CN111627717A - Carbon fiber cloth/poly (3, 4-ethylenedioxythiophene) nanotube composite material and preparation method thereof - Google Patents

Carbon fiber cloth/poly (3, 4-ethylenedioxythiophene) nanotube composite material and preparation method thereof Download PDF

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CN111627717A
CN111627717A CN202010512850.5A CN202010512850A CN111627717A CN 111627717 A CN111627717 A CN 111627717A CN 202010512850 A CN202010512850 A CN 202010512850A CN 111627717 A CN111627717 A CN 111627717A
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carbon fiber
fiber cloth
composite material
ethylenedioxythiophene
poly
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CN111627717B (en
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雷志斌
牛斐
韩喜盈
孙惠
郭瑞
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Shaanxi Normal University
Shaanxi Coal and Chemical Technology Institute Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/40—Fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

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Abstract

The invention discloses a carbon fiber cloth/poly (3, 4-ethylenedioxythiophene) nanotube composite material and a preparation method thereof. The composite material has high specific capacitance, good rate performance and excellent cycle stability; the growth of the PEDOT nanotubes improves the conductivity and flexibility of the carbon fiber cloth, the PEDOT serving as a pseudo-capacitance material improves the electrochemical performance of the carbon fiber cloth, the mutual interweaving of the PEDOT nanotubes is beneficial to the conduction of ions, and the wide application of the material in the field of energy storage is widened. The invention has the advantages of easily obtained raw materials and simple process, and opens up a new way for various conducting polymer-based electrodes to be used for high-speed electrochemical energy storage.

