CN110085441B - Cu-Ag/carbon nanofiber composite material and preparation method and application thereof - Google Patents

Cu-Ag/carbon nanofiber composite material and preparation method and application thereof Download PDF

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CN110085441B
CN110085441B CN201910349437.9A CN201910349437A CN110085441B CN 110085441 B CN110085441 B CN 110085441B CN 201910349437 A CN201910349437 A CN 201910349437A CN 110085441 B CN110085441 B CN 110085441B
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carbon nanofiber
silver
copper
nanofiber composite
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苏蕾
张春勇
江霖
程洁红
邓煜雨
黄琳娜
刘凤洁
舒莉
秦恒飞
朱炳龙
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Jiangsu University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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 OR LIGHT-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
    • 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

Abstract

The Cu-Ag/carbon nanofiber composite material prepared by the method has higher specific surface area and conductivity, the higher specific surface area can generate more active sites so as to enable electrons or ions to be transferred more easily, and when the Cu-Ag/CNF composite material is applied to an anode material of a super capacitor, an electrode material with large specific capacitance, good cycle performance, long service life and low pollution can be effectively generated, because metal Cu and Ag loaded on carbon fibers are beneficial to improving the conductivity of the electrode to a certain extent, the coulombic efficiency is improved, and the cycle performance of the electrode is finally improved; and the process reaction conditions are optimized, the synthesis process is greatly simplified, and the cost is reduced.

Description

Cu-Ag/carbon nanofiber composite material and preparation method and application thereof
Technical Field
The invention relates to the field of carbon fibers, in particular to a Cu-Ag/carbon nanofiber composite material and a preparation method and application thereof.
Background
Carbon-based materials have been widely used in various forms of supercapacitor electrode materials, and although carbon-based electrodes have excellent cycle stability, long life and high power density, the specific capacitance of carbon-based electrodes is generally low compared to metal oxides; although the application of the metal oxide on the electrode of the supercapacitor has certain advantages, particularly higher theoretical specific capacitance, the defects such as low conductivity and volume change generated in the charging and discharging process still exist, and the defects generally cause poor rate performance and long-term stability of the electrode, so that the practical application of the metal oxide in the supercapacitor is limited; thus, combining carbon-based materials with metal particles to form composite electrodes is an important research direction.
The method is found by searching aiming at the prior art: xuren published & lt & gt C @ MnO2Preparation of composite material and electrostatic spinning and hydrothermal treatment two-step method used in research on ultra-capacitance performance of composite material, CNF is prepared by electrostatic spinning, and MnO is subjected to hydrothermal method2The carrier is loaded on CNF, but the method is easy to introduce impurities in the preparation process, is complex to operate and is not easy to realize industrialization; the publication of the family of Lihua Yang of the family of2An article by the name of O/Ag composite as surface-enhanced Raman scattering substrates in a subsequent one-pot process, the final product contains metal oxide, which results in lower conductivity and poorer cycling stability.
At present, carbon black is mainly used as a carrier of an electrode material, and nano carbon fibers are continuously researched due to good performances of electric conduction, heat conduction and the like, so that nano carbon fibers are a novel carbon material with good application prospect due to various superior physical and chemical properties. At present, few researches on the aspect that nano metal particles Cu and Ag are loaded on carbon nano fibers to be used as electrode materials of a super capacitor are researched.
Disclosure of Invention
In order to solve the technical problems of low specific capacitance and poor cycle performance when the carbon nanofiber is used as a carbon-based electrode, a Cu-Ag/carbon nanofiber composite material and a preparation method and application thereof are provided.
The invention is realized by the following technical scheme:
a Cu-Ag/carbon nanofiber composite material is characterized in that elemental metal copper and silver are loaded on carbon nanofibers, and the loading wt% of the elemental metal copper and the loading wt% of the elemental metal silver are 17% -29% and 30% -58% respectively.
