阅读说明：本技术 阵列型掺杂多壁碳纳米管及其制备方法和电极材料 (Array type doped multi-walled carbon nanotube, preparation method thereof and electrode material ) 是由 万远鑫 黄少真 孔令涌 任望保 王敏 余永龙 于 2020-12-11 设计创作，主要内容包括：本申请提供了一种阵列型掺杂多壁碳纳米管,包括多壁碳纳米管和掺杂在多壁碳纳米管中的掺杂原子；该阵列型掺杂多壁碳纳米管具有径向导电通道,径向导电通道是由掺杂原子与多壁碳纳米管的相邻管壁通过共价键合形成,所述阵列型掺杂多壁碳纳米管的管径为1-100nm,长度为10μm-100μm。该阵列型掺杂多壁碳纳米管具有良好的导电性,将其应用在电极材料中能够提高电极材料的导电性。本申请还提供了阵列型掺杂多壁碳纳米管的制备方法。该制备方法工艺简单,操作便捷,所得的阵列型掺杂多壁碳纳米管的良品率高。本申请还提供了含有阵列型掺杂多壁碳纳米管的电极材料。(The application provides an array type doped multi-walled carbon nanotube, which comprises a multi-walled carbon nanotube and doping atoms doped in the multi-walled carbon nanotube; the array type doped multi-walled carbon nanotube is provided with a radial conductive channel, wherein the radial conductive channel is formed by covalently bonding doping atoms and adjacent tube walls of the multi-walled carbon nanotube, the tube diameter of the array type doped multi-walled carbon nanotube is 1-100nm, and the length of the array type doped multi-walled carbon nanotube is 10-100 mu m. The array type doped multi-walled carbon nanotube has good conductivity, and the conductivity of the electrode material can be improved by applying the array type doped multi-walled carbon nanotube to the electrode material. The application also provides a preparation method of the array type doped multi-walled carbon nanotube. The preparation method is simple in process and convenient and fast to operate, and the obtained array type doped multiwall carbon nanotube is high in yield. The application also provides an electrode material containing the array type doped multi-wall carbon nano-tube.)

1. The array type doped multi-wall carbon nanotube is characterized by comprising a multi-wall carbon nanotube and doping atoms doped in the multi-wall carbon nanotube; the array type doped multi-walled carbon nanotube is provided with a radial conductive channel, and the radial conductive channel is formed by covalent bonding of the doping atoms and the adjacent tube wall of the multi-walled carbon nanotube; the tube diameter of the array type doped multi-wall carbon nano tube is 1-100nm, and the length of the array type doped multi-wall carbon nano tube is 10-100 mu m.

2. The arrayed, doped multiwall carbon nanotube of claim 1, wherein the dopant atoms form a C-X-C covalent bond with carbon atoms on adjacent walls of the multiwall carbon nanotube, wherein X is the dopant atom; wherein the doping atoms include one or more of boron atoms, nitrogen atoms, phosphorus atoms, sulfur atoms, and silicon atoms.

3. The array-type doped multi-walled carbon nanotube of claim 1 or 2, wherein the mass percentage of the doping atoms is 0.01% to 10%.

4. The array-type doped multi-wall carbon nanotube of any one of claims 1 to 3, wherein the number of layers of the array-type doped multi-wall carbon nanotube ranges from 3 layers to 10 layers.

5. The array-type doped multi-walled carbon nanotubes of any of claims 1 to 4, wherein the interlayer spacing of the array-type doped multi-walled carbon nanotubes at the positions where the covalent bonds are formed is larger than the interlayer spacing at the positions where the covalent bonds are not formed.

6. The array-type doped multi-wall carbon nanotubes of any of claims 1-5, wherein said array-type doped multi-wall carbon nanotubes have a resistivity of 20m Ω -cm to 75m Ω -cm.

7. The array-type doped multi-wall carbon nanotube of any one of claims 1 to 6, wherein the specific surface area of the array-type doped multi-wall carbon nanotube is not less than 250m²/g。

8. A preparation method of an array type doped multi-wall carbon nanotube is characterized by comprising the following steps:

uniformly mixing a layered carrier, an intercalation agent, an active component source, a doping source and a solvent, and drying to obtain a catalyst precursor; the active component source comprises a soluble transition metal salt;

calcining the catalyst precursor, introducing water vapor in the calcining process, and cooling to obtain the catalyst, wherein the catalyst comprises the layered carrier, an active component and the doping source, the active component is loaded on the layered carrier, and the active component comprises transition metal active particles;

placing the catalyst in a reactor, introducing a carbon source in an inert atmosphere, forming a doped multi-walled carbon nanotube array on the layered carrier in a chemical vapor deposition mode, removing the catalyst, and removing the catalyst to obtain an array type doped multi-walled carbon nanotube; the array type doped multi-wall carbon nanotube comprises a multi-wall carbon nanotube and doping atoms doped in the multi-wall carbon nanotube; the array type doped multi-walled carbon nanotube is provided with a radial conductive channel, and the radial conductive channel is formed by covalent bonding of the doping atoms and the adjacent tube wall of the multi-walled carbon nanotube; the tube diameter of the array type doped multi-wall carbon nano tube is 1-100nm, and the length of the array type doped multi-wall carbon nano tube is 30-100 mu m.

9. A preparation method of an array type doped multi-wall carbon nanotube is characterized by comprising the following steps:

dispersing an active component source, a doping source, a layered carrier and a first carbon source in a solvent, and drying to obtain a catalyst precursor; the active component source comprises a soluble transition metal salt;

calcining the catalyst precursor in an inert atmosphere to obtain a carbon-coated material; the carbon coating material comprises a catalyst and a carbon coating layer coating the catalyst, the catalyst comprises a layered carrier, and an active component and a doping source which are loaded on the layered carrier, and the active component comprises transition metal active particles;

removing the carbon coating layer to obtain the naked catalyst;

placing the catalyst in a reactor, introducing a second carbon source in an inert atmosphere, and forming a doped multi-walled carbon nanotube array on the layered carrier in a chemical vapor deposition manner; then removing the catalyst to obtain the array type doped multi-walled carbon nanotube; the array type doped multi-wall carbon nanotube comprises a multi-wall carbon nanotube and doping atoms doped in the multi-wall carbon nanotube; the array type doped multi-walled carbon nanotube is provided with a radial conductive channel, and the radial conductive channel is formed by covalent bonding of the doping atoms and the adjacent tube wall of the multi-walled carbon nanotube; the tube diameter of the array type doped multi-wall carbon nano tube is 1-100nm, and the length of the array type doped multi-wall carbon nano tube is 10-100 mu m.

10. An electrode material comprising an electrode active material, a binder and a conductive agent, wherein the conductive agent comprises the arrayed doped multi-walled carbon nanotubes of any one of claims 1 to 7.

Technical Field

The application relates to the technical field of multi-walled carbon nanotubes, in particular to an array type doped multi-walled carbon nanotube, a preparation method thereof and an electrode material.

Background

The carbon nanotube is a one-dimensional quantum material with a unique nano hollow structure, and can be regarded as a seamless tube with a nano-scale diameter, which is formed by coiling one or more layers of graphene sheets according to a certain spiral angle. The carbon nanotubes can be divided into single-walled carbon nanotubes and multi-walled carbon nanotubes according to the number of layers of the graphene sheets, wherein the multi-walled carbon nanotubes are formed by curling multiple graphene sheets. The multi-walled carbon nanotube has a good conductive path in the axial direction, as shown in fig. 1, the dotted arrow indicates the axial conductive path of the multi-walled carbon nanotube, and electrons can migrate along the axial conductive path. However, since the wall of the carbon nanotube is formed by winding graphene sheets, electrons are difficult to transmit between graphene sheets, and thus the multi-walled carbon nanotube has poor conductivity in the radial direction, thereby limiting its application as a conductive agent in an electrode.

