CN109192552B - Method for preparing polyaniline-titanium dioxide nanotube array composite electrode in one step - Google Patents

Method for preparing polyaniline-titanium dioxide nanotube array composite electrode in one step Download PDF

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CN109192552B
CN109192552B CN201811121256.2A CN201811121256A CN109192552B CN 109192552 B CN109192552 B CN 109192552B CN 201811121256 A CN201811121256 A CN 201811121256A CN 109192552 B CN109192552 B CN 109192552B
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polyaniline
titanium dioxide
nanotube array
composite electrode
dioxide nanotube
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CN109192552A (en
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赵建玲
肖甜甜
王西新
李子庆
王晓柳
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Hebei University of Technology
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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
    • H01G11/84—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
    • 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
    • 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
    • H01G11/46—Metal oxides
    • 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
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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 relates to a method for preparing a polyaniline-titanium dioxide nanotube array composite electrode in one step. The method comprises the following steps: adding ammonium fluoride, aniline and concentrated sulfuric acid into the mixed solvent, and stirring for dissolving to obtain a mixed solution; using the mixed solution as electrolyte, using a metal titanium sheet as an anode and a platinum sheet as a cathode, and carrying out anodic oxidation for 1-5 hours at the temperature of 0-10 ℃ and the voltage of 20-50V; and washing the oxidized anode plate with deionized water, and drying to obtain the polyaniline-titanium dioxide nanotube array composite electrode. The invention greatly simplifies the process steps, shortens the process flow and obtains the electrode with excellent performance.

