, and alternately washing the solid with ethanol and water respectively to obtain the acid-doped aniline tetramer.
Thus, in the protonic acid solution, the protonic acid is carried out in the aniline tetramer skeleton in the form of a dopant, so that the conductivity of the material is improved.
Further, the protonic acid in S11 is selected from any one of hydrochloric acid, camphorsulfonic acid, perchloric acid, and p-toluenesulfonic acid.
Further, the aniline tetramer is prepared by the following steps:
s01, fully dispersing N-phenyl-1, 4-phenylenediamine in a hydrochloric acid solution to obtain a suspension of N-phenyl-1, 4-phenylenediamine, dropwise adding an oxidant solution into the suspension, and reacting in an ice bath for 4-8 hours, wherein the concentration of hydrochloric acid in the hydrochloric acid solution is 0.05-0.2mol/L, the oxidant is selected from any one of ammonium persulfate and ferric chloride or a mixture of the two in any proportion, and the quantity ratio of the oxidant to the N-phenyl-1, 4-phenylenediamine is 1-1.5: 1;
and S02, carrying out solid-liquid separation on the reaction solution to obtain an acid-doped aniline tetramer, and washing the acid-doped aniline tetramer with a hydrochloric acid solution, an alkali solution and ethanol and water alternately to obtain the aniline tetramer.
Firstly, polymerizing N-phenyl-1, 4-phenylenediamine in a hydrochloric acid solution under the condition of excessive oxidant to generate an aniline tetramer containing impurities, then removing impurities by the hydrochloric acid solution, cleaning by an alkali solution to remove impurities, and finally washing by ethanol and water alternately to obtain the undoped aniline tetramer with higher purity.
Further, in step S01, under a stirring condition, dropwise adding the oxidant solution to the suspension at a speed of 1-2 drops/S, wherein the temperature of the ice bath is 0-5 ℃, the hydrochloric acid solution and the oxidant solution respectively contain acetone, the volume fraction of acetone in the hydrochloric acid solution is 20-50%, the volume fraction of acetone in the oxidant solution is 20-50%, in step S01, the concentration of the oxidant in the reaction solution is 0.048-0.06 mol/L, and the concentration of N-phenyl-1, 4-phenylenediamine is 0.048-0.06 mol/L.
The speed of the reaction can be controlled by controlling the speed of adding the oxidant, the temperature of the ice bath and the concentration of the materials, so that the phenomenon that the viscosity of the reaction solution is too high due to too violent reaction is avoided, and the acetone is added to prevent the reaction solution from being excessively adhered to influence the yield and the purity of the aniline tetramer.
Preferably, in step S02, the concentration of hydrochloric acid in the hydrochloric acid solution is 0.05 to 0.2mol/L, and the alkali solution is 0.05 to 2mol/L of an ammonia solution.
The invention also provides the application of the composite thermoelectric material or the composite thermoelectric material prepared by the preparation method of the composite thermoelectric material, which is used for preparing a film with thermoelectric conversion performance.
Specifically, the film is obtained by tabletting the composite material through a die.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, and is not to be construed as limiting the invention.
Example 1
0.024mol of ammonium persulfate was dissolved in a mixed solvent of 25mL of 0.1mol/L dilute hydrochloric acid and 25mL of acetone, and then 0.024mol of N-phenyl-1, 4-phenylenediamine was magnetically suspended with stirring in a mixed solvent of 250mL of 1mol/L hydrochloric acid and 200mL of acetone. The ammonium persulfate solution is dropwise added into the suspension of the N-phenyl-1, 4-phenylenediamine, and the reaction is stirred in an ice bath for 4 hours. Then, the suspension is filtered under vacuum, and the precipitate is washed with 0.1mol/L dilute hydrochloric acid and repeated 2-3 times. Next, the precipitate was stirred with 0.1mol/L of 200mL ammonia water for 12h to dedoping, filtered, and then dried under vacuum at 50 ℃. Adding 4mg of aniline tetramer into 50ml of 1mol/L camphorsulfonic acid solution, stirring for 4 hours, then washing with a large amount of ethanol and deionized water, drying and collecting to obtain dark green acid-doped aniline tetramer. Weighing silver nitrate solid and acid-doped aniline tetramer with a molar ratio of 1:2, respectively dissolving the silver nitrate solid and the acid-doped aniline tetramer in N, N-dimethylformamide according to 1mol/L and 0.1mol/L, then adding a silver nitrate solution into the acid-doped aniline tetramer solution by using an injector, and stirring for 6 hours to obtain a metal complex solution of the acid-doped aniline tetramer. And then weighing the single-walled carbon nanotube according to the weight ratio of the single-walled carbon nanotube to the acid-doped aniline tetramer metal complex of 4:1, dissolving the single-walled carbon nanotube in the N, N-dimethylformamide solution, stirring for 6 hours, performing suction filtration and drying to obtain a powder sample, and finally performing tabletting to obtain the composite membrane.
