CN115376836B - Preparation method and application of caffeic acid modified chemically-cut carbon nano tube self-assembled composite material - Google Patents
Preparation method and application of caffeic acid modified chemically-cut carbon nano tube self-assembled composite material Download PDFInfo
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- QAIPRVGONGVQAS-DUXPYHPUSA-N trans-caffeic acid Chemical compound OC(=O)\C=C\C1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-DUXPYHPUSA-N 0.000 title claims abstract description 184
- ACEAELOMUCBPJP-UHFFFAOYSA-N (E)-3,4,5-trihydroxycinnamic acid Natural products OC(=O)C=CC1=CC(O)=C(O)C(O)=C1 ACEAELOMUCBPJP-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229940074360 caffeic acid Drugs 0.000 title claims abstract description 92
- 235000004883 caffeic acid Nutrition 0.000 title claims abstract description 92
- QAIPRVGONGVQAS-UHFFFAOYSA-N cis-caffeic acid Natural products OC(=O)C=CC1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-UHFFFAOYSA-N 0.000 title claims abstract description 92
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 74
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 26
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000005520 cutting process Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 5
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 5
- 229960005055 sodium ascorbate Drugs 0.000 claims description 5
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 28
- 239000007772 electrode material Substances 0.000 abstract description 10
- 239000003990 capacitor Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 15
- 238000002484 cyclic voltammetry Methods 0.000 description 14
- 239000008151 electrolyte solution Substances 0.000 description 11
- 229940021013 electrolyte solution Drugs 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
Classifications
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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
- H01G11/30—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
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- 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
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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
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- 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
- 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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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a preparation method and application of a caffeic acid modified chemically-cut carbon nano tube self-assembled composite material, which belong to the field of super capacitors, wherein caffeic acid and chemically-cut carbon nano tubes are respectively added into deionized water to be uniformly mixed, poured into a high-pressure reaction kettle to react, washed and dried to obtain a super capacitor electrode material with high specific capacitance, and the super capacitor electrode material has the advantages of simple synthesis method, safe operation, environment friendliness, short time consumption, low equipment requirement, low cost and the like, and the used raw materials are simple and easy to obtain; the material can be used for super capacitors to realize high specific capacitance, high rate performance and good cycle stability.
Description
Technical Field
The invention relates to the field of supercapacitors, in particular to a preparation method and application of a caffeic acid modified chemically-cut carbon nano tube self-assembled composite material.
Background
Supercapacitors play an important role in many applications as a new energy storage device. Materials of supercapacitors can be classified into two types according to energy storage mechanism: an electrochemical double layer capacitor material, one is a pseudocapacitor material. The electric double layer capacitor material stores and releases energy by desorbing/adsorbing ions, wherein the ions are reversibly adsorbed/desorbed at the interface of the electrode and the electrolyte, so that a material with a high specific surface area is required to obtain a high specific capacitance, and the main materials are carbon materials such as carbon nanotubes, graphene, activated carbon and the like. The pseudo-capacitance electrode material stores energy mainly through a rapid oxidation-reduction Faraday reaction on the electrode, and the specific capacitance of the pseudo-capacitance material is higher than that of the double-layer capacitance material because the oxidation-reduction reaction occurs in the charge-discharge process. The main materials of the catalyst are metal oxide, polymer and organic molecule.
Supercapacitors have the advantages of fast power delivery, excellent reversibility, low maintenance cost, fast charge and discharge rate, long cycle life, etc., but the energy density of supercapacitors is generally relatively low compared with batteries, and depends on the capacitance of electrode materials and the overall cell voltage, so that an electrode material is required to provide a large specific capacitance, further improving the electrochemical performance of the supercapacitors.
Disclosure of Invention
The invention aims to provide a preparation method and application of caffeic acid modified chemically-cut carbon nano tube self-assembled composite material. The material can be used for super capacitors to realize high specific capacitance and good cycle stability.