Description

Method for preparing polyaniline-titanium dioxide nanotube array composite electrode in one step
The technical field is as follows:
the invention belongs to the field of electrochemistry, and particularly relates to a preparation method of a polyaniline-titanium dioxide nanotube array composite electrode.
Background art:
the super capacitor is an electric energy storage device, has the advantages of high power capacity, fast energy storage, long service life and the like, and has important application in the aspects of new energy automobiles, aerospace, urban rail transit, solar energy systems, smart power grids, military equipment and the like.
The composition, morphology, preparation method and the like of the electrode have great influence on the performance of the supercapacitor, so that the preparation of the electrode of the supercapacitor is concerned widely. In order to obtain a better electrode, two or more materials are compounded together by different methods to prepare a plurality of composite electrodes so as to realize the complementary advantages of the materials.
Polyaniline is a conductive polymer and can be used as a pseudocapacitance material, and has the defect of poor electrochemical stability and cycling stability, which limits the wide application of the polyaniline in the field of capacitors. The titanium dioxide nanotube array with the highly ordered structure has larger specific surface area and better chemical stability, and the polyaniline-titanium dioxide nanotube array composite electrode prepared by compounding the polyaniline and the titanium dioxide nanotube array has excellent performance.
For example, Energy (2015,87, P578-585) reports a method for preparing a polyaniline-titanium dioxide nanotube array composite electrode, in which a titanium dioxide nanotube array is prepared by an anodic oxidation method, the array is calcined at a high temperature, and then polyaniline nanowires are deposited on the titanium dioxide nanotube array by a cyclic voltammetry method to prepare the composite electrode. Nanoscale (2011,3, P2202-2207) reports a method for preparing a polyaniline-titanium dioxide nanotube array composite electrode, wherein a titanium dioxide nanotube array is prepared by an anodic oxidation method, the obtained array is annealed at high temperature, and then polyaniline is deposited on the titanium dioxide nanotube array by a constant potential electrodeposition method to prepare the composite electrode. Electrochimica Acta (2014,120, P408-415) reports a preparation method of a polyaniline-titanium dioxide nanotube array composite electrode, a titanium dioxide nanotube array is prepared by an anodic oxidation method, the titanium dioxide nanotube array is calcined at high temperature, treated by steam in water vapor, soaked in acetone solution containing 3-aminopropyltriethoxysilane, kept stand, cleaned and dried; stirring in an aqueous solution containing aniline monomer and hydrochloric acid for 1 hour, stirring in an aqueous solution containing aniline monomer, hydrochloric acid and ammonium persulfate for 30min, standing at room temperature for 4 hours, cleaning and drying to obtain the composite electrode.
The methods firstly prepare the titanium dioxide nanotube array by an anodic oxidation method, and then deposit polyaniline into the titanium dioxide nanotube array by adopting different methods and technological processes to prepare the polyaniline-titanium dioxide nanotube array composite electrode, wherein the preparation process of the composite electrode is complex, and more waste liquid is generated; because interfacial tension exists among titanium oxide, aniline and polyaniline, the pipe diameter of the nano-tube is small, the interior of the nano-tube cannot be completely infiltrated by monomer solution, the generated polyaniline is difficult to fully cover the inner surface of the nano-tube, and the bonding force between the polyaniline and the titanium oxide is weak, so that the circulation stability of the composite electrode is still low.
The invention content is as follows:
the invention provides a preparation method of a composite electrode, aiming at the defects that the preparation of a polyaniline-titanium dioxide nanotube array composite electrode needs to be carried out in multiple steps, the cycling stability of the electrode is low and the like in the prior art. According to the method, reagents such as aniline and sulfuric acid are added into common electrolyte, process parameters are adjusted, and the polyaniline-titanium dioxide nanotube array composite electrode can be prepared only through one-step anodic oxidation. The invention greatly simplifies the process steps, shortens the process flow and obtains the electrode with excellent performance.
The technical scheme of the invention is as follows:
a method for preparing a polyaniline-titanium dioxide nanotube array composite electrode in one step comprises the following steps:
adding ammonium fluoride, aniline and concentrated sulfuric acid into the mixed solvent, and stirring for dissolving to obtain a mixed solution; using the mixed solution as electrolyte, using a metal titanium sheet as an anode and a platinum sheet as a cathode, wherein the distance between the anode and the cathode is 2cm, and anodizing for 1-5 hours at the temperature of 0-10 ℃ and the voltage of 20-50V; after the reaction is finished, washing the oxidized anode plate with deionized water, and drying to obtain the polyaniline-titanium dioxide nanotube array composite electrode;
wherein, the mixed solvent comprises 10-40% of ethanol, 1-20% of water and 50-80% of glycol by mass percent; 0.1-0.5g of ammonium fluoride, 1-5g of aniline and concentrated sulfuric acid with the same mass as aniline are added into each 100g of mixed solvent.
The concentration of the concentrated sulfuric acid is 98% by mass.
The invention has the beneficial effects that:
(1) the invention has the outstanding characteristics that the polyaniline-titanium dioxide nanotube array composite electrode is prepared by only one-step anodic oxidation method, thereby greatly simplifying the process steps and shortening the process flow.