The preparation method of the Cu-Ag/carbon nanofiber composite material comprises the following steps:
(1) preparing a spinning solution: dissolving polyacrylonitrile in a good solvent, and uniformly stirring to obtain a solution A; pouring copper salt into the solution A, and stirring at room temperature to obtain a mixed solution B; pouring silver salt into the mixed solution B, and stirring at room temperature to obtain a mixed solution C;
(2) preparing a precursor: carrying out electrostatic spinning on the mixed solution C, and drying at room temperature after the electrostatic spinning is finished to prepare a precursor Cu-Ag/PAN nano fiber;
(3) preparing a Cu-Ag/carbon nanofiber composite material: and (3) calcining the precursor obtained in the step (2) in inert gas to prepare the Cu-Ag/carbon nanofiber composite material (Cu-Ag/CNF).
Further, the good solvent in the step (1) is N, N-dimethylformamide.
Further, in the step (1), the copper salt is copper acetate, copper chloride or copper nitrate.
Further, the silver salt in the step (1) is silver acetate, silver chloride or silver nitrate.
Furthermore, the mass ratio of the copper salt, the silver salt and the polyacrylonitrile in the step (1) is 1:1 (0.1-5).
Preferably, the mass ratio of the copper salt, the silver salt and the polyacrylonitrile in the step (1) is 1:1 (0.5-5).
Further, the electrostatic spinning in the step (2) is carried out under the voltage of 10-20 kV, the flow rate of 0.8-2 mL/h and the height of 10-20 cm.
Further, the calcination in the step (3) is carried out at the temperature of 450-700 ℃ for 2-5 h.
Further, the inert gas in the step (3) is N2Or Ar.
The invention also provides application of the Cu-Ag/carbon nanofiber composite material to a super capacitor anode material.
It should be noted that: in the precursor Cu-Ag/PAN, Cu and Ag are not metal simple substances such as copper and silver in the final product, and the symbols Cu and Ag only express the existence of copper and silver in the precursor; in the final product Cu-Ag/CNF, Cu and Ag exist in the form of metal simple substances, and symbols Cu and Ag are chemical expressions of the metal simple substances, namely copper and silver.
Through a large number of experiments, the following results are found: if the mass ratio of the copper salt, the silver salt and the polyacrylonitrile is 1: x, when x is less than 0.2, the prepared sample cannot be completely filamentous and other impurities are generated; when x is more than 3, the synthesized nano fibers are easy to agglomerate together; if the voltage in the step (2) is lower than 10kv, the flow rate is higher than 2mL/h, and the height is higher than 20cm, the sprayed sample is reduced by the action of the electric field force, can not be completely filamentous, and the solution drops; if the voltage in the step (2) is higher than 20kv, the flow rate is lower than 1mL/h, and the height is lower than 15cm, electric sparks are generated, which is dangerous; if the calcination temperature in the step (3) is lower than 450 ℃ or the calcination time is less than 2 hours, the sample is not carbonized completely and impurities such as CuO are generated; if the calcination temperature in the step (3) is higher than 700 ℃ or the calcination time is longer than 5 hours, the Cu and Ag particles are not uniformly distributed and are agglomerated.
The invention has the beneficial effects that: the Cu-Ag/carbon nanofiber composite material prepared by the method has higher specific surface area and conductivity, the higher specific surface area can generate more active sites so as to enable electrons or ions to be transferred more easily, and when the Cu-Ag/CNF composite material is applied to an anode material of a super capacitor, an electrode material with large specific capacitance, good cycle performance, long service life and low pollution can be effectively generated, because metal Cu and Ag loaded on carbon fibers are beneficial to improving the conductivity of the electrode to a certain extent, the coulombic efficiency is improved, and the cycle performance of the electrode is finally improved; and the process reaction conditions are optimized, the synthesis process is greatly simplified, and the cost is reduced.
Drawings
FIG. 1 is the XRD pattern of the Cu-Ag/PAN precursor prepared in example 1.
FIG. 2 is an SEM topography of the Cu-Ag/PAN precursor prepared in example 1.