The invention aims at realizing the following technical scheme: the caffeic acid modified chemically-cut carbon nano tube self-assembled composite material is prepared by synthesizing caffeic acid and chemically-cut carbon nano tubes;
the chemical formula of the caffeic acid is as follows: c (C) 9 H 8 O 4 The structural formula is as follows:
preferably, the chemically cut carbon nanotubes are ultra-high purity single-wall carbon nanotubes with purity of more than 95%, diameter of 1-2 nm and length of 1-3 μm.
A method for preparing caffeic acid modified chemically-cut carbon nano tube self-assembled composite material, which comprises the following steps:
step S1: performing chemical oxidation cutting on the carbon nanotubes to obtain chemically cut carbon nanotubes;
step S2: and then respectively adding caffeic acid and the chemically cut carbon nano tube into deionized water, uniformly mixing, pouring into a high-pressure reaction kettle for reaction, washing and drying to obtain the composite material.
Preferably, the method for performing chemical oxidation cutting on the carbon nanotubes in the step S1 is as follows:
dispersing the carbon nano tube in a mixed solution of concentrated sulfuric acid and concentrated nitric acid under intense stirring, slowly adding potassium permanganate, carrying out ultrasonic treatment for 4-6 hours, adding deionized water, stirring, adding hydrogen peroxide, carrying out vacuum suction filtration on the diluted suspension, and washing with deionized water until the solution is neutral; then dispersing the solution in a flask by deionized water, and dropwise adding ammonia water to adjust the pH of the solution to 9-10; adding sodium ascorbate, and continuously stirring until the sodium ascorbate is completely dissolved; and placing the flask into an oil bath pot, refluxing for 2-3 hours at the temperature of 100 ℃, repeatedly washing and filtering with deionized water after cooling, and then drying in vacuum to obtain the chemically cut carbon nano tube.
Further, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is as follows: concentrated sulfuric acid: concentrated nitric acid = 3:1.
preferably, the specific steps of the step S2 are as follows:
dispersing the chemically cut carbon nano tube in deionized water, performing ultrasonic treatment for 0.5-2 hours, and heating and dissolving caffeic acid in the deionized water; mixing and stirring caffeic acid and the chemically cut carbon nano tube for 0.5-2 h, pouring the mixture into a high-pressure reaction kettle, and reacting for 12h at 150-200 ℃; and finally, cooling to room temperature, repeatedly washing with ethanol and deionized water respectively, and then drying in vacuum to obtain the composite material.
Further, the mass ratio of the caffeic acid to the chemically cut carbon nanotubes is as follows: caffeic acid: chemically cut carbon nanotubes = 1-3: 1.
the application of the caffeic acid modified chemically-cut carbon nano tube self-assembled composite material is that the caffeic acid modified chemically-cut carbon nano tube self-assembled composite material is used for manufacturing a working electrode, the caffeic acid modified chemically-cut carbon nano tube self-assembled composite material working electrode is respectively used as an anode and a cathode, and the working electrode is assembled into a symmetrical supercapacitor in sulfuric acid electrolyte.
Preferably, the preparation method of the caffeic acid modified chemically-cut carbon nano tube self-assembled composite material working electrode comprises the following steps:
according to the mass ratio, 8 parts of caffeic acid modified chemical cutting carbon nano tube self-assembled composite material, 1 part of acetylene black and 1 part of polytetrafluoroethylene emulsion are respectively taken, uniformly mixed and then coated on carbon paper.
Preferably, the concentration of the sulfuric acid solution is 1.00mol/L.
The invention has the following beneficial effects: 1. the invention is obtained by respectively adding caffeic acid and chemically cut carbon nano tubes into deionized water, uniformly mixing, pouring into a high-pressure reaction kettle for reaction, washing and drying to obtain the composite material, and synthesizing the composite material by a one-step method, and has the advantages of simple synthesizing method, safe operation, environmental friendliness, short time consumption, low equipment requirement and cost and the like; and the raw materials used are simple and easy to obtain.