Through testing, the electrical conductivity of the composite thermoelectric material prepared in the experimental example is 360.5Scm-1The seebeck coefficient is 56.9 mu VK-1PF of 116.7. mu. Wm-1K-2。
Example 2
0.03mol of ammonium persulfate is dissolved in 25mL of a mixed solvent of 0.1mol/L dilute hydrochloric acid and 25mL of acetone, and then 0.03mol of N-phenyl-1, 4-phenylenediamine is magnetically suspended in 250mL of a mixed solvent of 1mol/L hydrochloric acid and 200mL of acetone. The ammonium persulfate solution is dropwise added into the suspension of the N-phenyl-1, 4-phenylenediamine, and the reaction is stirred in an ice bath for 6 hours. Then, the suspension is filtered under vacuum, and the precipitate is washed with 0.1mol/L dilute hydrochloric acid and repeated 2-3 times. Next, the precipitate was stirred with 0.1mol/L of 200mL ammonia water for 12h to dedoping, filtered, and then dried under vacuum at 50 ℃. Adding 4mg of aniline tetramer into 50ml of 1mol/L hydrochloric acid solution, stirring for 4 hours, then washing with a large amount of ethanol and deionized water, drying and collecting to obtain dark green acid-doped aniline tetramer. Weighing copper chloride solid and acid-doped aniline tetramer with a molar ratio of 1:4, respectively dissolving the copper chloride solid and the acid-doped aniline tetramer in methanol according to 1mol/L and 0.1mol/L, then adding the copper chloride solution into the acid-doped aniline tetramer by using an injector, and stirring for 6 hours to obtain a metal complex solution of the acid-doped aniline tetramer. And then weighing the single-walled carbon nanotube according to the weight ratio of 3:2 of the metal complex of the single-walled carbon nanotube and the acid-doped aniline tetramer, dissolving the single-walled carbon nanotube in a methanol solution, stirring for 6 hours, performing suction filtration and drying to obtain a powder sample, and finally performing tabletting to obtain the composite membrane.
Through testing, the electrical conductivity of the composite thermoelectric material prepared in the experimental example is 298.7Scm-1The seebeck coefficient is 51.7 mu VK-1PF of 79.8. mu. Wm-1K-2。
Example 3
0.024mol of iron (III) chloride was dissolved in 25mL of a mixed solvent of 0.1mol/L dilute hydrochloric acid and 25mL of acetone, and then 0.024mol of N-phenyl-1, 4-phenylenediamine was magnetically suspended with stirring in 250mL of a mixed solvent of 1mol/L hydrochloric acid and 200mL of acetone. The ammonium persulfate solution is dropwise added into the suspension of the N-phenyl-1, 4-phenylenediamine, and the reaction is stirred in an ice bath for 8 hours. Then, the suspension is filtered under vacuum, and the precipitate is washed with 0.1mol/L dilute hydrochloric acid and repeated 2-3 times. Next, the precipitate was stirred with 0.1mol/L of 200mL ammonia water for 12h to dedoping, filtered, and then dried under vacuum at 50 ℃. Adding 4mg of aniline tetramer into 50ml of 1mol/L perchloric acid solution, stirring for 4 hours, then washing with a large amount of ethanol and deionized water, drying and collecting to obtain dark green acid-doped aniline tetramer. Weighing silver nitrate solid and acid-doped aniline tetramer with a molar ratio of 1:2, respectively dissolving the silver nitrate solid and the acid-doped aniline tetramer in chlorobenzene according to a molar ratio of 1mol/L and 0.1mol/L, then adding the silver nitrate solution into the acid-doped aniline tetramer by using an injector, and stirring for 6 hours to obtain a metal complex solution of the acid-doped aniline tetramer. And then weighing the single-walled carbon nanotube according to the weight ratio of the single-walled carbon nanotube to the metal complex of the acid-doped aniline tetramer of 1:1, dissolving the single-walled carbon nanotube in chlorobenzene solution, stirring for 6 hours, performing suction filtration and drying to obtain a powder sample, and finally performing tabletting to obtain the composite membrane.
