Abstract Single phases of olivine-type LiCoPO 4 and LiNiPO 4 were synthesized by thermal treatment of homogeneous lithium–metal–phosphate–formate precursors obtained by freeze drying of aqueous solutions of the corresponding metal formates and LiH 2 PO 4. The structure, thermal behavior, and morphology of the precursors were studied by IR spectroscopy, DTA, and SEM. Cobalt and nickel phosphate–formate precursors have a ...