FIG. 3 is an XRD pattern of Cu-Ag/CNF obtained in example 1.
FIG. 4 is an SEM topography of Cu-Ag/CNF prepared in example 1.
FIG. 5 is a graph showing specific capacitance data measured when Cu/CNF prepared in comparative example 1, Ag/CNF prepared in comparative example 2, Cu-CuO/CNF prepared in comparative example 3, and Cu-Ag/CNF prepared in example 1 were applied to an anode material for a supercapacitor.
FIG. 6 is a graph showing cycle performance data measured when Cu/CNF prepared in comparative example 1, Ag/CNF prepared in comparative example 2, Cu-CuO/CNF prepared in comparative example 3, and Cu-Ag/CNF prepared in example 1 were applied to an anode material for a supercapacitor.
Detailed Description
The invention is further described below with reference to the figures and specific examples, without limiting the scope of the invention.
Example 1
The preparation method of the Cu-Ag/carbon nanofiber composite material comprises the following steps:
(1) preparation of spinning solution: weighing 1.102g of polyacrylonitrile, dissolving in 12mL of N, N-dimethylformamide solvent, and uniformly stirring to obtain a solution A; weighing 1.332g of copper acetate, pouring the copper acetate into the solution A, and stirring the mixture for 3 hours at room temperature to obtain a mixed solution B; weighing 1.331g of silver acetate, pouring the silver acetate into the mixed solution B, and stirring for 2 hours at room temperature to obtain a mixed solution C;
(2) preparing a precursor: placing the mixed solution C in a needle cylinder, performing electrostatic spinning under the conditions of 15kV voltage, flow rate of 1mL/h and height of 15cm, and drying at room temperature overnight after the electrostatic spinning is finished to prepare a precursor Cu-Ag/PAN nanofiber;
(3) preparing a Cu-Ag/carbon nanofiber composite material: putting the precursor obtained in the step (2) into a porcelain boat, and introducing N2Heating the mixture from room temperature to 450 ℃ at the speed of 5 ℃/min, and calcining the mixture for 2.3 hours to obtain the Cu-Ag/CNF sample.
Calculating theoretical loading (theoretical mass percent of substances contained in the product): the loading of Cu was 20.73% and the loading of Ag was 42.11%.
The precursor Cu-Ag/PAN nanofiber prepared in step (2) in this example is subjected to X-ray diffraction, and the obtained XRD spectrogram is shown in fig. 1, and compared with the standard card, the structural phase diagram of the precursor Cu-Ag/PAN shows diffraction peaks of C and Ag, which are 23.3 °, 38.3 °, 44.5 °, 64.9 °, 77.8 °, and 81.8 °, respectively.
The scanning electron microscope observation of the precursor Cu-Ag/PAN of step (2) prepared in this example shows that the SEM morphology is shown in fig. 2, and it can be seen from fig. 2 that the precursor Cu-Ag/PAN nanofibers prepared in example 1 of the present invention are bead-chain shaped, and Cu and Ag are supported on PAN fibers together in a bead-like structure.
The product Cu-Ag/CNF obtained in this example was subjected to X-ray diffraction, and the obtained XRD spectrum is shown in fig. 3, and as can be seen from fig. 3, when comparing with the standard card, after carbonization, there are diffraction peaks corresponding to Cu and Ag at 38.7 °, 43.8 °, 45 °, 51 °, 64.9 °, 74.5 °, 77.8 °, and 81.8 °.
The scanning electron microscope observation is performed on the Cu-Ag/CNF prepared in this example, and the obtained SEM morphology is shown in fig. 4, and it can be seen from fig. 4 that the Cu-Ag/CNF composite material is also in the form of bead chain, the diameter of the carbon fiber monofilament is about 1 micron, and the metal Cu and Ag particles are uniformly and tightly loaded on the CNF surface.
The specific surface area and the conductivity of the Cu-Ag/CNF prepared by the implementation are tested, and the test results are shown in Table 1.