2. The caffeic acid modified chemically-cut carbon nano tube self-assembled composite material is a supercapacitor active material with high specific capacitance, and the material has high capacitance and rate capability and good stability, wherein the material performance is optimal when the mass ratio of CFA to rDSCNTs is 2; the material can realize high specific capacitance and good cycle stability when used in super capacitors.
3. The invention provides a preparation method of a caffeic acid modified chemically-cut carbon nano tube self-assembled composite material. With sulfuric acid as electrolyte, the specific capacitance of the material can reach 460F g under a three-electrode system -1 Better cycle performance (after 5000 cycles, the capacitance retention rate is 90.1%), and excellent rate performance (at 10A g) -1 The specific capacitance was 80.7% of the initial capacitance at the current density of (a).
4. The invention provides a preparation method of caffeic acid modified chemically-cut carbon nano tube self-assembled composite material and the assembled composite material is a symmetrical supercapacitor, the assembled symmetrical supercapacitor has good cyclicity (after 5000 cycles, the capacitance retention rate is 75.1%), and the multiplying power performance is excellent (at 10A g) -1 The specific capacitance was 79.6% of the initial capacitance). And when the power density is 0.75kW kg -1 When the battery voltage is 1.5V, the energy density can reach 18.75Wh kg -1 。
Drawings
FIG. 1 is a Cyclic Voltammogram (CV) plot of CFA, rDSCNTs, CFA-rDSCNTs supercapacitor material prepared in example 3.
FIG. 2 is a constant current timing charge-discharge (GCD) graph of CFA, rDSCNTs, CFA-rDSCNTs supercapacitor material prepared in example 3.
FIG. 3 is a sample of CFA-rDSCNTs (m) CFA :m rDSCNTs =2:1) Cyclic Voltammetry (CV) plot of supercapacitor material.
FIG. 4 is a sample of CFA-rDSCNTs (m) prepared in example 3 CFA :m rDSCNTs =2:1) constant current timed charge-discharge (GCD) plot of supercapacitor material.
FIG. 5 is a graph showing the results of rDSCNTs and CFA-rDSCNTs prepared in example 3 (m CFA :m rDSCNTs =2:1) ac impedance profile of the supercapacitor material.
FIG. 6 is a graph showing the results of rDSCNTs and CFA-rDSCNTs prepared in example 3 (m CFA :m rDSCNTs =2:1) partial magnified plot of the ac impedance curve of the supercapacitor material.
Fig. 7 is a Cyclic Voltammetry (CV) graph of a symmetric supercapacitor prepared in example 7.
Fig. 8 is a constant current timing charge-discharge (GCD) graph of the symmetric supercapacitor prepared in example 7.
Fig. 9 is a graph of two symmetrical supercapacitors prepared in example 7 in series lighting an LED lamp with a voltage of 2V.
FIG. 10 is a diagram of the process of preparing caffeic acid modified chemically cut carbon nanotube self-assembled supercapacitor materials according to the invention.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to be limiting.
Example 1, preparation of caffeic acid modified chemically cut carbon nanotubes self-assembled composite the preparation method of chemically cut carbon nanotubes was as follows:
the carbon nano tube is an ultra-high purity single-wall carbon nano tube (short), the purity is more than 95%, the diameter is 1-2 nm, the length is 1-3 mu m, and the carbon nano tube can be directly obtained in the market; pouring 80mL of a mixed solution of concentrated sulfuric acid and concentrated nitric acid (the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is that of concentrated sulfuric acid: concentrated nitric acid=3:1) into a beaker; dispersing 0.5g of carbon nano tube in 80mL of mixed solution of concentrated sulfuric acid and concentrated nitric acid under intense stirring, then weighing 1.5g of potassium permanganate, slowly adding into a beaker, carrying out ultrasonic treatment for 5h, adding 280mL of deionized water into the mixture, stirring, then adding 10mL of 30% hydrogen peroxide, carrying out vacuum suction filtration on the diluted suspension, and washing with deionized water until the solution is neutral; then the solution is dispersed in a 250mL round bottom flask by deionized water, and ammonia water is added dropwise to adjust the pH of the solution to 9-10. 1g of sodium ascorbate was added to the solution and stirred until completely dissolved. The round bottom flask was put in an oil bath, refluxed at 100 ℃ for 3 hours, repeatedly washed with deionized water after cooling, suction-filtered through a polytetrafluoroethylene film (pore diameter 0.25 μm), and vacuum-dried at 60 ℃ for 12 hours to obtain chemically cut carbon nanotubes, denoted rDSCNTs.
