Enhanced rate capability and high-voltage cycling stability of single-crystal nickel-rich cathode by surface...

The single-crystal Ni-rich Li(Ni_xCo_yMn_1-x-y)O₂ cathode (NCM) demonstrates better cycle performance, enhanced tap density and improved mechanical structure stability, compared with polycrystalline NCM.However, limited Li⁺ transports, (003) plane slips and microcracks in large single particles hinder rate capability and cycle performance. To overcome these shortcomings,single-crystal NCM cathodes have been modified by nanosized tetragonal BaTiO₃. Due to the dielectric properties, BaTiO₃ particles induce electric field concentration at the BaTiO₃-NCM-electrolyte interface. Thus, a large amount of lithium vacancies can be formed, providing sufficient sites for the hopping diffusion of lithium ions, thereby significantly enhancing the diffusion coefficient of Li⁺. Moreover, the redistribution of charges can inhibit the formation and accumulation of cathode-electrolyte-interface. Owing to the synergetic effect of BaTiO₃, the BT-modified single-crystal NCM with the optimized loading shows a remarkable initial discharge capacity of 138.5 mAh g^-1 and maintains 53.8% of its initial discharge capacity after 100 cycles under 5C at 4.5 V cut-off voltage. Overall, the proposed dielectric cathode-electrolyte-interface strategy can enhance Li⁺ ion transport and stabilize the interface structure, leading to improved rate performance. Meanwhile, the diffusion-induced state of charge gradient can also be inhibited, resulting in high structure stability of single-crystal NCMs under high rate and cut-off voltage cycling.