Example 2
The preparation method of the Cu-Ag/carbon nanofiber composite material comprises the following steps:
(1) preparation of spinning solution: weighing 0.302g of polyacrylonitrile, dissolving in 12mL of N, N-dimethylformamide solvent, and uniformly stirring to obtain a solution A; weighing 1.331g of copper acetate, pouring the copper acetate into the solution A, and stirring the mixture for 3 hours at room temperature to obtain a mixed solution B; weighing 1.332g of silver acetate, pouring the silver acetate into the mixed solution B, and stirring the mixture for 2 hours at room temperature to obtain a mixed solution C;
(2) preparing a precursor: placing the mixed solution C in a needle cylinder, performing electrostatic spinning under the conditions of 15kV voltage, flow rate of 1mL/h and height of 20cm, and drying at room temperature overnight after the electrostatic spinning is finished to prepare Cu-Ag/PAN nanofibers;
(3) preparing a Cu-Ag/carbon nanofiber composite material: putting the nano-fiber obtained in the step (2) into a porcelain boat, and introducing N2At 5 ℃ from room temperatureHeating to 600 ℃ at a speed of/min, and calcining for 2h to prepare a sample Cu-Ag/CNF.
Calculating theoretical loading (theoretical mass percent of substances contained in the product): the loading of Cu was 28.46% and the loading of Ag was 57.85%.
The composite material prepared in the embodiment was tested for specific surface area and conductivity, and the specific surface area was 640m2The specific conductivity was 19.1S/cm.
Example 3
The preparation method of the Cu-Ag/carbon nanofiber composite material comprises the following steps:
(1) preparation of spinning solution: weighing 0.801g of polyacrylonitrile, dissolving in 12mL of N, N-dimethylformamide solvent, and uniformly stirring to obtain a solution A; weighing 1.332g of copper acetate, pouring the copper acetate into the solution A, and stirring the mixture for 3 hours at room temperature to obtain a mixed solution B; weighing 1.335g of silver acetate, pouring the silver acetate into the mixed solution B, and stirring the mixture for 3.5 hours at room temperature to obtain a mixed solution C;
(2) preparing a precursor: placing the mixed solution C in a needle cylinder, performing electrostatic spinning under the conditions of 20kV voltage, flow rate of 0.8mL/h and height of 10cm, and drying at room temperature overnight after electrostatic spinning is completed to obtain Cu/PAN nanofibers;
(3) preparing a Cu-Ag/carbon nanofiber composite material: and (3) placing the nano-fiber obtained in the step (2) in a porcelain boat, heating the nano-fiber to 550 ℃ from room temperature at the speed of 5 ℃/min under the condition of introducing Ar, and calcining the nano-fiber for 3 hours to obtain a sample Cu-Ag/CNF.
Calculating theoretical loading (theoretical mass percent of substances contained in the product): the loading of Cu was 23.14% and the loading of Ag was 47.16%.
The composite material prepared in the embodiment was tested for specific surface area and conductivity, and the specific surface area was found to be 653m2The specific conductivity was 25.1S/cm.
Example 4
The preparation method of the Cu-Ag/carbon nanofiber composite material comprises the following steps:
(1) preparation of spinning solution: weighing 2.001g of polyacrylonitrile, dissolving in 12mL of N, N-dimethylformamide solvent, and uniformly stirring to obtain a solution A; weighing 1.333g of copper nitrate, pouring the copper nitrate into the solution A, and stirring the mixture for 3 hours at room temperature to obtain a mixed solution B; weighing 1.334g of silver nitrate, pouring the silver nitrate into the mixed solution B, and stirring for 3.5 hours at room temperature to obtain a mixed solution C;
(2) preparing a precursor: placing the mixed solution C in a needle cylinder, performing electrostatic spinning under the conditions of 15kV voltage, flow rate of 1.5mL/h and height of 15cm, and drying at room temperature overnight after the electrostatic spinning is finished to obtain Cu-Mn/PAN nanofibers;
(3) preparing a Cu-Ag/carbon nanofiber composite material: putting the nano-fiber obtained in the step (2) into a porcelain boat, and introducing N2Heating the mixture from room temperature to 500 ℃ at the speed of 5 ℃/min, and calcining the mixture for 5 hours to prepare the Cu-Ag/CNF sample.