Example 2, caffeic acid modified chemically cut carbon nanotube self-assembled composite material was prepared as follows:
the chemical formula of caffeic acid is: c (C) 9 H 8 O 4 The structural formula is as follows:
a certain mass of rDSCNTs was weighed and dispersed in 40mL of deionized water, sonicated for 1h, and then a certain mass of caffeic acid (CFA) was dissolved in 30mL of deionized water by heating. Then mixing and stirring the two materials for 1h, pouring the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining of 100mL, and reacting for 12h at 180 ℃. And finally, cooling to room temperature, repeatedly washing with ethanol and deionized water respectively, and vacuum drying at 60 ℃ for 12 hours to obtain the caffeic acid modified chemically-cut carbon nanotube self-assembled composite material CFA-rDSCNTs.
According to the method, the mass ratio of caffeic acid to rDSCNTs is as follows: m is m CFA :m rDSCNTs Materials were prepared separately =1-3:1.
Obtaining the mass ratio (m) of caffeic acid and rDSCNTs CFA :m rDSCNTs ) 1, 2 and 3, and the chemically cut carbon nano tube self-assembled material modified by caffeic acid.
Example 3 preparation of working electrode of caffeic acid modified chemically cut carbon nanotube self-assembled composite material, the preparation method is as follows:
the carbon paper was cut to 1 cm. Times.1.5 cm, ultrasonically cleaned with 1mol/L hydrochloric acid, absolute ethyl alcohol and deionized water, and dried under vacuum at 60℃for 12 hours. The caffeic acid modified chemically cut carbon nano tube self-assembled composite material prepared in example 2, acetylene black and 0.5 ωt% Polytetrafluoroethylene (PTFE) emulsion are respectively prepared according to the mass ratio of 8:1:1 (caffeic acid modified chemically cut carbon nanotube self-assembled composite: acetylene black: polytetrafluoroethylene emulsion=8:1:1) in an agate mortar until the slurry reaches a suitable paste. Weighing blank carbon paper, and marking the mass as m 1 And uniformly and respectively smearing the prepared slurry on carbon paper, and placing the electrode plates in a vacuum drying oven for vacuum drying at 60 ℃ for 12 hours. The mass of the weighing electrode plate is recorded as m 2 By m= (m 2 -m 1 ) And calculating the mass m of the caffeic acid modified chemically-cut carbon nano tube self-assembled composite material on each electrode slice to be 2-4 mg according to a formula of x 0.8.
For the subsequent experiments to compare the material properties of the embodiment, working electrodes of CFA and rDSCNTs were prepared according to the above method.
Example 4 application of each of the mass ratio caffeic acid modified chemically-cut carbon nanotube self-assembled composite working electrodes prepared in example 3 to a three-electrode system
The electrode prepared in example 3 was a working electrode using a conventional three electrode system with a platinum sheet electrode as the counter electrode and a Saturated Calomel Electrode (SCE) as the reference electrode.
In addition, the CFA electrode and rDSCNTs electrode prepared in example 3 were also used as working electrodes in the same systems as the above three-electrode system, respectively.
An electrolyte solution (1.00 mol/L sulfuric acid) was prepared.
To verify the technical effect, a series of electrochemical tests were performed in the above electrolyte solutions using CFA-rDSCNTs electrodes, CFA electrodes and rDSCNTs electrodes of different mass ratios for the three-electrode system.
