Method for preparation of metal intercalated fullerene-like metal chalcogenides

• US 6,217,843 B1
• Filed: 04/03/2000
• Issued: 04/17/2001
• Est. Priority Date: 11/29/1996
• Status: Expired due to Term

• Current Assignee: Yeda Research and Development Co. Ltd. (Weizmann Institute of Science)
• Original Assignee: Yeda Research and Development Co. Ltd. (Weizmann Institute of Science)
• Inventors: Homyonfer, Moshe, Tenne, Reshef, Feldman, Yishay
• Primary Examiner(s): TURNER, ARCHENE A
• Application Number:
  US09/308,663
• Time in Patent Office: 379 Days
• Field of Search: 423/592, 423/618, 423/624, 423/596, 423/598, 423/606, 423/608, 423/610, 423/635, 423/641, 423/566.2, 423/566.3, 427/372.2, 427/331, 427/335, 252/501.1, 252/518.1, 252/519.1, 252/519.14, 252/519.4, 508/108
• US Class Current: 423/593.1
• CPC Class Codes: C01G 39/02 Oxides; Hydroxides
• CPC Class Codes: C01G 39/06 Sulfides
• CPC Class Codes: C01G 41/006 Compounds containing, besides tungsten, two or more other elements, with the exception of oxygen or hydrogen
• CPC Class Codes: C01G 41/02 Oxides; Hydroxides
• CPC Class Codes: C01P 2002/02 Amorphous compounds
• CPC Class Codes: C01P 2002/20 Two-dimensional structures
• CPC Class Codes: C01P 2002/52 containing elements as dopants
• CPC Class Codes: C01P 2002/54 one element only
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2002/77 by unit-cell parameters, atom positions or structure diagrams
• CPC Class Codes: C01P 2002/84 by UV- or VIS- data
• CPC Class Codes: C01P 2002/85 by XPS, EDX or EDAX data
• CPC Class Codes: C01P 2004/04 obtained by TEM, STEM, STM or AFM
• CPC Class Codes: C01P 2004/10 extending in one dimension, e.g. needle-like
• CPC Class Codes: C01P 2004/13 Nanotubes
• CPC Class Codes: C01P 2004/22 with a polygonal circumferential shape
• CPC Class Codes: C01P 2004/32 Spheres
• CPC Class Codes: C01P 2004/62 Submicrometer sized, i.e. from 0.1-1 micrometer
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: C01P 2004/80 Particles consisting of a mixture of two or more inorganic phases
• CPC Class Codes: C01P 2006/40 : Electric properties
• CPC Class Codes: C01P 2006/60 : Optical properties, e.g. expressed in CIELAB-values
• CPC Class Codes: C01P 2006/80 : Compositional purity
• CPC Class Codes: C30B 29/605 : Products containing multiple oriented crystallites, e.g. columnar crystallites
• CPC Class Codes: C30B 7/00 : Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions from molten solvents C30B9/00; by normal or gradient freezing C30B11/00; under a protective fluid C30B27/00
• CPC Class Codes: G02F 1/1524 : Transition metal compounds
• CPC Class Codes: G02F 2202/36 : Micro- or nanomaterials
• CPC Class Codes: H01G 9/20 : Light-sensitive devices
• CPC Class Codes: H01G 9/2027 : comprising an oxide semiconductor electrode
• CPC Class Codes: H01G 9/2054 : comprising a semiconductor electrode comprising AII-BVI compounds, e.g. CdTe, CdSe, ZnTe, ZnSe, with or without impurities, e.g. doping materials H01G9/2027 takes precedence
• CPC Class Codes: H01M 10/052 : Li-accumulators
• CPC Class Codes: H01M 10/36 : Accumulators not provided for in groups H01M10/05-H01M10/34
• CPC Class Codes: H01M 4/131 : Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/48 : of inorganic oxides or hydroxides
• CPC Class Codes: H01M 4/485 : of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: H01M 4/581 : Chalcogenides or intercalation compounds thereof
• CPC Class Codes: H01M 4/90 : Selection of catalytic material
• CPC Class Codes: Y02E 10/542 : Dye sensitized solar cells
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02E 60/50 : Fuel cells
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y10S 977/724 : Devices having flexible or movable element
• CPC Class Codes: Y10S 977/734 : Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
• CPC Class Codes: Y10S 977/773 : Nanoparticle, i.e. structure having three dimensions of 100 nm or less
• CPC Class Codes: Y10S 977/84 : Manufacture, treatment, or detection of nanostructure
• CPC Class Codes: Y10S 977/89 : Deposition of materials, e.g. coating, cvd, or ald
• CPC Class Codes: Y10S 977/932 : for electronic or optoelectronic application

