Acta Phys. -Chim. Sin. ›› 2011, Vol. 27 ›› Issue (06): 1325-1334.doi: 10.3866/PKU.WHXB20110507

• THERMODYNAMICS, KINETICS, AND STRUCTURAL CHEMISTRY • Previous Articles     Next Articles

Reaction Kinetics of the Intermediate in Synthesis of LiCoPO4 by Solid-State Reaction

HUANG Ying-Heng1,2, TONG Zhang-Fa1, WEI Teng-You1, LI Bin1   

  1. 1. School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, P. R. China;
    2. Department of Metallurgy Engineering, Guilin University of Technology at Nanning, Nanning 530001, P. R. China
  • Received:2010-11-25 Revised:2011-02-22 Published:2011-05-31
  • Contact: TONG Zhang-Fa E-mail:zhftong@sina.com
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (20766001), Foundation for Young Scientists of Guangxi, China (0728101), and Research Foundation of Education Bureau of Guangxi, China (200505083).

Abstract:

A precursor NH4CoPO4 containing Li+ was synthesized using a low temperature solid-state reaction with ammonium dihydrogen phosphate, cobalt acetate, and lithium hydroxide. LiCoPO4 powder was manufactured by high temperature baking. The products were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) and thermogravimetry-differential thermal analysis (TG-DTA). The results showed that the formation of the intermediates was effected by the baking atmosphere. NH4CoPO4 containing Li+ was dehydrated and deaminated in air at 210?500 °C and then the (CoHPO4·LiCoPO4·Co2(OH)PO4·Li3PO4) intermediate (acid-base community) was emerged during the reaction process. The intermediate formation reaction mechanism followed the interfacial reaction power-law with an apparent activation energy of 50.0 kJ·mol-1. The kinetic function was found to be g(x)=(1-α)-1. The intermediate was dehydrated to form LiCoPO4 with an average apparent activation energy of 54.2 kJ·mol-1. The formation of the intermediate was not affected by the process of crystallization or non- crystallization of the materials. High temperatures accelerated the decomposition reaction of the intermediate and then the formation of LiCoPO4 crystals. A perfect crystal of LiCoPO4 was obtained by the decomposition of the intermediate at temperatures higher than 550 °C.

Key words: LiCoPO4, Lithium orthophosphate, Intermediate, Solid state reaction, Reaction mechanism, Kinetics

MSC2000: 

  • O643