Through testing, the electrical conductivity of the composite thermoelectric material prepared in the experimental example is 284.1Scm-1The seebeck coefficient is 47.3 mu VK-1PF of 63.6. mu. Wm-1K-2。
Example 4
0.024mol of iron (III) chloride was dissolved in 25mL of a mixed solvent of 0.1mol/L dilute hydrochloric acid and 25mL of acetone, and then 0.024mol of N-phenyl-1, 4-phenylenediamine was magnetically suspended with stirring in 250mL of a mixed solvent of 1mol/L hydrochloric acid and 200mL of acetone. The ammonium persulfate solution is dropwise added into the suspension of the N-phenyl-1, 4-phenylenediamine, and the reaction is stirred in an ice bath for 4 hours. Then, the suspension is filtered under vacuum, and the precipitate is washed with 0.1mol/L dilute hydrochloric acid and repeated 2-3 times. Next, the precipitate was stirred with 0.1mol/L of 200mL ammonia water for 12h to dedoping, filtered, and then dried under vacuum at 50 ℃. Adding 4mg of aniline tetramer into 50ml of 1mol/L camphorsulfonic acid solution, stirring for 4 hours, then washing with a large amount of ethanol and deionized water, drying and collecting to obtain dark green acid-doped aniline tetramer. Weighing copper chloride solid and acid-doped aniline tetramer with a molar ratio of 1:4, respectively dissolving the copper chloride solid and the acid-doped aniline tetramer in dimethyl sulfoxide according to a ratio of 1mol/L and 0.1mol/L, then adding the copper chloride solution into the acid-doped aniline tetramer by using an injector, and stirring for 6 hours to obtain a metal complex solution of the acid-doped aniline tetramer. And then weighing the single-walled carbon nanotube according to the weight ratio of the single-walled carbon nanotube to the metal complex of the acid-doped aniline tetramer of 2:3, dissolving the single-walled carbon nanotube in dimethyl sulfoxide solution, stirring for 6 hours, performing suction filtration and drying to obtain a powder sample, and finally performing tabletting to obtain the composite membrane.
Through testing, the electrical conductivity of the composite thermoelectric material prepared in the experimental example is 273Scm-1The seebeck coefficient is 45.2 mu VK-1PF is 55.8. mu. Wm-1K-2And has excellent thermoelectric performance and charge transport performance.
Although embodiments of the present invention have been described in detail above, those of ordinary skill in the art will understand that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (10)
1. A composite thermoelectric material is characterized by comprising a metal complex of an acid-doped aniline polymer and a single-wall carbon nanotube, wherein the single-wall carbon nanotube is combined with the metal complex of the acid-doped aniline polymer through weak interaction force, and the metal complex of the acid-doped aniline polymer is obtained by coordination complexing the acid-doped aniline polymer with a transition metal ion.
2. The composite thermoelectric material of claim 1, wherein the transition metal ions are selected from Cu2+、Ag+、Fe3+、Co2+、Mn2+、Ni2+Any one of them.
3. The composite thermoelectric material of claim 1, wherein the mass ratio of the metal complex of the acid-doped aniline polymer to the single-wall multi-carbon nanotubes is (1-9): (1-9).
4. A method for preparing a composite thermoelectric material as claimed in any one of claims 1 to 3, wherein the composite thermoelectric material is prepared by assembling a metal complex of an acid-doped aniline polymer and single-walled carbon nanotubes in an organic solvent selected from one or more of N, N-dimethylformamide, methanol, chlorobenzene and dimethylsulfoxide.
5. The method of producing a composite thermoelectric material according to claim 4, wherein the metal complex of the acid-doped aniline polymer is a metal complex of an acid-doped aniline tetramer, and the method of producing the composite thermoelectric material comprises the steps of:
s1, carrying out acid doping on the aniline tetramer to obtain the acid-doped aniline tetramer, and then dissolving the acid-doped aniline tetramer in the organic solvent to obtain a solution A; dispersing the single-walled carbon nanotube in the organic solvent to obtain a dispersion liquid B; dissolving a transition metal salt in the organic solvent to obtain a solution C;
s2, mixing the solution C with the solution A to obtain a solution of the metal complex of the acid-doped aniline tetramer;
and S3, mixing the solution of the metal complex of the acid-doped aniline tetramer with the dispersion liquid B, stirring for 1-6h, and carrying out solid-liquid separation to obtain the composite thermoelectric material of the metal complex of the acid-doped aniline tetramer and the single-walled carbon nanotube.
