Controlled Synthesis of Single-Crystalline Ni-Rich Cathodes for High-Performance Lithium-Ion Batteries

Single-crystalline LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) has been considered as one of the most promising cathode materials. It addresses the pulverization issue present in its polycrystalline counterpart by eliminating intergranular cracks. However, synthesis of high-performance single-crystalline NCM is still a challenge owing to the lower structure stability of NCM811 at high calcination temperatures (≥900 °C), which is often required to grow single crystals. Herein, we report a synthesis process for microsized single-crystalline NCM811 particles with exposed (010) facets on their lateral sides [named as SC-NCM(010)], which includes the preparation of a well-dispersed microblock-like Ni_0.8Co_0.1Mn_0.1(OH)₂ precursor through coprecipitation assisted with addition of PVP and Na₂SiO₃ and subsequent lithiation of the precursor at 800 °C. The SC-NCM(010) cathode exhibits an excellent capacity retention rate (91.6% after 200 cycles at 1 C, 4.3 V) and a high rate capability (152.2 mAh/g at 20 C, 4.4 V), much superior to those of polycrystalline NCM811 cathodes. However, despite the removal of interparticle boundaries, when cycled between 2.8 and 4.5 V, the SC-NCM(010) cathode still suffers from structural changes including lattice gliding and intragranular cracking. These structural changes are correlated with the interior structural inhomogeneity, which is evidenced by the coexistence of H2 and H3 phases in the fully deintercalated state.