A method for directly growing carbon nanotube arrays on fiber substrates

Abstract

The invention provides a method for directly growing a carbon nano tube array on a fiber substrate. The method comprises the following steps: (1) pre-treating the fiber substrate; (2) attaching a catalyst precursor on the surface of the substrate obtained in the step 1, wherein the catalyst comprises transitional metal elements such as Fe, Co, Ni, Cu, Au, Pt, Mo or Ag; (3) putting the substrate obtained in the step (2) in a reaction furnace, heating the substrate to a first temperature and maintaining for a preset time, and introducing inert gas to remove organic matters in the catalyst precursor; (4) heating to a second temperature and maintaining for a preset time, continuously introducing inert gas, introducing mixed gas of reductive gas and carbon source gas, maintaining the pressure in the reaction furnace, and growing high-density carbon nano tubes on the surface of the substrate; and (5) after reaction, stopping introduction of the reductive gas and carbon source gas, and continuously introducing inert gas till the temperature is reduced to room temperature.

Description

technical field

[0001] The invention belongs to the technical field of nanomaterial preparation, in particular to a method for directly growing carbon nanotube arrays on a fiber substrate. Background technique

[0002] Since its discovery in 1991, carbon nanotubes (CNTs) have attracted much attention due to their unique mechanical, chemical and electrical properties, unique one-dimensional tubular structure and broad application prospects. Carbon nanotubes have strong tensile strength, good charge transport performance, high thermal conductivity, and good thermal stability in air. For example, it can be used as an electrode material for green energy storage devices to promote electron transfer, such as fuel cells, supercapacitors, all-vanadium redox flow batteries and organic solar cells, and has broad application prospects.

[0003] At present, many researchers have grown carbon nanotube arrays on sapphire substrates, silicon substrates, quartz substrates, glass substrates...

Examples

Embodiment 1

[0041] The carbon fiber substrate was vacuum treated at 600°C for 2 hours, then ultrasonically cleaned with dilute hydrochloric acid, acetone, alcohol, and deionized water one by one, and dried for use. With 2M Fe(NO 3 ) 3 Solution and tetraethyl orthosilicate to prepare a sol, and the sol was uniformly coated on the surface of the carbon fiber substrate by the spin coating method, the spin coating speed was 4000 rpm, and the spin coating time was 1 minute. Place the carbon fiber substrate coated with Fe-containing sol in the chamber of the chemical vapor deposition system, start to heat up, the target temperature is 300°C, keep it for 1 hour, pass in inert gas nitrogen, and keep it for 30 minutes; the furnace temperature continues to rise to 650°C, continuously feed nitrogen for 60 minutes; simultaneously feed reducing gases hydrogen and methane. The hydrogen:methane:nitrogen ratio is 1:4:10. Control the closing degree of the vacuum butterfly valve to ensure that the air p...

Embodiment 2

[0043] The carbon fiber substrate pretreatment process is the same as in Example 1. With 1.5M Fe(NO 3 ) 3 The sol was prepared from the solution and methyl orthosilicate, and the sol was uniformly coated on the surface of the carbon fiber substrate by the dipping and pulling method, and the pulling speed was 10 cm / min. After the wet film was heat-treated at 100°C, it was dipped and pulled repeatedly, and the number of times of pulling was 5 times. Place the carbon fiber substrate coated with Fe-containing sol in the chamber of the chemical vapor deposition system, start to heat up, the target temperature is 400°C, keep it for 1 hour, pass in inert gas nitrogen, and keep it for 30 minutes; the furnace temperature continues to rise to At 750°C, nitrogen gas is continuously fed in for 60 minutes; at the same time, reducing gases hydrogen and methane are fed in. The hydrogen:methane:nitrogen ratio is 1:4:10. Control the closing degree of the vacuum butterfly valve to ensure th...