6. The method for preparing the composite thermoelectric material according to claim 5, wherein the step of preparing the acid-doped aniline tetramer by acid-doping the aniline tetramer in S1 comprises the following steps:
and dispersing the aniline tetramer into 0.5-2mol/L protonic acid solution, stirring for 1-6h, then carrying out solid-liquid separation, and alternately washing the solid with ethanol and water respectively to obtain the acid-doped aniline tetramer.
7. The method for producing a composite thermoelectric material according to claim 6, wherein the protonic acid is any one selected from hydrochloric acid, camphorsulfonic acid, perchloric acid, and p-toluenesulfonic acid.
8. The method for preparing a composite thermoelectric material according to claim 5, wherein the aniline tetramer is prepared by a process comprising the steps of:
s01, fully dispersing N-phenyl-1, 4-phenylenediamine in a hydrochloric acid solution to obtain a suspension of N-phenyl-1, 4-phenylenediamine, dropwise adding an oxidant solution into the suspension, and reacting the reaction solution in an ice bath for 4-8 hours, wherein the concentration of hydrochloric acid in the hydrochloric acid solution is 0.05-0.2mol/L, the oxidant is selected from any one of ammonium persulfate and ferric chloride or a mixture of the two in any proportion, and the quantity ratio of the oxidant to the N-phenyl-1, 4-phenylenediamine is 1-1.5: 1;
and S02, carrying out solid-liquid separation on the reaction solution to obtain an acid-doped aniline tetramer, and washing the acid-doped aniline tetramer with a hydrochloric acid solution, an alkali solution and ethanol and water alternately to obtain the aniline tetramer.
9. The method for preparing the composite thermoelectric material according to claim 8, wherein in step S01, the oxidant solution is added dropwise to the suspension at a rate of 1-2 drops/S under stirring, the ice bath temperature is 0-5 ℃, the hydrochloric acid solution and the oxidant solution respectively contain acetone, the volume fraction of acetone in the hydrochloric acid solution is 20-50%, the volume fraction of acetone in the oxidant solution is 20-50%, the concentration of the oxidant in the reaction solution is 0.048-0.06 mol/L in S01, and the concentration of N-phenyl-1, 4-phenylenediamine is 0.048-0.06 mol/L.
10. Use of a composite thermoelectric material according to any of claims 1 to 3 for the preparation of films having thermoelectric conversion properties.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110341431.4A CN113140666B (en) | 2021-03-30 | 2021-03-30 | Composite thermoelectric material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110341431.4A CN113140666B (en) | 2021-03-30 | 2021-03-30 | Composite thermoelectric material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113140666A true CN113140666A (en) | 2021-07-20 |
| CN113140666B CN113140666B (en) | 2023-09-26 |
Family
ID=76811643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110341431.4A Active CN113140666B (en) | 2021-03-30 | 2021-03-30 | Composite thermoelectric material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113140666B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114231027A (en) * | 2021-12-10 | 2022-03-25 | 武汉工程大学 | Phytic acid doped polyaniline and single-walled carbon nanotube composite film and preparation method and application thereof |
Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6977050B1 (en) * | 2003-04-07 | 2005-12-20 | Polyone Corporation | Synthesis of lignosulfonic acid-doped polyaniline using transition metal ion catalysts |
| CN101235199A (en) * | 2007-12-26 | 2008-08-06 | 华东理工大学 | Method for preparing carbon nano-tube modified polyaniline nano fiber composite material |
| US20100319745A1 (en) * | 2009-06-19 | 2010-12-23 | Tsinghua University | Method of using thermoelectric device |
| WO2011056903A1 (en) * | 2009-11-03 | 2011-05-12 | Henry Tran | Compositions and methods for generating conductive films and coatings of oligomers |
| JP2013089798A (en) * | 2011-10-19 | 2013-05-13 | Fujifilm Corp | Thermoelectric transducer |
| CN103137848A (en) * | 2013-02-06 | 2013-06-05 | 中国科学院上海硅酸盐研究所 | Method for obtaining high-performance polyaniline base thermoelectric materials |
| KR20130137364A (en) * | 2012-06-07 | 2013-12-17 | 롯데케미칼 주식회사 | The mass production method of 1-d intrinsic conducting polymer nanomaterial with high heat stability |
