CN112898739A - High-conductivity polymer carbon nanotube composite material and preparation method thereof - Google Patents
High-conductivity polymer carbon nanotube composite material and preparation method thereof Download PDFInfo
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- CN112898739A CN112898739A CN202110101494.2A CN202110101494A CN112898739A CN 112898739 A CN112898739 A CN 112898739A CN 202110101494 A CN202110101494 A CN 202110101494A CN 112898739 A CN112898739 A CN 112898739A
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C08J7/14—Chemical modification with acids, their salts or anhydrides
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- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
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- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
Abstract
The invention belongs to the field of organic semiconductors, and particularly relates to a high-conductivity polymer carbon nanotube composite material and a preparation method thereof. The invention relates to a method for preparing a compound by mixing PEDOT: dropping the blend of PSS and CNT into an acid solution followed by a filtration operation may first achieve self-assembly of CNT with PEDOT and remove a portion of the excess PSS. And in the subsequent sulfuric acid treatment step, the PEDOT and the PSS are further separated, more PSS is removed through water washing, the PEDOT is subjected to secondary doping, the carrier concentration and the mobility are improved, and the polymer/carbon nano tube composite material with high conductivity is finally obtained.
Description
Technical Field
The invention belongs to the field of organic semiconductors, and particularly relates to a high-conductivity polymer carbon nanotube composite material and a preparation method thereof.
Background
With the advancement of science and technology, especially the rapid rise of the organic semiconductor industry, people are forced to seek non-metallic conductors with light weight, corrosion resistance and good electrical conductivity so as to meet the development of fields such as portable electronic equipment, medical devices, sensors, solar cells and the like. The composite material based on the conductive polymer has good flexibility, higher conductivity, light weight, good stability and the like, so that the composite material becomes a research hotspot of people (Carbon,2019,149, 25-32; ACS, Appl, Mater, interfaces,2019,11, 6624-.
Among the numerous conductive polymers, poly (3, 4-ethylenedioxythiophene): poly (styrene sulfonate) (PEDOT: PSS) is one of the most studied conductive polymers at present because of its advantages of high conductivity, water solubility and good stability, and the PEDOT: PSS/CNT composite material prepared by compounding with Carbon Nanotubes (CNT) is widely studied (Carbon,2017,125, 649-. In the PEDOT PSS/CNT composite material, the CNT with the one-dimensional structure can form a conductive network to provide a channel for the directional transmission of charges. In addition, due to pi-pi interaction between PEDOT and CNT, the orderliness of PEDOT molecular chains or chain segments can be increased, and charge migration is facilitated. However, the PSS molecular chain is much longer than that of PEDOT: PSS, and electrostatic interaction exists between the PSS molecular chain and the PEDOT: PSS molecular chain, the PEDOT molecular chain is wrapped by the PSS and is in a curling state, and the PEDOT: PSS molecular chain cannot be effectively contacted with the CNT, so that the composite material with high conductivity cannot be obtained by directly compounding the PEDOT: PSS and the CNT. Therefore, it is of great significance to develop a method for preparing a polymer/carbon nanotube composite material having high conductivity.
Disclosure of Invention
In order to solve the above technical problems, the present invention aims to provide a highly conductive polymer carbon nanotube composite material and a preparation method thereof.
The technical scheme provided by the invention is as follows:
a preparation method of a high-conductivity polymer carbon nanotube composite material comprises the following steps:
1) mixing a PEDOT (PSS) material and a Carbon Nano Tube (CNT) dispersion liquid, then dripping the obtained mixed liquid into acid, filtering, dispersing the filtered solid into water to obtain a coating liquid, and then coating the coating liquid drop into a film to prepare the PEDOT (PSS) and carbon nano tube composite film;
2) soaking the PEDOT, PSS and carbon nanotube composite film obtained in the step 1) in a sulfuric acid solution, then carrying out at least one heating treatment, then washing the PEDOT, PSS and carbon nanotube composite film with deionized water, and drying the washed film to obtain the high-conductivity polymer carbon nanotube composite material.
