Particle size-controllable microwave-assisted solvothermal synthesis of the high-voltage cathode material LiCoPO4 using water/ethylene glycol solvent blends

Particle size-tuned platelets of the high-voltage cathode material LiCoPO4 for Li-ion batteries have been synthesized by a simple one-step microwave-assisted solvothermal process using an array of water/ethylene glycol (EG) solvent mixtures. Particle size control was achieved by altering the concentration of the EG co-solvent in the mixture between 0 and 100 vol%, with amounts of 0–80 vol% EG producing single phase, olivine-type LiCoPO4. The particle sizes of the olivine materials were significantly reduced from about 1.2 μm × 1.2 μm × 500 nm (0 vol% EG) to 200 nm × 100 nm × 50 nm (80 vol% EG) with increasing EG content, while specific surface areas increased from 2 to 13 m2 g-1. The particle size reduction could mainly be attributed to the modified viscosities of the solvent blends. Owing to the soft template effect of EG, the crystals exhibited the smallest dimensions along the [010] direction of the Li diffusion pathways in the olivine crystal structure, resulting in enhanced lithium diffusion properties. The relationship between the synthesis, crystal properties and electrochemical performance was further elucidated, indicating that the electrochemical performances of the as-prepared materials mainly depend on the solvent composition and the respective particle size range. LiCoPO4 products obtained from reaction media with low and high EG contents exhibited good electrochemical performances (initial discharge capacities of 87–124 mAh g−1 at 0.1 C), whereas materials made from medium EG concentrations (40–60 vol% EG) showed the highest capacities and gravimetric energy densities (up to 137 mAh g−1 and 658 Wh kg−1 at 0.1 C), excellent rate capabilities, and cycle life.