CN112750627B - Carbon nano tube and preparation method and application thereof - Google Patents

Carbon nano tube and preparation method and application thereof Download PDF

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CN112750627B
CN112750627B CN202011542391.1A CN202011542391A CN112750627B CN 112750627 B CN112750627 B CN 112750627B CN 202011542391 A CN202011542391 A CN 202011542391A CN 112750627 B CN112750627 B CN 112750627B
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carbonization
carbon nano
salt
nano tube
carbon
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CN112750627A (en
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丁兵
陈爽
张校刚
蔺青杨
胡奔
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Nanjing University of Aeronautics and Astronautics
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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
    • H01G11/84—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES 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
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • 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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 provides a carbon nano tube and a preparation method and application thereof, belonging to the technical field of carbon nano materials. The preparation method of the carbon nano tube provided by the invention comprises the following steps: ball-milling transition metal salt, phenolic compound and non-ionic block copolymer to obtain gel precursor material; and carbonizing the gel precursor material in a protective atmosphere, and then washing to obtain the carbon nano tube. The method is based on the solid-phase reaction and the sol-gel method to prepare the carbon nano tube, has simple operation and low cost, is suitable for large-scale preparation, and the prepared carbon nano tube has the advantages of wider diameter, large specific surface area, high graphitization degree, good conductivity and the like, and has great application value in electrochemical energy storage devices.

Description

Carbon nano tube and preparation method and application thereof
Technical Field
The invention relates to the technical field of carbon nano materials, in particular to a carbon nano tube and a preparation method and application thereof.
Background
Carbon nanotubes are a class of carbon nanotubes having sp2One-dimensional carbon nanomaterial with hybrid structure. Due to its unique mechanical, electrical, optical and thermal properties, carbon nanotubes are widely used in many fields. In the field of electrochemical energy storage, due to the ultrahigh electronic conductivity and relatively large specific surface area, the carbon nano tube can be directly used as an electrode material of devices such as a lithium ion battery, a super capacitor and the like, and can also be used as a conductive additive to be compounded with other active materials, so that the electrochemical performance is improved.
Currently, common methods for preparing carbon nanotubes include arc discharge, chemical vapor deposition, laser evaporation, templating, and the like. Among them, the chemical vapor deposition method has high controllability and is considered to be the most industrially valuable method for producing carbon nanotubes in large quantities. In the chemical vapor deposition process, a carbon source (gas phase) is adsorbed and reacted on the surface of a catalyst (solid phase), and carbon atoms are dissolved in the catalyst; when the carbon atoms in the catalyst reach saturation, the carbon atoms are continuously separated out and orderly assembled to finally form a tubular structure. The diameter of the grown carbon nanotube can be controlled by adjusting the size of the catalyst. However, the conventional chemical vapor deposition method requires introducing gases such as methane and acetylene as carbon sources during the preparation process, and requires strict control of the reaction pressure, which not only requires higher cost, but also has certain potential safety hazard.
The research on the method for preparing carbon nanotubes by using a solid carbon source has become a hot research in recent years. Recently, research work (j.mater.chem.a,2016,4,2137) has shown that the graphitized carbon/metallic nickel composite intermediate can be formed by calcining biomass as a carbon source together with a metallic catalyst (nickel); and then carrying out secondary calcination together with potassium hydroxide, wherein carbon-containing gas released by decomposing the carbon source can be used as the carbon source for carrying out in-situ vapor deposition. Mai et al (j.am. chem. soc.2017,139,8212) obtain carbon nanotubes by calcining a metal-organic framework compound in two steps, in which the metal in the metal-organic framework compound is reduced during high-temperature carbonization, and then serves as a catalyst to promote the formation of carbon nanotubes by surrounding carbon atoms. Compared with the chemical vapor deposition method, the two methods for directly calcining the solid carbon source have the advantages that the reaction conditions are easy to control, but the preparation process is relatively complicated, and the industrial production is not facilitated. Moreover, the carbon nanotube prepared by the method has the advantages of thin diameter and low specific surface area, and is limited in the application of electrochemical devices.
Disclosure of Invention
The invention aims to provide a carbon nano tube and a preparation method and application thereof, the method provided by the invention is simple to operate and low in cost, and the prepared carbon nano tube has the advantages of wider diameter and large specific surface area and has great application value in electrochemical energy storage devices.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a carbon nano tube, which comprises the following steps:
ball-milling transition metal salt, phenolic compound and non-ionic block copolymer to obtain gel precursor material;
and carbonizing the gel precursor material in a protective atmosphere, and then washing to obtain the carbon nano tube.