Embodiment 3

[0046] The silicon carbide fiber substrate treatment process is the same as in Example 1. With 1M Ni(NO 3 ) 3 The sol was prepared with methyl orthosilicate, and the sol was uniformly coated on the surface of the carbon fiber substrate by the spin coating method, the spin coating speed was 5000 rpm, and the spin coating time was 30 seconds. Place the carbon fiber substrate coated with Ni-containing sol in the chamber of the chemical vapor deposition system, start to heat up, the target temperature is 300°C, keep it for 1 hour, pass in the inert gas nitrogen, and keep it for 30 minutes; the furnace temperature continues to rise to 700°C, continuously feed nitrogen for 60 minutes; simultaneously feed reducing gases hydrogen and methane. The hydrogen:methane:nitrogen ratio is 1:5:10. Control the closing degree of the vacuum butterfly valve to ensure that the air pressure in the whole reaction process is about 1000Pa; after 30 minutes of reaction, the growth is complete. Stop ...

technical field

[0001] The invention belongs to the technical field of nanomaterial preparation, in particular to a method for directly growing carbon nanotube arrays on a fiber substrate. Background technique

[0002] Since its discovery in 1991, carbon nanotubes (CNTs) have attracted much attention due to their unique mechanical, chemical and electrical properties, unique one-dimensional tubular structure and broad application prospects. Carbon nanotubes have strong tensile strength, good charge transport performance, high thermal conductivity, and good thermal stability in air. For example, it can be used as an electrode material for green energy storage devices to promote electron transfer, such as fuel cells, supercapacitors, all-vanadium redox flow batteries and organic solar cells, and has broad application prospects.

[0003] At present, many researchers have grown carbon nanotube arrays on sapphire substrates, silicon substrates, quartz substrates, glass substrates...

Examples

Embodiment 1

[0041] The carbon fiber substrate was vacuum treated at 600°C for 2 hours, then ultrasonically cleaned with dilute hydrochloric acid, acetone, alcohol, and deionized water one by one, and dried for use. With 2M Fe(NO 3 ) 3 Solution and tetraethyl orthosilicate to prepare a sol, and the sol was uniformly coated on the surface of the carbon fiber substrate by the spin coating method, the spin coating speed was 4000 rpm, and the spin coating time was 1 minute. Place the carbon fiber substrate coated with Fe-containing sol in the chamber of the chemical vapor deposition system, start to heat up, the target temperature is 300°C, keep it for 1 hour, pass in inert gas nitrogen, and keep it for 30 minutes; the furnace temperature continues to rise to 650°C, continuously feed nitrogen for 60 minutes; simultaneously feed reducing gases hydrogen and methane. The hydrogen:methane:nitrogen ratio is 1:4:10. Control the closing degree of the vacuum butterfly valve to ensure that the air p...

Embodiment 2

[0043] The carbon fiber substrate pretreatment process is the same as in Example 1. With 1.5M Fe(NO 3 ) 3 The sol was prepared from the solution and methyl orthosilicate, and the sol was uniformly coated on the surface of the carbon fiber substrate by the dipping and pulling method, and the pulling speed was 10 cm / min. After the wet film was heat-treated at 100°C, it was dipped and pulled repeatedly, and the number of times of pulling was 5 times. Place the carbon fiber substrate coated with Fe-containing sol in the chamber of the chemical vapor deposition system, start to heat up, the target temperature is 400°C, keep it for 1 hour, pass in inert gas nitrogen, and keep it for 30 minutes; the furnace temperature continues to rise to At 750°C, nitrogen gas is continuously fed in for 60 minutes; at the same time, reducing gases hydrogen and methane are fed in. The hydrogen:methane:nitrogen ratio is 1:4:10. Control the closing degree of the vacuum butterfly valve to ensure th...

Embodiment 3

[0046] The silicon carbide fiber substrate treatment process is the same as in Example 1. With 1M Ni(NO 3 ) 3 The sol was prepared with methyl orthosilicate, and the sol was uniformly coated on the surface of the carbon fiber substrate by the spin coating method, the spin coating speed was 5000 rpm, and the spin coating time was 30 seconds. Place the carbon fiber substrate coated with Ni-containing sol in the chamber of the chemical vapor deposition system, start to heat up, the target temperature is 300°C, keep it for 1 hour, pass in the inert gas nitrogen, and keep it for 30 minutes; the furnace temperature continues to rise to 700°C, continuously feed nitrogen for 60 minutes; simultaneously feed reducing gases hydrogen and methane. The hydrogen:methane:nitrogen ratio is 1:5:10. Control the closing degree of the vacuum butterfly valve to ensure that the air pressure in the whole reaction process is about 1000Pa; after 30 minutes of reaction, the growth is complete. Stop ...

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