In addition, the carbon nanotubes can be divided into array type carbon nanotubes and clustered carbon nanotubes according to the dispersion state of the carbon nanotubes when the preparation is finished, wherein the array type carbon nanotubes are orderly arranged carbon nanotubes which grow on the surface of a substrate in order, have better orientation and uniform pipe diameter distribution, and are beneficial to improving the effects of electric conduction, heat conduction and the like; meanwhile, compared with the clustered carbon nanotubes, the clustered carbon nanotubes can be dispersed only with higher energy consumption, the substrate bearing the array carbon nanotubes is easier to remove, a plurality of dispersed carbon nanotubes with complete appearance are obtained, and the tube length of the dispersed carbon nanotubes is not broken and shortened after the dispersed carbon nanotubes are dispersed.

Therefore, there is a need to provide an array-type multi-walled carbon nanotube with excellent radial conductivity and high morphological integrity so as to obtain the array-type multi-walled carbon nanotube with excellent conductivity.

Content of application

In view of this, the present disclosure provides an array-type doped multi-walled carbon nanotube, which has a radial conductive channel and can promote the radial transmission of electrons along the multi-walled carbon nanotube, so that the array-type doped multi-walled carbon nanotube has good conductivity, and when the array-type doped multi-walled carbon nanotube is applied to an electrode material, the conductivity of the electrode material can be improved.

The application provides an array type doped multi-wall carbon nanotube, which comprises a multi-wall carbon nanotube and doping atoms doped in the multi-wall carbon nanotube; the array type doped multi-walled carbon nanotube is provided with a radial conductive channel, and the radial conductive channel is formed by covalent bonding of the doping atoms and the adjacent tube wall of the multi-walled carbon nanotube; the tube diameter of the array type doped multi-wall carbon nano tube is 1-100nm, and the length of the array type doped multi-wall carbon nano tube is 10-100 mu m.

The array type doped multi-walled carbon nanotube provided by the first aspect of the application has a radial conductive channel, and promotes the radial transmission of electrons in the multi-walled carbon nanotube, so that the array type doped multi-walled carbon nanotube has good conductivity and good electron conductivity, and the application of the multi-walled carbon nanotube is expanded. In addition, the array type doped multi-wall carbon nano tube has uniform size and uniform conductivity.

The second aspect of the application provides a preparation method of an array type doped multi-walled carbon nanotube, which comprises the following steps:

uniformly mixing a layered carrier, an intercalation agent, an active component source, a doping source and a solvent, and drying to obtain a catalyst precursor; the active component source comprises a soluble transition metal salt;

calcining the catalyst precursor, introducing water vapor in the calcining process, and cooling to obtain the catalyst, wherein the catalyst comprises the layered carrier, an active component and the doping source, the active component is loaded on the layered carrier, and the active component comprises transition metal active particles;

placing the catalyst in a reactor, introducing a carbon source in an inert atmosphere, forming a doped multi-walled carbon nanotube array on the layered carrier in a chemical vapor deposition manner, removing the catalyst, and removing the catalyst to obtain the array-type doped multi-walled carbon nanotube according to the first aspect of the present application.

The third aspect of the present application also provides a method for preparing an array type doped multi-walled carbon nanotube, comprising:

dispersing an active component source, a doping source, a layered carrier and a first carbon source in a solvent, and drying to obtain a catalyst precursor; the active component source comprises a soluble transition metal salt;

calcining the catalyst precursor in an inert atmosphere to obtain a carbon-coated material; the carbon coating material comprises a catalyst and a carbon coating layer coating the catalyst, the catalyst comprises a layered carrier, and an active component and a doping source which are loaded on the layered carrier, and the active component comprises transition metal active particles;

removing the carbon coating layer to obtain the naked catalyst;

placing the catalyst in a reactor, introducing a second carbon source in an inert atmosphere, and forming a doped multi-walled carbon nanotube array on the layered carrier in a chemical vapor deposition manner; and then removing the catalyst to obtain the array type doped multi-wall carbon nano tube according to the first aspect of the application.

In the preparation method of the array-type doped multi-walled carbon nanotube provided by the second aspect or the third aspect of the application, the array-type doped multi-walled carbon nanotube with the radial conductive channel is prepared by a chemical vapor deposition method, the process is simple, the operation controllability is strong, and the yield of the prepared array-type doped multi-walled carbon nanotube is high.

In a fourth aspect, the present application provides an electrode material comprising an electrode active material, a binder, and a conductive agent comprising the arrayed doped multi-walled carbon nanotubes provided in the first aspect of the present application.

The array type doped multi-walled carbon nanotube has good conductivity, can be used as a conductive agent to be added into an electrode material, and can reduce the using amount of the conductive agent in the electrode material, so that the content of an electrode active material in the electrode material is increased, and the electrode material has higher energy density. The electrode material has good conductivity, and can improve the energy density and the performance of the battery when applied to the battery.

Drawings

FIG. 1 is a schematic structural diagram of an undoped multi-walled carbon nanotube;

FIG. 2 is a schematic structural diagram of an array-type doped multi-walled carbon nanotube of the present application;

FIG. 3 is a scanning electron microscope image of the doped multi-walled carbon nanotube array prepared in example 1 of the present application;

FIG. 4 is a transmission electron microscope image of the array-type doped multi-walled carbon nanotube prepared in example 1 of the present application.

Detailed Description

The following is a preferred embodiment of the present application, and it should be noted that, for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present application, and these improvements and modifications are also considered as the protection scope of the present application.

The embodiment of the application provides an array type doped multi-wall carbon nanotube, which comprises a multi-wall carbon nanotube and doping atoms doped in the multi-wall carbon nanotube. The array type doped multi-walled carbon nanotube is provided with a radial conductive channel, the radial conductive channel is formed by covalent bonding of doping atoms and the adjacent tube wall of the multi-walled carbon nanotube, the tube diameter of the array type doped multi-walled carbon nanotube is 1-100nm, and the length of the array type doped multi-walled carbon nanotube is 10-100 mu m. Referring to fig. 2, the dotted arrows indicate the axial conductive paths of the multi-walled carbon nanotubes along which electrons can migrate; the solid arrows indicate the radial conductive paths of the multi-walled carbon nanotubes along which electrons can migrate.

In the embodiment of the present application, the walls of the array-type doped multi-walled carbon nanotubes only contain carbon atoms, and the doped atoms are located between the walls of the multi-walled carbon nanotubes. In the embodiment of the application, doping atoms are doped between the tube walls of the multi-wall carbon nanotube, so that the doping atoms and the carbon atoms of the adjacent tube walls in the multi-wall carbon nanotube form a C-X-C covalent bond, wherein X is a doping atom. The C-X-C covalent bonds between different tube walls connect the tube walls to form a radial conductive channel, and the radial conductive channel can promote the radial transmission of electrons in the multi-walled carbon nanotube, so that the conductivity of the multi-walled carbon nanotube is improved.

In the embodiment of the application, the array type doped multi-walled carbon nanotube is linear as a whole, and a bending part is formed locally, and the bending part has a corrugated fold. The bending part is formed by covalent bonds formed by the doped atoms on the tube wall of the multi-walled carbon nanotube, so that the interlayer acting force of the multi-walled carbon nanotube is damaged, the interlayer spacing between the tube walls of the array type doped multi-walled carbon nanotube is different, and the array type doped multi-walled carbon nanotube is enabled to be wrinkled and twisted and deformed. The change of interlayer spacing, the wrinkle and the torsional deformation are all defects of the multi-wall carbon nano tube after doping atoms. In the embodiment of the application, the defect proportion of the array type doped multi-wall carbon nano tube is 30-80%. By controlling the defect content of the array type doped multi-walled carbon nanotube, the sufficient number of radial conductive channels can be ensured, and the transmission rate of electrons along the axial direction of the array type doped multi-walled carbon nanotube is not influenced, so that the multi-walled carbon nanotube has good electron transmission rate in the axial direction and the radial direction.

