Phase-homogeneous LiFePO4 powders have been synthesized. The content of impurity crystalline phases was less than 0.1%, according to synchrotron diffractometry (SXRD) data. Anisotropic crystallite sizes L¯Vhkl were determined by XRD. A low resistance covering layer of mechanically strong ferric-graphite-graphene composite with impregnated ferric (Fe3+) particles 3+-containing protective layer of crystallites predominates at the first stage, and at the second stage Fe escapes into the electrolyte and to the anode. The crystallite size decreases due to amorphization that starts from the surface. The rate capability, Q(t), has been studied as a function of L¯Vhkl, of the correlation coefficients rik between crystallite sizes, of the Li diffusion coefficient, D, and of the electrical relaxation time, τel. For the test cathode with a thickness of 8 μm, the values of D = 0.12 nm2/s, τel = 8 s were obtained. To predict the dependence Q(t), it is theoretically studied in ranges closest to experimental values: D = 0.5 ÷ 0.03 nm2/s, τel = 8/1 s, average sizes along [010] L¯1 = 90/30 nm, averaged r¯ = 0/1.