Preferably, the transition metal salt includes at least one of a cobalt salt, a nickel salt, a zinc salt, an iron salt, a ferrous salt, a manganese salt, and a copper salt.
Preferably, the phenolic compound comprises at least one of phenolic resin, kaempferol, luteolin, apigenin, quercetin, catechin, epigallocatechin, pelargonidin, cyanidin, gallic acid, caffeic acid, resveratrol, curcumin, procyanidins, and tannic acid.
Preferably, the non-ionic block copolymer comprises at least one of Pluronic L31, L35, L43, L61, L64, L72, L81, L92, L101, L121, F38, F68, F88, F108, F127, P64, P65, P84, P85, P103, P104, P105 and P123.
Preferably, the mass ratio of the transition metal salt to the phenolic compound is 1: (0.1-10), wherein the mass ratio of the transition metal salt to the nonionic block copolymer is 1: (1-16).
Preferably, the rotation speed of the ball mill is 100-400 rpm, and the time is 0.5-12 h.
Preferably, the carbonization includes a first carbonization and a second carbonization performed in sequence; the temperature of the first carbonization is 200-500 ℃, and the heat preservation time is 1-10 h; the temperature of the second carbonization is 600-950 ℃, and the heat preservation time is 4-24 h.
Preferably, the temperature increase rate for increasing the temperature to the temperature required for the first carbonization is 1 to 10 ℃/min, and the temperature increase rate for increasing the temperature from the temperature for the first carbonization to the temperature required for the second carbonization is 1 to 10 ℃/min.
The invention provides the technical scheme that the preparation method is used for preparing the productThe carbon nanotube has a diameter of 80 to 120nm and a specific surface area of 100 to 200m2g-1Pore volume of 0.1-0.15 cm3g-1。
The invention provides the application of the carbon nano tube in the technical scheme in an electrochemical energy storage device.
The invention provides a preparation method of a carbon nano tube, which comprises the following steps: ball-milling transition metal salt, phenolic compound and non-ionic block copolymer to obtain gel precursor material; and carbonizing the gel precursor material in a protective atmosphere, and then washing to obtain the carbon nano tube. The method is based on solid-phase reaction and a sol-gel method to prepare the carbon nano tube, is simple to operate, low in cost and suitable for large-scale preparation, and the prepared carbon nano tube has the advantages of wider diameter and large specific surface area and has great application value in electrochemical energy storage devices.
Further, the invention directly ball-mills the transition metal salt, the phenolic compound and the non-ionic block copolymer to prepare the gel precursor material, and then carbonizes the gel precursor material at a lower temperature (less than or equal to 950 ℃) in protective atmosphere to obtain the carbon nano tube. The preparation method is based on the solid-phase reaction to prepare the gel-like precursor material, any solvent or activating agent is not needed in the whole preparation process, and any reducing atmosphere (such as hydrogen) or carbon-containing atmosphere (such as carbon monoxide, methane or acetylene) is not needed in the carbonization process, so that the preparation process of the carbon nano tube is greatly simplified, the preparation method is environment-friendly, the process safety is high, the preparation cost is reduced, and the large-scale preparation of the carbon nano tube is favorably realized.
Furthermore, the invention is convenient to realize the regulation and control of the carbon nano tube morphology (length, pipe diameter and the like), graphitization degree and specific surface area by changing the proportion of reaction raw materials, ball milling parameters and carbonization conditions, and is beneficial to obtaining the carbon nano tube with wider diameter, high graphitization degree and large specific surface area. Moreover, the preparation of the carbon nano-tubes with different graphitization degrees is convenient to realize by selecting the transition metal salts containing different metal elements; the preparation of the heteroatom-doped carbon nanotube is facilitated by selecting the phenolic compound containing the heteroatom.
Drawings
FIG. 1 is an X-ray diffraction pattern and a Raman spectrum of the carbon nanotube prepared in example 1;
FIG. 2 is a scanning electron micrograph of carbon nanotubes prepared in example 1;
FIG. 3 is a low power transmission electron micrograph and a high power transmission electron micrograph of the carbon nanotube prepared in example 1;
fig. 4 is a graph showing the absorption/desorption curves and the distribution of the pore diameters of the carbon nanotubes prepared in example 1;
FIG. 5 is a graph showing the cycle life of the carbon nanotube electrode prepared in application example 1;
fig. 6 is a rate performance curve of the carbon nanotube/sulfur electrode prepared in application example 2.