In the present application, the defect content of the array type doped multi-walled carbon nanotube is related to the kind and content of the doping atoms. In the embodiments of the present application, the doping atoms include one or more of boron atoms, nitrogen atoms, phosphorus atoms, sulfur atoms, and silicon atoms. By doping atoms between the walls of the multi-walled carbon nanotubes, the doping atoms can be bonded with carbon atoms on the adjacent walls to form one or more covalent bonds of C-B-C, C-N-C, C-P-C, C-S-C and C-Si-C, so that an electron transfer channel is effectively constructed between the walls of the multi-walled carbon nanotubes, and the radial transmission of electrons in the multi-walled carbon nanotubes is promoted. In the embodiment of the application, doping atoms in the multi-walled carbon nanotube can also cause the conductivity type of the multi-walled carbon nanotube to change. In some embodiments, the dopant atoms are boron atoms, and the array-type doped multi-walled carbon nanotubes form p-type conductivity and conduct electricity through holes. In other embodiments of the present application, the dopant atoms are nitrogen atoms, and the array-type doped multi-walled carbon nanotubes form n-type conduction and conduct with majority carriers. The array type doped multi-walled carbon nanotube can select different doping atoms according to actual requirements to adjust the conductivity of the array type doped multi-walled carbon nanotube.

In the embodiment of the application, the mass percentage of the doping atoms is 0.01-10%. Further, the mass percentage of the doping atoms is 1% to 10%, and specifically, but not limited to, 0.01%, 0.05%, 0.1%, 0.5%, 1.5%, 3%, 5%, or 10%. The number of radial conductive channels can be adjusted by controlling the content of the doped atoms, the electron transmission rate of the array type doped multi-walled carbon nanotube in the axial direction and the radial direction is ensured, and the conductivity of the array type doped multi-walled carbon nanotube is improved. In some embodiments of the present disclosure, the dopant atoms are boron atoms, and the mass percentage of the boron atoms is 5%.

In the embodiment of the application, the number of the layers of the array type doped multi-wall carbon nano tube is 3-10. Generally, when the number of layers of the multi-walled carbon nanotube is greater than or equal to 3, electrons are generally difficult to transmit between graphene sheets, and doping atoms into the multi-walled carbon nanotube can effectively promote the radial migration of the electrons in the multi-walled carbon nanotube and improve the conductivity of the multi-walled carbon nanotube; when the number of layers of the multi-walled carbon nanotube is less than or equal to 10, the doping atoms can be fully doped to each layer of the tube wall of the multi-walled carbon nanotube, so that a short electron transmission channel can be formed in the radial direction of the multi-walled carbon nanotube, and the electron transmission is promoted. The number of layers of the array-type doped multi-walled carbon nanotube may be, but is not limited to, 3, 4, 5, 7, 9, or 10. In some embodiments, the number of layers of the array-type doped multi-walled carbon nanotubes is 5 to 9. Optionally, the thickness of the tube wall of the array type doped multi-wall carbon nanotube is 2-3 nm.

In some embodiments, the diameter of the array-type doped multi-walled carbon nanotubes may be 3nm to 10nm, preferably 3nm to 8 nm. More preferably 3-7.5 nm. At the moment, the tube diameter of the array type doped multi-wall carbon nano tube is very small, the length-diameter ratio is extremely high, and the performance is excellent (such as low defect density and better conductivity).

In some embodiments, the length of the array-type doped multi-walled carbon nanotubes may be 30 μm to 100 μm. Further, the length may be 30 μm to 90 μm, 40 μm to 90 μm, 30 μm to 60 μm, or 35 μm to 55 μm.

In the embodiment of the application, the length-diameter ratio of the array type doped multi-wall carbon nano-tube is 10-33333. In some embodiments, the aspect ratio of the array-type doped multi-walled carbon nanotube can be 125-. Preferably 3750-33333, more preferably 4286-33333.

In the embodiment of the application, the specific surface area of the array type doped multi-wall carbon nano-tube is more than or equal to 250m²(ii) in terms of/g. The array type doped multi-walled carbon nanotube with larger specific surface area can better exert the conductivity when being used in the fields of battery electrode materials, super capacitor electrode materials and the like, and also has better liquid absorption when being used in batteries, thereby being beneficial to fully soaking the electrode materials.

In an embodiment of the application, the interlayer spacing of the array-type doped multi-walled carbon nanotubes at the positions where the covalent bonds are formed is larger than the interlayer spacing at the positions where the covalent bonds are not formed. When doping atoms into the tube walls of the multi-walled carbon nanotubes, due to the formation of covalent bonds, interlayer acting force between the tube walls of the multi-walled carbon nanotubes changes, so that the interlayer spacing of the tube walls at the position of the covalent bonds is enlarged, the multi-walled carbon nanotubes present a twisted structure, and further, the twisted structure can increase holes of the multi-walled carbon nanotubes for receiving electrons, thereby improving the conductivity of the multi-walled carbon nanotubes.

In the embodiment of the present application, the resistivity of the array-type doped multi-walled carbon nanotube is 20m Ω · cm to 75m Ω · cm. Specific electrical resistivity of the array-type doped multi-walled carbon nanotube may be, but is not limited to, 20m Ω · cm, 30m Ω · cm, 35m Ω · cm, 40m Ω · cm, 45m Ω · cm, 50m Ω · cm, 55m Ω · cm, 60m Ω · cm, 65m Ω · cm, or 75m Ω · cm. The array type doped multi-wall carbon nanotube has small resistivity value and good conductivity.

In the embodiments of the present application, the array-type doped multi-walled carbon nanotubes can be applied to battery electrode materials and supercapacitor electrode materials, but are not limited thereto.

According to the array type doped multi-walled carbon nanotube, the doping atoms are doped between the walls of the multi-walled carbon nanotube, so that the doping atoms and the adjacent walls of the multi-walled carbon nanotube form covalent bonds, the covalent bonds can extend the conjugated structure in the multi-walled carbon nanotube to the outer part of the multi-walled carbon nanotube, the multi-walled carbon nanotube is provided with a radial conductive channel, the radial conductive channel enriches the migration path of electrons in the multi-walled carbon nanotube, promotes the radial transmission of the electrons in the multi-walled carbon nanotube, and the array type doped multi-walled carbon nanotube has good conductivity and good electron conductivity, so that the application of the multi-walled carbon nanotube is expanded.

Accordingly, the present application provides a first method for preparing an array-type doped multi-walled carbon nanotube, comprising the steps of:

s100: uniformly mixing a layered carrier, an intercalation agent, an active component source, a doping source and a solvent, and drying to obtain a catalyst precursor; the active component source comprises a soluble transition metal salt;

s200: calcining the catalyst precursor, introducing water vapor in the calcining process, and cooling to obtain the catalyst, wherein the catalyst comprises the layered carrier, and an active component and the doping source which are loaded on the layered carrier, and the active component comprises transition metal active particles;

s300: placing the catalyst in a reactor, introducing a carbon source in an inert atmosphere, forming a doped multiwall carbon nanotube array on the layered carrier in a chemical vapor deposition mode, and then removing the catalyst to obtain an array type doped multiwall carbon nanotube; the array type doped multi-wall carbon nanotube comprises a multi-wall carbon nanotube and doping atoms doped in the multi-wall carbon nanotube; the array type doped multi-walled carbon nanotube is provided with a radial conductive channel, and the radial conductive channel is formed by covalent bonding of the doping atoms and the adjacent tube wall of the multi-walled carbon nanotube; the tube diameter of the array type doped multi-wall carbon nano tube is 1-100nm, and the length of the array type doped multi-wall carbon nano tube is 10-100 mu m.

In the first preparation method of the array type multi-walled carbon nanotube, the interlayer spacing of the layered carrier is enlarged by adopting the intercalating agent, so that the quantity of the active components loaded by the layered carrier is effectively increased, the intercalating agent can also inhibit the source agglomeration of the active components, and the formation of the active components with small particle size is facilitated, thereby promoting the formation of the array carbon nanotube with higher length-diameter ratio; the steam is used for pre-activating the catalyst, so that the safety is better, and the production cost is reduced; the doping source is introduced when the catalyst precursor is prepared, so that the doping source can be effectively combined with the catalyst formed by calcining the catalyst precursor, and doping atoms can be doped between the walls of the multi-walled carbon nanotubes. The array type doped multi-walled carbon nanotube prepared by the method has higher length-diameter ratio, good pipe diameter uniformity and excellent conductivity; the preparation method has the advantages of simple process and strong operation controllability, and can be applied to large-scale industrial production.

In step S100, the doping source may include one or more of magnesium borate, sodium borate, boron nitride, aluminum sulfate, and magnesium sulfate, but is not limited thereto. Optionally, the molar ratio of the doping atoms in the doping source to the transition metal atoms in the active component source is 1: (5-100) to take a dopant source and an active component source.

