Synthesis of Monodisperse and Discrete Ultra-High Nickel LiNi0.97Co0.02Mn0.01O2 Octahedral Single Crystals via Single Crystal Intermediates for Li-Ion Batteries.

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Micrometer-sized single crystal cathodes have garnered significant interest as promising cathode materials for lithium-ion batteries due to their ability to reduce surface area exposure to electrolytes and suppress side reactions, thereby enhancing electrochemical performance. One of the challenging issues with single crystal cathode materials is synthesizing monodisperse and discrete single crystals rather than agglomerated quasi-single crystals. However, conventional solid-state synthesis of most single crystals results in severe agglomeration and cation mixing, as it requires high temperatures to promote particle growth to several micrometers. In this study, a novel morphology-conserving reaction strategy that employs octahedron single crystal intermediates is introduced to synthesize discrete, monodisperse LiNi0.97Co0.02Mn0.01O2 octahedron single crystals. This scalable and cost-effective approach involves using rock-salt Ni0.97Co0.02Mn0.01O1+x octahedrons as single crystal intermediates, which are transformed in unreactive unary lithium salt melts (LiCl and Li2SO4) from spherical Ni0.97Co0.02Mn0.01(OH)2 obtained via coprecipitation. These intermediates are then subjected to a stoichiometric amount of Li precursor in a conventional solid-state synthesis to produce layered LiNi0.97Co0.02Mn0.01O2. This process is a morphology-conserving lithiation reaction, leading to the formation of discrete and monodisperse LiNi0.97Co0.02Mn0.01O2 octahedron single crystals. The resultant LiNi0.97Co0.02Mn0.01O2 single crystals demonstrate superior electrochemical performance, including stable capacity retention over 150 cycles, which surpasses that of typical quasi-single crystals produced through conventional methods. This is attributed to negligible crack formation during cycling, in contrast to significant cracking observed in conventional quasi-single crystals. This implies that single-crystal forms are preferred over agglomerated quasi-single crystal forms for enhancing cycle performance. These findings provide valuable insights into the industrial synthesis of discrete and monodisperse ultrahigh-nickel oxide cathode materials.