CN112047322B - Modified carbon microtube carbonized by silver willow and preparation method and application thereof - Google Patents

Modified carbon microtube carbonized by silver willow and preparation method and application thereof Download PDF

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CN112047322B
CN112047322B CN202010837651.1A CN202010837651A CN112047322B CN 112047322 B CN112047322 B CN 112047322B CN 202010837651 A CN202010837651 A CN 202010837651A CN 112047322 B CN112047322 B CN 112047322B
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micron tube
carbon
silver
modified carbon
carbon micron
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CN112047322A (en
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杨丹
李争晖
杨晓青
张国庆
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Guangdong University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the technical field of carbon material preparation, and discloses a modified carbon microtube carbonized by silver willow and a preparation method and application thereof. The modified carbon nanotube is prepared by calcining pretreated silver willow at 600-1300 ℃ under a protective atmosphere; and then, carrying out acid washing and water washing on the carbon micron tube until the pH value of the solution is neutral, dyeing and drying the carbon micron tube at the temperature of 60-90 ℃ by using a Congo red solution after drying, calcining the obtained dyed carbon micron tube at the temperature of 600-1300 ℃ under a protective atmosphere, washing until the pH value is neutral, and drying to obtain the carbon micron tube. The invention has the advantages of easily obtained raw materials, low cost, simple synthesis method and high repeatability. The modified carbon micron tube has regular structure and beautiful micro-appearance. Congo red selected is a micromolecular dye and can enter pores of the carbon micro-tubes, so that the specific surface area of the carbon micro-tubes is reduced, and the first coulomb efficiency can be improved.