Description

Carbon fiber cloth/poly (3, 4-ethylenedioxythiophene) nanotube composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of energy storage materials, and particularly relates to a carbon fiber cloth/poly (3, 4-ethylenedioxythiophene) nanotube composite material and a preparation method thereof.
Background
Electrochemical capacitors, also known as supercapacitors, have received much attention because of their ability to safely provide high power, rapid release of energy, and ultra-long cycle life. Meanwhile, the rapid development of miniaturized portable and wearable consumer electronics requires that the super capacitor not only stores more energy, but also has novel functions such as flexibility, stretchability and even compressibility. The textured carbon fiber cloth (TC) has a hollow structure and can be used as a growth substrate of an electrode material. Or directly applied to a supercapacitor in the form of an electrode, but the conductivity and low specific capacity thereof limit the application thereof.
PEDOT is a polymer of 3, 4-ethylenedioxythiophene monomer (EDOT). PEDOT has the characteristics of simple molecular structure, small energy gap, high conductivity and the like, and is widely used for research in the fields of organic thin-film solar cell materials, OLED materials, electrochromic materials, super capacitor electrode materials and the like. It is often combined with other poorly conductive electrodes to improve the conductivity and electrochemical performance of the electrode itself. However, because the morphology of PEDOT is usually nanoparticles, intrinsic properties of PEDOT are difficult to embody, which greatly limits the application and performance of PEDOT on the flexible electrode.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the two prior arts, and provide a method for growing the PEDOT hollow nanotubes on the carbon fiber cloth, so as to obtain the carbon fiber cloth/PEDOT nanotube composite material.
The carbon fiber cloth/poly (3, 4-ethylenedioxythiophene) nanotube composite material for solving the technical problems comprises the following steps:
1. pretreating carbon fiber cloth for 20-40 minutes by using UV-ozone, and then firstly, carrying out 0.3-0.6 mol/L KMnO4Treating in an aqueous solution for 30-60 minutes, and then immersing in a solution containing 12-18 mmol/L Zn (NO)3)2And carrying out hydrothermal reaction for 18-36 hours in 12-18 mmol/L aqueous solution of hexamethylenetetramine at the temperature of 80-95 ℃, and repeatedly washing with deionized water and ethanol to remove impurities to obtain the carbon fiber cloth/ZnO composite material.
2. Putting the carbon fiber cloth/ZnO composite material in the step 1 as a working electrode, a platinum sheet as a counter electrode and a saturated calomel electrode as a reference electrode into an electrolyte solution, and performing electrochemical deposition by a constant voltage method, wherein the deposition voltage is 1.0-3.0V, and the electrolyte solution contains 0.08-0.15 mol/L LiClO4And 0.05-0.15 mol/L sodium dodecyl sulfate and 0.01-0.05 mol/L EDOT monomer aqueous solution, wherein the deposition time is 5-20 minutes, and the carbon fiber cloth/ZnO/PEDOT composite material is obtained.
3. And (3) soaking the carbon fiber cloth/ZnO/PEDOT composite material obtained in the step (2) in 1-6 mol/L hydrochloric acid for 12-24 hours, and corroding ZnO to obtain the carbon fiber cloth/PEDOT nanotube composite material.
In step 1, the carbon fiber cloth is preferably pretreated with UV-ozone for 30 minutes, and then, 0.5mol/LKMNO is added4Treating in water solution for 60 min, and soaking in solution containing Zn (NO) 15mmol/L3)2And 15mmol/L of hexamethylenetetramine in water solution, carrying out hydrothermal reaction for 24 hours at 90 ℃, and repeatedly washing with deionized water and ethanol to remove impurities to obtain the carbon fiber cloth/ZnO composite material.
The carbon fiber cloth is obtained according to the method disclosed in publication No. CN107221454A and the invention name 'an all-solid-state flexible supercapacitor based on porous carbon fiber cloth and a preparation method thereof'.
In the step 2, the deposition voltage is preferably 1.0V, and the deposition time is preferably 8-12 minutes.
In the above step 2, the electricity is more preferably usedThe electrolyte solution contains 0.1mol/L LiClO40.1mol/L sodium dodecyl sulfate and 0.01mol/L3, 4-ethylenedioxythiophene aqueous solution.
In the step 3, the concentration of the hydrochloric acid is preferably 6mol/L, and the soaking time is preferably 24 h.
The invention has the following beneficial effects:
1. according to the invention, the carbon fiber cloth is used as a substrate, the carbon fiber cloth/PEDOT nanotube composite material is prepared by adopting a hydrothermal method and a constant potential electrochemical deposition technology, the conductivity of the obtained composite material is obviously improved compared with that of the original carbon fiber cloth, the PEDOT nanotubes are uniformly distributed, and the thickness is controllable.
2. Compared with the capacitance performance exerted by PEDOT in the composite electrode reported in the past, the carbon fiber cloth/PEDOT nanotube composite material prepared by the invention has high specific capacitance, good rate performance and excellent cycling stability. The PEDOT nanotube is beneficial to the transmission of electrolyte ions, and the application of the PEDOT nanometer composite material in the field of energy storage is widened.
3. Compared with the prior art, the method for preparing the PEDOT nanotube has the advantages of low production conditions, simple process, no toxicity, no harm, environmental friendliness, short production period and easiness in operation and control, and can be used for massively preparing the PEDOT nanotube with uniform appearance and height.
Drawings
FIG. 1 is a scanning electron micrograph of the TC/PEDOT nanotube composite obtained in example 1.
FIG. 2 is a TEM image of the TC/PEDOT nanotube composite obtained in example 1.
FIG. 3 is an X-ray diffraction pattern of the TC/PEDOT nanotube composite obtained in example 1.
FIG. 4 shows that the TC/PEDOT nanotube composite material obtained in example 1 is used as a supercapacitor electrode at 1.0M H2SO4Cyclic voltammograms in aqueous solution.
FIG. 5 is a graph of rate capability of the TC/PEDOT nanotube composite obtained in example 1.
FIG. 6 shows the cycling stability of the TC/PEDOT nanotube composite obtained in example 1.
FIG. 7 shows the conductivity change of the TC/PEDOT nanotube composite obtained in example 1 in different bending angle tests.
FIG. 8 is the change of conductivity of the TC/PEDOT nanotube composite obtained in example 1 in 10000 times of repeated bending and twisting tests.
FIG. 9 shows that the TC/PEDOT nanotube composite material obtained in example 1 is used as an electrode for assembling a conventional supercapacitor and an all-solid-state supercapacitor at 50mV s-1Cyclic voltammogram at scan rate.