(2) The invention is characterized in that the electrolyte contains ethanol, aniline and sulfuric acid. In the constant-voltage anodic oxidation process, polyaniline is generated while the titanium dioxide nanotube is formed, so that the polyaniline can be deposited in the titanium dioxide nanotube, and the contact area of the polyaniline and the titanium dioxide can be increased. The ethanol has the function of interfacial activity, and can reduce the interfacial tension between the aniline and the titanium oxide, which is beneficial to the polymerization and deposition of the aniline on the surface of the titanium oxide and the improvement of the bonding strength between the polyaniline and the titanium oxide. Sulfuric acid is added into the electrolyte, on one hand, the electrolyte is adjusted to be strongly acidic, and polyaniline generated under the condition contains more para-position structures, and on the other hand, the sulfuric acid has a doping effect on the polyaniline, and the effects of the two aspects can improve the conductivity of the polyaniline. These factors can improve the performance of the electrode.
(3) The invention is characterized in that the anodic oxidation process is carried out at 0-10 ℃. The reduction of the reaction temperature has two effects, namely, the proportion of para-position structures in the polyaniline can be improved, the conductivity of the polyaniline can be further improved, and the dissolution of the electrolyte on the titanium dioxide can be reduced.
In the technical scheme of the invention, all factors are an integral body which is mutually connected and restricted, for example, in order to obtain polyaniline with high conductivity, sulfuric acid is added into electrolyte, and anodic oxidation reaction is carried out at 0-10 ℃; the dissolution of the electrolyte can be enhanced by adding sulfuric acid into the electrolyte, and the solubility of the electrolyte can be reduced by reducing the reaction temperature, but the viscosity of the electrolyte can be increased; the addition of ethanol in the electrolyte can reduce the viscosity of the electrolyte and improve the bonding state between the polyaniline and the titanium dioxide. According to the relevant experiment results, the viscosity and the dissolution of the electrolyte have great influence on the formation of the titanium dioxide nanotube array, when the viscosity of the electrolyte is too high, mass transfer and heat transfer in the reaction process are not facilitated, and when the dissolution of the electrolyte on the titanium dioxide is strong, most of the titanium dioxide generated by anodic oxidation is dissolved, so that the titanium dioxide nanotube array is difficult to obtain. The invention realizes the formation of the titanium dioxide nanotube array and the polymerization and deposition of aniline under the same condition by adjusting the electrolyte composition and process parameters, and prepares the polyaniline-titanium dioxide nanotube array composite electrode only by one-step anodic oxidation.
The electrode obtained by the invention is circulated for 10000 circles, the GCD circulating curve shape of the composite electrode is almost unchanged, the capacitance retention value of the electrode is still as high as 97.3 percent and is far higher than the result reported by the literature, the circulation frequency of the polyaniline-titanium dioxide nanotube array composite electrode reported by the literature at present is generally not higher than 2000 circles, and the capacitance retention value is lower than 91 percent.
Drawings
Fig. 1 shows the surface morphology of the polyaniline-titanium oxide nanotube array composite electrode prepared in example 1 of the present invention.
Fig. 2 is an electrochemical cycling stability curve of the polyaniline-titanium oxide nanotube array composite electrode prepared in example 1 of the present invention.
The invention is further illustrated with reference to the following figures and examples.
The specific implementation mode is as follows:
example 1
20g of ethanol, 10g of water and 70g of ethylene glycol were mixed together, and 0.3g of ammonium fluoride, 3g of aniline and 3g of concentrated sulfuric acid (98% by mass, the same applies to the following examples) were added thereto and dissolved by stirring to obtain a mixed solution. The mixed solution was used as an electrolyte, a metallic titanium plate (purity 99%) as an anode, a platinum plate (purity 99.99%) as a cathode, and anodic oxidation was carried out at 5 ℃ and 40V for 3 hours with a distance of 2cm between the anode and the cathode. And after the reaction is finished, washing the electrolyzed anode plate with deionized water, and drying to obtain the polyaniline-titanium dioxide nanotube array composite electrode.
As can be seen from fig. 1, the prepared polyaniline-titanium dioxide nanotube array composite electrode is formed by compounding titanium dioxide and polyaniline, the shape of the nanotube array is that the opening of the tube is open, the cross-sectional view is shown in the upper left corner, and the polyaniline is uniformly distributed on the tube wall of the titanium dioxide nanotube and is tightly combined together.
The electrochemical cycle performance test of the composite electrode was performed in a three-electrode system, in which the composite electrode was a working electrode, a platinum sheet was a counter electrode, a saturated calomel electrode was a reference electrode, the charge and discharge test equipment was an electrochemical workstation (CHI660e, Chenhua, shanghai), and the test electrolyte was an aqueous solution containing 0.5M sodium sulfate. The test voltage window is-0.2-1V, and the test current density is 2mA/cm2. The test result is shown in fig. 2, after 10000 cycles of circulation, the GCD circulation curve shape of the composite electrode is almost unchanged, and the capacitance retention value of the electrode is as high as 97.3%. The circulation frequency of the polyaniline-titanium dioxide nanotube array composite electrode reported in the literature is generally not higher than 2000 circles, the capacitance retention value is lower than 91 percent, and the result of fig. 2 shows that the composite electrode prepared by the invention has good stability. The invention has the advantages that under specific conditions, the forming process of the nano tube and the synthesis process of the polyaniline are synchronously carried out in a unified way in one system, the contact area of the polyaniline and the titanium dioxide in the composite electrode is greatly improved, the bonding strength between the polyaniline and the titanium dioxide is enhanced, and the electrochemical stability of the composite electrode is further improved.