The technical scheme is that PEDOT: dropping the blend of PSS and CNT into an acid solution followed by a filtration operation may first achieve self-assembly of CNT with PEDOT and remove a portion of the excess PSS. And in the subsequent sulfuric acid treatment step, the PEDOT and the PSS are further separated, more PSS is removed through water washing, the PEDOT is subjected to secondary doping, the carrier concentration and the mobility are improved, and the polymer/carbon nano tube composite material with high conductivity is finally obtained.
Specifically, in step 1):
PSS accounts for 0.13-1.3 wt% of PEDOT in the mixed solution;
the weight percentage content of the carbon nano tube in the mixed solution is 0.1-1%;
the acid is selected from any one of sulfuric acid, hydrochloric acid, nitric acid, methanesulfonic acid or trifluoromethanesulfonic acid with the concentration of 0.1-10M, and the volume ratio of the acid to the mixed solution is (100-2): 1;
in the composite film of the PEDOT, the PSS and the carbon nano tube, the content of the PEDOT is 90 wt% -10 wt%, and the content of the carbon nano tube is 10 wt% -90 wt%.
Specifically, in the step 2):
the concentration of the sulfuric acid solution is 1-18.4M;
the treatment temperature of the heating treatment is (30-160) DEG C, the treatment time of each time is 1-5 minutes, and 3 times is preferred;
washing with deionized water to a pH greater than or equal to 6;
the drying temperature is 80-160 ℃.
Specifically, the method comprises the following steps:
PSS is Clevios PH 1000;
the carbon nanotube is a single-wall carbon nanotube (SWCNT), a double-wall carbon nanotube (DWCNT) or a multi-wall carbon nanotube (MWCNT).
The filtering process is normal pressure filtering or reduced pressure filtering.
The invention also provides the high-conductivity polymer carbon nanotube composite material prepared by the preparation method of the high-conductivity polymer carbon nanotube composite material.
The high-conductivity polymer carbon nanotube composite material has high conductivity.
Compared with the prior art:
according to the invention, the ionization effect of acid in aqueous solution is utilized in the first step, and ionized hydrogen protons and acid radicals can shield electrostatic attraction between PEDOT and PSS, so that the phase separation of the PEDOT and the PSS is realized, the exposed PEDOT and CNT have hydrophobicity, the PEDOT can be coated on the surface of the CNT in the acid solution, and the redundant PSS has hydrophilicity and can be removed along with the filtering process, thereby realizing the self-assembly of the PEDOT and the CNT;
PSS is separated, PEDOT molecular chains are subjected to conformation adjustment, the chain structures are regularly arranged, and redundant PSS is taken away when the PEDOT molecular chains are washed by deionized water; in the process, sulfuric acid also serves as a dopant to secondarily dope the PEDOT, so that the oxidation state of the PEDOT is converted into polarons and bipolars, and the carrier concentration is increased.
In summary, PEDOT: the unnecessary non-conductive PSS in PSS is removed, the regularity of PEDOT molecular chains is improved, and the pi-pi action of the interface of PEDOT and CNT is realized, so that the ratio of PEDOT: the carrier mobility of the PSS/CNT composite material is improved; the doping of sulfuric acid increases the carrier concentration; the CNT has good conductivity, and the combined action of the CNT, the CNT and the composite material promotes the composite material to have high conductivity.
The invention has simple process condition, high stability, low cost and obvious effect, does not need organic solvent and complex mechanical equipment, and is suitable for large-scale industrial production and application of the organic composite conductive material.
Drawings
Figure 1 is a polymer PEDOT according to example 4 of the present invention: scanning electron microscopy of composite films of PSS and carbon nanotube CNT.
Figure 2 is a polymer PEDOT according to example 4 of the present invention: transmission electron microscopy of composite films of PSS with carbon nanotubes CNT.