Fig. 10 is a charge and discharge curve of a conventional supercapacitor and an all-solid-state supercapacitor assembled by using the TC/PEDOT nanotube composite material obtained in example 1 as an electrode.
Detailed Description
The invention will be further explained in more detail below with reference to the drawings and examples, but the scope of protection of the invention is not limited to these examples.
Example 1
1. The carbon fiber cloth is pretreated by ozone for 30 minutes by a UV light cleaner to generate a large amount of oxygen-containing functional groups, so that the surface wettability of the carbon fiber cloth is improved. Firstly, pretreated carbon fiber cloth is subjected to 0.5mol/L KMnO4Treating in water solution for 60 min to obtain seed layer; then, the inoculated carbon fiber cloth was immersed in 100mL of a solution containing 15mmol/L Zn (NO)3)2And performing hydrothermal reaction in a 15mmol/L HMT aqueous solution at 90 ℃ for 24 hours, and repeatedly washing with a large amount of deionized water and ethanol to remove impurities to obtain the carbon fiber cloth/ZnO composite material.
2. Putting the carbon fiber cloth/ZnO composite material obtained in the step 1 as a working electrode, a platinum sheet as a counter electrode and a saturated calomel electrode as a reference electrode into an electrolyte solution, and performing electrochemical deposition by a constant voltage method, wherein the deposition voltage is 1.0V, and the electrolyte solution is LiClO containing 0.1mol/L4And 0.1mol/L sodium dodecyl sulfate and 0.01mol/L EDOT monomer, wherein the deposition time is 10 minutes, and the carbon fiber cloth/ZnO/PEDOT composite material is obtained.
3. And (3) soaking the carbon fiber cloth/ZnO/PEDOT composite material obtained in the step (2) in 6mol/L hydrochloric acid for 24 hours, and corroding the ZnO nanowires to obtain the carbon fiber cloth/PEDOT (marked as TC/PEDOT) nanotube composite material.
The inventor adopts a scanning electron microscope, a transmission electron microscope and an X-ray diffractometer to characterize the carbon fiber cloth/PEDOT nanotube composite material, and the results are shown in figures 1-3. As can be seen from fig. 1, vertical PEDOT nanorods grow around the carbon fibers like coralliform, forming a PEDOT array. It can be seen from the transmission diagram of fig. 2 that all PEDOT exhibits a typical open tubular structure. As can be seen from the X-ray diffraction pattern of fig. 3, the typical characteristic peak at 6.7 degrees for TC/PEDOT compared to the original TC, which corresponds to the (100) plane of PEDOT, and the presence of the (100) peak in the TC/PEDOT hybridization indicates that the PEDOT nanotubes tend to align more in a more ordered manner, which generally results in a high conductivity of the electrode.
The inventors further tested the electrochemical performance and the conductivity of the TC/PEDOT nanotube composite material, and the results are shown in FIGS. 4-6. As can be seen from fig. 4, 5 and 6, the cyclic voltammetry curves of the TC/PEDOT nanotube composite material still show good rectangles even at high scanning speed; the scanning speed and the current increase are in a linear relation, which shows that the composite material has higher conductivity and good capacitance retention rate; and the electrode is at 50mV s-1The capacitance retention rate can reach 87% after 10000 times of circulation at the scanning speed, which shows that the electrode has good circulation stability. As can be seen from fig. 7 and 8, the electrical conductivity of the composite material remained intact regardless of bending at different angles or at different times, indicating that the composite material has good flexibility and bending does not cause PEDOT to fall off. The obtained composite material is 0.5Ag-1The maximum specific capacitance value exerted by PEDOT under the current density can reach 181F g-1The multiplying power performance reaches 77%, and the conductivity is 790S m-1。
The obtained TC/PEDOT nanotube composite material is used as an electrode to assemble a traditional super capacitor and an all-solid-state super capacitor, and the specific assembly method is as follows:
assembling the traditional capacitor: adopting a Swaglock mold as a packaging material, putting the two pressed sandwich electrode plates into the mold as a positive electrode and a negative electrode, taking Celgard3501 membrane as a diaphragm, and dripping a proper amount of 1.0mol/L H2SO4And (3) wetting the electrode and the diaphragm by using the electrolyte, and then packaging the die.
All-solid-state flexible supercapacitor: two identical TC/PEDOT nanotube composite materials are taken and placed in PVA/H2SO4Soaking the gel electrolyte for 10 minutes, then taking out the gel electrolyte for natural curing for 20 minutes, and repeating the soaking and curing processes for more than 3 times; and then stacking the two electrode materials together, smearing a layer of gel electrolyte between the two electrode materials to serve as a diaphragm to form a sandwich structure, drying the sandwich structure at 60 ℃, and removing excessive moisture to assemble the all-solid-state flexible supercapacitor.
As can be seen from fig. 9 and 10, the charge and discharge curves of the conventional type supercapacitor and the all-solid-state supercapacitor almost coincide, which indicates that the electrochemical performance of the gel electrolyte is almost comparable to that of the water-based capacitor despite its low conductivity, and it can be seen that the high rate capability exhibited in both the aqueous electrolyte and the gel electrolyte again confirms that the graded TC/PEDOT composed of the highly conductive tubular PEDOT facilitates the transport of ions and electrons.
Example 2
In step 2 of this example, the deposition time was 5 minutes, and the other steps were the same as in example 1, to obtain a TC/PEDOT nanotube composite material. Electrochemical performance testing was performed as in example 1, and the resulting composite was found to be at 0.5A g-1The maximum specific capacitance value exerted by PEDOT under the current density can reach 151F g-1The multiplying power performance reaches 74 percent, and the conductivity is 640S m-1。
Example 3
In step 2 of this example, the deposition time was 15 minutes, and the other steps were the same as in example 1, to obtain a TC/PEDOT nanotube composite material. Electrochemical performance testing was performed as in example 1, and the resulting composite was found to be at 0.5A g-1The maximum specific capacitance value under the current density can reach 148F g-1The rate capability reaches 75 percent, and the conductivity is 680S m-1。
Example 4
In step 3 of this example, the concentration of hydrochloric acid was 6mol/L, and the other steps were the same as in example 1 to obtain a TC/PEDOT nanotube composite materialAnd (5) feeding. Electrochemical performance testing was performed as in example 1, and the resulting composite was found to be at 0.5A g-1The maximum specific capacitance value under the current density can reach 174F g-1The multiplying power performance reaches 76%, and the conductivity is 750S m-1。

