Atomic-Resolution In Situ Exploration of the Phase Transition Triggered Failure in a Single-Crystalline Ni-Rich Cathode.

Single-crystalline cathode materials LiNixCoyMn1-y-zO2 (x ≥ 0.6) are important candidates for obtaining better cyclic stability and achieving high energy densities of Li-ion batteries. However, it is liable to initiate phase transitions inside the grains during electrochemical cycling, and the processes and regions of these phase transitions have remained unknown. In this research, we conducted an intrinsic study, investigating the chemicals and microstructural evolution of single-crystalline LiNi0.83Co0.11Mn0.06O2 using in situ biasing transmission electron microscopy at an atomic scale. We observed that the layered structure on the surface of the single-crystalline material was degraded during the charging process, resulting in continuous phase transitions and the formation of surface oxygen vacancies, which can reduce both the structural and thermal stability of the material. Uneven delithiation led to the formation of high-density defects and discontinuous inactive electrochemical phases, such as local antiphase boundaries and the rock salt phase, in the bulk of the material. The non-uniformity of the structure and the coexistence of active and inactive phases introduce significant tensile stress, which can lead to intragranular cracks inside the grains. As the number of cycles increases, the structural degradation caused by the intragranular phase transition will further increase, ultimately affecting the cycling capacity and stability of the battery. This work has broad implications for creating lithium-ion batteries that are effective and long-lasting.

Optimizing Porous Metal-Organic Layers for Stable Zinc Anodes.

Aqueous zinc-ion batteries (ZIBs) have been considered as alternative stationary energy storage systems, but the dendrite and corrosion issues of Zn anodes hinder their practical applications. Here we report a series of two-dimensional (2D) metal-organic frameworks (MOFs) with Zr12 clusters, which act as artificial solid electrolyte interphase (SEI) layers to prevent dendrites and corrosion of Zn anodes. The Zr12-based 2D MOF layers were formed by incubating 3D layer-pillared Zr-MOFs in ZnSO4 aqueous electrolytes, which replaced the pillar ligands with terminal SO42-. Furthermore, the pore sizes of Zr12-based 2D MOF layers were systematically tuned, leading to optimized Zn2+ conduction properties and protective performance for Zn anodes. In contrast to the traditional 2D-MOFs with Zr6 clusters, Zr12-based 2D MOF layers as artificial SEI significantly reduced the polarization and increased the stability of Zn anodes in MOF@Zn||MOF@Zn symmetric cells and MOF@Zn||MnO2 full cells. In situ experiments and DFT computations reveal that the enhanced cell performance is attributed to the unique Zr12-based layered structure with intrinsic pores to allow fast Zn2+ diffusion, surface Zr-SO4 zincophilic sites to induce uniform Zn deposition, and inhibited hydrogen evolution by 2D MOF Zr12 layers.