(1) CV test: at a scanning speed of 5 mV.s -1 CV test is carried out under the scanning range of-0.1 to 0.9V (vs. SCE) to obtain the result shown in figure 1;
(2) GCD test: at a current density of 1 A.g -1 GCD test was performed at a voltage range of-0.1 to 0.9V (vs. SCE) to obtain the results shown in FIG. 2.
Analysis of FIGS. 1 and 2 shows that in the CFA-rDSCNTs supercapacitor material according to the embodiment 3 of the present invention, the mass ratio of CFA to rDSCNTs is 2 (m CFA :m rDSCNTs =2:1) supercapacitor material performs best at 1a·g -1 CFA-rDSCNTs (m CFA :m rDSCNTs =2:1) specific capacitance [ ]>450F.g -1 ) Much larger than the CFA specific capacitance.
Example 5 the caffeic acid modified chemically cut carbon nanotube self-assembled composite working electrode with optimal performance tested in example 4 was used in a three-electrode system, and the specific method is as follows:
(1) Preparing electrolyte solution: preparing electrolyte solution (1.00 mol/L sulfuric acid);
(2) A conventional three-electrode system is adopted, a platinum sheet electrode is adopted as a counter electrode, a saturated calomel electrode is adopted as a reference electrode, and a caffeic acid modified chemically-cut carbon nano tube self-assembled composite material is adopted as a working electrode;
(3) The working electrode was the best performing electrode CFA-rDSCNTs (m) obtained in example 4 CFA :m rDSCNTs ＝2:1)。
To verify the technical effect, the working electrode obtained by the method (3) was subjected to a series of electrochemical tests in the electrolyte solution of the method (1).
(1) CV test: at a scanning speed of 5 mV.s -1 ～100mV·s -1 CV test is carried out under the scanning range of-0.1 to 0.9V, and the result is shown in figure 3;
(2) GCD test: at a current density of 1 A.g -1 ～10A·g -1 GCD test was performed at a voltage ranging from-0.1 to 0.9V, and the results are shown in FIG. 4.
Analysis of FIGS. 3 and 4 shows that CFA-rDSCNTs (m CFA :m rDSCNTs =2; 1) The scanning rate of the electrode is 5-100 mV.s -1 CV curve in time. Obviously, with increasing scan rate, the CV curve area and peak current of the electrode material gradually increased, and the reversible redox peaks were still clearly visible, even at high scan rates, CFA-rdsccnts (m CFA :m rDSCNTs =2:1) the shape of the CV curve of the electrode material remains almost unchanged. At different current densities, CFA-rDSCNTs (m CFA :m rDSCNTs =2) all charging curves of the electrode material are symmetrical to the corresponding discharging curves. Description of CFA-rDSCNTs (m CFA :m rDSCNTs =2:1) electrode at 1M H 2 SO 4 The electrolyte has rapid electrolyte diffusion and excellent capacitance behavior.
Example 6 the caffeic acid modified chemically cut carbon nanotube self-assembled composite working electrode with optimal performance tested in example 4 and the rDSCNTs working electrode prepared in example 3 were used in a three-electrode system, and the specific method is as follows:
(1) Preparing electrolyte solution: preparing electrolyte solution (1.00 mol/L sulfuric acid);
(2) A conventional three-electrode system is adopted, a platinum sheet electrode is adopted as a counter electrode, a saturated calomel electrode is adopted as a reference electrode, and a caffeic acid modified chemically-cut carbon nano tube self-assembled composite material is adopted as a working electrode;
(3) The working electrode was the best performing electrode CFA-rDSCNTs (m) obtained in example 4 CFA :m rDSCNTs =2:1) and rDSCNTs working electrodes prepared in example 3.
To verify the technical effect, the working electrode obtained by the method (3) is subjected to electrochemical alternating current impedance test in the electrolyte solution of the method (1).
EIS test: at a voltage of 0.005V, a frequency in the range of 0.1-10 5 The EIS test was performed at Hz and the results are shown in FIGS. 5 and 6.