Description

Modified carbon microtube carbonized by silver willow and preparation method and application thereof
Technical Field
The invention belongs to the technical field of carbon material preparation, and particularly relates to a modified carbon nanotube carbonized by silver willow and a preparation method and application thereof.
Background
The carbon material has become one of the most widely used electrode materials for lithium ion batteries and sodium ion batteries due to its characteristics of good electrical characteristics, abundant resources, various structures, proper price and the like. The carbon material is generally prepared by taking a carbon-containing precursor as a raw material and carbonizing at high temperature. At present, the precursors for preparing carbon materials mainly comprise coal, petroleum, wood, polymers and biomass materials. Among them, biomass is popular among many researchers because of its wide source, reproducibility and regular geometric structure. However, the existing biomass carbon, such as water hyacinth, straw, seaweed, etc., is a porous material with a large specific surface area, which causes the first coulomb efficiency of the sodium ion battery to be low, and therefore, it is urgently needed to prepare a carbon nanotube with a low specific surface area to improve the first coulomb efficiency of the sodium ion battery.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the modified carbon micron tube carbonized by the silver willow is provided. The modified carbon microtube has a low specific surface area, and can improve the first coulombic efficiency of the sodium ion battery.
The invention also aims to provide a preparation method of the modified carbon micron tube.
The invention further aims to provide application of the modified carbon nanotube.
The purpose of the invention is realized by the following technical scheme:
a modified carbon micron tube carbonized by silver willows is characterized in that the modified carbon micron tube is prepared by calcining pretreated silver willows at 600-1300 ℃ under a protective atmosphere; and then, carrying out acid washing and water washing on the carbon micron tube until the pH value of the solution is neutral, dyeing and drying the carbon micron tube at the temperature of 60-90 ℃ by using a Congo red solution after drying, calcining the obtained dyed carbon micron tube at the temperature of 600-1300 ℃ under a protective atmosphere, washing until the pH value is neutral, and drying to obtain the carbon micron tube.
Preferably, the concentration of the Congo red solution is 3-5 wt%.
Preferably, the dyeing time is 1-3 h.
Preferably, the protective atmosphere is nitrogen or argon.
Preferably, the modified carbon micron tube has an outer diameter of 3-6 μm, an average wall thickness of 0.4-0.7 μm, and a specific surface area of 250-370 m2/g。
The preparation method of the silver willow carbonized modified carbon nanotube comprises the following specific steps:
s1, washing off surface dust of the silver willows by using deionized water, performing suction filtration, and drying in an oven to obtain pretreated silver willows;
s2, placing the pretreated silver willow into a tube furnace, heating to 600-1300 ℃ under a protective atmosphere, calcining, washing the product with acid and water until the pH value is neutral, and placing the product into an oven for drying to obtain a carbon micron tube;
s3, dyeing the carbon micro-tube with Congo red solution at 60-90 ℃, washing away floating color with deionized water, and drying to obtain a dyed carbon micro-tube;
and S4, placing the dyed carbon micron tube into a tube furnace, heating to 600-1300 ℃ under a protective atmosphere, calcining, pickling and washing with water until the pH value is neutral, and placing into an oven for drying to obtain the modified carbon micron tube.
Preferably, the drying temperature in the step S1 is 60-80 ℃, and the drying time is 12-24 h.
Preferably, the calcination time in step S2 is 2-3 h.
Preferably, the temperature rising rate in the steps S2 and S4 is 1-10 ℃/min.
The modified carbon microtube carbonized by the silver willow is applied to the field of preparation of negative electrode materials of sodium-ion batteries.
The carbon micron tube obtained by carbonizing the silver willow has larger specific surface area, so the carbon micron tube can be physically modified. Congo red is a small molecule, and can be filled in the pores of the carbon microtubes when the carbon microtubes obtained by carbonizing the silver willows are dyed, so that the specific surface area of the carbon microtubes is reduced, and the modified carbon microtubes after carbonization have lower specific surface area, thereby improving the first coulombic efficiency.
Compared with the prior art, the invention has the following beneficial effects:
1. the carbon micron tube is firstly carbonized by the silver willow, the carbon micron tube has good dye adsorption performance, and then the dyed carbon micron tube is carbonized to obtain the modified carbon micron tube, and the modified carbon micron tube has a regular structure and attractive micro appearance.
2. The Congo red selected by the invention is a micromolecular dye, can enter the pores of the carbon micron tube, reduces the specific surface area of the carbon micron tube, and enables the modified carbon micron tube after carbonization to have a lower specific surface area, thereby improving the first coulombic efficiency.
3. The invention has the advantages of easily obtained raw materials, low cost, simple synthesis method and high repeatability.
Drawings
FIG. 1 is a scanning electron microscope image of (a) a silver willow carbonized carbon micro-tube and (b) a carbonized modified carbon micro-tube after dyeing in example 1.
Fig. 2 is a nitrogen adsorption-desorption isotherm of the carbonized carbon nanotubes before and after dyeing in example 1.
FIG. 3 is a DFT pore size distribution of carbon nanotubes before dyeing and after carbonization in example 1.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
1. Washing 20g of silver willow with deionized water for 2 times, washing off surface dust, extruding surface moisture, and drying in a 70 ℃ oven for 24 hours; putting 8g of dried silver willow into a tube furnace, heating to 1300 ℃ at a speed of 5 ℃/min under a protective atmosphere, calcining and preserving heat for 2h, stirring and soaking for 60min by using 50mL of 1mol/L diluted hydrochloric acid, washing to be neutral, putting into a 70 ℃ oven, and drying to obtain the carbon micron tube, wherein the carbon micron tube is shown in (a) in figure 1.
2. Dyeing the carbon micron tube with Congo red solution with the mass fraction of 3% at 80 ℃ for 3h, washing away the flooding with deionized water, and drying at 70 ℃ to obtain the dyed carbon micron tube;
3. and (3) putting the dyed carbon micron tube into a tubular furnace, heating to 1300 ℃ at the speed of 5 ℃/min under the protective atmosphere, calcining for 2h, pickling and washing with water until the pH value is neutral, and putting the carbon micron tube into an oven for drying to obtain the modified carbon micron tube, wherein the step (b) is shown in figure 1.
The obtained modified carbon nanotube has an outer diameter of about 3-6 μm, an average wall thickness of about 0.4-0.7 μm, and a specific surface area of 250-370 m2/g。
FIG. 1 is a scanning electron microscope image of (a) a silver willow carbonized carbon micro-tube and (b) a carbonized modified carbon micro-tube after dyeing in example 1. As can be seen from fig. 1, the morphology of the carbonized modified carbon nanotube before and after dyeing was not changed, indicating that the structure retention of the modified carbon nanotube was good. Fig. 2 is a nitrogen adsorption-desorption isotherm of the carbonized carbon nanotubes before and after dyeing in example 1. FIG. 3 is a DFT pore size distribution of carbon nanotubes before dyeing and after carbonization in example 1. Wherein SW1300 is a carbon micron tube before dyeing, and SW + 3% CR is a modified carbon micron tube carbonized after dyeing. As can be seen from fig. 2 and 3, the number of micropores of the modified carbon nanotube carbonized after the carbon nanotube is dyed is reduced, and the specific surface area is reduced, thereby improving the first coulombic efficiency of the battery.
Example 2
The difference from example 1 is that: the congo red dyes are different in concentration. Table 1 shows the effect of congo red dye concentration on the specific surface area of the material. As can be seen from table 1, the higher the congo red concentration is, the more it enters the pores of the carbon nanotube, the more significantly the specific surface area of the carbon nanotube is reduced, and the modified carbon nanotube after carbonization has a lower specific surface area, so that the first coulombic efficiency of the sodium ion battery is higher.
TABLE 1 Effect of Congo Red dye concentration on specific surface area of electrode Material
Figure BDA0002640278660000041
Example 3
The difference from example 1 is that: the staining times were different. Table 2 shows the effect of dyeing time on the specific surface area of the material. As can be seen from table 2, the longer the dyeing time is, the lower the specific surface area is, the dye can enter the pores of the carbon nanotube, and the specific surface area of the carbon nanotube is reduced, so that the modified carbon nanotube after carbonization has a lower specific surface area, and the first coulomb efficiency of the sodium ion battery is higher.
TABLE 2 Effect of dyeing time on specific surface area of electrode Material
Figure BDA0002640278660000042
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.