FIG. 3 is a Raman spectrum of PEDOT, PSS/CNT directly blended without filtering treatment before and after the sulfuric acid treatment in example 4 of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1:
6mg CNT is sonicated in 2.4mL deionized water for 10min to form a suspension, 4154 μ L PEDOT: PSS aqueous solution (1.3 wt%) is added to the suspension, the mixture is sonicated and stirred to mix well, then the mixture is dropped into 50mL 1M sulfuric acid solution, and then filtration is carried out, and deionized water is continuously added during the filtration process until the pH value of the filtrate is close to neutral. When the filtrate was about to be drained, the slurry was transferred to a brown bottle and the final total concentration was adjusted to 6 mg/mL. And (3) dripping the suspension liquid on a glass sheet which is subjected to UVO treatment for 10min in advance, and drying at 70 ℃ to prepare a PEDOT (PSS)/CNT composite film, wherein the content of CNT is 10 wt%.
The film is placed on a 160 ℃ hot table, treated for 5min by dripping 1M sulfuric acid solution, washed for 2 times by deionized water, baked dry on the 160 ℃ hot table, and the process is repeated for 3 times. The PEDOT PSS/CNT composite material with the conductivity of 2106S/cm is obtained.
Example 2:
the amount of the aqueous solution of PEDOT: PSS used in example 1 was adjusted to 1864. mu.L, and the foregoing procedure of example 1 was repeated to prepare a PEDOT: PSS/CNT composite film material having a CNT content of 20 wt%, which was then subjected to sulfuric acid treatment under the procedure conditions of example 1. The PEDOT: PSS/CNT composite material with the conductivity of 2490S/cm is obtained.
Example 3:
the amounts of CNT and PEDOT/PSS aqueous solutions were adjusted to 12mg and 1384. mu.L, respectively, and the aforementioned steps of example 1 were repeated to prepare a PEDOT/PSS/CNT composite film material having a CNT content of 40 wt%, and sulfuric acid treatment was performed under the conditions of example 1. The PEDOT: PSS/CNT composite material with the conductivity of 2796S/cm is obtained.
Example 4:
the amounts of CNT, deionized water and PEDOT/PSS aqueous solution were adjusted to 18mg, 3.6mL and 923. mu.L, respectively, and the above-mentioned steps of example 1 were repeated to prepare a PEDOT/PSS/CNT composite film material with a CNT content of 60 wt%, and sulfuric acid treatment was performed according to the conditions of example 1. The PEDOT: PSS/CNT composite material with the conductivity of 5756S/cm is obtained.
As shown in FIG. 3, the Raman spectrum of the filtered PEDOT PSS/CNT is from 1432cm-1Move to 1430cm-1The Raman spectrum peak of the PEDOT PSS/CNT obtained by filtering treatment and acid treatment is further shifted to 1427cm-1The peak here corresponds to C in the PEDOT moleculeα＝CβThe stretching vibration of (2) shows that the regularity of the PEDOT molecular chain is improved after the filtration treatment and the sulfuric acid treatment.
Example 5:
the amounts of CNT, deionized water and PEDOT/PSS aqueous solution were adjusted to 24mg, 4.8mL and 462 μ L, respectively, and the foregoing steps of example 1 were repeated to prepare a PEDOT/PSS/CNT composite film material having a CNT content of 80 wt%, and sulfuric acid treatment was performed according to the conditions of example 1. The conductivity was most always measured to be 3852S/cm.
Example 6:
the amounts of CNT, deionized water and PEDOT/PSS aqueous solution were adjusted to 27mg, 5.4mL and 231. mu.L, respectively, and the foregoing steps of example 1 were repeated to prepare a PEDOT/PSS/CNT composite film material having a CNT content of 90 wt%, and sulfuric acid treatment was performed according to the conditions of example 1. The conductivity was found to be 3002S/cm in total.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The preparation method of the high-conductivity polymer carbon nanotube composite material is characterized by comprising the following steps of:
1) mixing a PEDOT PSS material and a carbon nano tube dispersion liquid, dripping the obtained mixed liquid into acid, filtering, dispersing the filtered solid into water to obtain a coating liquid, and coating the coating liquid drop into a film to prepare the PEDOT PSS and carbon nano tube composite film;
2) soaking the PEDOT, PSS and carbon nanotube composite film obtained in the step 1) in a sulfuric acid solution, then carrying out at least one heating treatment, then washing the PEDOT, PSS and carbon nanotube composite film with deionized water, and drying the washed film to obtain the high-conductivity polymer carbon nanotube composite material.