Calculating theoretical loading (theoretical mass percent of substances contained in the product): the loading of Cu was 17.00% and the loading of Ag was 31.89%.
The composite material prepared in the example was tested for specific surface area and conductivity, and the specific surface area was 645m2The specific conductivity was 20.8S/cm.
Example 5
The preparation method of the Cu-Ag/carbon nanofiber composite material comprises the following steps:
(1) preparation of spinning solution: weighing 2.504g of polyacrylonitrile, dissolving the polyacrylonitrile in 12mL of N, N-dimethylformamide solvent, and uniformly stirring to obtain a solution A; weighing 1.331g of copper chloride, pouring the copper chloride into the solution A, and stirring the mixture for 3 hours at room temperature to obtain a mixed solution B; weighing 1.330g of silver chloride, pouring the silver chloride into the mixed solution B, and stirring for 3.5 hours at room temperature to obtain a mixed solution C;
(2) preparing a precursor: placing the mixed solution C in a needle cylinder, performing electrostatic spinning under the conditions of 10kV voltage, flow rate of 2mL/h and height of 15cm, and drying at room temperature overnight after the electrostatic spinning is finished to prepare Cu-Ag/PAN nanofibers;
(3) preparing a Cu-Ag/carbon nanofiber composite material: putting the nano-fiber obtained in the step (2) into a porcelain boat, and introducing N2Is heated from room temperature to 700 ℃ at a rate of 5 ℃/min, calcinedAnd 5h, preparing a sample Cu-Ag/CNF.
Calculating theoretical loading (theoretical mass percent of substances contained in the product): the Cu loading was 18.90% and the Ag loading was 30.04%.
The composite material prepared in the example was tested for specific surface area and conductivity, and the specific surface area was 644m2The specific conductivity was 20.9S/cm.
Comparative example 1
The preparation method of the Cu/carbon nanofiber composite material comprises the following steps:
(1) preparation of spinning solution: weighing 1.203g of polyacrylonitrile, dissolving in 12mL of N, N-dimethylformamide solvent, and uniformly stirring to obtain a solution A; weighing 1.021g of copper chloride, pouring the copper chloride into the solution A, and stirring the mixture for 5 hours at room temperature to obtain a mixed solution B1;
(2) preparing a precursor: placing the mixed solution B1 in a needle cylinder, performing electrostatic spinning under the conditions of 20kV voltage, flow rate of 1mL/h and height of 16cm, and drying at room temperature overnight after electrostatic spinning is completed to obtain Cu/PAN nanofibers;
(3) preparing a Cu/carbon nanofiber composite material: putting the nano-fiber obtained in the step (2) into a porcelain boat, and introducing N2Heating the mixture from room temperature to 800 ℃ at the speed of 5 ℃/min, and calcining the mixture for 11 hours to obtain the Cu/CNF product.
The comparative example was subjected to specific surface area and conductivity tests, and the test results are shown in table 1.
Comparative example 2
The preparation method of the Ag/carbon nanofiber composite material comprises the following steps:
(1) preparation of spinning solution: weighing 1.105g of polyacrylonitrile, dissolving in 12mL of N, N-dimethylformamide solvent, and uniformly stirring to obtain a solution A; weighing 1.331g of silver nitrate, pouring the silver nitrate into the solution A, and stirring for 3 hours at room temperature to obtain a mixed solution C1;
(2) preparing a precursor: placing the mixed solution C1 in a needle cylinder, performing electrostatic spinning under the conditions of 15kV voltage, flow rate of 1mL/h and height of 15cm, and drying at room temperature overnight after electrostatic spinning is completed to obtain Ag/PAN nanofibers;
(3) preparing an Ag/carbon nanofiber composite material: putting the precursor obtained in the step (2) into a porcelain boat, and introducing N2Heating the mixture from room temperature to 450 ℃ at the speed of 5 ℃/min, and calcining the mixture for 2.3 hours to obtain the Ag/CNF sample.