Example 2
10g of ethanol, 20g of water and 70g of ethylene glycol were mixed together, and 0.4g of ammonium fluoride, 2g of aniline and 2g of concentrated sulfuric acid were added thereto and dissolved by stirring to obtain a mixed solution. The mixed solution was used as an electrolyte, a metallic titanium plate as an anode and a platinum plate as a cathode, the distance between the anode and the cathode was 2cm, and the anode was oxidized at 3 ℃ and 30V for 4 hours. And after the reaction is finished, washing the sample wafer by using deionized water, and drying to obtain the polyaniline-titanium dioxide nanotube array composite electrode, wherein the performance of the polyaniline-titanium dioxide nanotube array composite electrode is similar to that of the embodiment 1.
Example 3
40g of ethanol, 1g of water and 59g of ethylene glycol were mixed together, and 0.5g of ammonium fluoride, 5g of aniline and 5g of concentrated sulfuric acid were added thereto and dissolved by stirring to obtain a mixed solution. The mixed solution was used as an electrolyte, a metallic titanium plate as an anode and a platinum plate as a cathode, the distance between the anode and the cathode was 2cm, and the anode was oxidized at 0 ℃ and 50V for 1 hour. And after the reaction is finished, washing the sample wafer by using deionized water, and drying to obtain the polyaniline-titanium dioxide nanotube array composite electrode, wherein the performance of the polyaniline-titanium dioxide nanotube array composite electrode is similar to that of the embodiment 1.
Example 4
30g of ethanol, 20g of water and 50g of ethylene glycol were mixed together, and 0.4g of ammonium fluoride, 4g of aniline and 4g of concentrated sulfuric acid were added thereto and dissolved by stirring to obtain a mixed solution. The mixed solution was used as an electrolyte, a metallic titanium plate as an anode and a platinum plate as a cathode, the distance between the anode and the cathode was 2cm, and the anode was oxidized at 0 ℃ and 20V for 5 hours. And after the reaction is finished, washing the sample wafer by using deionized water, and drying to obtain the polyaniline-titanium dioxide nanotube array composite electrode, wherein the performance of the polyaniline-titanium dioxide nanotube array composite electrode is similar to that of the embodiment 1.
Example 5
15g of ethanol, 5g of water and 80g of ethylene glycol were mixed together, and 0.1g of ammonium fluoride, 1g of aniline and 1g of concentrated sulfuric acid were added thereto and dissolved by stirring to obtain a mixed solution. The mixed solution was used as an electrolyte, a metallic titanium plate as an anode and a platinum plate as a cathode, the distance between the anode and the cathode was 2cm, and the anode was oxidized at 10 ℃ and 50V for 2 hours. And after the reaction is finished, washing the sample wafer by using deionized water, and drying to obtain the polyaniline-titanium dioxide nanotube array composite electrode, wherein the performance of the polyaniline-titanium dioxide nanotube array composite electrode is similar to that of the embodiment 1.
Example 6
25g of ethanol, 15g of water and 60g of ethylene glycol were mixed together, 0.2g of ammonium fluoride, 2g of aniline and 2g of concentrated sulfuric acid were added thereto, and the mixture was dissolved by stirring to obtain a mixed solution. The mixed solution was used as an electrolyte, a metallic titanium plate as an anode and a platinum plate as a cathode, the distance between the anode and the cathode was 2cm, and the anode was oxidized at 8 ℃ and 40V for 2 hours. And after the reaction is finished, washing the sample wafer by using deionized water, and drying to obtain the polyaniline-titanium dioxide nanotube array composite electrode, wherein the performance of the polyaniline-titanium dioxide nanotube array composite electrode is similar to that of the embodiment 1.
Example 7
35g of ethanol, 5g of water and 60g of ethylene glycol were mixed together, 0.1g of ammonium fluoride, 3g of aniline and 3g of concentrated sulfuric acid were added thereto, and the mixture was dissolved by stirring to obtain a mixed solution. The mixed solution was used as an electrolyte, a metallic titanium plate as an anode and a platinum plate as a cathode, the distance between the anode and the cathode was 2cm, and the anode was oxidized at 5 ℃ and 40V for 3 hours. And after the reaction is finished, washing the sample wafer by using deionized water, and drying to obtain the polyaniline-titanium dioxide nanotube array composite electrode, wherein the performance of the polyaniline-titanium dioxide nanotube array composite electrode is similar to that of the embodiment 1.
Example 8
35g of ethanol, 15g of water and 50g of ethylene glycol were mixed together, and 0.3g of ammonium fluoride, 4g of aniline and 4g of concentrated sulfuric acid were added thereto and dissolved by stirring to obtain a mixed solution. The mixed solution was used as an electrolyte, a metallic titanium plate as an anode and a platinum plate as a cathode, the distance between the anode and the cathode was 2cm, and the anode was oxidized at 5 ℃ and 20V for 4 hours. And after the reaction is finished, washing the sample wafer by using deionized water, and drying to obtain the polyaniline-titanium dioxide nanotube array composite electrode, wherein the performance of the polyaniline-titanium dioxide nanotube array composite electrode is similar to that of the embodiment 1.
The invention is not the best known technology.

