Facile Synthesis of Spherical Porous Tricobalt Tetroxide and Metal Cobalt for High Quality Cobalt Production and Recycling

Abstract

Liquid-phase synthesis is suitable for controlling the morphological and structural properties of functional inorganic materials and such control is important because they strongly affect the functionality of the product. Cobalt-based materials is one group of materials that requires control of powder morphology and structure. Cobalt is an important metal element used in various industrial fields such as secondary batteries, superalloys, permanent magnets, hard metals, and catalysts. The ever-growing demand of cobalt highlights that there is an urgent necessity to develop high quality material synthesis methods and to secure cobalt resources for countries that rely on import like Japan. Especially, technologies to recycle cobalt in a form reusable for secondary batteries and catalysts are desired because further increase in demand is anticipated. Meanwhile, spherical porous tricobalt tetroxide secondary particles obtained by calcination of spherical cobalt carbonate precursors have been reported to be promising materials for battery applications. Moreover, porous metal cobalt obtained by hydrogen reduction of tricobalt tetroxide is known to be effective for catalyst applications. However, conventional methods to synthesize spherical cobalt carbonate requires addition of additives in the reaction mixtures or otherwise requires hydrothermal treatment in pressure vessels. These are unfavorable to develop a practical and sustainable process for cobalt-based material production and recycling. In this study, a facile room temperature synthesis method to prepare spherical cobalt carbonate precursors from solutions of cobalt chloride and ammonium hydrogen carbonate that does not require any additives or hydrothermal treatment is developed by optimizing the carbonate solution concentration, carbonate/cobalt salt molar ratio, and stirring time during reaction. Furthermore, we succeeded in obtaining porous tricobalt tetroxide and porous metal cobalt that carry on the exterior spherical morphology of the original cobalt carbonate precursor by calcination and hydrogen reduction. The developed process shall contribute to realize high quality cobalt-based material production and recycling.