Abstract

A method for the preparation of nanoparticles of metal oxides containing inserted metal particles and to metal-intercalated and/or metal-encaged “inorganic fullerene-like” (hereinafter IF) structures of metal chalcogenides obtained therefrom is provided, which comprises heating a metal I material with water vapor or electron beam evaporation of said metal I material with water or another suitable solvent, in the presence of a metal II salt, and recovering the metal II-doped metal I oxide, or proceeding to subsequent sulfidization, yielding bulk quantities of metal II-intercalated or metal II-encaged IF structures of the metal I chalcogenide. The metal II salt is preferably an alkaline, alkaline earth or transition metal salt, most preferably an alkali chloride. The intercalated and/or encaged IF structures are usable as lubricants. They also form stable suspensions, e.g. in alcohol, and electrophoretic deposition from said suspensions yields thin films of the intercalated IF materials, which have a range of potential applications.

Claims

1. A method for the preparation of nanoparticles or nanowhiskers of a metal II-doped metal I oxide, wherein said metal I is selected from In, Ga, Sn and a transition metal and said metal II is any metal, which method comprises:

(i) heating a metal I material with water in a vacuum apparatus at a base pressure of 10<sup>−

3</sup> to 10<sup>−

5</sup> Torr or electron beam evaporating a metal I material with water or with an oxygen-containing volatile solvent in a vacuum apparatus at a base pressure of 10<sup>−

5</sup> to 10<sup>−

6</sup> Torr, in the presence of a metal II salt;

, and

(ii) recovering the metal II-doped metal I oxide powder from the walls of the vacuum apparatus.

3. A method according to claim 1 wherein said metal II salt is an alkali metal chloride.

4. A method according to claim 1, wherein said metal II-doped metal I oxide is a metal II-doped mixed oxide of 2 or more different metal I atoms.

5. A method according to claim 1 for the preparation of nanoparticles or nanowhiskers of doped metal oxides selected from Na—

, K—

, Li—

or Cs-doped MoO<sub>3−

x</sub>, preferably MoO₂ and MoO_3,, or Na—

, K—

, Li—

or Cs13 doped WO<sub>3−

x</sub>, preferably WO₃ and W₁₈O₄₉ , and Na—

, K—

, Li—

or Cs-doped mixed Mo/W oxide consisting of Mo_xW<sub>1−

x</sub>O₃, wherein x is from 0 to 1.

6. A method according to claim 1, wherein said metal II salt is added to the water or to the oxygen-containing volatile solvent.

7. A method according claim 1, wherein said metal II salt is NaCl or KCl and it is already present in the water.

2. A method according to claim I wherein said transition metal I includes Mo, W, V, Zr, Hf, Pt, Re, Nb, Ta Ti, and Ru, and said metal II is selected from an alkali, alkaline earth or a transition metal.

