Varied morphology carbon nanotubes

Abstract

The present invention describes the preparation of carbon nanotubes of varied morphology, catalyst materials for their synthesis. The present invention also describes reactor apparatus and methods of optimizing and controlling process parameters for the manufacture carbon nanotubes with pre-determined morphologies in relatively high purity and in high yields. In particular, the present invention provides methods for the preparation of non-aligned carbon nanotubes with controllable morphologies, catalyst materials and methods for their manufacture.

Description

RELATED APPLICATIONS[0001]This application is a divisional of U.S. application Ser. No. 10 / 151,382, filed May 20, 2002, which claims priority to U.S. Provisional Application Ser. No. 60 / 292,486, filed on May 21, 2001, and the entirety of these applications are hereby incorporated herein by reference for the teachings therein.STATEMENT AS TO FEDERALLY SPONSORED RESEARCH[0002]The present invention was made with partial support from The US Army Natick Soldier Systems Center (DAAD, Grant Number 16-00-C-9227), Department of Energy (Grant Number DE-FG02-00ER45805) and The National Science Foundation (Grant Number DMR-9996289)FIELD OF THE INVENTION[0003]The present invention relates generally to carbon nanotubes of varied morphology, catalyst materials for their synthesis, and apparatus and methods for controllably manufacturing carbon nanotubes with pre-determined morphologies. More particularly, the present invention concerns non-aligned carbon nanotubes with controllable morphologies, c...

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Benefits of technology

[0011]The present invention also provides catalyst materials useful for the synthesis of CNTs of pre-determined morphologies and methods for utilizing them in the manufacture of varied morphology CNTs. The catalyst materials of the invention are contacted with a carbon source gas either by itself or in combination with a promoter gas at an elevated temperature within the confines of a reaction chamber. The catalyst materials of the present invention are comprised of a substrate that includes a metallic catalyst (such as for example, a transition metal) hereinafter referred to as “catalytic substrate”, a catalyst gas or “promoter gas” that is capable of promoting the activity of the catalytic substrate resulting in increased yield of the CNT products, or a combination thereof. For synthesis of linear CNTs, the catalyst material comprises a promoter gas and a catalytic substrate. For synthesis of branched CNTs, the catalyst material can comprise the catalytic substrate either by itself, or a combination of the catalytic substrate with the promoter gas. The substrate for the synthesis of symmetrical, branched (e.g., Y-shaped) CNTs comprises a transition metal that is supported on a metallic material or a non-metallic material, such as for example, a non-metallic oxide. The catalytic substrate can be either distributed within or deposited on the interior surface of the reaction chamber of the manufacturing apparatus of the invention. In one embodiment, the catalytic substrate is distributed on the surface of a reaction vessel as a thin layer. The reaction vessel containing the catalyst layer is then placed in a pyrolytic reaction chamber of a reactor apparatus comprising a heater assembly that enables deposition of carbon by pyrolysis of the carbon source gas at an elevated temperature. The carbon source gas in the methods of the present invention can additionally contain a promoter gas that enables rapid carbon deposition and CNT growth on the surface of the catalytic substrate.

[0013]In one aspect, the catalyst materials of the present invention comprise a particulate or micro-particulate, mesoporous catalyst substrate that can be used for synthesis of linear and branched CNTs. The catalytic substrate preferably is distributed on the surface of a reaction vessel as a thin layer, following which the reaction vessel containing the catalyst layer is placed in a reaction chamber of a reactor apparatus, such as for example, a chemical vapor deposition (CVD) reactor, comprising a heater assembly to enable chemical vapor deposition of carbon from a carbon source gas. In accordance with the methods of the invention, the carbon source gas is mixed with a promoter gas in the presence of the catalytic substrate at an elevated temperature within the reaction chamber. The promoter gas enables rapid chemical vapor deposition and graphitization of carbon on the catalytic substrate resulting in tubule growth on the surface and within the pores of the catalytic substrate.

