4.8 Article

Tailored Preparation Methods of TiO2 Anatase, Rutile, Brookite: Mechanism of Formation and Electrochemical Properties

Journal

CHEMISTRY OF MATERIALS
Volume 22, Issue 3, Pages 1173-1179

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/cm902613h

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Funding

  1. U.S. Department of Energy by UChicago Argonne, LLC [DE-AC02-06CH11357]

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Using a simple aqueous precipitation method based on a low-cost titanium oxysulfate precursor, we have prepared three TiO2 polymorphs: anatase, rutile, and brookite. Although the anatase form can be directly obtained from the thermolysis reaction of an oxysulfate solution, the rutile and the brookite have been prepared by the addition of oxalate species. Depending on the concentration, the oxalate anions have been shown to act either as a ligand with the stabilization of a titanium oxalate hydrate, Ti2O3(H2O)(2)(C2O4) center dot H2O, or as a chelating agent with the isolation of the rutile phase. The brookite form was obtained by thermal decomposition of the oxalate hydrate at a temperature as low as 300 degrees C. The resulting solid consisted of nanodomains of TiO2 brookite embedded in large micrometer-size particles and exhibited a high specific surface area of 255 m(2)/g because of the mesoporosity arising from the removal of water from the oxalate species. This type of morphology is of interest for lithium-ion batteries because of an easier coating process and a higher surface contact between the material kind the electrolyte that enhanced the electrochemical activity. Finally, based on electrochemical characterizations, TiO2 brookite provided higher volumetric energy density than comparable nanomaterials.

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