2. The method for preparing the highly conductive polymer carbon nanotube composite material according to claim 1, wherein in the step 1):
PSS accounts for 0.13-1.3 wt% of PEDOT in the mixed solution;
the weight percentage of the carbon nano tube in the mixed solution is 0.1-1%.
3. The method for preparing the highly conductive polymer carbon nanotube composite material according to claim 1, wherein in the step 1): the acid is selected from one or more of sulfuric acid, hydrochloric acid, nitric acid, methanesulfonic acid and trifluoromethanesulfonic acid, the concentration of the acid is 0.1-10M, and the volume ratio of the acid to the mixed solution is (100-2): 1.
4. The method for preparing the highly conductive polymer carbon nanotube composite material according to claim 1, wherein in the step 1): in the PEDOT/PSS/carbon nanotube composite film, the content of the PEDOT/PSS is 90 wt% -10 wt%, and the content of the carbon nanotube is 10 wt% -90 wt%.
5. The method for preparing the highly conductive polymer carbon nanotube composite material according to claim 1, wherein in the step 2): the concentration of the sulfuric acid solution is 1-18.4M.
6. The method for preparing the highly conductive polymer carbon nanotube composite material according to claim 1, wherein in the step 2): the treatment temperature of the heating treatment is 30-160 ℃, and the treatment time is 1-5 minutes each time.
7. The method for preparing the highly conductive polymer carbon nanotube composite material according to claim 1, wherein in the step 2): washing with deionized water to a pH greater than or equal to 6; the drying temperature is 80-160 ℃, and the drying time is not less than 5 min.
8. The method for preparing a highly conductive polymer carbon nanotube composite material according to any one of claims 1 to 7, wherein: and the PEDOT: PSS is Clevios PH 1000.
9. The method for preparing a highly conductive polymer carbon nanotube composite material according to any one of claims 1 to 7, wherein: the carbon nano tube is any one or mixture of a plurality of single-wall carbon nano tubes, double-wall carbon nano tubes or multi-wall carbon nano tubes.
10. A highly conductive polymer carbon nanotube composite material prepared by the method for preparing a highly conductive polymer carbon nanotube composite material according to any one of claims 1 to 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115287774A (en) * | 2022-06-22 | 2022-11-04 | 武汉工程大学 | High-conductivity organic composite thermoelectric fiber, preparation method and application |
| CN117586539A (en) * | 2024-01-18 | 2024-02-23 | 成都飞机工业（集团）有限责任公司 | Preparation method of high-conductivity self-supporting carbon nano tube composite film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100044647A1 (en) * | 2008-08-22 | 2010-02-25 | Tsinghua University | Method for manufacturing carbon nanotube-conducting polymer composite |
| CN105405977A (en) * | 2015-10-29 | 2016-03-16 | 华中科技大学 | Self-supporting PEDOT-PSS film, manufacturing method thereof and applications |
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- 2021-01-26 CN CN202110101494.2A patent/CN112898739A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100044647A1 (en) * | 2008-08-22 | 2010-02-25 | Tsinghua University | Method for manufacturing carbon nanotube-conducting polymer composite |
| CN105405977A (en) * | 2015-10-29 | 2016-03-16 | 华中科技大学 | Self-supporting PEDOT-PSS film, manufacturing method thereof and applications |
Non-Patent Citations (2)
| Title |
|---|
| 魏燕红等: "PEDOT:PSS导电性能优化方法的研究进展", 《塑料工业》 * |
| 魏燕红等: "PEDOT:PSS导电性能优化方法的研究进展", 《塑料工业》, vol. 44, no. 08, 20 August 2016 (2016-08-20), pages 2 - 3 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115287774A (en) * | 2022-06-22 | 2022-11-04 | 武汉工程大学 | High-conductivity organic composite thermoelectric fiber, preparation method and application |
| CN117586539A (en) * | 2024-01-18 | 2024-02-23 | 成都飞机工业（集团）有限责任公司 | Preparation method of high-conductivity self-supporting carbon nano tube composite film |
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