Claims (6)

1. A preparation method of a carbon fiber cloth/poly (3, 4-ethylenedioxythiophene) nanotube composite material is characterized by comprising the following steps:
(1) pretreating carbon fiber cloth for 20-40 minutes by using UV-ozone, and then firstly, carrying out 0.3-0.6 mol/L KMnO4Treating in an aqueous solution for 30-60 minutes, and then immersing in a solution containing 12-18 mmol/L Zn (NO)3)2And 12-18 mmol/L of hexamethylenetetramine in water solution, carrying out hydrothermal reaction for 18-36 hours at the temperature of 80-95 ℃, and repeatedly washing with deionized water and ethanol to remove impurities to obtain the carbon fiber cloth/ZnO composite material;
(2) putting the carbon fiber cloth/ZnO composite material in the step (1) as a working electrode, a platinum sheet as a counter electrode and a saturated calomel electrode as a reference electrode into an electrolyte solution, and performing electrochemical deposition by a constant voltage method, wherein the deposition voltage is 1.0-3.0V, and the electrolyte solution contains 0.08-0.15 mol/L LiClO40.05-0.15 mol/L sodium dodecyl sulfate and 0.01-0.05 mol/L3, 4-ethylenedioxythiophene aqueous solution, and the deposition time is 5-20 minutes to obtain the carbon fiber cloth/ZnO/poly (3, 4-ethylenedioxythiophene) composite material;
(3) and (3) soaking the carbon fiber cloth/ZnO/poly (3, 4-ethylenedioxythiophene) composite material in the step (2) in 1-6 mol/L hydrochloric acid for 12-24 hours, and corroding off ZnO to obtain the carbon fiber cloth/poly (3, 4-ethylenedioxythiophene) nanotube composite material.
2. The method for preparing the carbon fiber cloth/poly (3, 4-ethylenedioxythiophene) nanotube composite material according to claim 1, wherein: in the step (1), after the carbon fiber cloth is pretreated by UV-ozone for 30 minutes, 0.5mol/LKMNO is firstly adopted4Treating in water solution for 60 min, and soaking in solution containing Zn (NO) 15mmol/L3)2And 15mmol/L hexamethylenetetramine in an aqueous solution at 90And carrying out hydrothermal reaction at the temperature of 24 hours, and repeatedly washing with deionized water and ethanol to remove impurities to obtain the carbon fiber cloth/ZnO composite material.
3. The method for preparing the carbon fiber cloth/poly (3, 4-ethylenedioxythiophene) nanotube composite material according to claim 1, wherein: in the step (2), the deposition voltage is 1.0V, and the deposition time is 8-12 minutes.
4. The method for preparing the carbon fiber cloth/poly (3, 4-ethylenedioxythiophene) nanotube composite material according to claim 1, wherein: in the step (2), the electrolyte solution contains 0.1mol/L LiClO40.1mol/L sodium dodecyl sulfate and 0.01mol/L3, 4-ethylenedioxythiophene aqueous solution.
5. The method for preparing the carbon fiber cloth/poly (3, 4-ethylenedioxythiophene) nanotube composite material according to claim 1, wherein: in the step (3), the carbon fiber cloth/ZnO/poly (3, 4-ethylenedioxythiophene) composite material in the step (2) is soaked in 6mol/L hydrochloric acid for 24 hours.
6. The carbon fiber cloth/poly (3, 4-ethylenedioxythiophene) nanotube composite material prepared by the method of any one of claims 1 to 5.
CN202010512850.5A 2020-06-08 2020-06-08 Carbon fiber cloth/poly (3, 4-ethylenedioxythiophene) nanotube composite material and preparation method thereof Active CN111627717B (en)