| US20140065402A1 (en) * | 2012-09-02 | 2014-03-06 | Technion Research And Development Foundation Ltd. | Hybrid pani/carbon nano-composites for production of thin, transparent and conductive films |
| CN103866423A (en) * | 2014-03-06 | 2014-06-18 | 西安交通大学 | Preparation method of aniline tetramer nanowires with super capacitive performance |
| WO2014119468A1 (en) * | 2013-01-29 | 2014-08-07 | 富士フイルム株式会社 | Thermoelectric conversion material, thermoelectric conversion element, article for thermoelectric power generation using thermoelectric conversion element, and power supply for sensors using thermoelectric conversion element |
| WO2015005340A1 (en) * | 2013-07-08 | 2015-01-15 | 富士フイルム株式会社 | Thermoelectric conversion material, thermoelectric conversion element, and thermoelectricity-generating article and sensor-use power source in which same is used |
| CN105103316A (en) * | 2013-03-29 | 2015-11-25 | 富士胶片株式会社 | Thermoelectric conversion material, thermoelectric conversion element, thermoelectric power generation article, and sensor power source |
| CN106519666A (en) * | 2016-10-10 | 2017-03-22 | 湖北大学 | Taurine secondary doping polyaniline and preparation method thereof |
| CN109705574A (en) * | 2018-12-21 | 2019-05-03 | 武汉工程大学 | The preparation method of organic composite material film and the method for improving its thermoelectricity capability |
| CN110379915A (en) * | 2018-04-13 | 2019-10-25 | 中国科学院上海硅酸盐研究所 | A kind of metal halide phthalocyanine complex thermoelectric material and preparation method thereof |
| CN110832651A (en) * | 2017-07-18 | 2020-02-21 | 国立研究开发法人物质·材料研究机构 | Thermoelectric material, thermoelectric conversion module using same, method for manufacturing thermoelectric conversion module, and peltier element |
| US20200411743A1 (en) * | 2018-09-19 | 2020-12-31 | Council Of Scientific And Industrial Research | Thermoelectric Materials And Process For The Preparation Thereof |
-
2021
- 2021-03-30 CN CN202110341431.4A patent/CN113140666B/en active Active
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6977050B1 (en) * | 2003-04-07 | 2005-12-20 | Polyone Corporation | Synthesis of lignosulfonic acid-doped polyaniline using transition metal ion catalysts |
| CN101235199A (en) * | 2007-12-26 | 2008-08-06 | 华东理工大学 | Method for preparing carbon nano-tube modified polyaniline nano fiber composite material |
| US20100319745A1 (en) * | 2009-06-19 | 2010-12-23 | Tsinghua University | Method of using thermoelectric device |
| WO2011056903A1 (en) * | 2009-11-03 | 2011-05-12 | Henry Tran | Compositions and methods for generating conductive films and coatings of oligomers |
| JP2013089798A (en) * | 2011-10-19 | 2013-05-13 | Fujifilm Corp | Thermoelectric transducer |
| KR20130137364A (en) * | 2012-06-07 | 2013-12-17 | 롯데케미칼 주식회사 | The mass production method of 1-d intrinsic conducting polymer nanomaterial with high heat stability |
| US20140065402A1 (en) * | 2012-09-02 | 2014-03-06 | Technion Research And Development Foundation Ltd. | Hybrid pani/carbon nano-composites for production of thin, transparent and conductive films |
| WO2014119468A1 (en) * | 2013-01-29 | 2014-08-07 | 富士フイルム株式会社 | Thermoelectric conversion material, thermoelectric conversion element, article for thermoelectric power generation using thermoelectric conversion element, and power supply for sensors using thermoelectric conversion element |
| CN103137848A (en) * | 2013-02-06 | 2013-06-05 | 中国科学院上海硅酸盐研究所 | Method for obtaining high-performance polyaniline base thermoelectric materials |
| CN105103316A (en) * | 2013-03-29 | 2015-11-25 | 富士胶片株式会社 | Thermoelectric conversion material, thermoelectric conversion element, thermoelectric power generation article, and sensor power source |
| WO2015005340A1 (en) * | 2013-07-08 | 2015-01-15 | 富士フイルム株式会社 | Thermoelectric conversion material, thermoelectric conversion element, and thermoelectricity-generating article and sensor-use power source in which same is used |
| CN103866423A (en) * | 2014-03-06 | 2014-06-18 | 西安交通大学 | Preparation method of aniline tetramer nanowires with super capacitive performance |
| CN106519666A (en) * | 2016-10-10 | 2017-03-22 | 湖北大学 | Taurine secondary doping polyaniline and preparation method thereof |
