Single-crystal nickel-rich layered-oxide battery cathode materials: synthesis, electrochemistry, and intra-granular fracture

Electro-mechanical degradation is commonly observed in various battery electrode materials, which are often prepared as polycrystalline particles consisting of nanoscale primary grains. The anisotropic volume change during lithium extraction/insertion makes these materials intrinsically vulnerable to grain-boundary (intergranular) fracture that leads to rapid impedance growth and capacity decay. Here, guided by fracture mechanics analysis, we synthesize microsized single-crystal Ni-rich layered-oxide (NMC) cathode materials via an industrially-applicable molten-salt approach. Using single-crystal LiNi0.6Mn0.2Co0.2O2 as a model material, we show that the cycle performance of the Ni-rich NMC can be significantly improved by eliminating the internal grain boundaries and inter-granular fracture. The single-crystal LiNi0.6Mn0.2Co0.2O2 cathodes show high specific capacity (183 mAh g(-1) at 0.1 C rate, 4.3-2.8 V) and excellent capacity retention (94% after 300 cycles at 1C/1C cycling). Further, it is confirmed for the first time that the single-crystal LiNi0.6Mn0.2Co0.2O2 particles are stable against intra-granular fracture as well under normal operating conditions but do crack if severely overcharged. Electrochemical-shock resistant single-crystal NMC reveals an alternative path towards developing better battery cathode materials, beyond the traditional one built upon polycrystalline NMC.