Ni-rich cathode materials have become promising candidates for lithium-based automotive batteries due to the obvious advantage of electrochemical performance. Increasing the operating voltage is an effective means to obtain a higher specific capacity, which also helps to achieve the goal of high energy density (capacity × voltage) of power lithium-ion batteries (LIBs). However, under high operating voltage, surface degradation will occur between Ni-rich cathode materials and the electrolytes, forming a solid interface film with high resistance, releasing O2, CO2 and other gases. Ni-rich cathode materials have serious cation mixing, resulting in an adverse phase transition. In addition, the high working voltage will cause microcracks, leading to contact failure and repeated surface reactions. In order to solve the above problems, researchers have proposed many modification methods to deal with the decline of electrochemical performance for Ni-rich cathode materials under high voltage such as element doping, surface coating, single-crystal fabrication, structural design and multifunctional electrolyte additives. This review mainly introduces the challenges and modification strategies for Ni-rich cathode materials under high voltage operation. The future application and development trend of Ni-rich cathode materials for high specific energy LIBs are projected.
Keywords: Ni-rich cathode materials; high voltage; microcrack; modification; surface degradation.