In the application, the layered carrier has a large specific surface area and high loading capacity for the active component source, and the carrier used in the application has good adsorption capacity, so that the intercalation agent and the active component source can be attached to the surface of the carrier. In addition, the layered carrier can be used as a carrier of a catalyst for the growth of the carbon nano tube, so that a plane is provided for the growth of the carbon nano tube, and the carbon nano tube vertically grows to form a carbon nano tube array. Wherein the layered support comprises one or more of layered alumina, layered magnesia, pseudoboehmite, layered silica, vermiculite, expanded graphite, micaceous stone, hydrotalcite (LDH), montmorillonite, kaolin, and rectorite, but is not limited thereto. In the embodiments of the present application, the layered support has a transverse dimension of 0.02mm to 2 mm. The lateral dimension herein refers to the length or width of the layered support, etc. In particular, the transverse dimension of the layered support may be, but is not limited to, 0.03mm, 0.05mm, 0.1mm, 0.15mm, 0.3mm, 0.5mm, 1mm, 1.5mm or 2 mm. Controlling the transverse dimension of the layered carrier can ensure that the layered carrier, the intercalating agent, the active component source and the doping source can be fully mixed.

The active component refers to a component with catalytic activity, an active component source in the application can form the active component after calcination, and the active component can catalyze a carbon source and a doping source to form a doped carbon nanotube; in the present application, the source of the active component comprises a soluble transition metal salt, such that the resulting active component comprises an elemental transition metal. In the embodiment of the present application, the transition metal salt may specifically be a salt of at least one of iron, cobalt, nickel, manganese, titanium, molybdenum, tungsten, ruthenium, and palladium, and specifically may be one or more of a nitrate, a chloride, a sulfate, and a soluble organic salt of these transition metal elements. In some embodiments, the source of active component comprises one or more of a soluble titanium salt, manganese salt, iron salt, cobalt salt, nickel salt, ruthenium salt, and palladium salt, and correspondingly, the active component is at least one of titanium, manganese, iron, cobalt, nickel, ruthenium, and palladium.

In some embodiments of the present application, the active component source includes one or more of titanium sulfate, titanium nitrate, manganese sulfate, manganese nitrate, manganese chloride, iron acetate, iron sulfate, iron nitrate, cobalt sulfate, cobalt acetate, cobalt nitrate, nickel sulfate, nickel nitrate, ruthenium nitrate, and palladium nitrate, but is not limited thereto. Further, the active component source includes one or more of titanium nitrate, manganese nitrate, iron nitrate, cobalt nitrate, nickel nitrate, ruthenium nitrate, and palladium nitrate. During the calcination process, nitrate radicals are decomposed at high temperature, so that local high gas phase partial pressure is formed around the active component, and the gas phase partial pressure is favorable for carbon atoms to diffuse from the adsorbed crystal face to the crystal face of the carbon nano tube in the active component, so that the array carbon nano tube with uniform tube diameter and high long diameter ratio is formed.

In some embodiments of the present disclosure, an auxiliary agent source is further added during the process of uniformly mixing the layered carrier, the intercalating agent, the active component source, the doping source, and the solvent. In the calcination process of the catalyst precursor, the auxiliary agent source can form an auxiliary agent, the auxiliary agent not only plays a role in concerted catalysis, but also can promote the dispersion of the active component and reduce the particle size of the active component, so that the growth area of the carbon nano tube in the active component is reduced, and the array carbon nano tube with smaller tube diameter is formed. In embodiments of the present application, the source of the auxiliary agent comprises one or more of a soluble salt comprising molybdenum, a soluble salt comprising lanthanum, and a soluble salt comprising tungsten. In some embodiments of the present application, the source of promoter comprises one or more of sodium molybdate, ammonium molybdate, lanthanum nitrate, or tungsten nitrate. In the embodiment of the application, the mass ratio of the active component source to the auxiliary agent source is 1 (0.002-1). In some embodiments of the present application, the mass ratio of the active ingredient source to the auxiliary ingredient source is 1 (0.01-0.5). The mass ratio of the active component source to the auxiliary agent source may specifically be, but not limited to, 1:0.002, 1:0.01, 1:0.02, 1:0.05, 1:0.1, 1:0.4, 1:0.5, 1:0.7 or 1: 1.

In the application, the intercalation agent is added, so that the interlayer distance of the carrier can be effectively enlarged, the loading capacity of the layered carrier to the active component source is further improved, meanwhile, the intercalation agent can wrap the active component source, the active component source is prevented from being aggregated to form particles with large particle size in the calcining process, the dispersion uniformity of the active component in the layered carrier is improved, and the formation of the carbon nanotube doped array with uniform pipe diameter and high long-diameter ratio is facilitated. In the embodiments of the present application, the intercalating agent may be inserted into the carrier sheet by adsorption. In other embodiments of the present application, where the layered vehicle has a charge between its layers, an intercalating agent having a charge opposite to that of the layered vehicle may be selected so that the intercalating agent can be electrostatically intercalated into the vehicle sheets. Specifically, when the layered carrier is expanded graphite, an anionic intercalation agent can be selected and mixed with the expanded graphite, so that the effect of the intercalation agent on expanding the interlayer spacing of the expanded graphite is improved. In other embodiments of the present application, the intercalating agent may be intercalated into the sheets of the layered carrier by ion exchange. When the intercalation agent is loaded on the layered carrier, the wettability of the surface of the layered carrier can be improved, so that the solvent can fully infiltrate the layered carrier, an active component source can enter the interlayer of the layered carrier, and the loading capacity of the layered carrier to the active component source is improved.

In the present application, the intercalating agent is an organic intercalating agent. The organic intercalation agent has a larger space structure, and can well enlarge the interlayer spacing of the layered carrier; and the catalyst can be oxidized into carbon dioxide or other gaseous compounds in the calcining process, and the carbon dioxide or other gaseous compounds cannot remain in the catalyst to influence the activity of the catalyst; in addition, the organic intercalation agent has weak acid-base property and small influence on the activity of the catalyst. In embodiments of the present application, the intercalating agent may comprise one or more of an anionic intercalating agent, a cationic intercalating agent, and an organic amine intercalating agent.

In embodiments of the present application, the anionic intercalant includes one or more of an organic sulfonate and an organic sulfate. In some embodiments of the present application, the organic sulfonate comprises one or more of sodium dodecylbenzene sulfonate, sodium isethionate and sodium styrene sulfonate; organic sulfate salts include sodium lauryl sulfate. In embodiments of the present application, the cationic intercalating agent comprises one or more of alkyl quaternary ammonium salts and quaternary ammonium salts containing a benzene ring. Wherein, the alkyl quaternary ammonium salt comprises one or more of dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide. In an embodiment of the present application, the organic amine intercalating agent includes one or more of aliphatic amine organic amine, amide organic amine, and aromatic amine organic amine. In some embodiments of the present application, the fatty amine intercalating agent comprises one or more of ethanolamine, diethanolamine, triethanolamine, 3-propanolamine, isopropanolamine, N-dimethylethanolamine and N, N-diethylethanolamine; the amide intercalant comprises one or more of acetamide, propionamide, acrylamide, polyacrylamide and dimethylformamide; the aromatic amine intercalation agent comprises one or more of aniline, diphenylamine and the like. The intercalating agent has good affinity to the carrier in the application and can be effectively combined with the carrier, wherein the intercalating agent with larger molecular weight and longer chain length is selected, which is more beneficial to expanding the interlayer spacing of the layered carrier. In some embodiments of the present application, the intercalant has from 6 to 40 carbon atoms. In other embodiments of the present application, the intercalant has from 12 to 40 carbon atoms. When the carbon number is in the range of 6-40, the intercalation agent has better affinity with the layered carrier, can more effectively enlarge the interlayer spacing of the layered carrier, and is convenient for the active substance to enter the interlayer of the layered carrier; and the intercalation agent is easy to dissolve, and can better disperse the active component source.

