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Nanostructured Metal Oxides Comprising Internal Voids and Methods of Use Thereof

a metal oxide and nanostructure technology, applied in the field of nanostructures, can solve the problems of poor cyclability, limiting the use of such applications, and the method is often burdened with the challenge of uniform depositing of metal oxides (or their precursors) on templates, and achieves the effects of less cost, improved cyclability, and improved cyclability

Inactive Publication Date: 2010-10-14
CORNELL RES FOUNDATION INC
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0009]In another aspect, the present invention is directed to novel inexpensive, viable, high-yield methods for large-scale and industrial mass production of such hollow metal oxide nanostructures. In one embodiment, the invention comprises a template-free “one-pot” method, based on an inside-out Oswald ripening mechanism. This method comprises hydrothermal treatment of a metal-oxide precursor in a mixed solvent, usually a polar solvent in and water, and the mediation of general ionic and non-ionic surfactants, polymers, or crystal modifiers such as urea-based compounds at temperatures above about 140° C. and up to about 200° C. that allow for high-yield mass production of hollow metal oxide nanostructures with controllable sizes in the range of 200.0-500.0 nm.

Problems solved by technology

However, although metal oxides (for example, tin oxide (SnO2)) generally have a much higher theoretical specific lithium storage capacity area than more traditionally used materials such as graphite, the large volume changes in metal oxide nanostructures during charging / discharging processes result in poor cyclability, thus limiting their use in such applications. S. Han, B. Jang, T. Kim, S. M. Oh, T. Hyeon, Adv. Funct. Mater. 2005, 15, 1845; K. T. Lee, Y. S. Jung, S. M. Oh, J. Am. Chem. Soc.
Although conceptually simple and versatile, such methods are often burdened with the challenge of uniformly depositing metal oxides (or their precursors) on templates, a problem which has traditionally been dealt by prior surface modification, itself a tedious process. M. Yang, J. Ma, C. Zhang, Z. Yang, Y. Lu, Angew. Chem. Int. Ed.
However, many such existing methods for the production of nanostructures are often cumbersome involving multiple steps that are often difficult to control, and are cost-prohibitive which prevent them from being used in large-scale applications.
Moreover, many of these existing methods also result in poor yields of mono-disperse, hollow nanostructures, producing mixed hollow and solid nanostructures, or nanostructures with large-size distributions.

Method used

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  • Nanostructured Metal Oxides Comprising Internal Voids and Methods of Use Thereof
  • Nanostructured Metal Oxides Comprising Internal Voids and Methods of Use Thereof
  • Nanostructured Metal Oxides Comprising Internal Voids and Methods of Use Thereof

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example 1

[0056]Hollow SnO2 nanoparticles were prepared by a hydrothermal method in an ethanol / H2O mixed solvent. Potassium stannate trihydrate (K2SnO3; 3H2O, Aldrich, 99.9%) was added to 30 ml of ethanol / H2O mixture with an r value of 25-50%, to achieve potassium stannate concentrations of 4.7 mM-40 mM. After gentle shaking by hand for about 5 minutes, a slightly white translucent or clear solution (depending on values of r and c) was obtained, which was then transferred to a 40 mL Teflon-lined stainless steel autoclave. In certain experiments, urea, thiourea or ethyl diamine were also used as additives, typically with overall concentrations of about 0.1 mM. After heating in an electric oven at 150° C. for a period of 3-48 hours, the autoclave was gradually cooled down in air, or rapidly using tap water. The white product was harvested by centrifugation and washed with deionized water and ethanol before drying at 50° C. overnight.

[0057]The electrochemical properties of the hollow SnO2 nanosp...

example 2

[0060]Monodisperse silica nanospheres with different sizes were prepared from the well known Stobers method. W. Stober, A. Fink, E. Bohn, J. Colloid Interface Sci. 1968, 26, 62-69. Polycrystalline SnO2 shells were facilely deposited on silica templates without any prior surface modification by a hydrothermal method. Depending on the amount of nanostructures desired, 40-120 mg silica nanospheres were first dispersed by ultrasonication in 30 ml of ethanol / water (37.5 vol % ethanol) mixed solvent. To this white suspension, urea (0.9 g or 0.5 M) and potassium stannate trihydrate (˜144 mg or 16 mM; K2SnO3.3H2O, Aldrich, 99.9%) were added. After shaking by hand for about 5 minutes until the salt dissolved, the suspension was transferred to a 40 ml Teflon-lined stainless-steel autoclave, which was then heated in an airflow electric oven at 150-190° C. for 36 hours. After the autoclave cooled down naturally, the white product was harvested by centrifugation and washed with deionized water. ...

example 3

[0061]The Au / silica core / shell particles were prepared as described in detail by Liu et al. S. H. Liu, M. Y. Han, Adv. Funct. Matter. 2005, 15, 961-967. After extensive washing with water, the as-obtained Au / silica core / shell particles (˜50 mg) were directly used without drying as the template for the same SnO2 deposition.

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Abstract

The present invention relates to nano structures of metal oxides having a nanostructured shell (or wall), and an internal space or void. Nanostructures may be nanoparticles, nanorod / belts / arrays, nanotubes, nanodisks, nanoboxes, hollow nanospheres, and mesoporous structures, among other nanostructures. The nanostructures are composed of polycrystalline metal oxides such as SnO2. The nanostructures may have concentric walls which surround the internal space of cavity. There may be two or more concentric shells or walls. The internal space may contain a core such ferric oxides or other materials which have functional properties. The invention also provides for a novel, inexpensive, high-yield method for mass production of hollow metal oxide nanostructures. The method may be template free or contain a template such as silica. The nanostructures prepared by the methods of the invention provide for improved cycling performance when tested using rechargeable lithium-ion batteries.

Description

PRIORITY CLAIM[0001]The present application claims priority to U.S. Provisional Pat. App. 60 / 804,031 filed on Jun. 6, 2006, the contents of which are hereby incorporated by reference in their entirety.STATEMENT OF GOVERNMENT RIGHTS[0002]This invention was made with Government support under contract number DMR 0404278, awarded by the National Science Foundation. The government has certain rights in this invention.FIELD OF INVENTION[0003]The present invention relates to nanostructures and more particularly to nanostructures comprising nanostructured metal oxide shells enclosing internal voids, as well as methods for making and using the same.BACKGROUND[0004]Recently, hollow inorganic micro- and nanostructures have attracted considerable attention because of their promising applications as nanoscale chemical reactors, catalysts, drug delivery carriers, semiconductors, and photonic building blocks. X. W. Lou, C. Yuan, Q. Zhang, L. A. Archer, Angew. Chem. Int. Ed. 2006, 45, 3825. In part...

Claims

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Application Information

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IPC IPC(8): C01G49/08H01B1/08C01B13/14C01G19/02B05D5/12B29D22/04
CPCB82Y30/00Y10T428/13C01G1/02C01G19/02C01P2004/64C01P2006/40H01G9/2027H01M4/366H01M4/485H01M10/0525H01M2004/021H01M2004/027Y02E60/122H01M4/48C01B33/12Y02E60/10Y10T428/2984Y10T428/2991Y10T428/2993
Inventor ARCHER, LYNDEN A.LOU, XIONG WEN
Owner CORNELL RES FOUNDATION INC
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