The comparative example was subjected to specific surface area and conductivity tests, and the test results are shown in table 1.
Comparative example 3
The preparation method of the Cu-CuO/carbon nanofiber composite material comprises the following steps:
(1) preparation of spinning solution: weighing 1.104g of polyacrylonitrile, dissolving in 12mL of N, N-dimethylformamide solvent, and uniformly stirring to obtain a solution A; weighing 1.331g of copper acetate, pouring the copper acetate into the solution A, and stirring the mixture for 3 hours at room temperature to obtain a mixed solution B;
(2) preparing a precursor: placing the mixed solution B in a needle cylinder, performing electrostatic spinning under the conditions of 15kV voltage, flow rate of 1mL/h and height of 15cm, and drying at room temperature overnight after the electrostatic spinning is finished to prepare Cu-CuO/PAN nano-fiber;
(3) preparing a Cu-CuO/carbon nanofiber composite material: putting the precursor obtained in the step (2) into a porcelain boat, and introducing N2Heating the mixture from room temperature to 700 ℃ at the speed of 5 ℃/min, and calcining the mixture for 10.2 hours to prepare the Cu-CuO/CNF sample.
The comparative example was subjected to specific surface area and conductivity tests, and the test results are shown in table 1.
The specific surface area and conductivity results for the products of example 1 and comparative examples 1-3 are shown in Table 1.
TABLE 1 specific surface area and conductivity of the products of example 1 and comparative examples 1-3
Figure BDA0002043468060000071
Figure BDA0002043468060000081
As can be seen from Table 1, the specific surface area ratio and the conductivity of the Cu-Ag/CNF of example 1 are larger than those of the products of comparative examples 1-3, and the higher specific surface area can generate more active sites so as to enable electrons or ions to be transferred more easily; and the higher conductivity can improve the cycle performance of the Cu-Ag/CNF as an electrode material, thereby prolonging the service life. These two points are further reflected in the application examples.
Application example 1
The composite material prepared in the embodiment 1 is applied to an anode electrode material of a supercapacitor and subjected to electrochemical test; the products prepared in the comparative examples 1 to 3 are applied to the anode electrode material of the super capacitor and subjected to electrochemical tests.
The electrochemical performance tests are all completed on the Shanghai Chenghua CHI660 electrochemical workstation. A three-electrode system is adopted: glassy carbon electrode (GC) as working electrode
Figure BDA0002043468060000082
The platinum wire electrode is a counter electrode, and the Saturated Calomel Electrode (SCE) is a reference electrode. In the experiments, all potentials were relative to SCE and all experiments were performed at room temperature. The GC electrode was coated with Al prior to use2O3Powder of
Figure BDA0002043468060000083
And repeatedly polishing and burnishing the chamois leather, then sequentially ultrasonically cleaning the chamois leather by using absolute ethyl alcohol and distilled water, and airing the chamois leather for later use.
Preparing an electrode: 5mg of the sample, 1.25mL of water and 0.25mL of Nafion solvent were mixed and sonicated for 5 minutes to dissolve the sample sufficiently. Then 6.4 microliter of solution is taken by a pipette and dropped on a working electrode, and after drying for 2 hours in a vacuum drying oven at constant temperature of 80 ℃, the electrochemical performance test of cyclic voltammetry and constant current charging and discharging is carried out in 2M KOH electrolyte.