Claims (8)

1. The modified carbon nanotube carbonized by silver willows is characterized in that the modified carbon nanotube is prepared by calcining pretreated silver willows at 600-1300 ℃ under a protective atmosphere; then, the carbon micron tube is subjected to acid washing and water washing until the pH value of the solution is neutral, the carbon micron tube is dyed and dried at the temperature of 60-90 ℃ by using a Congo red solution after being dried, the dyed carbon micron tube is calcined at the temperature of 600-1300 ℃ under the protective atmosphere, the carbon micron tube is washed until the pH value is neutral, and the carbon micron tube is prepared by drying; the concentration of the Congo red solution is 3-5 wt%; the dyeing time is 1-3 h.
2. The silver willow carbonized modified carbon nanotube of claim 1, wherein the protective atmosphere is nitrogen or argon.
3. The silver willow carbonized modified carbon micron tube according to claim 1, wherein the modified carbon micron tube has an outer diameter of 3-6 μm, an average wall thickness of 0.4-0.7 μm and a specific surface area of 250-370 m2/g。
4. The method for preparing the silver willow carbonized modified carbon nanotube according to any one of claims 1 to 3, which is characterized by comprising the following specific steps of:
s1, washing off surface dust of the silver willows by using deionized water, performing suction filtration, and drying in an oven to obtain pretreated silver willows;
s2, placing the pretreated silver willow into a tube furnace, heating to 600-1300 ℃ under a protective atmosphere, calcining, washing a product with acid and water until the pH value is neutral, and placing the product into an oven for drying to obtain a carbon micron tube;
s3, dyeing the carbon micron tube for 1-3 h at 60-90 ℃ by using a Congo red solution with the concentration of 3-5 wt%, washing away floating color by using deionized water, and drying to obtain a dyed carbon micron tube;
and S4, placing the dyed carbon micron tube into a tube furnace, heating to 600-1300 ℃ under a protective atmosphere, calcining, pickling and washing with water until the pH value is neutral, and placing into an oven for drying to obtain the modified carbon micron tube.
5. The method for preparing the silver willow carbonized modified carbon micron tube according to claim 4, wherein the drying temperature in the step S1 is 60-80 ℃, and the drying time is 12-24 h.
6. The method for preparing the silver willow carbonized modified carbon micron tube according to claim 4, wherein the calcining time in the step S2 is 2-3 h.
7. The method for preparing the silver willow carbonized modified carbon micron tube according to claim 4, wherein the temperature rise rate in the steps S2 and S4 is 1-10 ℃/min.
8. The application of the silver willow carbonized modified carbon microtube disclosed in any one of claims 1 to 3 in the field of preparation of negative electrode materials of sodium ion batteries.
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