Recent progress and developments in lithium cobalt phosphate chemistry Syntheses, polymorphism and properties

This review summarizes the development, investigation, and optimization of polymorphic lithium cobalt phosphate LiCoPO4. One of the three polymorphs known to date, olivine-type or Puma-LiCoPO4, shows intriguing electrochemical properties as a high-voltage cathode material, which are of interest for next-generation lithium-ion batteries with higher energy density. Hence, scientists have developed optimization strategies to improve its performance for commercial applications. Herein, a number of procedures for the synthesis of Pnma-LiCoPO4 is presented, including thermodynamic as well as kinetically controlled approaches. The continuous improvement of its electrochemical performance is illustrated, which was realized by the development of solvothermal techniques that allow a precise particle size and morphology control. In the course of these investigations, two new polymorphs, Pna2(1)-LiCoPO4 and Cmcm-LiCoPO4, have been discovered which show different physical and structural properties compared to Pnma-LiCoPO4. Despite their significantly poorer electrochemical performance, these polymorphs allow interesting insights into the variable structure chemistry of transition-metal phosphates, which canalizes in intriguing magnetic and thermal properties. The similarities and differences in the chemical and physical properties of Puma-LiCoPO4, Pna2(1)-LiCoPO4, and Cmcm-LiCoPO4 are discussed.