The specific capacitance measured for example 1 and comparative examples 1 to 3 is shown in fig. 5, where Cs is the specific capacitance (F/g), I is the current (a), m is the electrode material mass (g), v is the scanning speed (v/s), and the specific capacitance means the amount of electricity that can be discharged per weight of the battery or active material, and Cs is calculated using the formula C ═ I/v, and Cs ═ C/m ═ I/m/v. As can be seen from FIG. 5, the specific capacitance of the Cu/CNF electrode was 78F/g at 5 mV/s; the specific capacitance of the Ag/CNF electrode is 110F/g at 5 mV/s; the specific capacitance of the Cu-CuO/CNF electrode is 88F/g at 5 mV/s; the specific capacitance of the Cu-Ag/CNF electrode material is larger than that of the other three materials, the specific capacitance value is reduced along with the increase of the scanning speed, and the maximum specific capacitance is 151F/g under 5 mV/s.
The specific capacitance of the composite material of examples 2 to 5 was measured to be about 147 to 153F/g.
Cycle durability is one of the most important electrochemical properties of supercapacitors. The measured cycle performance of example 1 and comparative examples 1 to 3 is shown in fig. 6, and fig. 6 shows the change of capacitance of the electrode at a current density of 10A/g in a constant current charge and discharge test performed for 2000 cycles. As can be seen from FIG. 6, the cycle performance of Cu-Ag/CNF is obviously superior to that of other three materials, the long-period operation is carried out under the condition of high current density, the capacity retention capacity of the capacitor is still good, and after 2000 cycles, the capacity retention rate of the Cu-Ag/CNF electrode is measured to be 95.4%, because the dense Ag and Cu metal particles can provide sufficient oxidation-reduction reaction, the electrode structure made of the Cu-Ag/CNF composite material is not easy to deform, and the service life is prolonged.
The cycle performance of the composite material electrodes of examples 2-5 was tested to be between 94% and 97% after 2000 cycles under the condition of high current density.
The Cu-Ag/CNF composite material prepared by the method has higher specific surface area and electrical conductivity, the higher specific surface area can generate more active sites to enable electrons or ions to be transferred easily, and when the Cu-Ag/CNF composite material is applied to an anode material of a super capacitor, an electrode material with large specific capacitance, good cycle performance, long service life and low pollution can be effectively generated, because metal Cu and Ag loaded on carbon fibers are beneficial to improving the electrical conductivity of the electrode to a certain extent, the coulombic efficiency is improved, and the cycle performance of the electrode is finally improved.

Claims (2)

1. The Cu-Ag/carbon nanofiber composite material is characterized in that the composite material is structurally characterized in that metal simple substance copper and silver are loaded on carbon nanofibers, and the loading weight percentages of the metal simple substance copper and the silver are 17% -29% and 30% -58% respectively; the Cu-Ag/carbon nanofiber composite material is applied to a super capacitor anode material;
the preparation method of the Cu-Ag/carbon nanofiber composite material comprises the following steps:
(1) preparing a spinning solution: dissolving polyacrylonitrile in a good solvent, and uniformly stirring to obtain a solution A; pouring copper salt into the solution A, and stirring at room temperature to obtain a mixed solution B; pouring silver salt into the mixed solution B, and stirring at room temperature to obtain a mixed solution C; the good solvent is N, N-dimethylformamide; the copper salt is copper acetate, copper chloride or copper nitrate; the silver salt is silver acetate, silver chloride or silver nitrate; the mass ratio of the copper salt to the silver salt to the polyacrylonitrile is 1:1 (0.5-5);
(2) preparing a precursor: carrying out electrostatic spinning on the mixed solution C, and drying at room temperature after the electrostatic spinning is finished to prepare a precursor Cu-Ag/PAN nano fiber; the electrostatic spinning is carried out under the voltage of 10-20 kV, the flow rate of 0.8-2 mL/h and the height of 10-20 cm;
(3) preparing a Cu-Ag/carbon nanofiber composite material: calcining the precursor obtained in the step (2) in inert gas to prepare a Cu-Ag/carbon nanofiber composite material; the calcination is carried out at the temperature of 450-700 ℃ for 2-5 h.
2. The Cu-Ag/carbon nanofiber composite material according to claim 1, wherein the inert gas in the step (3) is N2Or Ar.
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