Analysis of FIGS. 5 and 6 shows that CFA-rDSCNTs (m CFA :m rDSCNTs =2:1) electrode and rDSCNTs electrode each appear as a semicircle in the high frequency region, at low frequencyThe frequency region is a straight line that is inclined. And CFA-rDSCNTs (m CFA :m rDSCNTs =2:1) electrode was larger than rDSCNTs electrode, indicating CFA-rDSCNTs (m CFA :m rDSCNTs Charge transfer resistance value of electrode (r=2:1) ct ) Is larger than rDSCNTs electrode material. Indicating the presence of a charge transfer resistance and a fast faraday reaction within the electrode material. The intercept of the X-axis represents the equivalent series resistance (R L ) Including the resistance of the electrolyte, the inherent resistance of the active material, and the contact resistance between the current collector and the active material. And CFA-rDSCNTs (m CFA :m rDSCNTs =2:1) equivalent series resistance of electrode and rDSCNTs electrode (R L ) The gap is not very large.
In example 7, the caffeic acid modified self-assembled composite material working electrode with best performance, which is tested in example 4, is respectively used as a positive electrode and a negative electrode to be assembled into a symmetrical supercapacitor, and the specific method is as follows:
(1) Preparing an electrolyte solution: preparing electrolyte solution (1.00 mol/L sulfuric acid);
(2) The working electrodes of the chemical cutting carbon nano tube self-assembled composite material modified by caffeic acid are respectively positive and negative electrodes by using the independently purchased die;
(3) The positive and negative electrodes were the working electrodes CFA-rDSCNTs (m) CFA :m rDSCNTs ＝2:1)。
To verify the technical effect, the positive and negative electrodes obtained by the method (3) are assembled into a supercapacitor in the electrolyte solution of the method (1), and a series of electrochemical tests are performed.
(1) CV test: at a scanning rate of 5 mV.s -1 ～100mV·s -1 CV test is carried out under the voltage range of 0-1.5V, and the result is shown in figure 7;
(2) GCD test: at a current density of 1 A.g -1 ～10A·g -1 GCD test was performed at a voltage ranging from 0 to 1.5V, and the results are shown in FIG. 8.
Analysis of fig. 7 and 8 shows that the caffeic acid modified chemically-cut carbon nanotube self-assembled composite material has good redox reversibility and rate capability. The shape of the CV curve remains substantially unchanged at different scan rates; under the condition of large current density, the constant current charge-discharge curve can still have a symmetrical shape.
Example 8 two symmetrical supercapacitors were assembled according to the method described in example 7, and a red-emitting LED lamp with a voltage of 2V was lit as follows:
(1) Assembling two symmetrical supercapacitors according to the method of example 7;
(2) Connecting two symmetrical super capacitors and the LED small lamp in series by using a lead;
the LED lamp was turned on by charging the path in (2) with two 1.5V dry cells, and the result is shown in fig. 9.
Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection of the present invention.
Claims (7)
1. A preparation method of caffeic acid modified chemically-cut carbon nano tube self-assembled composite material is characterized by comprising the following steps: the preparation method comprises the following steps:
step S1: performing chemical oxidation cutting on the carbon nano tube to obtain a chemically cut carbon nano tube, wherein the method comprises the following specific steps of:
dispersing the carbon nano tube in a mixed solution of concentrated sulfuric acid and concentrated nitric acid under intense stirring, slowly adding potassium permanganate, carrying out ultrasonic treatment for 4-6 hours, adding deionized water, stirring, adding hydrogen peroxide, carrying out vacuum suction filtration on the diluted suspension, and washing with deionized water until the solution is neutral; then dispersing the solution in a flask by deionized water, and dropwise adding ammonia water to adjust the pH of the solution to 9-10; adding sodium ascorbate, and continuously stirring until the sodium ascorbate is completely dissolved; placing the flask into an oil bath pot, refluxing for 2-3 hours at the temperature of 100 ℃, repeatedly washing and filtering with deionized water after cooling, and then drying in vacuum to obtain the chemically cut carbon nano tube;
step S2: then respectively adding caffeic acid and chemically cut carbon nano tubes into deionized water, uniformly mixing, pouring into a high-pressure reaction kettle for reaction, washing and drying to obtain a composite material, wherein the specific steps are as follows:
dispersing the chemically cut carbon nano tube in deionized water, performing ultrasonic treatment for 0.5-2 hours, and heating and dissolving caffeic acid in the deionized water; mixing and stirring caffeic acid and the chemically cut carbon nano tube for 0.5-2 h, pouring the mixture into a high-pressure reaction kettle, and reacting for 12h at 150-200 ℃; and finally, after cooling to room temperature, repeatedly washing with ethanol and deionized water respectively, and then drying in vacuum to obtain the composite material, wherein the mass ratio of the caffeic acid to the chemically cut carbon nano tube is as follows: caffeic acid: chemically cut carbon nanotubes = 1-3: 1.
