Stabilizing Ni-Rich LiNi_0.83Co_0.12Mn_0.05O₂ with Cyclopentyl Isocyanate as a Novel Electrolyte Additive

Ni-rich layered structure materials are appealing cathodes for high-energy-density lithium-ion batteries developed for electric vehicles, drones, power tools, etc. However, poor interfacial stability between a Ni-rich cathode and carbonate electrolyte, especially at high temperatures, and fast capacity fading still hinder their mass market penetration. Here, we investigate cyclopentyl isocyanate (CPI) with a single isocyanate (-NCO) functional group as a bifunctional electrolyte additive for the first time to improve the interfacial stability of Ni-rich cathode LiNi0.83Co0.12Mn0.05O2 (NCM83). With an electrolyte containing 2 wt % CPI, the NCM83 cathode shows capacity retention of up to 92.3% after 200 cycles at 1C and 30 °C, much higher than that with the standard electrolyte (78.6%). It is demonstrated that the -NCO of CPI could largely inhibit the thermal decomposition of LiPF6 salt and scavenge water and hydrogen fluoride (HF) species, improving electrolyte stability. More importantly, the additive CPI could be preferentially oxidized, forming a stabilized and protective cathode electrolyte interphase (CEI) layer on the surface of NCM83, which effectively suppresses the parasitic side reactions and maintains the superior interfacial charge-transfer and lithium-ion diffusion kinetics. Both functions enable a significant improvement in electrochemical performance at both 30 and 60 °C.