Detailed Description
The invention provides a preparation method of a carbon nano tube, which comprises the following steps:
ball-milling transition metal salt, phenolic compound and non-ionic block copolymer to obtain gel precursor material;
and carbonizing the gel precursor material in a protective atmosphere, and then washing to obtain the carbon nano tube.
The invention ball-mills transition metal salt, phenolic compound and non-ionic block copolymer to obtain gel precursor material.
In the present invention, the transition metal salt preferably includes at least one of a cobalt salt, a nickel salt, a zinc salt, an iron salt, a ferrous salt, a manganese salt, and a copper salt; specifically, the cobalt salt preferably includes at least one of anhydrous cobalt chloride, cobalt chloride dihydrate, cobalt chloride hexahydrate, anhydrous cobalt nitrate, cobalt nitrate hexahydrate, anhydrous cobalt sulfate, cobalt sulfate monohydrate, cobalt sulfate hexahydrate, cobalt sulfate heptahydrate, anhydrous cobalt acetate, and cobalt acetate tetrahydrate; the nickel salt preferably comprises one or more of anhydrous nickel chloride, nickel chloride hexahydrate, anhydrous nickel nitrate, nickel nitrate hexahydrate, anhydrous nickel sulfate, nickel sulfate hexahydrate, nickel sulfate heptahydrate, anhydrous nickel acetate and nickel acetate tetrahydrate; the zinc salt preferably comprises one or more of anhydrous zinc chloride, zinc chloride monohydrate, zinc chloride dihydrate, zinc chloride trihydrate, zinc chloride tetrahydrate, anhydrous zinc nitrate, zinc nitrate tetrahydrate, zinc nitrate hexahydrate, anhydrous zinc sulfate, zinc sulfate hexahydrate, zinc sulfate heptahydrate, anhydrous zinc acetate and zinc acetate dihydrate; the ferric salt preferably comprises one or more of anhydrous ferric chloride, ferric chloride hexahydrate, anhydrous ferric nitrate, ferric nitrate hexahydrate, anhydrous ferric sulfate, ferric sulfate monohydrate, basic ferric acetate trihydrate, basic ferric acetate pentahydrate chloride, basic ferric acetate hexahydrate chloride, basic ferric acetate dihydrate nitrate, basic ferric acetate tetrahydrate nitrate, basic ferric acetate perchlorate, basic ferric acetate hexafluorophosphate and ferric glycolate; the ferrous salt preferably comprises anhydrous ferrous acetate and/or ferrous acetate tetrahydrate; the manganese salt preferably comprises one or more of anhydrous manganese chloride, dihydrate manganese chloride, tetrahydrate manganese chloride, anhydrous manganese nitrate and tetrahydrate manganese nitrate; the copper salt preferably comprises one or more of anhydrous copper chloride, copper chloride dihydrate, anhydrous copper nitrate, copper nitrate trihydrate, copper nitrate hexahydrate, anhydrous copper chloride, copper chloride pentahydrate and anhydrous copper acetate. The invention adopts transition metal salt to form a gel precursor material through interaction with a phenolic compound and a non-ionic block copolymer; the preparation of the carbon nano tube with different graphitization degrees is convenient to realize by selecting the transition metal salt containing different metal elements, and particularly, the graphitization degree of the carbon nano tube is favorably improved when cobalt salt, nickel salt or iron salt is adopted.
In the present invention, the phenolic compound preferably includes at least one of a phenolic resin, kaempferol, luteolin, apigenin, quercetin, catechin, epigallocatechin, pelargonidin, cyanidin, gallic acid, caffeic acid, resveratrol, curcumin, procyanidins, and tannic acid. The invention adopts phenolic compounds as carbon sources mainly to form carbon nano tubes through carbonization; specifically, the preparation of the heteroatom-doped carbon nanotube is facilitated by selecting the phenolic compound containing the heteroatom.
