Nano-rods in Ni-rich layered cathodes for practical batteries.

Lithium transition metal oxide layers, Li[Ni1-x-yCox(Mn and/or Al)y]O2, are widely used and mass-produced for current rechargeable battery cathodes. Development of cathode materials has focused on increasing the Ni content by simply controlling the chemical composition, but as the Ni content has almost reached its limit, a new breakthrough is required. In this regard, microstructural modification is rapidly emerging as a prospective approach, namely in the production of nano-rod layered cathode materials. A comprehensive review of the physicochemical properties and electrochemical performances of cathodes bearing the nano-rod microstructure is provided herein. A detailed discussion is regarding the structural stability of the cathode, which should be maximized to suppress microcrack formation, the main cause of capacity fading in Ni-rich cathode materials. In addition, the morphological features required to achieve optimal performance are examined. Following a discussion of the initial nano-rod cathodes, which were based on compositional concentration gradients, the preparation of nano-rod cathodes without the inclusion of a concentration gradient is reviewed, highlighting the importance of the precursor. Subsequently, the challenges and advances associated with the nano-rod structure are discussed, including considerations for synthesizing nano-rod cathodes and surface shielding of the nano-rod structure. It goes on to cover nano-rod cathode materials for next-generation batteries (e.g., all-solid-state, lithium-metal, and sodium-ion batteries), inspiring the battery community and other materials scientists looking for clues to the solution of the challenges that they encounter.

Mechanism Behind the Loss of Fast Charging Capability in Nickel-Rich Cathode Materials.

Fast charging technology for electric vehicles (EVs), offering rapid charging times similar to conventional vehicle refueling, holds promise but faces obstacles owing to kinetic issues within lithium-ion batteries (LIBs). Specifically, the significance of cathode materials in fast charging has grown because Ni-rich cathodes are employed to enhance the energy density of LIBs. Herein, the mechanism behind the loss of fast charging capability of Ni-rich cathodes during extended cycling is investigated through a comparative analysis of Ni-rich cathodes with different microstructures. The results revealed that microcracks and the resultant cathode deterioration significantly compromised the fast charging capability over extended cycling. When thick rocksalt impurity phases form throughout the particles owing to electrolyte infiltration via microcracks, the limited kinetics of Li+ ions create electrochemically unreactive areas under high-current conditions, resulting in the loss of fast charging capability. Hence, preventing microcrack formation by tailoring microstructures is essential to ensure stability in fast charging capability. Understanding the relationship between microcracks and the loss of fast charging capability is essential for developing Ni-rich cathodes that facilitate stable fast charging upon extended cycling, thereby promoting widespread EV adoption.

Intergranular Shielding for Ultrafine-Grained Mo-Doped Ni-Rich Li[Ni0.96 Co0.04 ]O2 Cathode for Li-Ion Batteries with High Energy Density and Long Life.

Deploying Ni-enriched (Ni≥95 %) layered cathodes for high energy-density lithium-ion batteries (LIBs) requires resolving a series of technical challenges. Among them, the structural weaknesses of the cathode, vigorous reactivity of the labile Ni4+ ion species, gas evolution and associated cell swelling, and thermal instability issues are critical obstacles that must be solved. Herein, we propose an intuitive strategy that can effectively ameliorate the degradation of an extremely high-Ni-layered cathode, the construction of ultrafine-scale microstructure and subsequent intergranular shielding of grains. The formation of ultrafine grains in the Ni-enriched Li[Ni0.96 Co0.04 ]O2 (NC96) cathode, achieved by impeding particle coarsening during cathode calcination, noticeably improved the mechanical durability and electrochemical performance of the cathode. However, the buildup of the strain-resistant microstructure in Mo-doped NC96 concurrently increased the cathode-electrolyte contact area at the secondary particle surface, which adversely accelerated parasitic reactions with the electrolyte. The intergranular protection of the refined microstructure resolved the remaining chemical instability of the Mo-doped NC96 cathode by forming an F-induced coating layer, effectively alleviating structural degradation and gas generation, thereby extending the battery's lifespan. The proposed strategies synergistically improved the structural and chemical durability of the NC96 cathode, satisfying the energy density, life cycle performance, and safety requirements for next-generation LIBs.