In the embodiment of the application, the mass ratio of the intercalation agent to the lamellar carrier is 1: 1-50. In some embodiments of the present application, the ratio of intercalating agent to lamellar carrier is 1:1 to 20 by mass. Further, the mass ratio of the intercalation agent to the lamellar carrier is 1: 1-10. The mass ratio of the intercalating agent to the lamellar carrier may specifically be, but is not limited to, 1:1, 1:3, 1:5, 1:10, 1:15, 1:20, 1:30, 1:40, or 1: 50. The control of the mass ratio of the intercalation agent to the lamellar carrier can ensure that the intercalation agent can enlarge the interlayer spacing of the lamellar carrier and does not influence the adsorption of the lamellar carrier on the active component source. In the embodiment of the application, the mass ratio of the active component source, the intercalation agent and the lamellar carrier is (5-50) to (1-10) to (10-50). In some embodiments of the present application, the mass ratio of the active ingredient source, intercalating agent, and layered carrier is (10-30): (2-7): (20-30). Controlling the mass ratio of each component is beneficial to forming the catalyst with more active components and uniformly dispersed active components. In some embodiments, the mass ratio of the active ingredient source to the layered carrier is (0.1-5):1, for example (0.33-1.5): 1.

The solvent in step S100 may include one or more of water, methanol, ethanol, and propanol, but is not limited thereto. The solvent can infiltrate the carrier, is beneficial to the full adsorption of the intercalation agent and the active component source by the layered carrier, and enhances the uniformity of the active component source on the layered carrier. In the embodiment of the application, the mass ratio of the solvent to the layered carrier is (1-10): (0.1-1). In some embodiments of the present application, the ratio of the solvent to the layered vehicle is (3-7): (0.1-1). The control of the mass ratio of the layered carrier to the solvent can ensure that the solvent fully infiltrates the layered carrier, thereby promoting the intercalation agent and the active component source to be effectively attached to the layered carrier.

In the embodiment of the present application, the manner of uniformly mixing the layered carrier, the intercalating agent, the active component source, the doping source, and the solvent may be stirring and mixing. In some embodiments of the present application, the mixing process further comprises sonication. The ultrasonic treatment is beneficial to promoting the intercalation agent to enter the carrier sheet layer. In the embodiment of the present application, the temperature of mixing is 15 ℃ to 50 ℃. At a higher mixing temperature, the molecular motion in the solution is accelerated, and the intercalation agent can better expand the interlayer spacing of the layered carrier.

In some embodiments of the present application, the layered support, the intercalating agent, the active component source, the doping source, and the solvent are mixed directly for a time period in the range of 1h to 15 h. In other embodiments of the present disclosure, the layered vehicle, the intercalating agent, and the solvent are mixed for 0.5h to 15h to form a first solution, and then a second solution formed by the active component source, the doping source, the auxiliary agent source, and the solvent is added to the first solution, wherein the mixing time of the first solution and the second solution is 1h to 5 h. The loading capacity of the layered carrier to the active component source and the doping source can be improved by adopting a step-by-step mixing mode, so that the active component source and the doping source are uniformly dispersed in the layered carrier. In other embodiments of the present disclosure, the layered carrier is first mixed with a solvent to form a first solution, wherein the mixing time is 0.5h to 3 h; after mixing, adding an intercalation agent into the first solution to form a second solution, wherein the mixing time of the second solution is 1-15 h; and adding a third solution formed by an active component source, a doping source, an auxiliary agent source and a solvent into the second solution, wherein the mixing time of the second solution and the third solution is 1-5 h. The lamellar carrier and the solvent are mixed in advance, so that the solvent can fully infiltrate the lamellar carrier, the intercalation agent can enter the lamellar carrier, and the interlayer spacing of the lamellar carrier is enlarged. In the embodiment of the application, the mixed solution is stirred, filtered to remove the filtrate, and the filter residue is dried to obtain the catalyst precursor. In the embodiment of the application, the filter residue can be dried in an oven or naturally.

In step S200, the calcining process may specifically be: calcining the catalyst precursor at the temperature of 300-800 ℃, preserving heat for 1-8 h, introducing a certain amount of water vapor, preserving heat for 0.5-4 h at the temperature of 300-550 ℃, and cooling to room temperature to obtain the catalyst. In the present application, the calcination temperature of the catalyst precursor affects the structure of the catalyst, and further, the catalyst structure affects the activity of the catalyst. In the present embodiment, the calcination temperature may be, but is not limited to, 300 ℃, 400 ℃, 500 ℃, 550 ℃, 600 ℃, 700 ℃, or 800 ℃. In some embodiments of the present application, the calcination temperature is from 300 ℃ to 550 ℃. The solvent and the intercalation agent in the catalyst precursor can be completely removed under the condition of the calcination temperature, and the interlayer spacing of the layered carrier can be further enlarged in the processes of decomposition and gasification of the intercalation agent and evaporation of the solvent, so that the steric hindrance of the growth of the array type doped multi-walled carbon nano-tube between layers can be reduced, and the formation of the doped carbon nano-tube array with high long-diameter ratio can be promoted. In the embodiment of the present application, the apparatus for calcining the catalyst precursor includes any one of a microwave high-temperature furnace, a high-temperature carbonization furnace, a medium-frequency induction high-temperature furnace, and a muffle furnace.

In the application, the active component source and the auxiliary agent source can be reduced into metal particles by introducing steam in the calcining process, so that the activation of the catalyst is realized, flammable and explosive reducing gas is not required to be introduced in the activating process, the safety production is facilitated, and the production cost is reduced. In addition, in the calcining process, carbon deposition formed by incomplete combustion of part of the intercalation agent covers the surface of the catalyst, so that the activity of the catalyst is reduced, the decomposition product of the intercalation agent can be effectively inhibited from forming the carbon deposition on the surface of the active component by introducing steam, and the steam can dissolve part of the reaction product of the intercalation agent, so that the impurity removal effect is achieved, and the catalyst is ensured to have rich active sites. In the embodiment of the present application, the amount of steam introduced is 50mL/min to 200 mL/min. The amount of water vapor introduced may be, but is not limited to, 50mL/min, 60mL/min, 80mL/min, 100mL/min, 110mL/min, 130mL/min, 170mL/min, 190mL/min, or 200 mL/min. The control of the introduction amount of the water vapor can ensure the full activation of the catalyst, and the decomposition of the intercalation agent is not influenced, thereby ensuring the full combustion of the intercalation agent and inhibiting the formation of carbon deposition. In the embodiment of the application, the preactivation time is 0.5h-4h by introducing water vapor. The preactivation time by passing through water vapor can be specifically but not limited to 0.5h, 1h, 1.5h, 2h, 2.5h, 3h and 4 h.

In step S300, the chemical vapor deposition process may specifically be: putting the catalyst in a reactor, introducing inert gas, heating to the reaction temperature of 600-900 ℃, introducing a carbon source gas and a doping source for deposition reaction for 10-100 min, introducing the inert gas after the reaction is finished, and cooling to the room temperature to obtain the multi-walled carbon nanotube doped array on the layered carrier. In some embodiments, a second doping source may be further introduced during the chemical vapor deposition process of step S300 to introduce doping atoms on the surface of the multi-walled carbon nanotube. The material of the second doping source may be the same as the doping source in step S100, or may be different (e.g., gaseous or liquid, etc., and inert gas may be used as a carrier to be delivered into the reactor).

In some embodiments, the temperature of the chemical vapor deposition may be 650 ℃ to 780 ℃ and the reaction time may be 20min to 90 min. The temperature of the chemical vapor deposition may be, but is not limited to, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 780 ℃, 800 ℃ or 900 ℃. The temperature of chemical vapor deposition is controlled, so that the catalyst has good activity and is not easy to inactivate, and the rate of forming carbon atoms by carbon source gas dehydrogenation is moderate; and the diffusion resistance of carbon atoms in the active components is small at the temperature, which is beneficial to the formation of the array type doped multi-wall carbon nano-tube. Wherein the inert gas may be one or more of nitrogen, helium and argon. The carbon source may be C₁-C₄Without limitation, alkane (e.g., methane, ethane, propane, butane), alkene (e.g., ethylene, propylene, butene), alkyne. The reactor may be any one of a box furnace, a tube furnace or a fluidized bed.