In the present invention, the nonionic block copolymer is a hydroxyl group-containing nonionic block copolymer. In the present invention, the nonionic block copolymer includes at least one of Pluronic L31, L35, L43, L61, L64, L72, L81, L92, L101, L121, F38, F68, F88, F108, F127, P64, P65, P84, P85, P103, P104, P105 and P123; in the present invention, the nonionic block copolymer is preferably a commercial product of Sigma-Aldrich. According to the invention, the hydrogen bond of the nonionic block copolymer and the phenolic compound form hydrogen bond mutual crosslinking, and the nonionic block copolymer can be used as a pore-forming agent, so that the finally obtained carbon nanotube has a porous structure.
In the present invention, the mass ratio of the transition metal salt to the phenolic compound is preferably 1: (0.1 to 10), more preferably 1: (0.5 to 5), and more preferably 1: (1-3), the mass ratio of the transition metal salt to the nonionic block copolymer is preferably 1: (1 to 16), more preferably 1: (1.5-10), more preferably 1: (2.5-5). The invention preferably controls the dosage of each component in the above range, which is beneficial to ensuring that the gel precursor material has proper polymerization degree, and ensuring that the carbon source and the catalyst (metal ions in the transition metal salt) are in proper proportion, can realize the control of the morphology (length and pipe diameter) of the carbon nano tube, and finally obtains the carbon nano tube with wider diameter, high graphitization degree and large specific surface area.
In the invention, the rotation speed of the ball mill is preferably 100-400 rpm, more preferably 200-300 rpm; the time is preferably 0.5 to 12 hours, more preferably 2 to 10 hours, and further preferably 4 to 6 hours. In the invention, in the ball milling process, the phenolic compound and the nonionic block copolymer contain abundant hydroxyl groups, mutual crosslinking can be realized through hydrogen bonds, metal ions in the transition metal salt and the hydroxyl groups on the nonionic block copolymer and the phenolic compound are crosslinked through electrostatic interaction, and finally the gel-like precursor material is obtained through ball milling. The invention preferably performs ball milling under the conditions, which is beneficial to ensuring that the gel precursor material has proper polymerization degree, can realize the control of the morphology (length and pipe diameter) of the carbon nano tube, and finally obtains the carbon nano tube with wider diameter, high graphitization degree and large specific surface area.
After obtaining the gel-like precursor material, the invention carbonizes the gel-like precursor material in protective atmosphere, and then washes to obtain the carbon nano tube. The type of the protective gas for providing the protective atmosphere is not particularly limited in the present invention, and a protective gas known to those skilled in the art may be used, specifically, nitrogen or argon.
In the present invention, the carbonization preferably includes a first carbonization and a second carbonization that are performed in this order. In the invention, the temperature of the first carbonization is preferably 200-500 ℃, and more preferably 300-400 ℃; the heat preservation time is preferably 1-10 h, and more preferably 1-5 h; the temperature of the invention is preferably raised from room temperature, in the embodiment of the invention, specifically 25 ℃; the temperature rise rate from room temperature to the temperature required for the first carbonization is preferably 1 to 10 ℃/min, more preferably 3 to 7 ℃/min, and still more preferably 5 ℃/min. In the invention, the temperature of the second carbonization is preferably 600-950 ℃, and more preferably 700-800 ℃; the heat preservation time is preferably 4-24 h, and more preferably 4-10 h; in the present invention, the temperature is preferably raised from the first carbonization temperature to the second carbonization temperature, and the rate of raising the temperature from the first carbonization temperature to the second carbonization temperature is preferably 1 to 10 ℃/min, more preferably 3 to 7 ℃/min, and still more preferably 5 ℃/min. In the present invention, in the carbonization process, the nonionic block copolymer is decomposed, the phenolic compound is carbonized, and the carbon nanotube is formed under the catalytic action of the metal ion in the transition metal salt. In the present invention, the temperatures of the first carbonization and the second carbonization are preferably controlled within the above ranges, so that the nonionic block copolymer can be effectively decomposed, carbonization of the phenolic compound can be ensured, and formation of a porous, highly graphitized carbon material is facilitated. The invention preferably controls the heating rate of the temperature to the temperature required by the first carbonization and the temperature required by the second carbonization within the range, can ensure the stable structure, avoids the collapse of the porous structure in the heating process, and is beneficial to forming the porous structure
After the carbonization, the obtained material is preferably cooled to room temperature, and then the obtained material is washed to remove impurity components, so that the carbon nano tube is obtained. In the present invention, the cooling method is preferably natural cooling. In the present invention, the washing preferably includes acid washing and water washing which are sequentially performed. In the invention, the acid solution used for acid washing is preferably hydrochloric acid, and the concentration of the hydrochloric acid is preferably 0.1-2 mol/L, and more preferably 1-1.5 mol/L; the present invention preferably removes metal impurities from the material by acid washing. In the present invention, the washing with distilled water is preferable, and the number of washing with distilled water is preferably 3 or more.
