WO2022093377A2 - Carbone graphitique comprenant du bore incorporé dans le réseau de graphite et son procédé de préparation - Google Patents

Carbone graphitique comprenant du bore incorporé dans le réseau de graphite et son procédé de préparation Download PDF

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Publication number
WO2022093377A2
WO2022093377A2 PCT/US2021/047979 US2021047979W WO2022093377A2 WO 2022093377 A2 WO2022093377 A2 WO 2022093377A2 US 2021047979 W US2021047979 W US 2021047979W WO 2022093377 A2 WO2022093377 A2 WO 2022093377A2
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WIPO (PCT)
Prior art keywords
boron
carbon
source
substrate
mesoscopic
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PCT/US2021/047979
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English (en)
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WO2022093377A3 (fr
Inventor
David N. Mcilroy
Elena M. ECHEVERRIA
Aaron J. AUSTIN
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The Board of Regents for the Oklahoma Agricultural and Mechanical Colleges
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Application filed by The Board of Regents for the Oklahoma Agricultural and Mechanical Colleges filed Critical The Board of Regents for the Oklahoma Agricultural and Mechanical Colleges
Publication of WO2022093377A2 publication Critical patent/WO2022093377A2/fr
Publication of WO2022093377A3 publication Critical patent/WO2022093377A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/205—Preparation

Definitions

  • the properties of carbon-based materials are highly dependent on their morphology and carbon bonding, i.e., sp2, sp3, or a mixture thereof.
  • graphite with sp2 bonding is conductive
  • diamond with sp3 bonding is a wide bandgap insulator.
  • the chirality of a carbon nanotube and/or its geometrical structure determines whether it will be a semiconductor or a conductor.
  • graphite is one option for Li- ion batteries; however, fast charging of the battery can lead to swelling and flaking or breaking of the graphite particles into smaller particles diminishing its storage capacity, cycle life or leading to catastrophic failure. Therefore, a more stable conductive carbon structure would be beneficial to several industrial applications.
  • the present disclosure provides a method of preparing a boron doped carbon mesoscopic structure.
  • the method comprises: providing a reaction chamber containing a substrate, said substrate having a melting point greater than 1100°C and said reaction chamber and substrate are free of any metal catalyst; heating said reaction chamber to a temperature between about 700°C and about 1100°C; providing a housing containing a carbon source and a boron source, said housing having a fluid inlet and a fluid outlet; heating the solution to a temperature between about 80°C and about 130°C; passing a non-reactive gas into said housing through said fluid inlet and passing the non- reactive gas through the solution at a rate sufficient to carry said solution out of said housing through the fluid outlet as a vapor; passing said non-reactive gas carrying said vapor to said reaction chamber; passing said non-reactive gas carrying said vapor over said substrate; and, growing graphite layers on said substrate by decomposing said carbon source on said substrate to yield boron doped carbon mesoscopic structures on said
  • the resulting boron doped carbon mesoscopic structures are free of sulfur.
  • the present disclosure describes a boron doped carbon mesoscopic structure characterized as open and closed tubular filaments having wall thicknesses between about 20 nm and about 100 nm.
  • the boron doped carbon mesoscopic structure further characterized as comprising an atomic concentration of boron between about 0.1% and about 15%. Additionally, the boron doped carbon mesoscopic has a length between about 9 pm and about 20 pm.
  • FIGS. 1 A - ID depict images of the graphitic carbon with boron incorporated into the graphite lattice at different magnifications.
  • FIG. 1 A is at a magnification of 2000X.
  • FIG. IB is at a magnification of 10000X.
  • FIG. 1C is at a magnification of 27000X.
  • FIG. ID is at a magnification of 58000X.
  • FIGS. 2A - 2D provide transmission electron microscopy images of a bundle of graphitic carbon with boron incorporated into the graphite lattice.
  • FIG. 2A is at a magnification of 60000X.
  • FIG. 2B is at a magnification of 200000X.
  • FIG. 2C is at a magnification of 400000X.
  • FIG. 2D is at a magnification of 500000X.
  • FIG. 3A is a scanning electron microscope image of graphitic carbon with boron incorporated into the graphite lattice at the early stage of formation
  • FIG. 3B is a scanning electron microscope image of a fully formed filament of graphitic carbon with boron incorporated into the graphite lattice.
  • FIG. 4A depicts the surface morphology of a pseudo-graphite.
  • FIG. 4B depicts the surface morphology of graphitic carbon with boron incorporated into the graphite lattice.
  • FIG. 5 provides a theoretical model of the incorporation of boron into the graphite lattice of the graphitic carbon.
  • FIG. 6A is a schematic representation of the pseudo-graphite of FIG. 4A.
  • FIG. 6B is a schematic representation of the tubular form of the graphitic carbon with boron incorporated into the graphite lattice.
  • FIG. 7 is a schematic representation of the equipment and method suitable for preparing the graphitic carbon with boron incorporated into the graphite lattice.
  • the boron doped carbon mesoscopic structures will be referred to as BOD-Carbon.
  • the term “doped” refers to the inclusion of boron in the lattice structure of the resulting carbon form. See FIG. 5.
  • the term carbon mesoscopic structure refers to carbon structures that have physical dimensions that are between microscopic and macroscopic.
  • the disclosed BOD- Carbon has diameters between about 1 pm and about 2 pm with wall thicknesses between about 20 nm and about 100 nm. The final dimensions can be varied depending on how the following method is fine tuned.
  • the filament typically tapers from a narrow open end to a broader closed base.
  • FIGS. 1A - ID depict the BOD-Carbon under scanning electron microscopy.
  • the tubular filaments can be seen as a medium density array under magnification of 2000X.
  • FIG. IB taken at a magnification of 10000X, reveals open ended tubular filaments having lengths of about 9 pm to about 20 pm with some filaments having closed ends. If an open second end is desired, then the overall length will typically be 10 pm or less. However, the lengths can be significantly longer depending on fine tuning of the following method.
  • FIG. 1C taken at a magnification of 27000X, depicts many filaments in a top down view revealing the hollow nature of the BOD- Carbon.
  • FIG. ID taken at a magnification of 58000X, reveals that the BOD-Carbon filaments have outer diameters between about ten nanometers and about 5 pm and have wall thicknesses of about 50 nm to about 100 nm.
  • the BOD-Carbon filaments are significantly larger than single wall and multi-wall carbon nanotubes.
  • FIGS. 2A-B The transmission electron micrographs of FIGS. 2A-B confirm that the BOD-Carbon filaments are hollow but lack the concentric cylinders type morphology common to multi-wall carbon nanotubes. As such, the BOD-Carbon filaments represent a new mesoscopic morphology of carbon. Additionally, FIGS. 2A and 2B depict three types of terminations for the BOD- Carbon filaments: flared outward, straight and closed. Additionally, the inner diameter of the filament typically increases while the outer diameter typically remains constant. FIG. 2A was taken at a magnification of 60000X while FIG. 2B was taken at a magnification of 200000X. With reference to FIGS.
  • Further characterization of the BOD-Carbon filaments can be made by determining the energy state of the resulting boron substituted graphitic lattice. Without being limited by theory, the resulting BOD-Carbon is believed to be a consequence of boron induced strain of the hexagonal sp2 bonded carbon lattice and disorder associated with increased sp3 bonded carbon. The modeling of the inclusion of boron in the lattice structure and the resulting lattice distortions supports this conclusion. The lowest energy state of the graphitic structure with substituted boron was determined using an open source three-dimensional molecular structure editing software known as Avogadro to determine the corresponding geometry. The resulting modeled structure of the BOD-Carbon is depicted in FIG. 6.
  • FIG. 5 depicts the reduced energy state for the three calculated geometries of graphitic lattice with boron substitution.
  • boron substitution reduced the energy state of structure A from 4828.1 kJ/mole to 1204.4 kJ/mole in the substituted structure D.
  • boron substitution of structure B reduced the energy state from 1610.1 kJ/mole to 289.7 kJ/mole for substituted structure E.
  • boron substitution of structure C reduced the energy state from 2174.3 kJ/mole to 761.8 kJ/mole for substituted structure F.
  • the presence of boron in the lattice structure of BOD- Carbon produces an upward curving morphology relative to the substrate.
  • the upward curve results from the additional strain, out of plane or between planes, generated by the sp3 carbon sites.
  • the Raman spectrum of BOD-Carbon supports the conclusion of Boron induced strain. Specifically, the G band of BOD-Carbon is at 1593 cm' 1 .
  • tensile strain produces a shift of the G band of graphite and graphene related materials.
  • FIGS. 4A and 6A compare a non-doped pseudo-graphite to the newly developed BOD-Carbon.
  • pseudo-graphite refers to a carbon structure that has the hexagonal atomic lattice structure of graphite.
  • the pseudo-graphite structure is highly disordered which differs from the long range order commonly associated with graphite.
  • the non-doped pseudo-graphite used for comparison to the BOD-Carbon can be exfoliated in the same manner as graphite.
  • BOD-Carbon cannot be exfoliated and further differs structurally from the non-doped pseudographite as discussed herein.
  • the non-doped pseudo-graphite was prepared using a pressure chemical vapor deposition (APCVD) process.
  • APCVD pressure chemical vapor deposition
  • the pseudo-graphite has overlapping downward curving structures.
  • the pseudo-graphite is characterized as a layered structure that exfoliates; however, unlike graphite, the thickness of the exfoliated layers is on the order of microns.
  • the pseudo-graphite in an agglomeration of carbon hemispheres having diameters ranging from 50 nm to 100 nm.
  • substrate 14 supporting the growth of the pseudo-graphite as the reference point, the carbon hemispheres have a downward curve toward the substrate, as depicted in FIG.
  • the backside of the pseudo-graphite When grown and subsequently delaminated from a substrate, the backside of the pseudo-graphite has a relatively smooth structure with a few circular pits when examined using an atomic force microscope (AFM). See FIG. 4A.
  • the RMS roughness of the backside of the pseudo-graphite is 0.3 nm in the pit free regions and the average diameter of the pits is 58 ⁇ 12 nm.
  • the isolated top corner of the FIG. depicts the line analysis for that region.
  • line analysis refers to the practice of removing noise and artifacts from an image.
  • FIGS. 3A and 3B depict the closed core and ellipsoidal follicle (3 A) that tapers prior to formation of the hollow filament of FIG. 3B.
  • the BOD-carbon structures disclosed above can be prepared according to the following atmospheric pressure chemical vapor deposition method. The following method will also be described with reference to FIG. 7. As depicted schematically in FIG. 7, the method may be carried out in a heated reaction chamber or furnace 10.
  • the interior of reaction chamber 10 contains a clean substrate 14 suitable for supporting growth of the BOD-carbon.
  • Reaction chamber 10 also has a fluid inlet 16 and a fluid outlet 18.
  • a housing 20 contains the solution or suspension of reaction materials. Housing 20 has a fluid inlet 22, fluid outlet 24, a heating mechanism (not shown) and an agitation mechanism (not shown). Reaction materials may be added to housing 20 through fluid inlet 22, fluid outlet 24 or through another opening not shown.
  • fluid inlet 22 extends downward into housing 20 such that the fluid level of reactants in housing 20 is above the exit point of fluid inlet 22. Additionally, housing 20 will preferably provide for the continuous agitation or stirring of the reaction materials.
  • a carrier gas source is in fluid communication with fluid inlet 22 of housing 20 and fluid outlet 24 is in fluid communication with fluid inlet 16 of reaction chamber 10.
  • Substrate 14 is selected to withstand the reaction temperature. Typically, substrate 14 may be any suitable material having a melting point in excess of 900°C. More typically, the material will have a melting point greater than 1100°C. Common substrates include but are not limited to: silicon, alumina, quartz, sapphire, carbon.
  • Reaction chamber 10 can have any shape. For example, a tube furnace having a fluid inlet and fluid outlet may be used as reaction chamber 10.
  • the atmospheric pressure chemical vapor deposition method for forming BOD-carbon begins by placing the reactants in housing 20.
  • the reactants include a carbon source, a boron source and optionally a sulfur source.
  • the carbon source may be a liquid or gaseous hydrocarbon such as, but not limited to: aliphatic alcohols, alicyclic alcohols, aromatic alcohols, heterocyclic alcohols, ethylene and acetylene.
  • the carbon source is an organic compound, such as cyclohexanol.
  • Suitable boron sources included but are not limited to: ortho-carborane (also known as ortho-closo-dicarbadodecaborane), meta-closo-dicarbadodecaborane, para-closo- dicarbadodecaborane, boric acid, metaboric acid, decaborane, tri ethylborane, borazane and borazine.
  • the source of sulfur will be elemental sulfur; however, other sources such as but not limited to thiols, mercaptans, hydrogen sulfide (H2S), dimethyl sulfoxide (DMSO) will also perform satisfactorily.
  • the agitation mechanism of housing 20 provides sufficient movement of the carbon source to convert the mixture of reactants into a homogeneous dispersion or suspension or when components are soluble into a solution.
  • the reactants are present in housing 20 as a suspension, dispersion or solution.
  • solution we will use the term solution; however, one skilled in the art will recognize that nature of the mixture will be based on the components used.
  • the boron source When using a gaseous hydrocarbon, the boron source will typically be diborane (B2H6) in which case the sulfur source can be H2S.
  • the final solution of reactants in housing 20 will contain a sufficient concentration of the boron source to supply the equivalent of approximately 2% to about 50% by weight of elemental boron in the solution. If sulfur is included in the final solution of reactants, the source of sulfur shall provide the equivalent of about 1% to about 30% sulfur by weight in the solution. The remaining portion of the suspension is the carbon source.
  • the atmospheric pressure chemical vapor deposition begins by preheating the reactants in housing 20 to a temperature between about 80°C and about 130°C and heating reaction chamber 10 to a temperature between 700°C and about 1100°C.
  • the minimum temperature within reaction chamber 10 is that temperature sufficient to decompose the carbon and boron sources.
  • a second optional heating step of housing 20 takes place.
  • the suspension of reactants is heated to a temperature sufficient to aid in the entrainment of the reactant solution as a vapor in a non-reactive gas passing through the solution of reactants.
  • the reactant solution will be heated to a temperature between about 80°C and about 200°C, more typically 80°C to about 120°C. In most instances, the final temperature of the reactant solution is about 120°C.
  • a non-reactive gas is passed through housing 20 via inlet 22.
  • the non- reactive gas passes directly into and through the solution of reactants acting as a bubbler or vaporizer, thereby vaporizing the reactants.
  • the vaporized reactants carried by the non-reactive gas subsequently pass out of housing 20 through outlet 24.
  • the flow rate of the non-reactive gas through housing 20 will vary depending on the size of housing 20 and the size of reaction chamber 10.
  • Suitable gases are gases which are non- reactive with the reactants in housing 20.
  • Non-limiting examples would include common carrier gases such as nitrogen, argon and helium.
  • the carrier gas flowed at a rate of about 130 seem and 160 seem, to carry the vaporized reactants from housing 20 into reaction chamber 10.
  • the flow rate remained within this range as the reactants passed over substrate 14.
  • the boron source and carbon source decomposed through pyrolysis on the surface of substrate 14 initiating the growth of the BOD-carbon.
  • the decomposition of both the carbon source and the boron source on the surface of the substrate will produce a carbon lattice structure with boron incorporated into the lattice of the mesoscopic structure of BOD-Carbon.
  • the interfacial energy at the carbon-silicon interface i.e. the interface with substrate 14 is modified leading to the upward curved structures relative to the upper surface of substrate 14.
  • the growth of the BOD-Carbon continues for a period between about 5 minutes and about 120 minutes. More typically, the time allowed for growth will be between about 15 minutes and about 30 minutes.
  • the sulfur acts as a promoter of carbon nucleation to enhance formation of the resulting structure.
  • sulfur does not become part of the resulting BOD-Carbon mesoscopic carbon structure. Rather, the BOD-Carbon is free of sulfur and does not contain any other catalyst material.
  • the final BOD-Carbon structure has the characteristics discussed above.