In step S300, the method for removing the catalyst (including the layered carrier and the active component) is acid washing, and the specific process may be: adding the crude product of the array type doped multi-walled carbon nanotube array obtained by chemical vapor deposition into an acid solution, soaking for 2-30 h at the temperature of 40-100 ℃, washing the crude product to be neutral, and drying to obtain the array type doped multi-walled carbon nanotube. In the embodiment of the present application, the acid solution may be one or more of a nitric acid solution, a hydrochloric acid solution, and a sulfuric acid solution. In the embodiment of the present application, the mass fraction of the acid solution is 2 wt% to 15 wt%, and specifically, may be, but is not limited to, 2 wt%, 5 wt%, 10 wt%, 13 wt%, or 15 wt%. In some embodiments of the present application, the temperature of the acid washing is 50 ℃ to 80 ℃, and the time of the acid washing is 12h to 24 h.

The first preparation method of the array type doped multi-walled carbon nanotube provided by the application is simple in process, wide in raw material source, strong in operation controllability, small in pipe diameter, high in long-diameter ratio, uniform in size and length, regular in product, good in consistency, good in conductivity and low in cost, and is suitable for large-scale industrial preparation.

The application also provides a second preparation method of the array type doped multi-wall carbon nanotube, which comprises the following steps:

s1: dispersing an active component source, a doping source, a layered carrier and a first carbon source in a solvent, and drying to obtain a catalyst precursor; the active component source comprises a soluble transition metal salt;

s2: calcining the catalyst precursor in an inert atmosphere to obtain a carbon-coated material; the carbon coating material comprises a catalyst and a carbon coating layer coating the catalyst, the catalyst comprises the layered carrier, and an active component and the doping source which are loaded on the layered carrier, and the active component comprises transition metal active particles;

s3: removing the carbon coating layer to obtain the naked catalyst;

s4: placing the catalyst in a reactor, introducing a second carbon source in an inert atmosphere, forming an array of doped multi-walled carbon nanotubes on the layered carrier in a chemical vapor deposition mode, and then removing the catalyst to obtain the array type doped multi-walled carbon nanotubes; the array type doped multi-wall carbon nanotube comprises a multi-wall carbon nanotube and doping atoms doped in the multi-wall carbon nanotube; the array type doped multi-walled carbon nanotube is provided with a radial conductive channel, and the radial conductive channel is formed by covalent bonding of the doping atoms and the adjacent tube wall of the multi-walled carbon nanotube; the tube diameter of the array type doped multi-wall carbon nano tube is 1-100nm, and the length of the array type doped multi-wall carbon nano tube is 10-100 mu m.

In the second preparation method of the array type doped multi-walled carbon nanotube, the catalyst precursor containing the active component source, the doping source, the layered carrier and the first carbon source is calcined, so that the active component source can be decomposed in the calcination process and is decomposed by the reducing gas (such as H) obtained by pyrolysis of the first carbon source₂CO) is reduced into an active component, the active component is loaded on a layered carrier (particularly can be distributed on the surface of the layered carrier and between layers of the layered carrier), the active component and a doping source are coated by amorphous carbon obtained by pyrolysis of a first carbon source to obtain a carbon coating material, and then the carbon coating layer is removed to obtain the exposed catalyst for growing the carbon nano tube. The doping source is introduced when the catalyst precursor is prepared, so that the doping source can be effectively combined with the catalyst formed by calcining the catalyst precursor, and doping atoms can be doped between the walls of the multi-walled carbon nanotubes; the existence of the carbon coating layer in the carbon coating material can effectively limit the particle size growth of the catalyst particles, so that the particle size of the obtained catalyst particles is smaller, such as less than or equal to 8 nm. Finally, the catalyst is used for generating an array of doped multi-walled carbon nanotubes with small tube diameter by a chemical vapor deposition method.

The active ingredient source and the layered vehicle in step S1 are made of the same materials as described above in step S100. In some embodiments, the active component source may be a salt of at least one transition metal element of iron, nickel, cobalt, manganese, molybdenum, tungsten. The transition metal salts have high carbon dissolving capacity, can form certain carbides, and carbon atoms have high diffusion rate in the transition metals, so that the carbon nano tubes are beneficial to nucleation and growth.

On one hand, the first carbon source can perform a complex reaction with metal ions to form a stable complex, so that the impregnation efficiency of the metal active substance and the layered carrier is effectively improved, and meanwhile, the agglomeration of metal active substance particles in the reaction process can be avoided; on the other hand, the catalyst is used for carbon coating to inhibit the crystal growth of the catalyst in the calcining process, and the particle size of the active component is controlled, so that the particle size of the active component in the catalyst is smaller, and the small-diameter carbon nano tube is synthesized by guiding the catalyst. In some embodiments, the first carbon source is selected from at least one of citric acid, malic acid, tartaric acid, oxalic acid, salicylic acid, succinic acid, glycine, ethylenediaminetetraacetic acid, sucrose, glucose.

In step S1, in some embodiments, in order to improve the dispersibility of the active component source, the doping source, the layered carrier, and the first carbon source in the solvent, the active component source and the doping source are first dissolved in the solvent to form a saturated solution, the layered carrier is then added under stirring to form a uniformly dispersed suspension, and finally the first carbon source is added under stirring to form a uniformly dispersed suspension. In some embodiments, the mass ratio of the active component source and the layered carrier is controlled to be (0.1-10):1, and the mass of the first carbon source is 10% -500% of the total mass of the active component source and the layered carrier. The coating is not uniform due to too small addition amount of the first carbon source, so that the formed active components have non-uniform particles and large particles are generated, and the pipe diameter of the obtained doped carbon nanotube array is larger; the first carbon source is added in too much amount, so that on one hand, the cost is too high and waste is caused, and on the other hand, incomplete removal is easily caused when the carbon coating is removed, so that the catalyst is easily inactivated, and the yield of the doped carbon nanotube is not high. Optionally, the molar ratio of the doping atoms in the doping source to the transition metal atoms in the active component source is 1: (5-100) to take a dopant source and an active component source.

In some embodiments, the drying process in step S1 is freeze drying, which can prevent the metal active material particles from agglomerating and make the diameter of the obtained carbon nanotube smaller. In some embodiments, the catalyst precursor is subjected to suction filtration before being dried to remove redundant active component sources, so that the active component sources which cannot be loaded on the surface of the layered carrier are reduced, and the high-purity doped carbon nanotube array is obtained.

In some embodiments, in S2, the calcination process is performed in an inert atmosphere to avoid burning of the carbon material to generate carbon dioxide gas under high temperature conditions. Specifically, the inert atmosphere is at least one of nitrogen, argon, and helium. In some embodiments, the calcination treatment is calcination at 300 ℃ to 700 ℃ for 1h to 10 h. By controlling the temperature of the calcination treatment, the particles of the active components can be prevented from being too large due to overhigh temperature, and the tube diameter of the generated carbon nano tube can be prevented from being too large. Specifically, typical but not limiting calcination treatment temperatures are 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃; typical but not limiting calcination treatment times are 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10 h.

The manner of removing the carbon-coated material in S3 is calcination, which decomposes amorphous carbon into carbon dioxide gas. The calcination should be carried out in a non-inert atmosphere and a non-reducing atmosphere. In some embodiments, the calcining is in an atmosphere of at least one of air, oxygen, carbon dioxide, at 500 ℃ to 700 ℃ for 1h to 10 h. When the carbon dioxide is calcined in the carbon dioxide atmosphere, the carbon dioxide can react with the amorphous carbon to form carbon monoxide, so that the purpose of removing the carbon coating is achieved. By controlling the temperature and the calcination time of the calcination treatment, the carbon coating can be fully removed, and the catalytic activity of the obtained catalyst is improved. Specifically, typical but non-limiting calcination treatment temperatures are 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃; typical but not limiting calcination treatment times are 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10 h.

In step S4, the second carbon source is mainly used to provide carbon for the cvd growth of the carbon nanotubes, and the specific choice of the second carbon source also has a significant effect on the length of the array-type carbon nanotubes. In some embodiments, the second carbon source is selected from at least one of methane, ethane, propane, ethylene, propylene, absolute ethanol, carbon monoxide, but is not limited thereto. In some embodiments, when the transition metal salt is nickel nitrate, nickel chloride and/or a soluble organic salt of nickel, at least one of methane, ethane, propane is used as the second carbon source; when the transition metal salt is nitrate, chloride and/or soluble organic salt of iron or cobalt, ethylene and propylene are used as the second carbon source.