8. A method for the preparation of metal II-intercalated and/or metal II-encaged inorganic fullerene-like (IF) structures of a metal I chalcogenide, wherein said metal I is selected from In, Ga, Sn and a transition metal and said metal II is any metal, which method comprises:

(i) heating a metal I material with water in a vacuum apparatus at a base pressure of 10<sup>−

3</sup> to 10<sup>−

5</sup> Torr or electron beam evaporating a metal I material with water or with an oxygen-containing volatile solvent in a vacuum apparatus at a base pressure of 10<sup>−

5</sup> to 10<sup>−

6</sup> Torr, in the presence of a metal II salt;

(ii) aimealing the metal II-doped metal I oxide obtained in step (i) in a reducing atmosphere with a H₂X gas, wherein X is S, Se, or Te; and

(iii) recovering the metal II-intercalated and/or metal II-encaged inorganic fullerene-like (IF) structures of the metal I chalcogenide.

9. A method according to claim 8 wherein said metal II-intercalated and/or metal II-encaged inorganic fullerene-like structures of a metal I chalcogenide are structures having one layer or nested layers which form a closed cage which may encage a core or may form a stuffed nested layer structure, particularly structures selected from single and double layer inorganic fullerene-like structures, nested layer inorganic fullerene-like structures, stuffed inorganic fullerene-like structures, structures with negative curvature (Schwartzites), single layer nanotubes, nested nanotubes and stuffed nanotubes.

10. A method according to claim 8 wherein nanoparticles of the metal oxide obtained in step (i) produce single layer IF and nested layer IF, and nanowhiskers of the metal oxide obtained in step (i) produce single layer and nested layer nanotubers.

11. A method according to claim 8, wherein said transition metal includes Mo, W, V, Zr, Hf, Pt, Re, Nb, Ta Ti, and Ru, and said metal II is selected from an alkali, alkaline earth or a transition metal.

12. Metal II-intercalated and/or metal II-encaged inorganic fullerene-like (IF) structures of a metal I chalcogenide, wherein said metal I is selected from In, Ga, Sn and a transition metal and said metal II is any metal.

13. The metal II-encaged inorganic fullerene-like (IF) structures of a metal I chalcogenide according to claim 12, wherein said structures include 1-2 layers of the metal I chalcogenide encaging a core of the metal II-doped metal I oxide.

14. A tip for scanning probe microscope coated with a single layer of a metal II-intercalated and/or metal II-encaged IF of metal I chalcogenide according to claim 13.

15. The metal II-intercalated inorganic fullerene-like (IF) structures of a metal I chalcogenide according to claim 12, wherein said structures include more than 2 layers of the metal I chalcogenide intercalated by metal II and encaging a core of the metal II-doped metal I oxide.

16. The metal II-encaged inorganic fullerene-like (IF) structures of a metal I chalcogenide according to claim 12, wherein said structures include more than 2 layers of the metal I chalcogenide intercalated with metal II and devoid of a core.

17. Metal II-intercalated and/or metal II-encaged inorganic fullerene-like (IF) structures of a metal I chalcogenide, according to claim 12, wherein said transition metal I includes Mo, W, V, Zr, Hf, Pt, Re, Nb, Ta Ti, and Ru, and said metal II is selected from an alkali, alkaline earth or a transition metal.

18. Use of metal II-intercalated and/or metal II-encaged inorganic fullerene-like (IF) structures of a metal I chalcogenide according to claim 12 as lubricant, particularly in solid lubrication.

19. A stable suspension in a polar solvent of at least one of a metal II-intercalated IF structure and a metal II-encaged IF structure of a metal I chalcogenide, wherein said metal I is selected from the group consisting of In, Ga, Sn and a transition metal, and said metal II is any metal.

20. A method for the production of thin films of metal II-intercalated and/or metal II-encaged IF structures of metal I chalcogenides, which comprises subjecting a stable suspension according to claim 19 to evaporation of the solvent or to electrophoretic deposition onto a conductive substrate.

21. Use thin films of metal II-intercalated and/or metal II-encaged IF structures of metal I chalcogenides obtained according to claim 20, as the photosensitive element in solar cells, for the fabrication of secondary batteries and in electrochromic devices.