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Abstract

L'invention divulgue un graphite mésoscopique dopé au bore et un procédé de préparation d'un graphite mésoscopique dopé au bore. Le graphite mésoscopique dopé au bore est caractérisé par un filament tubulaire ouvert et fermé ayant des épaisseurs de paroi comprises entre environ 50 nm et environ 100 nm. Le procédé divulgué est un procédé de dépôt chimique en phase vapeur par pression atmosphérique dans lequel les réactifs subissent une pyrolyse dans une chambre de réaction conduisant à la croissance du graphite mésoscopique dopé au bore sur un substrat.
PCT/US2021/047979 2020-10-29 2021-08-27 Carbone graphitique comprenant du bore incorporé dans le réseau de graphite et son procédé de préparation WO2022093377A2 (fr)

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EP2459483A2 (fr) * 2009-07-31 2012-06-06 Massachusetts Institute of Technology Systèmes et procédés associés à la formation de nanostructures à base de carbone
US9388513B2 (en) * 2011-07-01 2016-07-12 The University Of Kentucky Research Foundation Crystallographically-oriented carbon nanotubes grown on few-layer graphene films
CN103407985B (zh) * 2013-07-16 2016-05-11 清华大学 一种杂原子掺杂碳纳米管-石墨烯复合物及其制备方法

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