In some embodiments, a reducing gas is further introduced to reduce the oxide of the active component in the catalyst to be in a simple metal state and reduce the oxidized carbon nanotubes during the chemical vapor deposition reaction in step S4. Specifically, the reducing gas is hydrogen, and has the advantages of strong reducing property, easily obtained raw materials and relatively low cost. Similar to the above step S300, in some embodiments, a second doping source may be further introduced during the cvd reaction, so as to introduce doping atoms on the surface of the multi-walled carbon nanotube, thereby further improving the conductivity.

In some embodiments, the chemical vapor deposition reaction is at 600 ℃ to 1000 ℃ for 30min to 120 min. In some embodiments, when an olefin is employed as the carbon source, the temperature of the chemical vapor deposition reaction is set to 600 ℃ to 750 ℃; when alkane is adopted as a carbon source, setting the temperature of the chemical vapor deposition reaction to be 800-1000 ℃; when alkane is used as a carbon source or an active component source is nickel nitrate, nickel chloride and/or soluble organic salt of nickel, the rate of carbon nanotube generation is relatively low because the activity of metallic nickel as an active component is relatively poor, and therefore the time of the chemical vapor deposition reaction is set to be 60min to 120 min. When olefin is used as a carbon source or transition metal salt is nitrate, chloride and/or soluble organic salt of iron or cobalt, the reaction time is relatively short because the activity of the metal iron and the metal cobalt as active substances is relatively high and the rate of generating the carbon nano tube is also high, and the time of the chemical vapor deposition reaction is set to be 30min-90 min. Specifically, typical but not limiting chemical vapor deposition reaction temperature is 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃; typical, but not limiting, chemical vapor deposition reaction times are 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120 min.

After the chemical vapor deposition reaction, the obtained doped carbon nanotube array vertically grows on the surface of the layered carrier, and the catalyst (i.e. the layered carrier and the active component) needs to be removed, so as to finally obtain the high-purity doped carbon nanotube. In some embodiments, methods of removing the catalyst include, but are not limited to, acid washing, graphitization, and the like. Wherein, the acid cleaning method is to add the crude product after the chemical vapor deposition reaction into the acid solution for full infiltration, stir and react for 1h-20h at the temperature of 60 ℃ -100 ℃, and then obtain the purified doped carbon nano tube after filtration, washing and drying. The graphitization method is to preserve the temperature of a product crude product after the chemical vapor deposition reaction for 0.5h-10h at 1500-3000 ℃ in the environment with the vacuum degree lower than 20Pa to obtain the purified doped carbon nano tube.

The second preparation method of the array type doped multi-walled carbon nanotube provided by the application is simple in process, strong in operation controllability, small in pipe diameter, higher in long diameter, uniform in size and length, regular in product, good in consistency and good in conductivity, and suitable for large-scale industrial preparation, and the prepared array type doped multi-walled carbon nanotube with the radial conductive channel is small in pipe diameter, high in long diameter ratio, low in cost and uniform in length.

The application also provides an electrode material, which comprises an electrode active material, a binder and a conductive agent, wherein the conductive agent comprises the array type doped multi-wall carbon nano-tube provided by the first aspect of the application.

The electrode active material may include one or more of nano silicon, silicon dioxide, silicon carbon alloy, silicon tin alloy, lithium titanate, lithium cobaltate, lithium nickelate, lithium manganate, lithium ferrous silicate, lithium manganese phosphate, lithium manganese iron phosphate and lithium iron phosphate. Wherein the binder may include one or more of carboxymethyl cellulose, hydroxypropyl methyl cellulose, polyvinylidene fluoride, polyacrylonitrile, polyvinyl alcohol, sodium alginate, chitosan, and styrene butadiene rubber. In some embodiments of the present application, the conductive agent may comprise only the array-type doped multi-walled carbon nanotubes of the present application. In other embodiments of the present application, the conductive agent may further include other conductive agent materials, for example, the conductive agent is a composition of the array-type doped multi-walled carbon nanotube and one or more of graphite, carbon black, graphene, carbon fiber and acetylene black. Optionally, the mass percentage of the electrode active material in the electrode material is 85.0-97.0%, the mass percentage of the array type doped multi-walled carbon nanotube is 0.1-3.0%, and the mass percentage of the adhesive is 2.0-12.0%.

In some embodiments of the present application, the electrode material is prepared by the following steps: mixing lithium iron phosphate, the array type doped multi-walled carbon nanotube and polyvinylidene fluoride to obtain electrode slurry, and preparing the electrode slurry into an electrode material through the steps of coating, drying, rolling, die cutting and the like. In some embodiments of the present application, the volume resistivity of the lithium iron phosphate electrode material comprising 2% by mass of the array-type doped multi-walled carbon nanotubes is 0.7 Ω · cm to 2 Ω · cm. In other embodiments of the present application, the electrode material is prepared by: mixing nano silicon, the array type doped multi-walled carbon nanotube and sodium carboxymethyl cellulose to obtain electrode slurry, and preparing the electrode material by the electrode slurry through the steps of coating, drying, rolling, die cutting and the like.

The electrode material provided by the application has better conductivity due to the use of the array type doped multi-walled carbon nanotube, and electrons can conduct in multiple directions in the electrode material due to rich conductive channels of the array type doped multi-walled carbon nanotube. The electrode material is applied to the battery, so that the conductivity of the battery can be improved, and the performance of the battery can be enhanced.

The following will further describe the embodiments of the present application by dividing into a plurality of examples.

Example 1

A preparation method of array type doped carbon nanotubes comprises the following steps:

(1) adding 30g of hydrotalcite into 150mL of water, stirring for 0.5h, then adding 20g of sodium dodecyl benzene sulfonate, and stirring for 12h at 25 ℃ to form a uniform suspension; adding 48g of cobalt nitrate hexahydrate, 8g of lanthanum nitrate hexahydrate and 5g of magnesium borate into the suspension, stirring and filtering to obtain filter residues, and drying the filter residues at 100 ℃ to obtain a catalyst precursor.

(2) Calcining the catalyst precursor in a muffle furnace at 550 ℃ for 2h, introducing water vapor at 550 ℃ for preactivation for 30min, and cooling to room temperature to obtain a catalyst; the catalyst comprises hydrotalcite, magnesium borate loaded on the hydrotalcite and metal cobalt particles.

(3) Adding 0.3g of catalyst into a quartz boat, moving the quartz boat into a fixed bed reactor, heating the quartz boat to 750 ℃ at the speed of 10 ℃/min in the atmosphere of nitrogen protection gas, stopping introducing nitrogen, introducing ethylene instead, and reacting for 30min at 750 ℃ to form the boron-doped multi-walled carbon nanotube array.

(4) And (4) mixing the product obtained in the step (3) with 5% nitric acid solution at 80 ℃ for 12h to remove the catalyst, and performing suction filtration, washing and drying to obtain the array type boron-doped multi-walled carbon nanotube.

The doped multi-walled carbon nanotube array and the array-type doped multi-walled carbon nanotube in example 1 were characterized by using a scanning electron microscope and a transmission electron microscope, respectively, and the results are shown in fig. 3 and 4. As can be seen from fig. 3 and 4, the size of the array-type doped multi-walled carbon nanotube prepared in example 1 of the present application is uniform, the morphological integrity after removing the catalyst is still high, and it is found that the tube diameter of the boron-doped multi-walled carbon nanotube in example 1 is 5-8nm, the length is 40-80 μm, and the length-diameter ratio is high and is within the range of 5000:1 to 16000: 1. In addition, the boron-doped multi-walled carbon nanotube is linear as a whole, a bending part is formed locally, and the bending part has corrugated folds because boron-doped atoms introduced between tube walls cause different layer distances between the tube walls, so that folds, deformation and the like occur. In addition, the resistivity of the boron-doped multi-walled carbon nanotube in example 1 was measured to be 0.02 Ω · cm.

Preparation of an electrode test sample comprising the steps of: mixing lithium iron phosphate, the boron-doped multi-walled carbon nanotube in the embodiment 1 and polyvinylidene fluoride to obtain electrode slurry, wherein the mass percentage of the lithium iron phosphate is 94.0%, the mass percentage of the boron-nitrogen-doped multi-walled carbon nanotube is 1.5%, and the mass percentage of the polyvinylidene fluoride is 4.5%. And coating the electrode slurry on the insulating layer, and drying to prepare an electrode test sample. As a result, the volume resistivity of the electrode test sample was measured to be 0.5. omega. cm.

Example 2

A preparation method of array type doped carbon nanotubes comprises the following steps:

(1) in 200mL of water and ethanolMixed solution (V) of_{Water (W)}：V_Ethanol1:1) adding 30g of expanded graphite and 25g of hexadecyl trimethyl ammonium bromide, and stirring at 40 ℃ for 12h to form a uniform suspension; adding 50g of nickel nitrate, 6g of tungsten nitrate and 8g of aluminum sulfate into the suspension, stirring and filtering to obtain filter residue, and drying the filter residue at 100 ℃ to obtain a catalyst precursor.

(2) Calcining the catalyst precursor in a muffle furnace at 500 ℃ for 3h, introducing water vapor at 500 ℃ for preactivation for 60min, and cooling to room temperature to obtain a catalyst; the catalyst comprises expanded graphite, metallic nickel particles and tungsten particles which are loaded on the expanded graphite, and aluminum sulfate.

(3) Adding 0.5g of catalyst into a quartz boat, moving the quartz boat into a fixed bed reactor, heating the quartz boat to 950 ℃ at 15 ℃/min under the atmosphere of nitrogen protection gas, stopping introducing nitrogen, changing into introducing methane, and reacting for 60min at 950 ℃ to form the sulfur-doped multi-walled carbon nanotube array.

(4) And (4) soaking the product obtained in the step (3) in a 10% nitric acid solution at 80 ℃ for 24 hours to remove the catalyst, and performing suction filtration, washing and drying to obtain the array-type sulfur-doped multi-walled carbon nanotube.

The tube diameter of the boron-doped multi-walled carbon nanotube in the embodiment 2 is 3-6nm, the length is 40-80 μm, the length-diameter ratio is 6666: 1-26666: 1, and the resistivity is 0.021 omega cm.

Preparation of an electrode test sample comprising: mixing lithium iron phosphate, the boron-doped multi-walled carbon nanotube in the embodiment 2 and polyacrylonitrile to obtain electrode slurry, wherein the mass percentage of the lithium iron phosphate is 94.0%, the mass percentage of the boron-doped multi-walled carbon nanotube is 2.0%, and the mass percentage of the polyacrylonitrile is 4.0%. And coating the electrode slurry on the insulating layer, and drying to prepare an electrode test sample. The volume resistivity of the electrode test sample was measured to be 0.4 Ω · cm.

Example 3

A preparation method of array type doped carbon nanotubes comprises the following steps:

(1) adding 20g of micaceite, 1g of aluminum nitride and 10g of diethanolamine into 200mL of water, and stirring for 5 hours at 50 ℃ to form a uniform suspension; 40g of ferric nitrate and 3g of ammonium molybdate were added to the suspension, stirred and filtered to obtain a filter residue. Drying the filter residue at 100 ℃ to obtain the catalyst precursor.

(2) Calcining the catalyst precursor in a muffle furnace at 600 ℃ for 2h, introducing water vapor at 550 ℃ for preactivation for 90min, and cooling to room temperature to obtain the catalyst.

(3) Adding 0.5g of catalyst into a quartz boat, moving the quartz boat into a fixed bed reactor, heating the quartz boat to 850 ℃ at 15 ℃/min in the atmosphere of nitrogen protection gas, stopping introducing the nitrogen, and instead introducing ammonia and ethane, wherein the ratio of the ammonia to the ethane is 1: 10. Reacting for 30min at 850 ℃ to form the multi-walled carbon nanotube array doped with nitrogen.

(4) And (4) soaking the product obtained in the step (3) in a 10% nitric acid solution at 80 ℃ for 24 hours to remove the catalyst, and performing suction filtration, washing and drying to obtain the array type nitrogen-doped multi-walled carbon nanotube.

The tube diameter of the boron-doped multi-walled carbon nanotube in the embodiment 3 is 7-10nm, the length is 30-50 μm, the length-diameter ratio is 3000: 1-7142: 1, and the resistivity is 0.022 omega cm.

Preparation of an electrode test sample comprising: mixing lithium iron phosphate, the nitrogen-doped multi-walled carbon nanotube in the embodiment 3 and sodium carboxymethylcellulose to obtain electrode slurry, wherein the mass percentage of the lithium iron phosphate is 96.0%, the mass percentage of the nitrogen-doped multi-walled carbon nanotube is 1.3%, and the mass percentage of the sodium carboxymethylcellulose is 2.7%. And coating the electrode slurry on the insulating layer, and drying to prepare an electrode test sample. The volume resistivity of the electrode test sample was measured to be 0.6 Ω · cm.

Example 4

A preparation method of doped carbon nanotubes comprises the following steps:

500g of ferric nitrate hexahydrate, 45g of aluminum sulfate and 55g of citric acid were dissolved in 1000mL of deionized water, and 50g of layered alumina was added to form a suspension. Stirring for 24h at normal temperature, and drying by using a freeze dryer to obtain the catalyst precursor. The obtained precursor was calcined at 300 ℃ for 10 hours in a nitrogen atmosphere, and then the temperature was raised to 500 ℃ for 10 hours in air to obtain 182g of the catalyst. Cooling to room temperature, placing 0.3g of the obtained catalyst in a quartz boat, introducing nitrogen to 700 ℃, introducing propylene, reacting at 700 ℃ for 60min, and depositing on layered alumina to obtain a sulfur-doped carbon nanotube array; and after the deposition is finished, soaking the obtained product in 5% nitric acid solution at 80 ℃ for 12h to wash out the catalyst, and performing suction filtration, washing and drying to obtain the sulfur-doped multi-walled carbon nanotube.

The tube diameter of the sulfur-doped multi-wall carbon nano-tube in example 4 is measured to be 5-8nm, the length is measured to be 30-50 μm, and the specific surface area is measured to be 272m²And a resistivity of 0.035. omega. cm. The sulfur-doped multi-walled carbon nanotubes of example 4 were prepared as electrode test samples in the manner described in example 1, and the volume resistivity of the electrode test samples was measured to be 0.7 Ω · cm.

Example 5

A preparation method of doped carbon nanotubes comprises the following steps:

50g of nickel nitrate hexahydrate, 100g of glucose were dissolved in 500mL of deionized water, and 50g of vermiculite and 10g of aluminum nitride were added to form a suspension. Stirring for 48h at normal temperature, and drying by using a freeze dryer to obtain the catalyst precursor. Calcining the obtained precursor for 1h at 700 ℃ in an argon atmosphere, keeping the temperature at 700 ℃, and introducing carbon dioxide gas to continue calcining for 3h to obtain 67g of catalyst. Cooling to room temperature, placing 0.3g of the obtained catalyst in a quartz boat, introducing argon to 900 ℃, introducing methane and ammonia gas with the volume ratio of 1:20, performing chemical vapor deposition reaction at 900 ℃ for 120min, and depositing on vermiculite to obtain a nitrogen-doped carbon nanotube array; and after the deposition is finished, putting the obtained product into a 5% nitric acid solution, soaking for 12h at 80 ℃, and performing suction filtration, washing and drying to obtain the boron-nitrogen doped multi-walled carbon nanotube.

The tube diameter of the nitrogen-doped multi-wall carbon nano-tube in example 5 is measured to be 7-8nm, the length is measured to be 30-50 mu m, and the specific surface area is measured to be 258m²The resistivity was 0.038. omega. cm/g. The boron-nitrogen co-doped multi-walled carbon nanotubes of example 5 were prepared as electrode test samples in the manner described in example 1, and the volume resistivity of the electrode test samples was measured to be 0.8 Ω · cm.

The above-described embodiments are merely illustrative of several exemplary embodiments of the present application, which are described in more detail and detail, but are not to be construed as limiting the scope of the present application. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent shall be subject to the appended claims.