| CN110832651A (en) * | 2017-07-18 | 2020-02-21 | 国立研究开发法人物质·材料研究机构 | Thermoelectric material, thermoelectric conversion module using same, method for manufacturing thermoelectric conversion module, and peltier element |
| CN110379915A (en) * | 2018-04-13 | 2019-10-25 | 中国科学院上海硅酸盐研究所 | A kind of metal halide phthalocyanine complex thermoelectric material and preparation method thereof |
| US20200411743A1 (en) * | 2018-09-19 | 2020-12-31 | Council Of Scientific And Industrial Research | Thermoelectric Materials And Process For The Preparation Thereof |
| CN109705574A (en) * | 2018-12-21 | 2019-05-03 | 武汉工程大学 | The preparation method of organic composite material film and the method for improving its thermoelectricity capability |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114231027A (en) * | 2021-12-10 | 2022-03-25 | 武汉工程大学 | Phytic acid doped polyaniline and single-walled carbon nanotube composite film and preparation method and application thereof |
| CN114231027B (en) * | 2021-12-10 | 2024-02-06 | 武汉工程大学 | Composite film of polyaniline doped with phytic acid and single-walled carbon nanotube, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113140666B (en) | 2023-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8362239B2 (en) | Heteroaromatic phthalonitriles | |
| Shalini et al. | Design and fabrication of PANI/GO nanocomposite for enhanced room-temperature thermoelectric application | |
| CN109830661B (en) | Selenium-doped MXene composite nano material and preparation method and application thereof | |
| CN101955631B (en) | Preparation method of polyaniline modified multi-wall carbon canotube/epoxy resin composite material | |
| CN101191016A (en) | Polyaniline/palygorskite nano composite material and preparation method thereof | |
| CN106784288B (en) | Preparation method for enhancing performance of composite thermoelectric material | |
| JPS5984917A (en) | Stable electroconductive polymer and manufacture | |
| CN113140666B (en) | Composite thermoelectric material and preparation method thereof | |
| CN111217994B (en) | Polyarylether polymer with D-A structure in side chain, preparation method and application thereof | |
| CN1305935C (en) | Serial electrically active polyaryl ether ketone polymers and their prepn process | |
| Yang et al. | Multipolar Conjugated Polymer Framework Derived Ionic Sieves via Electronic Modulation for Long‐Life All‐Solid‐State Li Batteries | |
| CN112961163A (en) | High-capacity metal ion battery organic electrode material and preparation method and application thereof | |
| CN114957578B (en) | Covalent organic framework material based on thienyl and oxazinyl, and preparation method and application thereof | |
| CN113036217B (en) | Silicotungstic acid-inner salt end-capped polystyrene hybrid electrolyte material and preparation method thereof | |
| CN110835406B (en) | Free radical monomer containing diphenylamine structure and preparation method and application of polymer thereof | |
| CN110305313B (en) | Purple refined functionalized polyarylether electrode active material and preparation method thereof | |
| CN113121362A (en) | Aniline oligomer, composite material thereof, preparation method and application thereof | |
| Xu et al. | Characterization and electrochemical properties of poly (aniline-co-o-methoxyaniline)/multi-walled carbon nanotubes composites synthesized by solid-state method | |
| CN103044680B (en) | Synthetic method of polyaniline/carbon fiber composite material with nano-ordered structure | |
| JPH02218716A (en) | Organic semiconductor and production thereof | |
| CN110951253A (en) | High-performance polypyrrole-based ternary composite thermoelectric material and preparation method thereof | |
| Packiaraj et al. | Preparation of novel flexible freestanding conducting polyaniline nanocomposite films using recent generation polycarboxylate ether | |
| CN116836387B (en) | Polyimide-linked porous organic polymer based on cage-like organic molecules, composite material, preparation thereof and lithium ion battery application | |
| CN115558089B (en) | Electronic-ion mixed conductive polymer, preparation method and application thereof in preparation of high-magnification water-based zinc ion battery | |
| Chiguma et al. | Template-Free Synthesis of Aligned Polyaniline Nanorods/Tubes and Copper/Copper Hydroxide Nanowires for Application as Fillers in Polymer Nanocomposites |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |