Methods of manufacture and use of phosphates of transition metals are described as positive electrodes for secondary lithium batteries, including a process for the production of LiMPO.sub.4 with controlled size and morphology, M being Fe.sub.xCo.sub.yNi.sub.zMn.sub.w, where 0.ltoreq.x.ltoreq.1,0.ltoreq.y.ltoreq.1, 0.ltoreq.w.ltoreq.1, and x+y+z+w=1. According to an exemplary embodiment, a process is described for the manufacture of LiFePO.sub.4 including the steps of providing an equimolar aqueous solution of Li.sup.1+, Fe.sup.3+ and PO.sub.4.sup.3-, evaporating water from the solution to produce a solid mixture, decomposing the solid mixture at a temperature of below 500.degree. C. to form a pure homogeneous Li and Fe phosphate precursor, and annealing the precursor at a temperature of less than 800.degree. C. in a reducing atmosphere to produce the LiFePO.sub.4 powder. The obtained powders can have a particle size of less than 1 .mu.m, and can provide superior electrochemical performance when mixed for an appropriate time with an electrically conductive powder.