Claims (2)

1. A method for preparing a polyaniline-titanium dioxide nanotube array composite electrode in one step is characterized by comprising the following steps:
adding ammonium fluoride, aniline and concentrated sulfuric acid into the mixed solvent, and stirring for dissolving to obtain a mixed solution; using the mixed solution as electrolyte, using a metal titanium sheet as an anode and a platinum sheet as a cathode, wherein the distance between the anode and the cathode is 2cm, and anodizing for 1-5 hours at the temperature of 0-10 ℃ and the voltage of 20-50V; after the reaction is finished, washing the oxidized anode plate with deionized water, and drying to obtain the polyaniline-titanium dioxide nanotube array composite electrode;
wherein, the mixed solvent comprises 10-40% of ethanol, 1-20% of water and 50-80% of glycol by mass percent; 0.1-0.5g of ammonium fluoride, 1-5g of aniline and concentrated sulfuric acid with the same mass as aniline are added into each 100g of mixed solvent.
2. The method for preparing the polyaniline-titanium dioxide nanotube array composite electrode in one step as claimed in claim 1, wherein the concentration of the concentrated sulfuric acid is 98% by mass.
CN201811121256.2A 2018-09-26 2018-09-26 Method for preparing polyaniline-titanium dioxide nanotube array composite electrode in one step Expired - Fee Related CN109192552B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101625930A (en) * 2009-06-19 2010-01-13 东南大学 Ordered nano-tube array structure electrode material, preparation method and stored energy application
CN102418148A (en) * 2011-11-17 2012-04-18 东南大学 Titanium dioxide-based polypyrrole jacket nanotube array as well as preparation method and energy storage application thereof
CN105185601A (en) * 2015-09-28 2015-12-23 华南理工大学 Titanium dioxide nanotube/polyaniline composite electrode, preparation and application thereof

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
CN101625930A (en) * 2009-06-19 2010-01-13 东南大学 Ordered nano-tube array structure electrode material, preparation method and stored energy application
CN102418148A (en) * 2011-11-17 2012-04-18 东南大学 Titanium dioxide-based polypyrrole jacket nanotube array as well as preparation method and energy storage application thereof
CN105185601A (en) * 2015-09-28 2015-12-23 华南理工大学 Titanium dioxide nanotube/polyaniline composite electrode, preparation and application thereof

Non-Patent Citations (1)

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Title
TiO2-聚苯胺纳米复合薄膜的电沉积制备;郝臣等;《江苏大学学报（自然科学版）》;20130131;第34卷(第1期);第112-115、124页 *

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