2. the method for preparing the caffeic acid modified chemically cut carbon nanotube self-assembled composite material according to claim 1, wherein the method comprises the following steps: the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is as follows: concentrated sulfuric acid: concentrated nitric acid = 3:1.
3. the caffeic acid modified chemically-cut carbon nanotube self-assembled composite material prepared by the method for preparing the caffeic acid modified chemically-cut carbon nanotube self-assembled composite material of claim 1, which is characterized in that:
the composite material is prepared by synthesizing caffeic acid and chemically cut carbon nano tubes;
the chemical formula of the caffeic acid is as follows: c (C) 9 H 8 O 4 The structural formula is as follows:
4. the caffeic acid modified self-assembled composite of chemically cut carbon nanotubes of claim 3, wherein the chemically cut carbon nanotubes are ultra-high purity single-walled carbon nanotubes having a purity of greater than 95%, a diameter of 1-2 nm, and a length of 1-3 μm.
5. Use of a caffeic acid modified chemically cut carbon nanotube self-assembled composite according to any one of claims 3-4, characterized in that: and manufacturing a working electrode by using the caffeic acid modified chemical cutting carbon nano tube self-assembled composite material, respectively taking the caffeic acid modified chemical cutting carbon nano tube self-assembled composite material working electrode as a positive electrode and a negative electrode, and assembling the positive electrode and the negative electrode into the symmetrical supercapacitor in sulfuric acid electrolyte.
6. The use of caffeic acid modified chemically cut carbon nanotube self-assembled composites according to claim 5, wherein: the preparation method of the caffeic acid modified chemically-cut carbon nano tube self-assembled composite material working electrode comprises the following steps:
according to the mass ratio, 8 parts of caffeic acid modified chemical cutting carbon nano tube self-assembled composite material, 1 part of acetylene black and 1 part of polytetrafluoroethylene emulsion are respectively taken, uniformly mixed and then coated on carbon paper.
7. The use of caffeic acid modified chemically cut carbon nanotube self-assembled composites according to claim 5, wherein: the concentration of the sulfuric acid solution is 1.00mol/L.
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| CN105271204A (en) * | 2015-11-20 | 2016-01-27 | 复旦大学 | Graphene/graphene nanoribbon compound hydrogel and preparation method thereof |
| CN109637839A (en) * | 2018-11-14 | 2019-04-16 | 五邑大学 | Carbon nanotube/manganese dioxide composite material electrode preparation method |
| WO2022168092A1 (en) * | 2021-02-03 | 2022-08-11 | Yeda Research And Development Co. Ltd. | A noncovalent hybrid comprising carbon nanotubes (cnt) and aromatic compounds and uses thereof |
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| CN109637839A (en) * | 2018-11-14 | 2019-04-16 | 五邑大学 | Carbon nanotube/manganese dioxide composite material electrode preparation method |
| WO2022168092A1 (en) * | 2021-02-03 | 2022-08-11 | Yeda Research And Development Co. Ltd. | A noncovalent hybrid comprising carbon nanotubes (cnt) and aromatic compounds and uses thereof |
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