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US20070273264A1 (en) * 2006-05-26 2007-11-29 Samsung Electronics Co., Ltd., Method of preparing patterned carbon nanotube array and patterned carbon nanotube array prepared thereby
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CN102610393A (en) * 2012-03-26 2012-07-25 北京化工大学 Preparation method of ultracapacitor material with layered double hydroxide-poly(3, 4-ethylenedioxythiophene) core-shell structure
JP2012188484A (en) * 2011-03-09 2012-10-04 National Institute Of Advanced Industrial Science & Technology Method for producing electroconductive polymer having controlled shape
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KR20140014765A (en) * 2012-07-26 2014-02-06 서울대학교산학협력단 Fabrication method of multidimensional conducting polymer nanotubes via vapor deposition polymerization
CN104829815A (en) * 2015-05-17 2015-08-12 北京化工大学 Preparation method of ZnO@PEDOT nanowire
CN106558423A (en) * 2016-11-21 2017-04-05 华中科技大学 Fe2O3Laminar nano array, the Fe with layer structure2O3/ PPy flexible composites and preparation and application
CN108529600A (en) * 2017-03-02 2018-09-14 中国科学院大连化学物理研究所 A kind of method of steam auxiliary ozone functionization processing nano-carbon material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070273264A1 (en) * 2006-05-26 2007-11-29 Samsung Electronics Co., Ltd., Method of preparing patterned carbon nanotube array and patterned carbon nanotube array prepared thereby
CN101481500A (en) * 2009-02-11 2009-07-15 南京大学 Preparation of conductive polymer / carbon nano-tube composite mesoporous nano-tube
JP2012188484A (en) * 2011-03-09 2012-10-04 National Institute Of Advanced Industrial Science & Technology Method for producing electroconductive polymer having controlled shape
CN102610393A (en) * 2012-03-26 2012-07-25 北京化工大学 Preparation method of ultracapacitor material with layered double hydroxide-poly(3, 4-ethylenedioxythiophene) core-shell structure
KR20140014765A (en) * 2012-07-26 2014-02-06 서울대학교산학협력단 Fabrication method of multidimensional conducting polymer nanotubes via vapor deposition polymerization
CN103343377A (en) * 2013-07-10 2013-10-09 四川农业大学 Poly (3,4-ethylenedioxythiophene) nano-tube array, as well as preparation method and application thereof
CN104829815A (en) * 2015-05-17 2015-08-12 北京化工大学 Preparation method of ZnO@PEDOT nanowire
CN106558423A (en) * 2016-11-21 2017-04-05 华中科技大学 Fe2O3Laminar nano array, the Fe with layer structure2O3/ PPy flexible composites and preparation and application
CN108529600A (en) * 2017-03-02 2018-09-14 中国科学院大连化学物理研究所 A kind of method of steam auxiliary ozone functionization processing nano-carbon material

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