The carbon nano tube prepared by the preparation method provided by the invention has the advantages that the diameter is 80-120 nm, the specific surface area is 100-200 m2g-1Pore volume of 0.1-0.15 cm3g-1. In the present invention, the carbon nanotube mainly exhibits a mesoporous structure.
The invention provides the application of the carbon nano tube in the technical scheme in an electrochemical energy storage device. In the invention, the carbon nanotube can be specifically used for preparing a lithium ion battery electrode or a lithium sulfur battery electrode. The method of applying the carbon nanotubes of the present invention is not particularly limited, and a method known to those skilled in the art may be used.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Weighing 0.5g of cobalt chloride hexahydrate, 0.75g of tannic acid and 2g F127, and carrying out ball milling for 4 hours at the rotating speed of 200rpm to obtain a gel precursor material; in N2In the atmosphere, heating the gel precursor material from room temperature (25 ℃) to 300 ℃ at the speed of 5 ℃/min, carrying out heat preservation treatment for 1h at the temperature of 300 ℃, then heating to 800 ℃ at the speed of 5 ℃/min, and carrying out heat preservation treatment for 4h at the temperature of 800 ℃; naturally cooling the obtained material to room temperature with a concentration ofThe material was washed with 1mol/L hydrochloric acid, and then washed 3 times with distilled water to obtain carbon nanotubes.
Fig. 1 is an X-ray diffraction pattern and a raman spectrum of the carbon nanotube prepared in example 1, wherein a is the X-ray diffraction pattern and b is the raman spectrum. It can be seen from a in fig. 1 that the metal impurities in the carbon nanotubes have been completely removed, and from b in fig. 1 that the carbon nanotubes exhibit a high degree of graphitization.
Fig. 2 is a scanning electron micrograph of the carbon nanotube prepared in example 1, and it can be seen from fig. 2 that the material has a distinct tubular structure.
Fig. 3 is a low power transmission electron micrograph and a high power transmission electron micrograph of the carbon nanotube prepared in example 1, wherein a is the low power transmission electron micrograph and b is the high power transmission electron micrograph. As can be seen from a in fig. 3, the material has a distinct tubular structure, consistent with the results shown in fig. 2; as can be seen from b in fig. 3, the carbon nanotube is highly graphitized.
Fig. 4 is a graph showing an absorption/desorption curve and a pore size distribution of the carbon nanotube prepared in example 1, wherein a is the absorption/desorption curve and b is the pore size distribution. As can be seen from a in FIG. 4, the BET specific surface area of the carbon nanotube is 147m2g-1Pore volume of 0.13cm3g-1(ii) a As can be seen from b in fig. 4, the carbon nanotubes mainly exhibit a mesoporous structure.
Example 2
Ball-milling 0.5g of ferric chloride hexahydrate, 0.75g of tannic acid and 2g of F127 at the rotating speed of 200rpm for 4 hours to obtain a gel precursor material; in N2In the atmosphere, the gel precursor material is heated to 300 ℃ from room temperature (25 ℃) at the speed of 5 ℃/min, heat preservation treatment is carried out for 1h at the temperature of 300 ℃, then the temperature is heated to 800 ℃ at the speed of 5 ℃/min, heat preservation treatment is carried out for 4h at the temperature of 800 ℃, the obtained material is naturally cooled to room temperature, hydrochloric acid with the concentration of 1.5mol/L is adopted to wash the material, and then distilled water is adopted to wash for 3 times, so that the carbon nano tube is obtained.
Application example 1
The application of the carbon nano tube in the lithium ion battery comprises the following steps:
the carbon nanotubes prepared in example 1, the conductive carbon black and PVDF in a mass ratio of 85: 10: 5, and assembling 2016 type button cell by using metal lithium as counter electrode, wherein the solute in the electrolyte is LiPF6(concentration is 1mol/L) and the solvent is EC and EMC (EC and EMC volume ratio is 1: 1).