[0014]An important aspect of the present invention is the preparation and utilization of different types of catalyst materials for obtaining CNTs of specific morphologies. For synthesis of linear CNTs, the catalyst material comprises a particulate or micro-particulate mesoporous catalytic substrate in combination with a promoter gas in a CVD process that provides CNT growth initiation and facilitates rapid CNT tubule growth at reaction temperatures of about 600° C., which is substantially lower than typical initiation temperatures by conventional methods (≧700° C.) in relatively high yield (up to about 700% based on catalyst weight). For synthesis of branched Y-shaped CNTs, the catalyst substrate comprises a catalytic metal composed of at least one transition metal that is supported on a metallic or non-metallic material (for example, a non-metallic oxide), which may be in particulate or micro-particulate form. The catalytic metal can be deposited on the surface of the metallic or non-metallic material as a coating on the supporting material. A promoter gas or gas mixture component additionally can be introduced in the reaction chamber during the synthesis of branched CNTs to enable rapid carbon deposition and CNT growth initiation with high graphitization. The use of the catalyst gas in the methods of the invention enables CNT growth on substrates that have relatively low strain / melting point ratios, such as for example, glass substrates used in flat panel display (strain / melting point ≦666° C.).

[0015]The present invention provides CNTs with controlled morphology (e.g., shape, tubule diameter, wall thickness and length, and graphitization) in relatively high yields and in large quantities (kilogram scale) that are easily purified by a solvent wash, and methods for their preparation and manufacture. Solvents useful for purification of CNTs of the present invention include inorganic acids, such as for example, hydrofluoric acid (HF). The carbon nanotubes formed by methods of the present invention have several applications. They can be used as an additive to provide improved strength and reinforcement to plastics, rubber, concrete, epoxies, and other materials, using currently fiber reinforcement methods for improving material strength. Furthermore, the methods of the invention provide large quantity, cost efficient synthetic processes for producing linear and branched CNTs that are suited for applications in hydrogen storage devices, electrochemical capacitors, lithium ion batteries, high efficiency fuel cells, semiconductors, nanoelectronic components and high strength composite materials.

Problems solved by technology

A major limitation to their large-scale commercialization however, has remained the need for large quantity, cost-effective production methods.

They however, require relatively expensive and complex reactor apparatus, and typically require a high vacuum (10−5 to 10−7 torr) environment.

Furthermore, such methods are only capable of providing a uniform flat surface layer of the metal catalyst on the substrate on which CNT formation and growth can occur.

Since CNT yield is directly related to surface area of the catalytic surface, substantially large areas of metal coated substrate is required to synthesize large quantities of CNTs, which is impractical in terms of existing limitations of the reaction apparatus.

According to Li et al., preparation of such large area catalytic substrate is hampered by the inherent tendency to shrink, crack and shatter during their preparation.

Imperfect catalyst preparation can severely limit yields of CNT product.

Also, CNT synthesis by the process of Li et al. requires a reaction temperature of 700° C., which is impractical for substrates such as flat panel glass.

Such methods however, require high vacuum conditions, which is difficult to achieve in large reactors in a commercially viable CNT manufacturing processes.

Although such methods are capable of providing highly pure, aligned CNTs, they are not best suited for large-scale production due to low volume (typically several milligrams to grams per batch), low yields based on amount of catalyst and high manufacturing cost.

Furthermore, existing methods do not allow control of nanotube morphology, tubule diameter, tubule wall thickness and other structural elements that are important in achieving desired material properties that may required for specific applications.

Such drawbacks are limiting factors that restrict the widespread use of CNTs in potential applications.

Although it is theoretically possible to introduce a wide range of structural defects with useful electronic properties in CNTs, synthetic limitations have precluded such introduction of systematic structural defects.

Furthermore, currently available methods do not allow controlled alteration of linear tubule structures during their growth.

Post growth modifications of CNTs have been difficult to implement and are prone to uncontrolled and random defects.

The branched Y-shaped CNTs obtained by the method however, are not symmetrical with respect to arm length, straightness and angles between arms, since their shape and symmetry is determined by limitations in fabrication of the aluminum mold in which they are formed.

Such processes are also not suited for large scale manufacture of CNTs and are, therefore, not economically viable for use in a commercial process.

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