FIG. 5 shows the carbon nanotube electrode at 200mAg-1Cycle life plot under current density conditions. As can be seen from FIG. 5, the first-turn discharge capacity and the first-turn charge capacity of the carbon nanotube electrode were 1371mA g-1And 677mAg-1Coulombic efficiency 49%; the capacity of the carbon nano tube electrode is stabilized at 500mAg in the 300 times circulation process-1The above; after 300 cycles, the discharge capacity is 570mAg-1And the compound shows good cycling stability.
Application example 2
The application of the carbon nano tube in the lithium-sulfur battery comprises the following steps:
fully grinding 40mg of the carbon nanotube prepared in the example 2 and 60mg of elemental sulfur powder in an agate mortar, filling the ground powder material into a sealed reaction vessel, carrying out heat preservation treatment at 155 ℃ for 10h, then naturally cooling to room temperature (25 ℃) to obtain the carbon nanotube loaded with sulfur, and marking as a carbon nanotube/sulfur composite material.
Mixing the carbon nano tube/sulfur composite material, the conductive carbon black and PVDF according to a mass ratio of 80: 10: 10 to form a carbon nano tube/sulfur electrode which is used as a positive electrode, a metal lithium is used as a negative electrode to assemble a 2016 button cell, and the solutes of the electrolyte are LiTFSI (the concentration is 1mol/L) and LiNO3(concentration is 1mol/L), and the solvent is DOL and DME (volume ratio is 1: 1). The voltage range of the constant current charge and discharge test is 1.7-3V (vs Li)+/Li)。
Fig. 6 is a graph of rate performance of a carbon nanotube/sulfur electrode. As can be seen from FIG. 6, the carbon nanotube/sulfur electrode was at 0.1C (1675 mAg)-1) The discharge capacity at the rate is 1200mAh g-1(ii) a When the current was increased to 0.2C, 0.5C, 1C and 2C, the discharge capacity of the carbon nanotube/sulfur electrode was 1025mAh g, respectively-1、834mAh g-1、745mAh g-1And 593mAh g-1(ii) a When the current is reduced to 0.5C again, the discharge capacity of the carbon nano tube/sulfur electrode is rapidly recovered to 845mAh g-1And excellent rate performance is shown.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A method for preparing carbon nanotubes is characterized by comprising the following steps:
ball-milling transition metal salt, phenolic compound and non-ionic block copolymer to obtain gel precursor material;
and carbonizing the gel precursor material in a protective atmosphere, and then washing to obtain the carbon nano tube.
2. The method of claim 1, wherein the transition metal salt comprises at least one of a cobalt salt, a nickel salt, a zinc salt, an iron salt, a ferrous salt, a manganese salt, and a copper salt.
3. The method of claim 1, wherein the phenolic compound comprises at least one of a phenolic resin, kaempferol, luteolin, apigenin, quercetin, catechin, epigallocatechin, pelargonidin, cyanidin, gallic acid, caffeic acid, resveratrol, curcumin, procyanidins, and tannic acid.
4. The method of claim 1, wherein the non-ionic block copolymer comprises at least one of Pluronic L31, L35, L43, L61, L64, L72, L81, L92, L101, L121, F38, F68, F88, F108, F127, P64, P65, P84, P85, P103, P104, P105, and P123.
5. The method according to any one of claims 1 to 4, wherein the mass ratio of the transition metal salt to the phenolic compound is 1: (0.1-10), wherein the mass ratio of the transition metal salt to the nonionic block copolymer is 1: (1-16).
6. The preparation method of claim 1, wherein the rotation speed of the ball mill is 100-400 rpm, and the time is 0.5-12 h.
7. The production method according to claim 1, wherein the carbonization includes a first carbonization and a second carbonization that are performed in this order; the temperature of the first carbonization is 200-500 ℃, and the heat preservation time is 1-10 h; the temperature of the second carbonization is 600-950 ℃, and the heat preservation time is 4-24 h.
8. The production method according to claim 7, wherein a rate of temperature increase to the temperature required for the first carbonization is 1 to 10 ℃/min, and a rate of temperature increase from the temperature required for the first carbonization to the temperature required for the second carbonization is 1 to 10 ℃/min.
9. The carbon nanotube produced by the production method according to any one of claims 1 to 8, wherein the diameter is 80 to 120nm, and the specific surface area is 100 to 200m2 g-1Pore volume of 0.1-0.15 cm3 g-1。
10. Use of the carbon nanotubes of claim 9 in electrochemical energy storage devices.
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